TOC Application Handbook2 14F

Sum Parameter
Applications
Release 2
Content
1. Environmental Analysis
1.1. TOC determination in drinking water
1.2. TOC determination in wastewater
1.3. TOC determination in surface water and groundwater
1.4. TOC determination in seawater
1.5. TOC determination in solid samples using the suspension
method
1.6. TOC determination in particle-containing samples
cellulose test according EN 1484
1.7. Determination of particulate organic after filtration

(glass fiber suspension)
1.8. TOC determination in solids
1.9. Determination of microbial biomass in soils
TOC in soil science
2. Pharmaceutical Industry
2.1. TOC determination in ultrapure water
comparison of the various oxidation techniques
2.2. TOC determination in cleaning validation final Rinse
2.3. TOC determination in cleaning validation
SWAB Method
2.4. TOC determination according to EP 2.2.44

2.5. TOC determination in ultra pure water with wet chemical
oxidation
2.6. TOC determination according to USP 643 (USP 36-NF 31)
3. Chemical Industry
3.1. TOC determination in hydrochloric acid
3.2. TOC determination in nitric acid
3.3. TOC determination in sulfuric acid
3.4. TOC determination in brine solution
3.5. TOC determination in sodium hydroxide solution
3.6. TOC determination in soda solution
3.7. TOC determination in ammonia or ammonium salt

solution
3.8. TOC determination in sodium nitrate and sodium nitrite
3.9. TOC determination in phosphoric acid (TOC-V WP)
3.10. TOC determination in diluted hydrofluoric acid
4. TOC special application

4.1. TOC determination in algal biomass suspension
method
4.2. TOC determination in liquid manure and fermentation
fluids suspension method
5. TOC in daily practice
5.1. TOC determination methods according to EN 1484
5.2. Determination of the purgeable organic carbon (POC)
5.3. TNb total bound nitrogen
5.4. Kit for high-salt samples
5.5. Kit for small sample volumes
5.6. Kit for manual injections
5.7. Calibration with automatic dilution function
5.8. Blank value consideration in TOC analysis
5.9. TOC measurement principle catalytic combustion at
680C
6. TOC process analysis
6.1. Continuous TOC/TN determination in wastewater treatment plants
6.2. TOC process analysis in the paper industry
6.3. Continuous TOC determination in the chemical industry
6.4. Continuous condensate monitoring using the TOC-4200
4.3. Carbon dioxide determination in beer

4.4. Measurement of TOC in Mineral Water
4.5. Monitoring of Algae Growth by TOC Measurement
4.6. Characterization of Algae by TOC Measurement
5.10. TOC-L detection limit normal catalyst

5.11. TOC determination with wet chemical UV-oxidation
5.12. Silanisation of syringe TOC determination of surfactant
5.13. TOC determination with solid module SSM-5000A
5.14. Comparison of different sum parameters COD, BOD
and TOC
5.15. COD and TOC correlation factor conversion examples
5.16. TOC control samples and control cards
6.5. TOC-4200 with high sensitivity option

6.6. Continuous TOC determination on airports
6.8. TOC-4200 measurement range up to 55,000 mg/L TOC
1. Environmental analysis
1. Environmental analysis
1.1. TOC determination in drinking water
1.2. TOC determination in wastewater
1.3. TOC determination in surface water and groundwater
1.4. TOC determination in seawater
1.5. TOC determination in solid samples using the suspension
method
1.6. TOC determination in particle-containing samples

cellulose test according EN 1484
1.7. Determination of particulate organic after filtration
1.8. TOC determination in solids
1.9. Determination of microbial biomass in soils
TOC in soil science
A clean environment is the basis for a healthy life. Whether

water, soil or air keeping the environment clean for the protection of all creatures should be the primary responsibility of
any society. In Europe alone, there are numerous laws, ordinances and administrative regulations describing the environmental conditions needed to ensure a certain environmental
standard. Instrumental analysis is a useful tool to measure the
status of environmental conditions.
TOC analysis is therefore carried out in a wide variety of environmental matrices: from groundwater to seawater, from
drinking water to wastewater, from soils to sewage sludge.
The diversity in environmental applications creates many different challenges for the analytical systems being used. In addition to the different concentration ranges, TOC analysis repeatedly faces different types of conditions such as salt content or
number of particles.
Looking at the numbers of possible chemical contaminations

(compounds), the group of organic compounds is the largest.
With an estimated number of more than 19 million, it is impossible to detect and quantify each and every one of them.
Shimadzu offers various solutions for these different applications. The TOC-L family is module-based. Two basic analyzer
types can be equipped with many options, kits and numerous
accessories and customized to any particular application. This
makes the TOC-L one of the most universal TOC analyzers.
The sum parameter TOC (Total Organic Carbon) is one of the

most important parameters used in many environmental applications. TOC analysis enables the determination of the sum of
all organically bound carbons in the abovementioned organic
compounds and is, therefore, a measure of organic pollution
in a matrix.
The relevance of the TOC parameter becomes clear when looking at the parameter lists of various regulations in European
countries: the Waste Disposal Ordinance, the Waste Technical
Guidelines, the Landfill Ordinance, the Ordinance pertaining
to the Recovery of Waste, the Stowing Directive, the Drinking
Water Ordinance and the Wastewater Ordinance are just some
that mention TOC as a valuable parameter.
Further details can be found in the individual application notes

(for instance TOC determination in drinking water, wastewater
or suspensions). In addition to environmental analysis, there
are also application notes and information on Pharmaceutical
industry, Chemical Industry, TOC special applications, TOC
in daily practice and TOC process analysis.
Sum parameter Total Organic Carbon
TOC Determination in drinking water
No. SCA-130-101
Drinking water is one of the main important
and life-sustaining food stuffs and is essential
to the survival of all known organism. It is a
crucial component for metabolic processes
and serves as solvent for many bodily
solutes. Water for human consumption must
be free from pathogens, pleasant to drink and
pure. Continuous monitoring is carried out
according to European Drinking Water
Regulation to ensure the greatest possible
security
European Drinking Water Directive

The Directive is intended to protect human
health by laying down healthiness and purity
requirements which must be met by drinking
water within the European Union (EU).
The directive applies to all water intended for
human consumption apart from natural
mineral waters and water which are medicinal
products.
The European drinking water directive
includes the category of indicator parameter
value specifications. These are not directly
linked to health problems but have an
indicator
function.
This list of indicator parameters also includes

the TOC value (total organic carbon), which
has not been assigned a limiting value or
criterion but can be considered as a
cautionary warning for action under unusual
circumstances. Another indicator parameter
included in the list is oxidizability. This is a
measure for the sum of all chemically
oxidizable organically bound compounds
present in water.
With reference to drinking water limiting
values, this parameter is no cause for direct
health concern but can lead to regermination
or undesirable disinfection byproducts.
Oxidizability is proportional to the sum of
organically
bound
carbons
that
are
determined as DOC (dissolved organic
carbon) or TOC. Oxidizability can therefore
be replaced by the TOC parameter. The
frequency of determination of the parameter
indicators depends on the volume of water
that is produced or released in a water supply
area.
TOC determination in drinking water

When examining carbon compounds in
drinking water, it is apparent that the amount
of inorganic carbons, such as carbonates and
hydrogen carbonates, is much higher than
the organic fraction.
SCA-130-101
Example:
TC = 100 mg/l (RSD = 2%) 2 mg/l
(98 102 mg/l)
IC = 98 mg/l (RSD = 2%) 1,96 mg/l
(96,04 99,96mg/l)
Based on error propagation the total error is
3,96 mg/l
TOC (calc.) = 2 mg/l 3,96mg/l
(- 1,96 - 5,96 mg/l)
The total error is bigger than the TOC-result,
negative results are possible.
According to European Standardization EN
1484 (instructions for the determination of
total organic carbon and dissolved organic
carbon), the difference method can only be
applied when the TIC value (total inorganic
carbon) is smaller than the TOC value.
For drinking water analysis the NPOC
method (non purgeable organic carbon) is
therefore used. The drinking water sample is
first acidified to a pH value of 2. This way the
carbonates and hydrogen carbonates are
transformed into carbon dioxide. The CO2 is
then removed via sparging with carrier gas.
The amount of volatile and therefore
purgeable organic carbon can be disregarded
in drinking water. What remains is a solution
of non-volatile organic carbon compounds.
These can be oxidized to CO2 and detected
via NDIR.
TOC-L Series
The sample preparation for the NPOC
method (acidification and sparging) is automatically done in the TOC-L analyzer. The
removing of the TIC can be performed either
in the syringe of the ISP-Module or in the
autosampler with the external spare kit.
The ISP (integrated sample preparation)
module consists of an 8-port valve and a
syringe with sparging gas connection. In
addition to acidification and sparging in the
syringe, the ISP also enables automatic
dilution. This feature facilitates an extended
measuring
range,
dilution
of
highly
contaminated samples and the preparation of
a series of calibration samples from a stock
solution. The ISP module can therefore
considerably reduce time-consuming sample
handling steps.
Example of drinking water analysis:
NPOC-Method
Acidification: 1,5%
Sparge time: 5 minutes
10
9
Signal[mV]
The organic fraction is only 1% of the total

carbons. A TOC determination via the
difference method (TOC = TC - IC) will not be
appropriate in this case, as the calculated
TOC value is prone to large statistical errors.
6
3
0
-1
0
14
Zeit[min]
Recommended analyzer / Configuration

TOC-L CPH
ASI-L (40ml), External Sparge-Kit.
TOC-VWP with ASI-V (40ml)
TOC Determination in wastewater
SCA-130-102
Wastewater is water that has been

contaminated by use. In terms of its
composition, wastewater is not homogeneous
but as diverse as its possible sources.
Sewage also includes the liquids that are

discharged and collected from waste
treatment and storage plants.
This diversity of wastewaters should also be
taken into account during the analysis.
Wastewater can thus contain small amounts
of organic pollutants with little matrix, as well
as highly saline products with high amounts
of organic components.
According to the German Water Resources

Act
(Wasserhaushaltsgesetz,
WHG)
wastewater is defined as follows:
Example of wastewater measurement

Below, a strongly saline wastewater from the
chemical industry was analyzed. In addition
to various substances present in low
amounts, the wastewater mainly contained
high amounts of phenolic substances
originating from production processes.
Wastewater is
1) water whose properties have been
changed by domestic, commercial,
agricultural or other use and the water
(sewage) discharged with it during dry
weather conditions as well as
2) the run-off and collected water (rainwater)
from built-up or paved areas following
precipitation.
Fig. Result of the wastewater
SCA-130-102
A TOC-LCPN was used for the analysis. To

ensure efficient use of the instrument for
large sample quantities, the fully automated
dilution function and the additional high-salt
sample kit were applied. With a dedicated
function, samples could be diluted up to a
factor of 1:50. For the phenol-containing
wastewater, the sample was diluted by a
factor of 1:10. The high-salt sample kit
increases the lifetime of the catalyst for high
salt loads.
In many cases, wastewater contains

particles. Where the wastewaters are not
filtered, the particles need to be held in
suspension by stirring. In order to prevent in
homogeneity
of
the
particles
by
sedimentation within the syringe body,
multiple injections from the same syringe may
not be carried out in this case.
Recommended Analyzer / Configuration

TOC-L CPN with normal sensitive Catalyst or
kit for high salt samples (B-Type-Scrubber)
ASI-L (40ml) with stirrer option (for samples
with particles) and External Sparge-Kit
Fig. Combustion tube (of salt kit)

after the long term test
To test long-term stability, more than 300

injections of the saline wastewater were
compared.
The
graph
shows
the
stability
of
measurement of over 300 injections with a
standard deviation of 1.7%. Mean value was
3042 mg/L.
Useful instrument parameters::

Use of integrated dilution function for
automated sample dilution
In the presence of particles: deactivation
of multiple injection via the syringe.
TOC Determination in surface and

groundwater
SCA-130-103
The
German
Water
Resources
Act
(Wasserhaushaltsgesetz, WHG) serves the
purpose of sustainable water management
to protect waters as a component of the
ecological balance, as a basis of human
existence, as a habitat for animals and plants
as well as a usable good. The various water
types are defined in this act.
exhibit high levels of TOC concentrations

caused by natural substances or dissolved
harmful substances from the environment.
Surface water
Typical TOCConcentrations in
mg/l
Clean spring water
1-2
Weakly polluted rivers

and streams
25
Nutrient-rich stagnant
lakes
5 - 10
Polluted waters
50 - >100
Clean groundwater
(well water)
1 -2
Typical TOC-Concentrations (1)
Definitions according to WHG

Groundwater is defined as water that is
below the surface of the ground in the
saturation zone and in direct contact with the
ground or subsoil. Surface water is
permanently or temporarily confined flowing
or standing waters, and unconfined waters
from natural springs. Surface waters include
bodies of water above ground such as lakes,
rivers and streams as well as coastal waters.
Rainwater that has not yet flowed away is
also included.
Surface waters are often contaminated with
particles and harmful substances. They can
only be used as drinking water after
undergoing a treatment process (Wikipedia).
By definition, these waters can be very
different due to regional conditions. They can
Depending on the region, high TIC

concentration (> 100 mg/L) can also occur in
surface water as well as in groundwater.
At TOC concentrations of far below 10 mg/L,
it needs to be ensured that inorganic carbon
is being purged from the solution.
SCA-130-103
The excellent particle tolerance of the

analyzers enables analysis of particlecontaining surface waters. Using the
automatic dilution function, multi-point
calibrations can be generated from a single
standard. In the investigation of unknown
surface waters or groundwater, one of the
samples may exceed the calibration range. In
this case, the TOC Control-L software offers
an option for automatic dilution to bring the
sample back within the calibration range.
Example: River water

20
14
Signal[mV]
TOC-L
To prepare the sample accordingly, the ISP
module of the TOC-L automatically acidifies
the sample and strips the CO2 originating
from the TIC.
0
-2
0
NPOC-Method
Acidification: 1,5%
Sparge-time: 5 Minutes
TOC-Concentration: 3,4 mg/l
RSD (3 Injections): 1,4%

- TOC-LCPH
- ASI-L (40ml) with stirrer option
- External Sparge-Kit
(1)Source:Wikipedia
TOC Determination in seawater
SCA-130-104
TOC is an important indicator of the degree of

organic contamination. TOC determination is
used extensively to detect and study
environmental and seawater pollution. In
recent years, increased attention is being
paid to the measurement of the nitrogen
compounds (TN = Total Nitrogen) responsible
for eutrophication.
Seawater samples
Seawater has an average salinity of 3.5%
mass fraction. The total salinity fluctuates
depending on each ocean. The Baltic Sea
has a salinity of 0.2 to 2%. Some inland seas
without outlets have far higher water
salinities. The Dead Sea is known for its
salinity of 28%. Chloride ions constitute the
main component of the anions, followed by
sulfate ions. Sodium ions dominate among
the cations, which is why the major proportion
of crystallized sea salts consists of sodium
chloride (common salt). Magnesium, calcium
and potassium ions are represented in
smaller amounts.
Are high salt loads a problem?

During thermal catalytic combustion of the
test sample, the dissolved salts crystallize.
Depending on the salt concentration, this can
affect or clog the system.
Maintenance
measures (for instance exchanging the
catalyst) would then be required in order to
render the instrument operational again. Of
course, it is desirable to keep the
maintenance intervals as long as possible.
TOC-L Series
The TOC-L series offers various possibilities
to keep the maintenance need for highly
polluted samples as low as possible. The
analyzers are operated under catalytic
combustion at 680 C. This temperature is
lower than the melting point of sodium
chloride and therefore prevents deactivation
of the active centers of the catalyst by a melt.
The use of the platinum catalyst ensures
complete conversion of organic carbon
compounds to CO2.
The highly sensitive NDIR detector allows
small injection volumes (typically 20 - 50 L)
that reduce absolute sample input onto the
catalyst.
SCA-130-104
Kit for high-salt samples

The TOC-L series features a kit for high-salt
samples, which significantly increases
instrument availability.
Using this kit in a seawater application, it was
possible to carry out 2500 injections without
maintenance (injection volume of 40 L).
The kit consists of a combustion tube with a
special geometry and a unique catalyst
mixture.
Compound
Melting point
NaCl
801C
KCl
773C
Na2SO4
888C
MgCl2
708C
CaCl2
782C
K2SO4
1.069C
Tab. Melting point of different salts
Simultaneous TN determination using

the TNM-L
Based on the similar oxidation process, the
TNb determination can be carried out
simultaneously with the TOC measurement.
For this application, the TNM-L option is
installed on the main TOC-L system.
In this application, sample acidification is

carried out with sulfuric acid which is used to
modify the sample matrix. While NaCl has a
melting point of 801 C, the melting point of
NaSO4 is higher (888 C). The potassium
salts of sulfuric acid also have a significantly
higher melting point than those of
hydrochloric acid. This has a positive effect
on the lifetime of the combustion tube.
Figure: Simultaneous TOC/TN-Determination

TOC-L CPN
TNM-L
TOC determination in solid samples

using the suspension method
SCA-130-105
The TOC content in solids plays an important

role in the classification of soils, sludges and
sediments. According to the German
Ordinance on Environmentally Compatible
Storage of Waste from Human Settlements
(Abfallablagerungsverordnung,
AbfAblV),
TOC in solid materials is one of the key
parameters for the characterization of wastes
as part of the acceptance control of landfills.
This important control measure requires a
fast and simple TOC determination method
and, at the same time, a robust and
statistically reliable method that is based on
the inhomogeneous composition of soils.
Suspension method
Several years ago, Shimadzu developed the
so-called suspension method in cooperation
with responsible authorities and the Albo-tec
environmental
laboratory
in
Bochum,
Germany. In this method, the solid sample is
processed in a specific way so that it can
subsequently be treated as a liquid, particlecontaining sample. This method was
successfully applied in several round robin
tests and has, since June 2009, also been
described in the draft DIN EN 159536. This
new standard is intended to replace DIN EN
13137 and describes the established solid
sample combustion method as well as the
novel suspension method (see annex).
Analytical process
To date, the established regulations describe

a method whereby a weighed solid sample is
combusted in a stream of air or oxygen. The
CO2 generated during combustion is
subsequently detected and quantified using a
calibration curve. The inhomogeneity of the
soils has a direct effect on the distribution of
the measuring data each weighed solid
sample can only be combusted once.
Approximately 200 mg of the dried and

ground sample is weighed into an Erlenmeyer
flask. The sample is subsequently suspended
in a diluted hydrochloric acid solution. The
acidic solution serves to break down the
carbonates present in the sample and, at the
same time, form the suspension medium.
SCA-130-105
The suspension is homogenized for several

minutes at a speed of 17,000 18,000 rpm
using a dispersion unit. It is critically
important to select a suitable precision tool.
After homogenization, the suspension is
transferred directly to autosampler vials.
Critical for subsequent measurement is the
use of a magnetic stirrer in the autosampler
to ensure that the suspension remains
homogeneous during sampling. After all, the
small particles should not sediment, but
remain uniformly distributed throughout the
solution. The suspensions can now be
repeatedly injected and analyzed.
Example of suspension determination
NPOC-Method (Acidification is done by

creation of the suspension)
Sparge-time: 5 Minutes
Injection volume: 90l
Multi-Injection is deactivated
Statistic
This method enables not only automated

solid sample analysis using an autosampler,
but also parallel measurement of solid and
liquid samples in the same sample table and
the same sample tray. In addition to speed,
this method is also impressive in terms of
robustness. The possibility of multiple
injections enables differentiation of small
variations due to weighing and measuring.
Peak-No
Areas
1
2
3
4
5
6
7
8
9
10
MW
RSD in%
183,7
180,9
189,0
183,8
179,9
179,9
179,9
186,9
181,6
177,6
182,2
1,88
Result of
suspension
TOC in mg/l
24,71
24,23
25,61
24,72
24,06
24,06
23,89
25,25
24,35
23,67
24,5
2,52
Result of
Sample TOC
in %
2,47
2,42
2,56
2,47
2,41
2,41
2,39
2,53
2,37
2,37
2,45
2,49

TOC-L CPN
ASI-L (40ml) with stirrer option and
external Sparge-Kit.
TOC determination in particle-containing

samples - Cellulose test according to EN 1484
SCA-130-106
Depending on their origin, different effluents
can contain substantial amounts of insoluble
solids. These include clearly visible
components that, in some cases, sediment
very quickly. This applies particularly to heavy
particles such as sand grains. Suspended
solids such as fibers or flakes are naturally
less likely to sediment. However, they also
cause a certain inhomogeneity of the sample
matrix.
A variant of TOC determination is the

detection of DOC, Dissolved Organic Carbon.
The wastewater sample is filtered through a
membrane filter with a 0.45 m pore size and
subsequently measured. In contrast to DOC,
TOC (Total Organic Carbon) determinations
must detect the total organic carbon in a
sample, including the insoluble components.
According to DIN 1484, the suitability of a

TOC measurement system for the analysis of
wastewater samples that contain solid matter
must be tested. This is carried out using the
so-called cellulose test (Appendix C of the
above-mentioned standard).
Cellulose test according to DIN EN 1484
The cellulose test is based on an aqueous
cellulose suspension with a carbon content of
100 mg/L. This corresponds to 225 mg
cellulose. The particle size ranges from 20
m to 100 m. Homogenization may only be
carried out under stirring. Alternative methods
such as ultrasound can break up the particles
and thereby provide erroneous results. Large
particles in particular have a tendency
tosediment rapidly.
Stirring speed is critical for this reason. Very
slow stirring leads to increased particle
sedimentation. Extremely high stirring speeds
lead to inhomogeneous particle distribution
due to centrifugal force. DIN 38402 part 30,
dealing with sample homogenization, serves
in this context as an excellent reference. A
solution should be stirred in such a way that
the vortex will amount to 10% of the filling
level.
For three consecutive injections, the mean
value must lie within the range of 90 mg C/L
to 110 mg C/L (corresponding to a recovery
of 90 110 %). The relative standard
deviation (RSD) may not exceed 10 %.
SCA-130-106
Particle tolerance of the TOC-L series

This test was carried out using a TOC-L
system (TOC-LCPH including ASI autosampler
with integrated stirring option).
Settings
Injection volume 90 L
TC measurement for the particle test
NPOC measurement in the autosampler
Stirrer in the ASI-L,
medium stirring speed
No multiple injection
Used Cellulose-Standard:
Cellulose powder MN 100
Particle size: 20-100m
Supplier: Machery-Nagel
System Configuration
- TOC-L CPX
- ASI-L (40ml recommended) with particle
needle l
- Stirrer option
- Offline-Port can be used too
Results
The cellulose suspension was injected five
times according to the above settings.
NPOC = 98,4 2,2 mg/l (RSD = 2,27 %).
This corresponds to a recovery of 98,4 %.
.
The TOC-LCPH was first calibrated using the

automated dilution function in the range of 10
100 mg/L.
Abb.2 Peak graph of cellulose-suspension
These values are clearly within EN DIN

specifications
Figure 1 Calibration curve 10-100mg/L
SCA-130-107
Determination of particulate organic

carbon after filtration
A limnological research laboratory tackled the

problem of determining the particulate TOC
content of the sample independently of DOC
(Dissolved Organic Carbon) content. The
water sample was filtered through filters of
varying pore sizes. Particles of varying sizes
remain on the filter. The question arose, how
particulate TOC can be best measured.
The field test

A TOC analyzer with autosampler was used
for the field test. After calibration of the TOC
system, the test solution was measured 10
times. The test solution consisted of a glass
fiber suspension in hydrochloric acid (five
glass fiber filters dispersed in 500 mL) that
was
continuously
stirred
during
measurement. To test the catalyst, a
standard solution with a TOC of 50 mg/L was
injected after each 10th measurement. After
100 injections and visual inspection of the
catalyst and the catalyst tube, the measuring
cycle was somewhat increased. Function of
the catalyst was now checked using the
standard test solution only after every 20
injections of the glass fiber suspension.
Fig. Used glass fiber filter
A possibility would be to shred the filter and

disperse it in water, and to measure the
obtained suspension directly using the TOC
system. This requires use of TOC-free glass
fiber filters. This uncommon question requires
a field test. Based on the melting range of
glass fiber (about 550 C) it was necessary to
ensure that the glass fiber content would not
clog or deactivate the catalyst (680 C) and to
establish where the oxidizing power
diminishes.
After a total of 450 injections, no visible

change of the catalyst could be detected. Nor
did the oxidative properties change or
deteriorate in any way. Reproducibility of the
results also did not reveal any change.
SCA-130-107
Statistics
As an example, the figure below shows the
final 20 injections of the field test. Relative
standard deviation was 1.8%.
The standard solution after the last glass fiber
suspension injection cycle resulted in a TOC
recovery of 97.6%.
The TOC field test clearly showed that the
oxidative power of the catalyst, even after
several hundred glass fiber suspension
injections, did not deteriorate. Active centers
of the catalyst were not affected, nor did they
fuse.
Injection
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Mean Value
SD
RSD in %
Conc. In mg/l
0,7430
0,6947
0,6819
0,6850
0,6959
0,6930
0,6966
0,6831
0,6901
0,6997
0,6943
0,6890
0,6896
0,6871
0,6945
0,6934
0,6982
0,6936
0,6951
0,6924
0,6945
0,0124
1,78
Tab. Peak areas and statistics

of the last 20 injections
Fig. Peak graphs of the last 20 injections

TOC-L CPN
ASI-L (40ml) with stirrer option and external
Sparge-Kit.
Shimadzu Deutschland GmbH
Info@shimadzu.de
www.shimadzu.de/home
TOC determination in soils, sludges and

sediments using the solid sample module
SCA-130-108
To characterize soils, sludges or sediments,
the total organic carbon parameter (TOC) is
regularly used. In addition to naturally
occurring organic components in these solids,
undesirable organic contaminations caused
by man and industry are also often present.
These organic compounds frequently are
risks. Solids to be disposed or utilized must
be tested on their TOC content. The organic
contaminations can contaminate ground
water, for instance when leached out. In
addition, hazardous gases such as methane
can be formed through biological activities in
the soil and compromise the safety of
landfills. The formation of such gases or the
biological decomposition of organic materials
in soils, inevitably lead to the formation of
cavities that reduce the stability of the
materials and renders them unsuitable for
specific application areas, such as road
construction.
TOC determination
To investigate the TOC in soils or other solids
such as sediments or sludges, a solid sample
module is used which enables TOC
determination using the difference method
and the NPOC method.
Here, a subsample of the dried solids is

weighed into a ceramic boat and combusted
at 900 C in a stream of oxygen. To ensure
complete conversion to CO2, the generated
gases are passed over a mixed catalyst
(cobalt/platinum)
for
catalytic
postcombustion.
The determination of the inorganic carbon is
carried out in a separate furnace of the
module. Phosphoric acid is added to the
sample and the resulting CO2 is purged at
200 C and measured.
This is why different TOC limit values are

specified for soil replacement and for
deposits in landfills.
The SSM-5000A solid sample module does

not have its own detector, but is coupled to
the NDIR detector of the main instrument
(TOC-V or TOC-L). The detector is equipped
with two coupled measuring cells that way to
complete the measurement of solids and
liquids consecutively without any additional
conversion.
SCA-130-108
The module is fully integrated into the TOCControl

software
which
automatically
calculates the TOC-content.
Calibration of the IC is carried out in the same

way, for instance using sodium hydrogen
carbonate.
NPOC determination
For the NPOC method, the sample is
acidified in order for the CO2 to be purged
from
the
carbonates
and
hydrogen
carbonates. This pretreated sample is then
used to determine the TC (and thus the
NPOC).
Detection limit
The detection limit for this method is at
0.1 mg C. For a soil sample weight of 1 g, a
theoretical detection limit of 0.01 wt.% TOC is
obtained.
Small amounts of additives such as vanadium

(V) oxide or tungsten oxide are added to such
samples. They act as catalysts and ensure
complete determination.
Calibration
Calibration can be performed in different
ways. Usually, the calibration is carried out in
the solid sample module using different
sample weights of a solid with known carbon
content, for instance glucose which contains
40% carbon. For the different sample weights
(in g absolute carbon), the absolute amount
of carbon is plotted on the X-axis of the
calibration graph.
Sample weight: 1st Peak: 110 mg

2nd Peak: 190 mg
Result:
1.) 4.04 % TC
2.) 4.08 % TC
Mean value: 4.06% TC

1000
Signal[mV]
Additives
Large amounts of earth-alkali compounds
such as barium or calcium carbonate can be
difficult to determinate. Bicarbonate, for
instance, needs temperatures up to 1200C
to be thermally decomposed.
Example of a solid sample measurement

Sample type: contaminated soil
600
300
0
-100
0
10
Zeit[min]
Abb.: Peaks for various sample weights.
Kal. Kurve
2136,2
Recommended instrument / equipment

TOC-LCXX
TOC-VWX
SSM-5000A
Flche
1500
1000
500
0
0
4000
8000
Abs C [ug]
12000
18101,6
Abb.: TOC calibration in the SSM-5000A using

Glucose.
Determination of microbial biomass in soils TOC in soil science
No.SCA-130-109
Fertile soils contain a multitude of microorganisms. They are responsible for the
degradation of organic substances and
protection of the nutrient cycle. To evaluate
soils in terms of their biodegradability and their
fertility, the microbial biomass of the soil, i.e.
the organic carbon fraction that is bound to
these tiniest organisms, is determined.
The fumigation-extraction method is a

commonly used method for the determination
of microbial biomass in soils. The microbial
biomass is described regarding extractable
organic carbon compounds before and after
killing off the microorganisms.
In the fumigation-extraction method, a
subsample of the soil is treated with
chloroform gas in a suitable apparatus (e.g. a
desiccator) over an extended period of time of
at least 24 hours. This destroys the cell walls
and kills off the microorganisms. After
fumigation, the chloroform remaining in the
soil is removed.
DOC Determination
Subsequent to fumigation, each fumigated
subsample and one non-fumigated soil
sample is mixed with a 0.5 M (mol/L)
potassium sulfate solution and then shaken.
After filtration of the eluate, the DOC
(dissolved organic carbon) of the extracts is
determined. Since experience has shown, not
all cells are destroyed and extracted, and an
empirical correction factor is additionally
applied. (An exact description of the
fumigation-extraction method is found in the
EN ISO 14240-2:2011 standard).
Kit for high salt loads
The kit for high salt loads was used for these
measurement because the extraction solution
alone has a salt load of approximately 87 g/L.
High salt loads can lead to clogging of the
catalysts and the combustion tube. This
special kit consists of a combustion tube
featuring a specific geometry and a unique
catalyst mixture. This particular catalyst can
handle up to 12 times more salt than a
conventional catalyst.
SCA-130-109
Here in comparison the peak graphic of

injection 1-20
20
14
Signal[mV]
Long-term test with 600 injections

A long-term test should show that an
application, such as the analysis of soil
extracts from a 0.5 M potassium sulfate
solution can be carried out problem-free using
a kit for high salt load samples. For this test, a
0.5 M K2SO4 solution (corresponding to 87 g/L)
was injected 600 times onto the kit for high-salt
samples.
0
-2
0
10
20
Zeit[min]
30
40
and the peak graphic of injection 581-600

20
Results
Area
Mean value
Standard
deviation
Standard
deviation in %
17,01
NPOCconcentration
[mg/l]
6,66
0,392
0,153
2,3
2,3
14
Signal[mV]
Method parameter
NPOC preparation: automated
Acidification:
2%
Sparging:
6 Minutes
Injection volume:
50 l
Calibration:
0,5 mg/l to 10 mg/l.
0
-2
0
10
20
Zeit[min]
30
40
Conclusion
As one can see, the TOC-L in combination
with the kit for high salt load samples is highly
suitable for TOC determination of saltcontaining samples, such as soil extracts from
a 0.5 M potassium sulfate solution.
Recommended Analyser / Configuration
TOC-LCXX
Kit for high salt loads
Even after 600 injections, the peak shapes

remain exactly the same as at the start of the
injection series.
Sequence(areaandconcentration)ofthe600injections
2. Pharmaceutical industry
2. Pharmaceutical industry
2.1. TOC determination in ultrapure water comparison of the
various oxidation techniques
2.2. TOC determination in cleaning validation final Rinse
2.3. TOC determination in cleaning validation SWAB
Method
2.4. TOC determination according to EP 2.2.44

2.5. TOC determination in ultra pure water with wet chemical
oxidation
2.6. TOC determination according to USP 643 (USP 36-NF 31)
Pharmaceutics is an ancient science that has supported people

with remedies to help alleviate pain and heal illnesses. After
medication, certain substances are expected to unfold their
beneficial effects while side effects from interfering substances and contaminations are undesirable. This is why it is
important to use the purest possible substances and purified
equipment and materials in the production of drugs.
Many drugs are manufactured in batch mode operation. Prior

to the production of the next batch, materials and working
equipment must be extensively cleaned. In order to verify that
the equipment is free from the previous drug batch, the TOC
parameter is used for the evaluation of the cleaning process.
The TOC not only mirrors the presence of drugs, but also reveals other contaminants such as those from cleaning agents.
To meet this standard, legislators have published Pharmacopoeias. These include methods and rules for the manufacture,
storage, quality and testing of drugs. For drug manufacturers,
complying with the rules and methods of the Pharmacopoeia is
mandatory.
With its TOC analyzers, Shimadzu offers systems that are suitable for many different TOC analysis issues in the pharmaceutical industry. In addition to the lowest detection sensitivity, the
robust analyzers offer the highest precision and accuracy. Just
like the analyzers themselves, the operation and evaluation
software complies with all requirements of the FDA and the
Pharmacopoeia.
TOC determination is also described in the Pharmacopoeia (for

instance the European Pharmacopoeia = EP). The sum parameter serves as a measure of contamination by organic compounds. Not only the method itself is described, but also a test
to verify the suitability of a TOC analyzer for the analysis.
In addition to ultrapure water required for the manufacture of
drugs, water for injections water that is directly injected into
the bloodstream of the human or animal body is also tested
for its TOC content. The Pharmacopoeia actually specifies a
maximum TOC limit value for such specific waters.
Further information can be found in the individual application

notes (for instance TOC determination in ultrapure water,
cleaning validation or in accordance with EP 2.2.44). In addition to pharmaceutical applications, there are also application
notes and information on Environmental analysis, Chemical
industry, TOC special applications, TOC in daily practice and
TOC process analysis.
SCA-130-201
TOC determination in ultrapure water

Comparison of the various oxidation
techniques
Ultrapure water is one of the most widely

used excipients in the production of
pharmaceuticals. It is also used for cleaning
purposes. Different application areas require
different grades of ultrapure water quality.
These grades are defined in the European
Pharmacopoeia, which distinguishes between
Purified Water, Highly Purified Water and
Water for Injection (The United States
Pharmacopoeia, however, does not use the
same classification as the European
Pharmacopoeia).
Water Purified is used in the manufacture of

pharmaceuticals that do not require any other
standard. The organic content is determined
either via the TOC value (0.5 mg/L) or via the
permanganate test (purified water in bulk).
TOC determination in ultrapure water
Two oxidation techniques are now commonly
used in TOC analysis:
1. Catalytic combustion, where carbon
compounds are converted into CO2 using a
catalyst under high temperatures with
subsequent detection of the resulting CO2
using an NDIR detector.
2. Wet chemical oxidation, which uses a
combination of UV irradiation and persulfate
for oxidation. Both methods can be applied
for the determination of ultrapure water.
Water for injection is used for the

preparation of injection solutions and is
produced by distillation. The TOC content
may not exceed 0.5 mg/L (water for injection
in bulk).
Water Highly Purified is a sterile ultrapure
water for the manufacture of pharmaceuticals
that do not require a Water for Injection'
standard. It is also often used for the final
rinse during cleaning and is usually produced
by reversed osmosis. The TOC content may
not exceed 0.5 mg/L.
.
TOC-LCPH: Oxidation via catalytic

combustion
The TOC-L CPH uses the proven catalytic
oxidation at 680 C.
SCA-130-201
The integrated ISP sample preparation unit

(an 8-position switching valve with syringe
and sparging gas connection) considerably
reduces the users workload, as the
instrument carries out dilution, acidification
and sparging fully automatically.
detection limit (0.5g/L) and excellent

reproducibility in the lower ppb range. The
TOC-VWP/WS is therefore highly suitable for
TOC determination in the ultra-trace range.
TOC-V WP Sample measurement
Method:
NPOC (3% Acid, 3 min sparge)
Persulfatsol.: 1,5mL
Injection vol.: 20,4 mL
Result: 2,44 0,42 g/L TOC (NPOC)
Fig. NPOC- Calibration (Blank and 500g/L)
When using the high sensitivity catalyst, the

detection limit is approximately 4g/L. In
addition, the combustion technique can be
used in combination with the TNM-L module,
whereby a single injection is sufficient for
simultaneous determination of the total bound
nitrogen.
Simultaneous
TOC/TNb
determination is highly suitable for cleaning
validation, as this enables differential
determination between cleaning agent and
product.
TOC-VWP/WS: Wet chemical oxidation
The key technique of the TOC-VWP/WS
analyzer is the powerful oxidation via the
combination of sodium persulfate and UV
oxidation at 80 C. The TOC-VWP/WS features
an automatic reagent preparation function
that eliminates possible contamination of the
persulfate solution. This ensures that the
TOC value truly originates from the sample
and not from the reagent solution used. The
large injection volume (up to 20.4 mL) in
combination with the highly sensitive NDIR
detector, leads to an extremely low
Abb. Peak graphik of TOC-VWP measurement
Conclusions
Both types of instruments with their different
oxidation methods can be used for TOC
determination according to the European
Pharmacopoeia. The advantage of the
combustion method is its high oxidation
potential, particularly for samples containing
particulate matter. Moreover, simultaneous
TOC/TNb measurements can be carried out,
leading to a higher information content of the
analysis. The advantage of wet-chemical
oxidation is its high injection volume, which
leads to higher sensitivity and therefore
enables high precision measurements in the
lower ppb range.
TOC-L CPH with high sensitivity catalyst
TOC-VWP with ASI-V (40ml)
TOC determination in cleaning validation

final rinse
SCA-130-202
The highest purity and most careful handling

of substances and active ingredients is an
important requirement in the manufacture of
pharmaceuticals. An effective removal of
production residues in pharmaceutical plants
is an essential precondition. A well-cleaned
pharmaceutical production system prevents
contamination
and,
consequently,
the
adulteration of the produced drug. This is
particularly important in the production of
active ingredients in batch processes, as the
system is used for different products and
contamination of the next product must be
prevented.
Because time and temperature, as well as the

use of cleaning agents and solvents are
optimized, CIP cleaning is highly effective.
Moreover, automatic cleaning allows a
standardized and, therefore, an easily
validated procedure.
Sampling and analysis
In case of CIP cleaning, the rinsing liquid of
the final rinse solution is sampled and
analyzed. This is a very simple, easily
automatable and fast method. When water is
used as a solvent, TOC analysis is suitable
for subsequent analysis.
TOC-Analysis
TOC analysis is applied for the determination
of the total organic carbon content as a sum
parameter. The carbon content of the sample
is oxidized to CO2 and detected by an NDIR
detector. Analysis of final rinse samples is,
therefore, fast and simple (analysis time:
approx. 4 min). The determined TOC value
reflects any contamination by starting
materials, products, byproducts or cleaning
agents, as long as they contain carbon.
Cleaning methods: Clean in Place

CIP cleaning (clean in place) is performed
automatically and without disassembly of the
production system. The production system
must, therefore, have a CIP design. This
includes the use of rinsing heads, no dead
volumes, collection tank and recycling
possibilities
for
the
detergents.
Shimadzu TOC Series

With its TOC-L series, Shimadzu offers a
highly suitable tool for cleaning validation.
The modular design simplifies the analysis
no matter whether one wants to measure final
rinse samples or swab samples.
SCA-130-202
For users who prefer wet-chemical oxidation

for the determination of TOC, the TOC-VWP
analyzer with its various options, is available.
The key technique of the TOC-VWP analyzer
is the powerful oxidation via the combination
of sodium persulfate and UV oxidation at
80C.
The TOC-LCPH employs the proven catalytic

oxidation at 680 C. The integrated sample
preparation (ISP) module greatly reduces the
users
workload,
as
the
instrument
automatically carries out the dilution,
acidification and degassing steps.
Practical Example:
Instrument / Measurement parameter
Unit:
TOC-LCPH
Catalyst:
High sensitivity catalyst
Meas.-typ:
NPOC
Cal-Curve:
2-Punkt Calibration Curve
0-3 mgC/L (KHP)
Injection vol.: 500 L
Results
Compound
Blank
Tranexamic acid
Anhydrous caffeine
Isopropylantipyrine
Nifedipine
Gentashin ointment
Rinderon ointment
TOCResult
0,030mg/L
2,14mg/L
2,19mg/L
2,20mg/L
2,17mg/L
0,117mg/L
0,333mg/L
Recovery
105 %
108 %
109 %
107 %
4,35 %
15,2 %
From the results, it can be concluded that the

final rinse method only shows good
recoveries for water-soluble compounds.
(Further information is available in the
application note Japan TOC O41)
Fig. ISP-Module of TOC-L series
The possibility for simultaneous determination

of the TNb (total nitrogen) using the TNM-L
module
enables,
if
necessary,
a
differentiation between cleaning agent and
product. This may be of great importance,
particularly for biopharmaceutical products.
TOC Determination in cleaning

validation - swab method
SCA-130-203
Cleaning
validation
substantiates
the
effectiveness of a cleaning process and
ensures that no residues remain on the
surfaces of the production equipment. For the
detection of contaminations, validated
analytical methods must be used that are
sensitive enough to determine the defined
acceptable residue level. In general, residue
limits of 10 ppm or 1/1000 of the usual
therapeutic dose of an active substance are
used as acceptance criteria.
Sampling and analysis

In COP cleaning, the wiping method (swab) is
used for sampling of visible residues. These
include coatings, crusts, material deposited in
corners and edges, and especially poorly
soluble substances. The swab can be
extracted in a solvent and the extracted
solution is subsequently analyzed. If water is
used for extraction, TOC analysis is suitable
for subsequent analysis. Alternatively, the
swab can also be measured directly (using a
carbon-free swab) using a TOC solid-sample
module.
Measuring system for the swab test
The modular design of Shimadzus TOC-L
series
now
enables
the
additional
determination of the swabs using the same
instrument. For this purpose, a solid-sample
module (SSM-5000A) was connected to the
main instrument, either a TOC-L series
combustion system or the wet-chemical
model of the TOC-V series.
Cleaning methods: Clean out of Place

For COP cleaning, the entire production
system must be disassembled and the
components must be cleaned individually.
This procedure is very time consuming and
labor intensive. Due to the individual
cleaning,
this
procedure
cannot
be
standardized. Advantages are, however, the
low investment costs of the system and the
possibility of visual inspection.
For TC determination, the swab is placed in a

ceramic boat and transferred into the oven,
which is heated to 900 C.
SCA-130-203
There, all carbon compounds are oxidized to

CO2. To ensure complete oxidation, there is
an additional catalyst in the combustion tube.
The resulting CO2 is then transported to the
detector in the main instrument. The NDIR
detector of the TOC-L series contains a
tandem cell that consists of a long cell (200
mm) and a short cell (1 mm). By default, the
long cell is used for water analysis and the
short cell for solid-sample analysis. To attain
a higher sensitivity for the analysis of solids,
the solid-sample module can also be
connected to the long, and thus the more
sensitive, measuring cell. This can be
realized using an upstream switching valve.
This way, the system can now readily be
used for cleaning validation without any loss
in flexibility of switching between water and
solid-sample analysis.
Preparation
As the TOC analysis involves a sum
parameter, it is important to ensure that the
measured carbon really originates from the
sampled surface. Some preparation is,
therefore, important.
First, the swabs used must be carbon-free.
This is why fiber optics swabs are used,
which are annealed at 600 C and are stored
under dry conditions using an inert gas. The
same pretreatment is required for the ceramic
boat. All tools used, such as tweezers and
glass containers must be free from carbon.
Swab test
For the wiping test, two pretreated swabs are
sampled, the lower swab is moistened with
water and the defined surface is wiped
according to the prescribed procedure. The
used swab is now folded, placed in the clean
ceramic boat and transferred to the TOC
measuring system.
Depending on the expected concentration or

defined limit value, the system configuration
and calibration curve is selected. The
calculated amount of carbon is now
correlates directly to the area of the wiped
surface.
Practical example:
Instrument/ Measurement parameter
Unit:
TOC-LCPH + SSM-5000A
(shortcut of IC-flow line)
Detector cell: Short Cell
Carrier gas: 400 mL/min oxygen (SSM)
Meas.-typ:
TC
Cal-Curve:
1-Point Calibration curve wiht
30L of 1%C Glucose solution
Swab:
Advantec QR-100 quartz glass
Filter paper (45 mm)
Prepared at 600C,15min
Result
Blank
Tranexamic acid
TOCResult
0,00
202 gC
101 %
Anhydrous caffeine
Isopropylantipyrine
Nifedipine
Gentashin ointment
Rinderon ointment
201 gC
210 gC
212 gC
200 gC
209 gC
100 %
105 %
106 %
100 %
104 %
Compound
Recovery
(Further information is available in the

application note Japan TOC O41)
TOC-Determination according to
EP 2.2.44
SCA-130-204
Since
the
USP
(United
States
Pharmacopoeia)
regulations
for
the
determination of Aqua Purificata and Aqua ad
injectabilia has been implemented into the
European
Pharmacopoeia
(EP),
TOC
analysis has become increasingly established
in quality control. Users who test the TOC
content in pharmaceutical water must
regularly test their TOC system using a
system suitability test according to the
method described in the EP 2.2.44
guidelines.
System suitability test

For the system suitability test, a standard
sucrose solution with a carbon content of 0.5
mg/L is prepared. A control solution of 1,4benzoquinone with the same carbon content
was subsequently prepared. The blank water
(ultra-pure water) used for this purpose may
not exceed a TOC content of 0.1 mg/L. For
the system suitability test, all solutions
including the blank water are subsequently
measured and the resulting signals are
recorded.
Blank water: rw
Standard solution (sucrose): rs
Control solution (benzoquinone): rss
The peak area of the blank water is
subtracted from the peak areas of both
standard solutions. The recovery of the
benzoquinone standard is then calculated
with respect to the sucrose standard.
European Pharmacopeia
The EP 2.2.44 guidelines do not prescribe
any particular oxidation technique for TOC
determination. The TOC systems, however,
must be able to differentiate between
inorganic and organic carbon. This can be
carried out either via removal of the inorganic
carbon (NPOC method), or via a separate
determination (difference
method). The limit of detection for TOC
should be at least 0.05 mg /L. The
applicability of the method must be
determined via a system suitability test.
Recovery in %:
rss rw
100
rs rw
Results between 85 - 115% are acceptable.

The ultrapure water sample corresponds to
the guidelines when its response signal (ru)
does not exceed rs - rw.
SCA-130-204
TOC-Control L software
The TOC-Control L software simplifies the
implementation of the system suitability tests
using integrated templates for the creation of
calibration curves and the measurement of
the control sample.
The determination of benzoquinone is set in

the sample / method properties wizard.
Fig. Calibration curve wizard
The following figure shows an example of an

EP calibration curve (2 points, blank and 500
g/L).
Fig. Benzochinone-Determination
After measuring the benzoquinone sample,

the software automatically calculates the
recovery according to EP 2.2.44, whereby the
peak area values for the blank sample and
the sucrose sample are obtained from the
calibration curve. The result is listed under
the column Notes in the sample table
(Figure below).
Fig. Calibration Curve
Fig. Result of system suitability test in sample table
TOC determination in ultra pure water with

wet chemical oxidation
SCA-130-205
The quality of ultra pure water is of crucial
significance in a large number of application
areas such as monitoring of water quality in
water treatment plants, and in industries such
as chip manufacture or pharmaceutical
production. Determination of Total Organic
Carbon (TOC) is playing an increasingly
important role in quality control.
the resulting CO2 using an NDIR detector.

Wet-chemical oxidation uses a combination
of UV irradiation and persulfate oxidation.
Both methods are suitable for TOC
determination in ultrapure water.
The EP 2.2.44 guidelines do not specify any
particular oxidation technique for TOC
determination. However, the TOC systems
must differentiate between inorganic and
organic carbon. This can be carried out via
removal of the inorganic carbon species
(NPOC method), or using a separate
determination (difference method). The limit
of detection for TOC should be at least 0.05
mg carbon/L. Applicability of the method must
be determined via a system suitability test.
TOC-V WP with wet chemical oxidation
The TOC value indicates whether ultra pure

water still contains any organic contaminants.
TOC determination is fast and accurate and
is defined in the European Pharmacopoeia
(EP) as a control parameter for WFI-water
(water for injection).
TOC determination in ultra pure water
used in TOC analysis: catalytic combustion
and wet-chemical oxidation. In catalytic
combustion,
carbon
compounds
are
converted to CO2 using high temperatures
and a catalyst, with subsequent detection of
The fundamental technique of the TOC-V

WP/WS analyser is powerful oxidation via the
combination of sodium persulphate and UV
oxidation at 80 C. These features guarantee
that all dissolved carbon species will be
detected. An automatic reagent preparation
function eliminates possible contamination of
the reagent solution and minimizes the blank
value of the instrument. These features,
together with the high injection volume (up to
20.4 mL) and the highly sensitive NDIR
detector, result in extremely low detection
limits and excellent reproducibilities in the low
ppb-range.
SCA-130-205
This is why the TOC-VWP/WS is especially

suitable for TOC determination in the ultratrace range.
Calibration:
Method:
Acidification:
Sparge time:
Oxidizer:
Injection volume:
NPOC
3%
3 minutes
1,5%
20,4 ml
Data according to DIN 32645

Limit of detection:
0,3g/l TOC (NPOC)
Limit of quantification: 2,2g/l TOC (NPOC)
TOC-Control V Software
In the pharmaceutical industry TOC systems
are used in a regulated laboratory
environment and therefore these systems are
subject to various regulations that particularly
apply to instrument software.
The TOC-Control V software running the
TOC-V series provides full support for
complying with the regulations, while still
remaining extremely user-friendly.
Already during software installation, the
operating criteria of the software are decided.
The selected parameters cannot be
deactivated later.
The software use is enabled via user access

rights. It offers user accounts on four different
levels, each protected through own
passwords. The administrator can individually
change access rights for each user. The
software allows changing of login during
ongoing operation. This is especially
important for laboratories working under
multiple shift operation
All
software
operations
are
stored
automatically in the audit trail. This happens
entirely in the background. Only when
existing parameters are changed is a user
comment required. Data storage takes place
in an MSDE database.
The TOC-Control V software simplifies the
implementation of the system suitability tests
using integrated templates for the creation of
calibration curves and the measurement of
the control sample.
The system suitability test is defined in a
special control sample template. Subsequent
to the measurement of the control sample
(benzoquinone), the recovery is calculated
automatically,
compared
with
the
predetermined limits (85 115 %) and
documented.
TOC Determination according to USP 643

(USP 36-NF 31)
SCA-130-206
In 1996, the US Pharmacopeia has
introduced the TOC parameter for the
determination of impurities in purified water
and water for injections. For other waters
used in the pharmaceutical industry, the wetchemical potassium permanganate test
continued to be used. Meanwhile however,
TOC determination has proven to be so
effective that it now replaces the wetchemical test.
In the current version of the UPS <643> (USP

36-NF 31) a distinction is made between bulk
water and sterile water. The chapter Bulk
Water includes purified waters that are to be
used right away as purified water, water for
injection, water for hemodialysis and as
condensate of pure steam. The following
known
conditions
apply
to
TOC
determinations:
Limit of detection:
Blank water, rw:
Standard (sucrose), rs:
SST (benzoquinone), rss:
Permitted response:
Limit response (waters) ru:
< 0.05 mg/L C

max. 0.1 mg/L C
0.5 mg/L C
0.5 mg/L C
85 115%
< (rs-rw)
The chapter Sterile Water is new. It includes

sterile purified water, sterile water for
injections, sterile water for irrigation and
sterile water for inhalation. Sterile water can
be
stored
in
various
packaging
configurations. In comparison to bulk water,
however,
other
conditions
for
TOC
determination apply:
Limit of detection:
Blank water, rw:
Standard (sucrose), rs:
SST (benzoquinone), rss:
Permitted response:
Limit response (waters) ru:
< 0.05 mg/L C

max. 0.1 mg/L C
8 mg/L C
8 mg/L C
85 115%
< (rs-rw)
Impact of the new determination

The present requirements of the UPS <643>
(bulk water) are consistent with the
requirements of the European Pharmacopeia
(limit of detection, concentration of the
standard solution (sucrose) and system
suitability solution (benzoquinone and
response). Validation of the TOC system for
both determinations is therefore sufficient.
In accordance with the new USP <643>, the
implementation of a system suitability test
using higher concentrations is required.
For users of Shimadzus TOC systems, this
just means the creation of an additional
calibration curve (sucrose, 8 mg/L, see figure
1) and control sample (benzoquinone, 8
mg/L, see figure 2) as well as extension of
the current validation process with these
data.
SCA-130-206
instance in cleaning validation) to highly

polluted waters (such as wastewaters).
Shimadzu TOC-Systems.
Figure.1 : Calibration Curve, Sucrose 8mg/L
Additional modifications of the TOC system

are not necessary.
Shimadzu TOC-System
Shimadzu offers two systems that are ideally
suitable for TOC determination in ultrapure
water. The TOC-VWP/WS uses wet-chemical
oxidation, whereas the TOC-LCPH uses
catalytic combustion at 680 C. With their
wide measuring range of 0.5 g/L up to
30,000 mg/L, the instruments support any
application from ultrapure water (for
Both types of instrument with their different

oxidation methods can be used for TOC
determination in accordance with the new
United States Pharmacopeia (USP <643>)
and the European Pharmacopeia (EP 2.2.44).
The advantage of the combustion method is
its high oxidation potential, especially for
samples containing particulate matter.
Moreover,
simultaneous
TOC/TNb
measurements can be carried out, leading to
a higher information content of the analysis.
The advantage of wet-chemical oxidation is
its very high injection volume, which leads to
higher sensitivity and therefore enables high
precision measurements in the lower ppb
range.
TOC-L CPH with high sensitive catalyst
ASI-L (40ml), external sparge kit
TOC-VWP
ASI-V (40ml), external sparge kit
Figure. 2: SST, Benzochinone 8mg/L
3. Chemical industry
3. Chemical industry
3.1.
3.2.
3.3.
3.4.
3.5.
3.6.
TOC determination in hydrochloric acid

TOC determination in nitric acid
TOC determination in sulfuric acid
TOC determination in brine solution
TOC determination in sodium hydroxide solution
TOC determination in soda solution
The most commonly used compound in the chemical industry is

water not only as a solvent in processing, but also as an energy carrier in the cooling or heating cycle. As vast amounts of
water are needed, chemical industries are often located close
to large bodies of flowing water. Water used as processing water or as cooling water is cleaned and subsequently led back to
the river or stream. For environmental protection, these waters
are subject to specific control and monitoring measures. As the
TOC non-specifically detects all organic compounds, this parameter has also proven to be invaluable here.
Large chemical industrial parks have their own wastewater
treatment plants for cleaning wastewaters emanating from the
various chemical plants. In order to evenly distribute the waste
water charges over the participating companies, the TOC load
of the individual wastewaters is often used as a basis for calculation. Companies delivering higher TOC loads are required to
pay higher charges.
Incoming goods control is important in the chemical industry.
Impurities present in reagents often also constitute the impurities in products. In addition to the targeted analysis of known
compounds, sum parameters can help to assess the raw chemicals in terms of their impurities. The TOC plays an important
role here: this parameter describes the contamination through
organic compounds and specifies the total amount of organic
carbon. TOC can, therefore, also be used for the assessment of
inorganic chemicals.
3.7. TOC determination in ammonia or ammonium salt

solution
3.8. TOC determination in sodium nitrate and sodium nitrite
3.9. TOC determination in phosphoric acid (TOC-V WP)
3.10. TOC determination in diluted hydrofluoric acid
The great challenge for TOC measurements in chemical products is to develop protective mechanisms to help protect instruments and their components, as well as to prevent damage by,
for instance, acid fumes or high salt loads. For this purpose,
Shimadzus TOC-L series offers several gas washers and options
to ensure safe and problem-free analyses.
A further challenge is to attain a stable and reproducible oxidation to ensure that no fluctuating or strongly tailing peaks are
recorded. In addition, the measuring values should remain stable over a longer measuring interval.
In order to cover this wide range of analytical tasks in the
chemical industry, flexible systems are needed that are easily
adapted to the task in question via various options, kits and
modules. Shimadzu offers TOC systems that are highly suitable
for such analytical problems. Because of their modular design,
the instruments in the TOC-L series can be equipped for any
possible measurement task.
The individual application notes (for instance TOC determination in hydrochloric acid, brines or sodium hydroxide) contain
further information. In addition to applications in the chemical
industry, application notes are also available on Pharmaceutical industry, Environmental analysis, TOC special applications, TOC in daily practice and TOC process analysis.
TOC Determination in hydrochloric acid
SCA-130-301
Acids, in particular concentrated hydrochloric

acid, represent a large group of inorganic
chemicals frequently used in the chemical
industry. TOC determination in concentrated
hydrochloric acid poses an enormous
challenge to the analyzers that are used for
this purpose.
In general, it is possible to greatly dilute the

substance to be analyzed in order to
eliminate matrix interferences. But sometimes
it is necessary to achieve very low limits of
detection (with reference to 37% hydrochloric
acid) of 1 mg/L.
TOC Measuring Method

The 37% hydrochloric acid solution was
manually diluted to a ratio of 1:2 with water in
order to obtain an 18.5% hydrochloric acid
solution.
TOC-L CPH with OCT-L
Acid challenge
The great challenge is to develop protective
mechanisms to help protect instruments and
their components, as well as to prevent
damage by acidic fumes. For this purpose,
the TOC-L series offers several gas washers
that bind and eliminate the chlorine gas
formed in the flow line of the system in
various ways.
Another challenge is to attain a stable and

reproducible oxidation process to ensure that
no fluctuating or tailing peaks are being
recorded. In addition, the measuring values
should remain stable over a longer measuring
interval.
Abb.2 Mehrpunktkalibration mit

Verdnnungsfunktion
Calibration was carried out in the range of 0.5

to 10 ppm. The automatic dilution function of
the analyzer automatically executes this
calibration from a single stock solution. The
injection volume was 150 L. In case the
TOC contamination of the hydrochloric acid
exceeds the measuring range of the
calibration, the automatic dilution function of
the analyzer will readjust the hydrochloric
acid solution to fit the measuring range.
Verification the measuring method
After calibration, the TOC content of the
concentrated hydrochloric acid solution was
determined.
SCA-130-301
To investigate matrix influences, a potassium

hydrogen
phthalate
solution
was
subsequently
added
to
the
18.5%
hydrochloric acid solution to increase the
TOC by 5 ppm (Figure 3 and Table 1).
The relative standard deviation

measurements was 3.4%. The
graph shows the progression of
values of the hydrochloric acid
over all
following
the TOC
injections.
Fig.4: Result of longterm stability

Fig.3: Results of original and spiked hydrochloric
solution
Blank values and standards (10 ppm) were

alternately measured between the individual
measurements.
Figure 3 and Table 1 show the results of the

individual measurements of the hydrochloric
acid as well as the measurements of the
spiked hydrochloric acid.
TOC result of 18,5% hydrochloric acid in mg/l
Injection
Original
Spiked with
5ppm TOC
1
4,901
10,46
2
4,858
10,24
3
4,91
10,39
4
4,716
10,64
5
4,728
10,28
6
4,739
10,35
7
4,966
10,34
8
4,71
10,36
9
4,662
10,42
10
4,733
10,33
11
4,659
10,11
12
4,625
10,27
13
4,552
10,06
Mean value
4,75
10,33
SD
0,12
0,15
RSD in %
2,6
1,4
Tab. 1: Values of each injection
Long-term stability
To investigate the long-term stability of the
method, the 37% hydrochloric acid solution
was again diluted to a ratio of 1:2 with water
and injected 76 times (150 L).
Fig. 5: Sequence of hydrochloric acid, blank (pure

water) and Standards (10 mg/l)
Recommended analyzer / configuration

TOC-LCPH with a normal sensitive catalyst
(without glass wool at the bottom of the
catalyst tube)
B-Type scrubber with SnCl2 solution
Copper bead scrubber with pH paper
Bypassing the blank check vessel
Substituting water for phosphoric acid (IC
vessel)
OCT-L 8-port sampler
TOC Determination in nitric acid
SCA-130-302
Organic contaminants present in basic

chemicals may constitute the impurities in
products. This is why quality control of the
reactants is indispensable.
Calibration of the TOC-L system was carried

out using the automatic dilution function in the
range of 0.5 mg/L to 10 mg/L.
Fig. Multi-point calibration

with dilution function
The determination of organic contaminations

in concentrated nitric acid (69%) becomes a
challenge when the required detection limit
does not allow large dilution steps.
An example is the TOC determination in a
69% HNO3 solution with a detection limit of <
10 mg/L.
Sample preparation
For sample preparation, the 69% HNO3
solution was diluted to a ratio of 1:10 with
ultrapure water.
Compound
(concenDilution
Conz. [%]
tration)
1 : 10 diluted with
Nitric Acid
water
Ca. 7%
(69%)
(5ml / 50ml)
To protect the NDIR detector, the B-type

scrubber was used together with the halogen
scrubber.
Matrix interferences
In addition to CO2, various nitrogen oxides
are formed from the organic components
during the combustion of nitric acid.
Excessively high levels of NO3 can lead to
significant amounts of N2O (nitrous oxide).
Nitrous oxide exhibits absorption bands in the
same IR detection range as CO2 and can,
therefore, be misinterpreted for CO2. In
addition, nitrous oxide can cause tailing and
can affect the peak symmetry.
Due to the high solubility of N2O in water, the
gas is dissolved in the B-type scrubber and
will not reach the detector.
SCA-130-302
Result
The duplicate NPOC determination of a nitric
acid produced the following results:
Sample
NPOC
[mg/l]
RSD
[%]
36,9
1,4
33,4
3,0
Nitric Acid
(69%)
Nitric Acid
(69%)
To investigate this matrix influence, an

additional dilution (1:10) of a 69% nitric acid
solution was carried out and a potassium
hydrogen phthalate stock solution was
subsequently added to increase the NPOC
content by 5 ppm. (Note: This corresponds to
an increase to 50 ppm for the 1:10 dilution).
Sample
Nitric Acid (69%)
Nitric Acid (69%)
Spiked with 50 ppm
KHP
NPOC
[mg/l]
25,1
RSD
[%]
1,3
76,2
1,8
The use of suitable gas washers (scrubbers)

enables reproducible TOC measurements in
concentrated nitric acid.

TOC-L CPH with normal sensitive Catalyst
B-Type-Scrubber
OCT-L (8-port Sampler)
TOC Determination in sulfuric acid
SCA-130-303
Acids are a group of frequently used

inorganic chemicals used in the chemical
industry. In particular, sulfuric acid is used in
a wide range of applications.
The following SO2 scrubbers are available:
Sulfix (WAKO Chemicals, Fuggerstr. 12,

41468 Neuss, Germany). The Sulfix
scrubber is installed underneath the
normal sensitive catalyst and enables
selective filtration of the formed SO2.
Mist scrubber (cartridge)

Just like the halogen scrubber, the Mist
scrubber is used in the flow line for SO2
absorption.
In the experiment described below, the

NPOC content of a 98% sulfuric acid solution
is determined.
Sulfuric acid in a concentration range to
1%.can be directly measured using a TOC-L
analyzer Higher sulfuric acid concentrations
can lead to tailing and, consequently to
increased measurement values because high
sulfate concentrations (> 5000 mg/L) can
lead to the formation of large amounts of SO2
vapors. SO2 exhibits absorption bands in the
therefore, be misinterpreted for CO2.
To determine organic contaminations in
highly concentrated sulfuric acid, additional
SO2 scrubbers are used.
The required purity criterion and the required

limit of detection was < 10 mg/L.
Sample preparation
The concentrated sulfuric acid was diluted
with ultrapure water to a ratio of 1:10 to
decrease the concentration as well as the
viscosity of the sulfuric acid.
Compound
(ConcenDilution
Conc.
tration)
Sulfuric
acid (98%)
1 : 10 diluted
with water
(5m/50ml)
Ca. 10%
The dilution has to be carried out with the

utmost care and caution, as the sulfuric acid
reacts violently upon the addition of water
(heat generation).
SCA-130-303
The system is calibrated using the automatic

dilution function in the range of 0.5 mg/L to 10
mg/L.
Result
The duplicate determination of sulfuric acid
yielded the following results:
Sample
Sulfuric acid
(98%)
Sulfuric acid
(98%)
NPOC
[mg/l]
RSD
[%]
<10 (4,6)
<10 (5,4)

The sulfuric acid fulfilled the required purity

criteria of TOC < 10 mg/L.

For the determination, a TOC-LCPH equipped
with a kit for high salt loads was used. The kit
consists of a special catalyst tube, a special
mixture of various catalyst beads and a
ceramics grid, which replaces the platinum
net.
The use of suitable gas washers (scrubbers)

enables reproducible TOC measurements in
concentrated sulfuric acid.
Sample acidification when using the high-salt

kit, is carried out with sulfuric acid. Sulfuric
acid is used to modify the sample matrix.
While NaCl has a melting point of 801 C, the
melting point of NaSO4 is higher (881 C).
This has a positive effect on the lifetime of the
combustion tube.
For this reason, sulfuric acid is measured
directly
using
the
high-salt
kit.

TOC-L CPH
OCT-L
High-Salt-Kit
B-Type-Scrubber with diluted hydrochloric
acid with wire net.
Mist-Scrubber
TOC Determination in brines
SCA-130-304
The determination in difficult matrices, such

as brines or heavily contaminated wastewaters, presents a special challenge for TOC
analyzers. In the chemical industry, brines
with a salt load (NaCl) of up to 28% are used
for chlor-alkali electrolysis. For this process it
is important to know the TOC content.
The unique feature of this application does
not inherently lie in the conversion of the
carbon components to carbon dioxide, but in
the salt load associated with the matrix. This
leads to higher maintenance needs, as the
salt can crystallize in the combustion system.
Kit or high-salt samples
samples, which significantly increases the
instruments availability. The kit consists of a
combustion tube of a special geometry and a
unique catalyst mixture.

carried out with sulfuric acid. Sulfuric acid
modifies the sample matrix. Whereas the
melting point of NaCl ia 801 C, NaSO4 has
a higher melting point is (888 C). The
potassium salts of sulfuric acid also have a
significantly higher melting point than those of
hydrochloric acid. This extends the lifetime of
the combustion tube.
Compound
Melting point
NaCl
801C
KCl
773C
Na2SO4
888C
MgCl2
708C
CaCl2
782C
K2SO4
1.069C
Sample preparation
The determination of organic contaminations
in a pure brine (30% sodium chloride
solution) is described below. For such highly
concentrated salt solutions, the principle of
diluting the sample as much as possible
applies. As the required detection limit was at
< 1 mg/L, the samples were diluted with
ultrapure water to a ratio of 1:1. Dilution was
carried out manually in a 50 mL volumetric
flask under the addition of several drops of
concentrated sulfuric acid (25%).
SCA-130-304
Compound
(Concentration)
Brine
solution
(30%)
Dilution
Conc.
1 : 2 diluted with
water (25ml/50ml)
add. 1-2 drops
Sulfuric acid until
pH<7
ca.
15%ig
Initially, a blank value and a control standard

(10 mg/L) were measured, and the NaCl
solution was subsequently injected.
The control standards were tested after 110
and 220 injections of the brine solution,
respectively.
For the analysis a TOC-LCPH equipped with a

kit for high salt loads was used. The system
is calibrated using the automated dilution
function in the range of 0.5 mg/L to 10 mg/L.
Maintenance of the combustion tube and the

catalyst was not necessary after the
measurements were completed. Only the TCslider needed to be cleaned. The figure
above shows the excellent reproducibilitys
and the stability of the measurement.

Result
The duplicate determination of the TOC
analysis yielded the following results:
Sample
Brine solution (30%)
Brine solution (30%)
NPOC
[mg/l]
3,6
3,6
RSD
[%]
1,8
1,8
Stability test
In this test, the long-term stability of the
combustion system was tested. The system
was calibrated to 10 mg/L with an injection
volume of 50 L.
A 28% NaCl solution was prepared and
spiked with a KHP solution to obtain a 5 mg/L
TOC solution and a 15% sulfuric acid solution
was added.

TOC-LCPH
High-Salt-Kit
B-Type-Scrubber
TOC Determination in sodium

hydroxide solution
SCA-130-305
Organic contaminants in basic chemicals may
lead to impurities in the products. Therefore,
quality control of the reactants is necessary.
Several mL of ultrapure water were placed in

a 50 mL volumetric flask. Subsequently, 5 mL
of the concentrated sodium hydroxide was
pipetted into the flask. Finally, concentrated
sulfuric acid was added until the solution has
reached a pH < 2. The flask was then filled
with ultrapure water up to the mark. The
addition of sodium hydroxide, as well as the
addition of sulfuric acid to the water must be
done with the utmost care and caution, as a
violent chemical reaction occurs.
Compound
(Concentration)
The TOC determination in sodium hydroxide

can lead to various problems. The catalyst
and the combustion tube wear out very
rapidly. This, in turn, will lower the sensitivity
at an equally fast rate and leads to very poor
reproducibilities.
NaOH can also absorb CO2 from the
environment. As air contains approximately
400 ppm CO2, direct TC determination in
sodium hydroxide can lead to much higher
values. The NPOC method is, therefore,
recommended for the determination of
organic contaminations in sodium hydroxide.
The sample should also be diluted as much
as possible.
Dilution
1 : 10 diluted
Sodium
hydroxide
solution
(50%)
approx.
(5 ml / 50 ml) add.
5%
1-2 drops Sulfuric
+ Sulfuric
acid until pH<7
acid
(Note: generation of
heat)

out using the automatic dilution function
within the range of 0.5 mg/L to 10 mg/L.
In the present case, a 50% sodium hydroxide

solution was analyzed. The purity criterion
and the required limit of detection was < 10
mg/L.
Sample Preparation
The sample was first manually diluted to a
ratio of 1:10 with ultrapure water and a
suitable amount of acid.
Conz.
[%]

SCA-130-305
10
9
Signal[mV]
Kit for high salt samples

For the determination, a TOC-LCPH was
equipped with a kit for high salt loads. The kit
consists of a special catalyst tube, a special
mixture of various catalyst beads and a
ceramics grid, which replaces the platinum
net.
0
-1
0
10
Zeit[min]
Fig. Example peaks of 50% sodium hydroxide

solution

When using the high-salt kit, sample
acidification is carried out with sulfuric acid,
which is used here to modify the sample
matrix. Compared to NaCl with a melting
point of 801 C, the melting point of NaSO4 is
higher (881 C) which extends the lifetime of
the combustion tube.
Results
The 5% sodium hydroxide can now be
measured using the NPOC method. The
duplicate determination of the sodium
hydroxide yielded the following results.
Sample
NPOC
[mg/l]
RSD
[%]
Sodium hydroxide
(50%)
Sodium hydroxide
(50%)
<10 (8,2)
<10 (8,3)
The sodium hydroxide met the required purity

criteria of < 10 mg/L TOC.
TOC-L CPH
OCT-L (8-port samples)
High-Salt-Kit
B-Type-Scrubber
TOC Determination in soda solution
SCA-130-306
Impurities in products can be caused by

organic contaminants present in basic
chemicals to. That is a reason why quality
control of the reactants is indispensable.
In
the
determination
of
organic
contaminations
in
concentrated
soda
solutions, various issues must be considered.
In comparison to organic carbon, the soda
solution to be investigated has a very high
inorganic carbon content in the form of
carbonates. In addition, the solution has a
high pH value and tends to absorb carbon
dioxide from the air.
A soda solution must, therefore, be analyzed
using the NPOC method.
In the case described here, a 50% soda

solution was investigated. The required
detection limit was 10 mg/L.
Sample preparation
The sample was first manually diluted to a
ratio of 1:10 with ultrapure water and a
corresponding amount of acid. Several mL of
ultrapure water were placed in a 50 mL
volumetric flask. Subsequently, 5 mL of the
concentrated soda solution was pipetted into
the flask. Finally, concentrated sulfuric acid
was added until the solution has reached a
pH < 2.
The flask was then filled with ultrapure water
up to the mark.
Compound
Dilution
Conc.
(Concentration)
Soda
hydroxide
solution
1 : 10 diluted
with water
(5ml/50ml)
(50%)
add. 1-2 drops

Sulfuric acid
until pH<7
Approx.
5%
Caution: During the addition of the sulfuric

acid, the carbonates decompose under a
violent reaction (heat dissipation / gas
formation).
SCA-130-306

out using the automatic dilution function in the
The higher melting point point of NaSO4 (881

C) compared to NaCl (801 C) has a positive
influence on the lifetime of the combustion
tube.
Results
The duplicate determination of the soda
solution yielded the following results:
Sample
For the determination, a TOC-LCPH was

equipped with a kit for high salt loads. A
special catalyst tube, a special mixture of
various catalyst beads and a ceramics grid,
which replaces the platinum net are part of
the kit.
RSD
[%]
56,4
7,1
54,8
4,9
10
9
Signal[mV]

Soda solution
(50%)
Soda solution
(50%)
NPOC
[mg/l]
0
-1
0
10
Zeit[min]
Fig. Peak graphs of a diluted soda solution

(ca.5%)
Sample acidification when using the high-salt

kit, is carried out with sulfuric acid in order to
modify the sample matrix.

TOC-L CPH
ASI-L
High-Salt-Kit
B-Type- Scrubber
15
TOC Determination in ammonia or

ammonium salt solutions
SCA-130-307
Basic chemicals may contain organic
contaminants polluting end products. This is
why quality control of the reactants is a must.
In the TOC determination of ammonia water
or concentrated ammonium salt solutions,
various issues must be considered. Ammonia
and some ammonium salts are alkaline. The
catalyst and combustion tube are sensitive to
alkaline media and are subjected to
increased wear.
Sample preparation
The ammonium nitrate solution was diluted
with ultrapure water to a ratio of 1:10. Dilution
was carried out manually in a 50 mL
volumetric flask under addition of several
drops of concentrated sulfuric acid (25%).
Compound
(Concentration)
Dilution
Conc.
Ammonium
nitrate
solution
(40%)
1 : 10 diluted
(5 ml / 50 ml)
add. 1-2 drops
Sulfuric acid until
pH<7 (Note:
generation of heat)
Approx.
4%
Calibration of the TOC-L system was

executed using the automatic dilution function
in the range of 0.5 mg/L to 10 mg/L.
The solutions should, therefore, be acidified

and possibly be diluted.
The decomposition during oxidation of the
ammonium or ammonia proceeds to
completion without the formation of residues
on the catalyst. Therefore, it is not necessary
to use a high-salt kit.
In the case described below, the NPOC
content of a 40% ammonium nitrate solution
was determined. The required detection limit
was < 10 mg/L.

SCA-130-307
Results
The
duplicate
determination
of
ammonium nitrate solution yielded
following results:
40
30
Signal[mV]
Interferences
In addition to CO2 formed from the organic
components, various nitrogen oxides are
formed during the combustion of ammonium
salts or ammonia water. Excessively high
nitrogen levels can lead to the formation of
significant amounts of N2O (nitrous oxide).
A B-type scrubber is used to eliminate
possible interference by nitrous oxide. Due to
the high solubility of N2O in water, the gas is
dissolved in the B-type scrubber and will not
reach the detector.
20
10
0
-4
0
14
Zeit[min]
Fig. Example peaks of 40% ammonium nitrate

solution
the
the
Probe
Ammonium
nitratesolution
(40%)
Ammonium
nitratesolution
(40%)
NPOC
[mg/l]
RSD
[%]
56,5
0,8
56,7
1,2
TOC-L CPH
OCT-L (8-port sampler)
B-Type- Scrubber
TOC Determination in sodium nitrate

and sodium nitrite
SCA-130-308
Basic chemicals may contain organic
contaminants influencing the quality of
products. Quality control procedures of the
reactants are, therefore, necessary in order to
detect impurities.
For
the
determination
of
organic
contaminations in salts, solutions of these
salts can be prepared and subsequently
measured using a TOC-L analyzer.
Compound
(Concentration)
Sodium nitrate
(>99,9%)
Sodium nitrite
(>99,9%)
Dilution
Weighted Sample
5 g / 50 ml
add. 1-2 drops
Sulfuric acid until
pH<7
Weighted Sample
5 g / 50 ml
add. 1-2 drops
Sulfuric acid until
pH<7
Conz.
approx.
10%
approx.
10%
Caution: Nitrogen
oxide gas is
released
Caution: Nitrite salts react to form of toxic

nitrous gases. Sample preparation should,
therefore, always be carried out under a
hood. The samples should only be removed
from the hood, when no more nitrous gases
escape.
High salt concentrations generally present a

problem for TOC analysis. These salts can
crystallize in the combustion system and lead
to higher maintenance needs.
Calibration of the TOC-L system was done

applying the automatic dilution function in the
In the case described below, the NPOC

content of two salts was determined. The
difficulty was the required detection limit of 10
mg/kg.
Sample preparation
For sample preparation, 5 g of both salts
(sodium nitrite and sodium nitrate) were
weighed into a 50 mL volumetric flask and
diluted with ultrapure water. During dilution,
the solutions were acidified with concentrated
sulfuric acid (25%).

SCA-130-308

samples, which significantly increases the
instruments availability. The kit consists of a
unique catalyst mixture.
Results
The duplicate determination of the salt
solutions yielded the following results:
Sample
Sodiumnitrate(>99,9%)
NPOC
[mg/kg]
22,8
24,0
<10
(9,0)
10,2
RSD
[%]
4,7
6,8
5,4
Signal[mV]
10
9
0
-1
0
10
Zeit[min]
15
20
Fig. Example peaks: Sodium nitrate

modify the sample matrix. Due to the higher
melting point of NaSO4 (888 C) compared to
801 C of NaCl the lifetime of the combustion
tube is longer.
Interferences
The combustion of nitrogen compounds can
lead to the formation of nitrous oxide gas.
A B-type scrubber is used to eliminate
possible interference by nitrous oxide. Due to
the high solubility of N2O in water, the gas is
dissolved in the B-type scrubber and will not
reach the detector.

TOC-LCPH
ASI-L
High-Salt-Kit
B-Type-Scrubber
TOC determination in phosphoric acid
No.SCA-130-309
Phosphoric acid is one of the most frequently

used inorganic acids in industrial applications.
It is applied as starting material for the
manufacture
of
phosphate-containing
fertilizers as well as for the production of
water-softening agents such as detergent
additives.
Phosphoric acid is also used in the food
industry as acidification agent and
preservative in beverages or as antioxidant in
meats and meat products.
Particularly for these types of applications, it

is important to apply acids that are pure and
free from foreign substances. Manufacturers
and processors of phosphoric acids are
increasingly using the TOC (Total Organic
Carbon) sum parameter for quality control.
This parameter is a measure of the
contamination of phosphoric acids by organic
components.
The TOC method by using the catalytic
combustion is not suitable for the
determination
of
phosphoric
acid,
because the phosphoric acid damages the

combustion tube and the catalyst.
Due to this, the wet chemical TOC method is
used to measure TOC in phosphoric acid.
Wet-chemical UV oxidation at 80 C
The determination of the TOC content in
phosphoric acid is carried out via wetchemical UV oxidation using Shimadzus
TOC-VWP.
Its core technology is the powerful oxidation

applying a combination of sodium persulfate
and UV oxidation at 80 C. This ensures that
all dissolved carbon compounds are
converted to CO2.
In the presence of persulfate ions and UV
illumination, OH-radicals are formed which
have a strong oxidative effect and convert
organic compounds to carbon dioxide. A
carrier gas transports the carbon dioxide
formed to the NDIR detector where they are
detected.
SCA-130-309
Automated reagent preparation eliminates

any contamination of the reagent solutions
and minimizes the blank value of the
instrument.
TOC determination
Due to lower TOC concentration, the
instrument is calibrated in a range of 0,1 1
mg/L.
Figure: Calibration of NPOC between 0,1 1 mg/l.
Concentration of the phosphoric acid does

not play a significant role in the
determination; it is only necessary to ensure
that the acid is not too viscous. The 85%
phosphoric acid solution was therefore diluted
1:5 with water.
The resulting 17% acid solution was
transferred into the instrument using an OCT1 autosampler.
The autosampler OCT-1 has a big advantage

for the measurement of aggressive matrices,
because its parts are done of Teflon.
Method
of
phosphoric
acid
measurement
The concentrated phosphoric acid (85%) is
diluted by 1:5.
TOC determination in phosphoric acid was
carried out using the NPOC (Non-Purgeable
Organic Carbon) method. Prior to TOC
determination, neutral or alkaline samples are
acidified in order to decompose all inorganic
carbonates and bicarbonates. This step could
be omitted for phosphoric acid.
Acidification:
Sparge-time:
Injection volume:
0%
2 minutes
3000l
Results
Abb.: Peak graph of diluted phosphoric acid(17%)
The 17% phosphoric acid solution measured

in this way resulted in a TOC concentration of
0.61 mg/L. The relative standard deviation
over three injections was 1.8%.
- TOC-VWP/WS
- OCT-1
TOC Determination in diluted hydrofluoric

acid
SCA-130-310
Hydrofluoric acid is the only acid that attacks
glass (glass etching). Because of this
chemical property, it plays a distinct role in
several industrial processes, for instance in
the manufacturing of solar cells and wafers
as well as in microchip production.
Hydrofluoric acid is the most widely used
etching agent in the semiconductor industry.
TOC determination
In the following measurement, a 4%
hydrofluoric acid was manually diluted to 1:10
with water and measured using the TOCLCPH. Given the acidity of the hydrofluoric
acid, the IC content can be neglected. With
regard to the dilution, the solution was slightly
acidified and sparged for 3 minutes. The
NPOC was subsequently determined by
means of combustion oxidation.
An aliquot of the sample is injected onto a hot
(680 C) platinum catalyst. The organic
substances are converted to CO2 and
detected via an NDIR detector.
When carrying out etching processes, it is

important to ensure that the etching agent
used will etch the respective layers and not
leave any contaminants.
This raises questions on the impurities of
etching agents, where both the purity of the
starting acid and that of the etching solutions
after the etching process are of interest.
To determine the degree of contamination,
the TOC parameter is particularly suitable, as
it is a sum parameter that detects all organic
carbon compounds.
Calibration
Due to mostly working in a small measuring
range, calibration was carried out in a range
of 0.25 mg/L 5.0 mg/L. For dilutions, the
automatic dilution function of the TOC-L
system was applied. The injection volume
was 150 L respectively.
Kal. Kurve
69,047
60
50
Flche
40
30
20
10
0
0
3
Konz[mg/L]
Figure: Calibration curve, TC 5 mg/L.
5,5
SCA-130-310
Measurement example
A total of 3 different hydrofluoric acids (0,4%)
were measured:
Hydrofluoric acid prior to etching
(HF1)
Hydrofluoric acid after etching (a
seemingly clean wafer (HF2))
Hydrofluoric acid after etching (a
seemingly dirty wafer (HF3))
NPOC method
Acidification:
1.5%
Purging time:
3 minutes
Injection volume:
150 L
Number of injections: 3
Protection and safety

For such measurements, comprehensive
protective measures for dealing with
hydrofluoric acid must be urgently observed.
This also includes wearing protective
clothing, gloves and safety goggles.
Signal[mV]
40
30
20
10
-4
0
1
Zeit[
After measurement, the instrument

rinsed several times with water. In
20 injections with ultrapure water
carried out.
Nevertheless the lifetime of
combustion tube and catalyst
shortening, due to HF solution.
must be
addition,
must be
syringe,
will be
Figure: Peaks of the diluted HF solution.
The measurements were already stable after

two or three injections. It is advantageous to
carry out several HF injections prior to the
actual sample measurement.
Results
Sample
HF 1
HF 2
HF 3
NPOC
[mg/L]
2.42
3.09
4.38
RSD
[%]
4.8
3.2
2.1
Recommended instrument/ equipment

TOC-LCPH / CPN
OCT-L
4. TOC special applications
4. TOC special applications

4.1. TOC determination in algal biomass suspension
method
4.2. TOC determination in liquid manure and fermentation
fluids suspension method
4.3. Carbon dioxide determination in beer
4.4. Measurement of TOC in Mineral Water

4.5. Monitoring of Algae Growth by TOC Measurement
4.6. Characterization of Algae by TOC Measurement
Due to its informative significance, the TOC sum parameter is

widely applicable. It mirrors the total concentration of organically bound carbon or organic compounds.
The possibility to detect and quantify all organic compounds

within a simple analytical run always leads to new, often unusual, applications. Some only seem to be useful for a one-time
use while others seem to revolutionize entire analytical application areas.
In addition to the environmental, pharmaceutical and chemical

industries, the TOC parameter is used in numerous other applications. The users scientific curiosity and ingenuity often
wants to solve an analytical problem or simplify complex analytics, and then finds the TOC as a key to the answer.
The TOC parameter can be determined easily and reliably. The
experienced user can control and calculate interferences that
can be attributed to the matrix. Various options, kits and modules enable interference-free analyses in a wide range of applications.
With its TOC analyzers, Shimadzu offers flexible systems that
can be modularly upgraded using various kits, modules and options. In this way, the TOC analyzer can be customized to the
specific measurement task.
Further information can be found in the individual application

notes (for instance TOC determination in algae, liquid manure
or carbon dioxide determination in beer). In addition to TOC
special applications, there are also application notes and information on Pharmaceutical industry, Chemical Industry, Environmental analysis, TOC in daily practice and TOC process
analysis.
TOC-determination in algal biomass

suspension method
SCA-130-401
Innovative methods
To determine the biomass in the
photobioreactor, a TOC analyzer was used.
The carbon content of the algal soup is
directly proportional to the biomass.
The excessive global CO2 emissions from the

burning of fossil fuels (for instance in power
plants) causes the search for climate-friendly
uses of carbon dioxide.
One of the approaches for environmentally
sound recycling is to convert the emitted CO2
into biomass using photobioreactors.
The CO2 gas is introduced into the
photobioreactor in order to be used for the
growth of algae. The biomass, or algae, can
be used in many different application areas:
in the cosmetics industry, the construction
industry, and the food segment, in agriculture
as fertilizer or for energy utilization.
Test methods for implementation
The efficiency of the photobiorectors and the
yield of growth are continuously monitored.
To this end, various methods are available,
including the determination of dry mass
(gravimetric) or the photometric determination
of chlorophyll (by absorption). These methods
either require a high expenditure in terms of
time and personnel, or they are nonspecific
and inaccurate.
TOC Measurement method

Depending on the type of algae used in the
reactor, either the difference method or the
direct method (NPOC) is suitable. In both
cases, one should test which method will
most accurately detect each particular type of
algae. This can be compared with the results
of the reference method.
Information on the analysis:
calibration of the TC/NPOC and the IC
parameters via the automated dilution
function
sample is generally measured undiluted
injection volume: 90 L
at least 3 to 5 injections for statistical
confidence
rinse several times, depending on the
sample
SCA-130-401
Sample preparation
The 4 10 m large micro-algae of the
Chlorella vulgaris species can be measured
directly after sampling from the reactor
without any further sample preparation. The
difference method was used for the biomass
determination. The method is suitable for all
other single-cell algae that exhibit a stable
carbon content under different growth
conditions.
Using the difference method, the TC and TIC
were determined and the TOC was
subsequently calculated from these values.
Calibration using the resulting dry mass of the
algae makes it possible to draw conclusions
on the dry biomass content in the sample
from the TOC.
Corrrelation
The TOC correlation (algae biomass/TOC)
must be determined for each type of algae
specifically. It can also be calibrated against
the determined dry mass.
the extracellular substances produced by the

algae or released into the culture medium
after the algae have died off. The TOC
determined this way is the carbon content of
the investigated algae. To draw conclusions
on the dry mass yield, the percentage carbon
content in the algae must be determined.
Several direct and indirect methods are
available. The most simple and, at the same
time, highly reliable method is to combust the
washed and dried algae in a solid-matter
TOC analyzer. A second method is to filter
the algae, dry them and then determine their
mass. In combination with TOC and
photometry measurements, a correlation
between the TOC value and the algal dry
mass can be determined, which provides
information on the carbon content of the
algae. From the carbon mass fraction and the
TOC value, the dry mass of the algae solution
can be very accurately calculated.
DrymassTOCCalibration

TOC-L CPH
Sparge-Kit
First, the algae sample is measured and the
TOC is determined. Subsequently, the
sample is filtered through a 0.2 m syringe
filter and measured again in the TOC
analyzer to be able to distinguish between the
TOC content originating from the algae and
the carbon content possibly originating from
SCA-130-402
TOC-determination in liquid manure and

fermentation fluids
suspension method
Biogas is one of the energy sources of the

future and can be used in the generation and
supply of energy, or it can be fed into the
natural gas networks in the form of
biomethane. The generation of energy from
renewable or regenerative energy sources,
which include water, wind, solar and other
types of biomass, replaces the use of fossil
fuels.
For the production of biogas from, for
instance, various liquid manures or maize
silages, pretreatment methods for liquid
manure and the optimization of the
fermentation process and biogas yield are
investigated.
Fig. Experimental setup to generate bio gas in the
laboratory
Efficiency
Reactors with various volumes are used for

production testing. The prepared liquid
manure or mixtures of other substrates are
used for fermentation. The generated biogas
is diverted via pipelines, the resulting volume
is pneumatically determined and the gas
composition is analyzed.
To evaluate the efficiency of the reactor and

the method, biogas was analyzed in different
ways. An important parameter is the gas
chromatographic
determination
of
the
methane content. In order to be able to
compare the biogas yield of the various
substrates, the biogas volume or methane
volume was expressed in terms of the
organic dry matter present in the substrate
(Nl/kg ODM). This requires the accurate
determination of the initial concentration of
the organic substance in the liquid manure.
SCA-130-402
For this determination, proven methods are

available. First, the dry matter (DM) of the
liquid manure is determined at 105 C. The
dried liquid manure is subsequently annealed
to a constant mass at 550 C in a muffle
furnace. The loss of mass during annealing
corresponds to the organic content of the
liquid manure. The ratio of methane gas
concentration
and
organic
content
corresponds to the biogas production yield
(fermentation) and is a key criterion for the
fermentation of different types of biomass and
for the assessment of the efficiency of
fermentation processes.
Innovative methods
In order to avoid long annealing times for the
ODM determination, an alternative method for
the determination of the organic substance
was sought. The TOC suspension method
was considered suitable for this purpose. The
dried sample was weighed into an
Erlenmeyer flask and mixed with hydrochloric
acid to convert the inorganic carbon
compounds, such as carbonates and
hydrocarbonates, to carbon dioxide. In the
next step, a dispersion device was used to
break up and homogenize the suspension.
During this process, most of the generated

carbon dioxide was also removed. The final
solution is subsequently transferred into the
autosampler vials of the analyzer and
automatically analyzed. For this purpose, a
small fraction is injected onto the 720 C hot
platinum catalyst. The organic substances
are then converted into carbon dioxide and
measured using an NDIR detector.
The advantage of this alternative method lies
in its suitability for automation. This way,
many
samples
can
be
processed
automatically in sequence.
With the possibility of multiple injections, the
method also offers statistical reliability. In the
muffle furnace, a combusted weighed sample
yields an ODM value. The suspensions are
generally analyzed at least four times to
establish a mean value.
NPOC-Determination
For the determination of the organic content
in liquid manure (duplicate determination from
two different approaches with each 5
separate injections) yielded the following
results:
Liquid manure
(dried and
powdered)
Sample 1
Sample 1
Sample 2
Sample 2
NPOC
[mass.%]
44,1
44,2
44,2
42,5
RSD
[%]
0,8
1,9
1,6
1,4
Signal[mV]
1000
900
600
300
0
-100
0
10
Zeit[min]
Fig. NPOC-Peaks of suspension

Fig. Homogenisation of the suspension
15
SCA-130-402
TNb-Determination
The TOC determination using catalytic
combustion oxidation allows the simultaneous
measurement of the total bound nitrogen
(TNb), since, in addition to the carbon dioxide
from organic substances, NO is formed from
nitrogen-containing compounds.
For the
conversion of NO to NO2, the measuring gas
ozone was fed to the chemiluminescence
detector connected in-series. The photons
emitted during this reaction are detected and
are used in the calculation of the TNb value.
Nitrogen compounds also play an important
role when it comes to liquid manure.
.
Conclusion
The TOC suspension method offers a good
alternative for the fast, straightforward and
accurate analysis of the organic content in
liquid manure samples. The possibility for codetermination of the nitrogen content also
enables users to acquire additional useful
information for the evaluation of liquid manure
samples.
Signal[mV]
100
90
60
30
0
-10
0
10
Zeit[min]
15
20
Fig.4: Peak graphs of TN-determination
Simultaneously with the organic content, the

TNb was determined (duplicate determination
from two different approaches with 5 separate
injections each) yielding the following results:
Liquid manure
(dried and
powdered)
Sample 1
Sample 1
Sample 2
Sample 2
TNb
[mass.%]
RSD
[%]
1,84
1,80
1,76
1,68
1,5
0,9
2,2
1,4

TOC-L CPN with normal sensitive Catalyst
for TNb-Determination: TNM-L Module
Sparge-Kit.
Carbon dioxide determination in beer
SCA-130-403
Carbon dioxide is an important ingredient in
many soft drinks. This is also the case for
beer. It creates a sparkling and refreshing
(tangy) taste and is important for the
formation of foam.
The CO2 content of a beer affects the
threshold values for various fragrance and
aroma components. In addition, bottling
under CO2 increases the shelf life of beer..
In order to develop a method that does not

have these disadvantages, a TOC analyzer
was used.
Innovative methods
In this method, the sample (beer) is directly
placed in a 40 mL autosampler vial. 5 mL of a
32% NaOH solution was added to the
autosampler vial to preserve the CO2.
The sample is subsequently added directly to
the autosampler and the IC (inorganic
carbon) content is measured.
In the manual of the central- European

brewery technological analysis commission)
(MEBAK)
various
methods
for
the
determination of CO2 are listed. These are
generally based on manometric or titrimetric
method, or they are methods that use
specialized detectors.
Disadvantages of these methods are often
the lack of selectivity for CO2 (other gases or
substances are also determined), high
expenditure in terms of personnel and time,
and the lack of possibilities for automation.
Preservationstep:
-
CO + OH
2
HCO
CO + 2 OH
2
2-
CO
+HO
2
In the TOC analyzer, the sample is injected in

a concentrated phosphoric acid solution
(25%). The CO2 is subsequently released
again and is transferred via the carrier gas to
a CO2-selective NIDR detector where it is
detected.
SCA-130-403
Displacement reaction: (the strong acid

displaces the weak acid from its salt)
HCO + H
2-
CO
H O + CO
2
+2H
H O + CO
2
dioxide in bottled or canned beer. In this step,

5 mL of a 32% solution of NaOH was directly
added to the freshly opened bottle or can for
preservation.
Comparison of the methods
The following graph shows the good
agreement between the TOC method (blue
bars) and the Corning method (green bars).
6,00
To calculate the results, the IC function of the

TOC system is calibrated using a sodium
hydrogen carbonate standard in the range of
100 1000 mg/L. The dilution of the
individual calibration points is performed
automatically via the dilution function of the
instrument.
5,00
4,00
3,00
2,00
1,00
0,00
Advantages of this method

can be automated to a high degree
fast
good reproducibility and high accuracy
(precision)
multiple determinations from one sample
is possible
effortless calibration
simple operation
highly specific
Using the modern TOC-L software,
evaluation can be carried out automatically or
can be recalculated manually. Another
function enables further processing of the
measurement results. This way the carbon
dioxide content can be directly presented in
the desired dimension. Due to the possibility
for multiple injections, the evaluation contains
all the important statistical quantities
Another sample preparation variant is to be
carried out during the determination of carbon
TOCLCPH
ASIL(40ml)
LAAN-A-TC-E022
Application
News
Total Organic Carbon Analysis
Measurement of TOC in Mineral Water
O47
No.
Mineral water and soft drinks use water as their raw

material, but the quality of that water may have a
significant impact on the quality of the final water
product.
The water quality standard of the Water Supply Act was
amended in 2005 in Japan, and TOC (total organic
carbon) was adopted as an indicator of organic matter
in tap water. Similarly, organic matter included in
mineral water and source water can also be evaluated
using a TOC analyzer.
Here, we introduce an example in which the TOC-LCPH
total organic carbon analyzer was used to conduct TOC
measurements of commercially available mineral water.
n Measurement Method
The samples, consisting of 6 types of commercially
available mineral water in plastic bottles, were analyzed
using the Shimadzu TOC-L CPH total organic carbon
analyzer. The instrument was calibrated according to
the "Total Organic Carbon Analyzer Measurement
Method: Calibration Curve Generation" method
specified in the Water Supply Act using aqueous
s o l u t i o n s o f p o t a s s i u m h y d ro g e n p h t h a l a t e a t
concentrations of 0, 0.3, 1.0, 2.0 and 3.0mgC/L
(carbon concentration 3.0mg/L), and a calibration
curve was generated. To eliminate the influence of the
carbon content in the pure water used to prepare the
standard solutions, the calibration curve was corrected
by shifting it so as to pass through the origin.
Mineral Water Samples
Sample name
A
B
C
D
E
F
Source Designation
Deep well water
Deep well water
Spring water
Mineral water
Mineral water
Mineral water
n Calibration Curve
The generated 5-point calibration curve is shown in Fig. 1.
Fig. 1 Calibration Curve Data

Measurement Conditions
Analyzer :
Shimadzu TOC-LCPH Total Organic Carbon Analyzer
Catalyst
: High Sensitivity Catalyst
Injection volume : 1000L
Measurement item : TOC (= NPOC: TOC by acidification and sparging)
Calibration curve : 5-point calibration curve using aqueous solutions
of potassium hydrogen phthalate at carbon
concentrations of 0 0.3 1.0 2.0 3.0mgC/L
Samples
:
C ommercially available plastic bottles of
mineral water
Application No. O47

News
Table 1 TOC Measurement Results for Mineral Water
n Results
The TOC analysis results obtained using 6 types of
bottled mineral water are shown in Table 1 and Fig. 2.
The TOC values of the samples were low, ranging from
0.04 to 0.3mgC/L, but the measurements were
conducted with good accuracy.
Sample name
A
B
C
D
E
F
Sample A
Sample B
Sample C
Sample D
TOC Concentration [mgC/L]

0.108
0.042
0.063
0.281
0.089
0.333
Fig. 2 TOC Measurement Data for Mineral Water
First Edition: Nov. 2013
www.shimadzu.com/an/
For Research Use Only. Not for use in diagnostic procedures.

The content of this publication shall not be reproduced, altered or sold for any commercial purpose without the written approval of Shimadzu.
The information contained herein is provided to you "as is" without warranty of any kind including without limitation warranties as to its
accuracy or completeness. Shimadzu does not assume any responsibility or liability for any damage, whether direct or indirect, relating to the
use of this publication. This publication is based upon the information available to Shimadzu on or before the date of publication, and subject
to change without notice.
Shimadzu Corporation, 2013
LAAN-A-TC-E026
Application
News
Monitoring of Algae Growth by TOC Measurement
O49
No.
Global warming due to the excessive use of fossil fuels

is becoming a problem which has prompted and
accelerated the search for alternative fuels. Among the
more attractive alternatives is biomass fuel, which is
attracting considerable attention. Microalgae can be
used for the production of oil without competing with
food production, and to a greater extent than other
biofuels, its productivity per unit time and area is high,
while arable land selection possibilities are great. As for
the practical use of microalgal biomass, various studies
have been conducted at each stage of its production,
including stock selection and breeding, cultivation,
harvesting, oil extraction, and purification.
The Shimadzu TOC-L Series combustion-type total
organic carbon analyzer, with its powerful organic
substance oxidation features, permits the complete
oxidization and measurement of samples such as
microalgae cell culture suspensions.
Here, we introduce an example of a unique application
in which the TOC-LCPH total organic carbon analyzer is
used to track the growth process of microalgae by
directly measuring, without conducting any
pretreatment, the TOC content in a suspended culture
of microalgae cells.
The data presented here was provided by the University
of Tsukuba Shiraiwa laboratory.
T. Iharada, M. Tanaka
50 m
Fig. 1 Algae
n Analytical Method
n Measurement Results
The microalgae was cultured for 8 days, and from the

starting day, TOC measurement was conducted once
per day for both Sample 1, which consisted of culture
along with suspended microalgae cells, and Sample 2,
which consisted of culture only obtained by removing
the microalga cells from Sample 1 through centrifugal
sedimentation. Then, from the difference in organic
carbon (TOC) between Sample 1 and Sample 2, we
obtained the value of TOC present in the organic
matter of the microalgae cells. Further, we measured
the turbidity of Sample 1, and that value was taken as
an index of cell mass.
A microscopic image of the microalgae cells of Sample 1
is shown in Fig. 1.
Fig. 2 shows the measurement results for the total

carbon (TC), total organic carbon (TOC) and inorganic
carbon (IC) associated with the cell mass during the
culture period. Also, the ratios of TOC to IC in the
microalgae cells are shown in Fig. 3. From these results,
it was possible to obtain information regarding the
increase and decrease of TC, IC and TOC values
associated with the microalgae cells throughout the
culture process.
One essential element in the practical realization of
microalgal biomass is establishment of the culture
conditions, and it is clear from this study that
information regarding the carbon balance can be
obtained using a TOC analyzer.
<Measurement Conditions>
Analyzer
: Shimadzu TOC-L CPH total organic carbon analyzer
Catalyst
: Standard catalyst
Measurement item
: TOC (TCIC)
Calibration curve
: 1-point calibration curve using 1000mg/L potassium hydrogen phthalate aqueous solution
Sample 1
: Culture solution containing suspended microalgae cells
Sample 2
: Culture solution with microalgae cells removed using centrifugal sedimentation
Water sampling method : Sample 1 water was sampled while stirring with a magnetic stirrer
Application No. O49

News
n Shimadzu TOC-L Series Total Organic Carbon Analyzer

Carbon Content / Turbidity (mg/L)
200
The Shimadzu TOC-L Series Total Organic Carbon

Analyzer can be used to conduct the following types of
measurements.
150
Measurement
TC
IC
TOC
100
50
Thus, the TOC-L series can be utilized for such

applications as the following types of microalgae
research.
-50
of total carbon and nitrogen content in

water, quantity dissolved, quantity suspended*
Measurement of total carbon, organic carbon,
inorganic carbon in water
Measurement of dissolved CO2 in water
Obtain
10
Culture Period (days)

Fig. 2 Changes in TC, IC, TOC Quantity in Microalgae Cells
(Conversion value per turbidity unit)
information related to the physiological state

and the properties of microalgae.
Understand the changes in cell material with respect
to changes over time in the culture and changes due
to light and dark environment.
Understand quantitatively the carbon and nitrogen
balance in the culture system.
The TOC-L Series instruments can be used to conduct
measurements using very small volumes of sample in
the range of 10 to 20mL, making it suitable for
laboratory-scale studies.
* The TNM-L Total Nitrogen Unit option is required for nitrogen (TN)
measurement. In addition, filtering and centrifugal separation, etc.
are required for separate measurement of samples in the dissolved
state and suspended state.
TOC/TC or IC/TC (ratio)
1
0.8
0.6
TOC/TC
IC/TC
0.4
0.2
0
10
Culture Period (days)
Fig. 3 Changes in TOC/TC and IC/TC in Microalgae Cells
Fig. 4 TOC-L Total Organic Carbon Analyzer + TNM-L Total

Nitrogen Unit
First Edition: Apl. 2014

LAAN-A-TC-E027
Application
News
Characterization of Algae by TOC Measurement
O50
No.
Global warming due to the excessive use of fossil fuels

is becoming a problem which has prompted and
accelerated the search for alternative fuels. Among the
more attractive alternatives is biomass fuel, which is
attracting considerable attention. Microalgae can be
used for the production of oil without competing with
food production, and to a greater extent than other
biofuels, its productivity per unit time and area is high,
while arable land selection possibilities are great. As for
the practical use of microalgal biomass, various studies
have been conducted at each stage of its production,
including stock selection and breeding, cultivation,
harvesting, oil extraction, and purification.
The Shimadzu TOC-L Series combustion-type total
organic carbon analyzer, with its powerful organic
substance oxidation features, permits the complete
oxidization and measurement of samples such as
microalgae cell culture suspensions.
Here, we introduce an example of a unique application
in which the TOC-LCPH total organic carbon analyzer is
used to characterize microalgae by directly measuring,
without conducting any pretreatment, the TOC content
in a suspended culture of microalgae cells.
The data presented here was provided by the University
of Tsukuba Shiraiwa laboratory.
T. Iharada, M. Tanaka
n Analytical Method
Five types of microalgae A E were cultured for 3 to 14
days, and at the start, after several days, and at the end
of culturing, TOC measurement was conducted for
sample 1, consisting of the various types of microalgae
cells suspended in culture medium, and for sample 2,
consisting of culture obtained by removing the
microalga cells through filtration of sample 1. Then,
from the difference in organic carbon content (TOC) in
samples 1 and 2, we determined the TOC in the
organic material of the various types of microalgae
cells. Also, the turbidity of sample 1 was measured, and
that value was taken as an index of cell mass.
<Measurement Conditions>
Analyzer
: Shimadzu TOC-L CPH total organic carbon analyzer
Catalyst
: Standard catalyst
Measurement item : TOC (TCIC)
Calibration curve : 1-point calibration curve using 1000mg/L potassium
hydrogen phthalate aqueous solution
Sample 1
: Culture solution containing suspended microalgae cells
Sample 2
: Culture solution with microalgae cells removed by filtration
Water sampling method : Sample 1 water was sampled while stirring with a
magnetic stirrer.
n Measurement Results
The increase in total carbon (TC), total organic carbon
(TOC) and inorganic carbon (IC) in five types of
microalgae culture and cells are shown in Fig. 1 and
Fig. 2, respectively.
It became apparent from the results that organic
material take-up and release by the cells varied
depending on the type of microalgae and the duration
of the culture period. Further, in regard to the
microalgae that form the shells of calcium carbonate,
the results suggested that such shell formation
information can be obtained using IC measurement.
To express these pieces of information that include the
type, nature and growth state of microalgae, a TOC
analyzer can be utilized for screening of the microalgae
and investigation of culture conditions.
Application No. O50

News
Microalgae A
Microalgae B
Microalgae C
Microalgae D (3-day culture)
Microalgae E (4-day culture)
-50
50
150
TOC (g)
250
350
Fig. 1 TOC/OD in Culture (Conversion value per turbidity unit)
Microalgae A
Microalgae B
Microalgae C
TOC
IC

0
200
400
600
800 1000
TOC and IC (mg)
1200
1400
1600
Fig. 2 TOC and IC/OD in Cell (Conversion value per turbidity unit)
n Shimadzu TOC-L Series Total Organic Carbon Analyzer

The Shimadzu TOC-L Series Total Organic Carbon
Analyzer can be used to conduct the following types of
measurements.
Measurement
of total carbon and nitrogen content in

water, quantity dissolved, quantity suspended*
Measurement of total carbon, organic carbon,
inorganic carbon in water
Measurement of dissolved CO2 in water
Thus, the TOC-L series can be utilized for such
applications as the following types of microalgae
research.
Obtain
information related to the physiological state

and the properties of microalgae.
Understand the changes in cell material with respect
to changes over time in the culture and changes due
to light and dark environment.
Understand quantitatively the carbon and nitrogen
balance in the culture system.
The TOC-L Series instruments can be used to conduct
measurement using very small volumes of sample in the
range of 10 to 20mL, making it suitable for laboratory
scale studies.
* The TNM-L Total Nitrogen Unit option is required for nitrogen (TN)
measurement. In addition, filtering and centrifugal separation, etc.
are required for separate measurement of samples in the dissolved
state and suspended state.
Fig. 3 TOC-L Total Organic Carbon Analyzer + TNM-L Total

Nitrogen Unit
First Edition: Apl. 2014


5.1. TOC determination methods according to EN 1484
5.2. Determination of the purgeable organic carbon (POC)
5.3. TNb total bound nitrogen
5.4. Kit for high-salt samples
5.5. Kit for small sample volumes
5.6. Kit for manual injections
5.7. Calibration with automatic dilution function
5.8. Blank value consideration in TOC analysis
5.9. TOC measurement principle catalytic combustion at
680C
5.10. TOC-L detection limit normal catalyst

5.11. TOC determination with wet chemical UV-oxidation
5.12. Silanisation of syringe TOC determination of surfactant
5.13. TOC determination with solid module SSM-5000A
5.14. Comparison of different sum parameters COD, BOD
and TOC
5.15. COD and TOC correlation factor conversion examples
5.16. TOC control samples and control cards
As market leader in TOC analysis, Shimadzu connects tradition

with experience. This enables users to profit from personal support or by attending seminars and user meetings organized by
Shimadzu. These application-oriented meetings serve for the
exchange of information and experiences.
This chapter also applies to the individual modules, kits or options of Shimadzus TOC analyzers. Useful functions are also
described.
In this particular field of application notes, specific sets of subjects TOC in daily practice are listed that are not covered by
one of the special applications. These are subjects that are related to the TOC parameter, independently of the matrix.
The wealth of experience in TOC analysis naturally finds its way
into the development of our TOC systems. Whether online analyzers or laboratory TOC systems they all impress by their
great flexibility, high availability, extreme robustness and stability, simple and intuitive operation and advanced operating
and evaluation software. Many additional functions facilitate
the users work and provide more freedom for other important
tasks.
Further details are available in the individual application notes

(for instance TOC determination methods, Total nitrogen determination or Blank values). In addition to the information
on TOC in daily practice, there are also application notes on
Pharmaceutical industry, Chemical Industry, TOC special applications, Environmental analysis and TOC process analysis.
TOC Determination methods according

to EN 1484
SCA-130-501
The EN 1484 standard Guidelines for the
determination of total organic carbon (TOC)
and dissolved organic carbon (DOC) defines
various terms and parameters.
Definitions according to EN 1484
TC:
Total carbon the sum of organically
bound and inorganically bound carbon
present in water, including elemental carbon.
TIC: Total inorganic carbon the sum of
carbon present in water, consisting of
elemental carbon, carbon monoxide, carbon
dioxide (also carbonates and hydrogen
carbonates),
cyanide,
cyanate,
and
thiocyanate. TOC instruments mainly detect
CO2, originating from hydrogen carbonates
and carbonates, just like TIC.
The following graph

parameters are linked:
shows
how
the
TC
TOC
NPOC
IC
POC
Determination methods
The TOC can be determined according to
three different methods:
TOC: Total Organic Carbon organically

bound carbon present in water, bonded to
dissolved or suspended matter. Cyanate,
thiocyanate and elemental carbon are also
determined.
POC: Purgeable Organic Carbon the TOC
content that is purgeable under the conditions
of this method.
NPOC: Non Purgeable Organic Carbon the
TOC content that is not purgeable under the
conditions of this method.
Difference method
For the difference method, the parameters
TC and IC are measured. The TOC is then
determined by way of calculation.
TC: The analysis of the total organic carbon
is carried out via oxidation (thermal or wetchemical) and subsequent determination of
the resulting carbon dioxide using NDIR
detection.
TIC: Through acidification of the sample
using a mineral acid at room temperature and
subsequent NDIR detection of the expelled
carbon dioxide the inorganic carbon is
detected.
SCA-130-501
The TOC is calculated from the difference

between TC and TIC: TOC = TC - TIC
Limitations of the difference method
The inorganic carbon content may not be too
high in comparison to the TOC.
Error propagation can result in a high level of
uncertainty for the calculated TOC value. The
EN 1484 standard recommends that the TOC
value, when using the differential method,
should be higher or equal to the TIC value
(TOC TIC).
Example:
TC Value = 100 mg/l (RSD = 2%) 2 mg/l
(98 102 mg/l)
IC Value = 98 mg/l (RSD= 2%) 1,96 mg/l
(96,04 99,96mg/l)
TOC = 2 mg/l 3,96mg/l (- 1,96 - 5,96 mg/l)
Due to error propagation, the total error is
3.96 mg/L.
According to the difference method, the error
of the total result is larger than the calculated
TOC content! In the worst case, this can
result in a negative TOC value.
Addition method
For the addition method, the parameters POC
and NPOC are measured. The TOC is then
calculated.
POC: Degassing of the volatile compounds
with subsequent catalytic combustion at
680C and determination of the resulting
carbon dioxide using NDIR detection.
NPOC: Measurement of the non-purgeable
organic compounds, after POC analysis
using catalytic combustion at 680C and
subsequent determination of the resulting
carbon dioxide using NDIR detection.
The TOC is calculated via addition:
TOC = POC + NPOC
Direct method
For the direct or NPOC method, it is assumed
that the sample does not contain any
significant amounts of volatile or purgeable
organic compounds. According to this
assumption, the TOC is directly determined
as NPOC.
NPOC: Acidification of the sample using a
mineral acid (for instance HCL) to a pH < 2,
whereby
carbonates
and
hydrogen
carbonates are completely converted to
carbon dioxide. The carbon dioxide is
removed from the sample solution via a
sparge gas. Direct NPOC measurement
(similar to TC measurement) via oxidation to
CO2. Subsequent NDIR detection.
The TOC corresponds to the NPOC:
TOC = NPOC
Determination of the purgeable organic

carbon (POC)
SCA-130-502
According to EN 1484, which contains the
instructions for TOC determination, the POC
(purgeable organic carbon) is the TOC
content that can be expelled under the
conditions of this method. This information is
very unspecific and should be described here
in more detail.
The instruments in the TOC-L series can be
extended with an option to include
measurement of the POC parameter. The
core feature of this option is the LiOH trap,
which is placed in the flow line of the
analyzer.
Here, the volatile organic compounds are

converted to CO2 and detected via NDIR
detector.
TOC
NPOC
POC
Fig. The addition method (NPOC + POC)
During the course of the addition method, the

remainder is used for NPOC determination.
However, in the drinking water application or
ultrapure water application, the POC content
is completely negligible. Here, TOC = NPOC
The POC can, nevertheless, play an
important role in wastewaters, particularly in
industrial effluents.
For POC determination, the sample is

aspirated using the TOC-L injection syringe,
acidified with HCL and subsequently purged
using carrier gas. In this step, CO2 originating
from carbonates and hydrogen carbonates as
well as all volatile organic compounds (POC)
are purged from the solution. The LiOH trap
binds the CO2 from the gas mixture
(originating from the TIC). The volatile
compounds pass the trap and reach the
catalyst.
Calibration
Particular attention should be paid to
calibration of the POC. Standards that are
prepared with volatile, purgeable organic
substances are inherently very unstable. This
is why IC standard solutions (prepared from
carbonates and/or hydrogen carbonates) are
used for POC calibration. Sampling of the IC
solutions for POC determination is carried out
using the TOC-L injection syringe. The IC
solution is acidified in the syringe. The
inorganic substances of the standard solution
are converted to CO2 and transferred to the
NDIR detector using a carrier gas.
SCA-130-502
POC-Peak:
NPOC-Peak:
Fig. POC-Calibration with IC-standard
System testing
In POC analysis, it is of great importance that
the LiOH trap functions perfectly. A test
should, therefore, be carried out to confirm
the efficiency of the CO2 trap. This test
should be carried out each working day:
An IC control solution (TIC = 1000 mg/L) is
prepared and analyzed as a POC sample.
For efficient functioning of the LiOH trap, the
POC measuring result must be < 0.1 mg/L.
Result:
TOC=4,05mg/l
POC=4,05mg/l => 100%
NPOC=0mg/l
Example of a POC measurement

Sample: Toluene in ultrapure water
Toluene is a compound that is fully
purgeable. In the addition method, the
toluene sample is completely determined as
POC.
POC measuring method:
Injection volume:
Purging time:
800 L
3 min

TOC-LCXX
ASI-L
POC-Option
TNb total bound nitrogen
SCA-130-503
Although nitrogen compounds are essential

for nature and the environment, high nitrogen
depositions can lead to problems. Nitrogen
compounds enter the environment primarily
through agricultural processes. Nitrogencontaining fertilizers constitute the largest
proportion. But nitrogen compounds can also
enter the environment via chemical industrial
processes.
Excessively high concentrations of nitrogen
compounds in the environment can cause
eutrophication of water bodies. Eutrophication
is the process of uninhibited growth of algae
and other organisms due to an excess supply
of nutrients. This overgrowth results in a lack
of oxygen in the water, which can lead to fish
mortality and to the formation of aquatic dead
zones.
Total nitrogen TNb

The variety of possible nitrogen compounds
necessitated the definition of a sum
parameter that represents the total nitrogen
compounds. For this purpose, the so-called
TNb (total bound nitrogen) was defined and
standardized.
The TNb is the total nitrogen content of a
sample in the form of ammonium, nitrite,
nitrate, as well as organic compounds. The
TNb does not include dissolved or gaseous
nitrogen (N2). A differentiation between
inorganic and organic nitrogen compounds is,
by definition, not possible.
Bound nitrogen occurs in nearly all waters,

mostly in the form of ammonia, nitrate, nitrite
or organic compounds.
Determination according EN 12260

EN 12260 describes the determination of
nitrogen in the form of free ammonia,
ammonium, nitrite, nitrate and organic
compounds that can be converted under the
described oxidative conditions.
SCA-130-503
The conversion of the nitrogen containing

compounds takes place via combustion in an
oxygen atmosphere higher than 700 C to
nitrogen oxide, which reacts with ozone to
activated nitrogen dioxide (NO2*). In the
subsequent reaction to NO2, light quanta are
emitted (chemiluminescence) that are
measured by the detector.
Subsequently, the gas mixture enters the

chemiluminescence detector, connected in
series, where the nitrogen content is
determined (See Figure below).
Simultaneous TN determination using

the TNM-L
Based on the similar oxidation process, the
TNb determination can be carried out
simultaneously with the TOC measurement.
For this application, the TNM-L option is
installed on the top of the main TOC-L
system.
Fig. Simultaneous TOC/TN-Determination
Fig. TOC-L CSH with TNM-L Modul
The benefit is that no additional laboratory

space is required.
For the simultaneous determination, the
sample is injected onto the catalyst at 720 C.
All carbon atoms present in the sample are
converted to CO2 and, in parallel, the nitrogen
atoms to NO. The gas mixture is then
transported by the carrier gas stream through
the NDIR detector, where the carbon dioxide
content is measured.
It should be noted that an optimal injection

volume must be selected for both
parameters.
TOC-L CXX with TNM-L
ASI-L
SCA-130-504
Samples with high-salt loads generally are a

problem for TOC analysis. The problem is
less the conversion of organic compounds to
CO2 than the effects of the salt on the
catalyst. This leads to higher maintenance
needs, as the salt can crystallize in the
combustion system.
In many applications for the instruments in
the TOC-L and the TOC-4110/4200 series,
the kit for salt-containing samples is an
important component. It consists of a
unique mixture of catalyst beads.
While NaCl has a melting point of 801 C, the

melting point of Na2SO4 is higher (888 C).
The potassium salts of sulfuric acid also have
a significantly higher melting point than those
of hydrochloric acid. This has a positive effect
on the lifetime of the combustion tube.
Compound
Melting point
NaCl
801C
KCl
773C
Na2SO4
888C
MgCl2
708C
CaCl2
782C
K2SO4
1.069C
Results indicate that the stability of the

catalyst is increased, and that up to 12 times
the number of samples can be measured
before the catalyst must be exchanged and
the instrument needs servicing.
Sample preparation
modify the sample matrix.
Fig. Catalyst filling
SCA-130-504
Endurance test
To determine the performance of this option,
a brine solution was measured in a long-term
test. For this purpose, a 28 % NaCl solution
(matrix adapted with a 15 % sulfuric acid
solution and spiked to a 5 ppm TOC solution
using a KPH solution) was injected 220 times.
Initially, a blank value and a control standard
with 10 ppm TOC were measured. The
control standards were tested after 110 and
220 injections, respectively. The injection
volume was 50 L.
The following figure shows the excellent
reproducibilities and the stability of the
measurement.
Concentratoin
Area
10
50
40
30
6
4
20
10
Area
Concentration[mg/L]
H i g h Sa l tConbuti uontube 28%N a Cl i n 5mg /LKH P[Inj :50uL A ci d:15%]
0
0
50
100
150
Injections
200
250
Fig. Results of endurance test
Related application
The high-salt kit is used for many different
applications in order to keep the maintenance
need for difficult matrices as low as possible.
Examples:
104 TOC-Determination in seawater
304 TOC-Determination in brine solution
306 TOC-Determination in soda solution
308 TOC-Determination in sodium nitrate
603 TOC-Determination in chemical
industry

TOC-L CXX
ASI-L
B-Type Scrubber
(At very high halogen concentrations in the
matrix, the B-type scrubber is recommended.
This scrubber protects the detector cell of the
NDIR detector.)
Kit for small sample volumes
SCA-130-505
The instruments of the TOC-L series are

designed to successively analyze many
different types of samples of different
concentrations. For the autosampler, sample
trays for different sample numbers and
sample volumes are available.
Small sample volumes

It can also occur, however, that only a few mL
of sample are available. This is usually the
case when there is only little sample
available, the sampling process is complex or
the sample is very valuable. For such cases,
the kit for small sample volumes is available.
The 5 mL syringe body can be exchanged for
a 500 L syringe in a rapid conversion step.
Moreover, the injection slider has to be
exchanged too.
Specification
With this option, automatic dilution,
acidification and sparging is not possible and
the specifications are, therefore, changed as
follows:
To eliminate cross-contamination between

analyses of the different samples, the number
of rinsing steps can be defined in the
software. There is usually enough sample
volume available to rinse the tubing and the
injection system of the TOC-L several times.
Depending on the measuring method,
injection volume, measurement range and
rinsing steps, 10 20 mL of the sample is
needed.
Measurement range: TC, IC: to 2,000 mg/L

TN: to 200 mg/L
Injection volume:
150l maximal
Diameter:
0.2 mm
NPOC-Measurement: In ASI-L with external
Sparge kit
ASI-L:
9ml Rack
Example
5 mL sample is sufficient for NPOC
determination using an ASI-L, 9mL vials
(3 injections with 150 L injection volumes)
Kit for manual injection
SCA-130-506
The manual injection kit enables the analysis
of water samples and gases. The sample for
TC determination is directly injected into the
combustion chamber using a L syringe. This
is interesting for applications where only a
very small sample volume is available.
The kit for small sample volumes is a module

for TOC analyzers that can be used for
automated sample preparation and analysis
of small sample amounts. The methods can
be optimized in such a way that only a few
mL of the sample are required. Optimization
should, however, not be at the expense of the
intermediate rinsing step.
When even smaller amounts than the few
milliliters are available, the TOC-L user can
fall back on the manual injection kit.
For gas samples, a distinction can be made

between total carbon (for instance CO or
CH4) and CO2.
The kit consists of two injection blocks, which
can be easily installed in the TOC system.
One of the injection blocks is used instead of
the IC-port; the other block replaces the TC
injection block.
This conversion does not take longer than

one minute.
Specification
For liquid samples:
Measurement range:
Injection volume:
Measurement time:
Reproducibility:
For gas samples:
Measurement range:
Injection volume:
Measurement time:
Reproducibility:
TC, IC: to 20.000 mg/L

150l maximal
TC, IC: 3 minutes
RSD: 2%
(over 8.000mg/L: 3% )
6ppm to 100% CO2
20l bis 10mL
2 4 Minuten
RSD: 2%
Calibration with automatic dilution

function
SCA-130-507

function
To create calibration curves, the dilution
function is activated via the wizard:
The core feature of the TOC-L series is the

ISP
module
(Integrated
Sample
Pretreatment). The ISP module consists of an
8-port valve and a syringe with sparging gas
connector. In addition to acidification and
sparging in the syringe, the system enables
automated dilution. This allows for the wide
measuring range, dilutes highly polluted
samples and enables the creation of dilution
series from a stock solution. The various
possibilities offered by the ISP module thus
reduce the time expenditure by the user.
Fig. ISP-Module of TOC-L

series
When filling the data of the calibration points,

the concentration of the standard solution
(stock) is entered first, followed by the
desired calibration curve point. The software
calculates the required dilution factor:
Since fractional factors are allowed, it is

possible to create a 10-point calibration curve
with equidistant concentration intervals from
one standard solution.
SCA-130-507
The following fgure shows the list of

calibration points of a 10-point calibration
curve in the range of 1 to 10 mg/L:

function over two decades
In addition, there is the possibility to use
different standard solutions for the dilution.
Calibration was carried out from 1 to 100
mg/L using two standard solutions (10 and
100 mg/L).
The measured calibration curve exhibits a

linear range with a very good correlation
coefficient (r = 0.9995).
Also here, the measured calibration curve

exhibits a linear range with a very good
correlation coefficient (r = 0.9995).
Blank value consideration in TOC analysis
SCA-130-508
Water plays a dual role in TOC trace

analysis. On one hand, it is applied as a
measuring medium and consumable in the
TOC analyzer. It is used to prepare standards
and to rinse the instrument. The automatic
dilution function of the TOC-L uses ultrapure
water for dilution of the samples or the
standard solutions for multi-point calibration.
On the other hand, ultrapure water is a
sample type in TOC analysis. In ultrapure
water applications, including the analysis of
water for injection and cleaning validation,
ultrapure water samples are analyzed to
determine their organic impurities.
For the determination of low concentrations at

the trace-level, knowledge on the blank value
is essential. The blank value is usually
composed of several components. First, there
is the instrument blank, secondly residual
concentrations can occur in the solvent and in
the reagents used. The influence of the blank
value is particularly significant in TOC
analysis, as carbon compounds are present
everywhere and a widespread carbon input
can, therefore, not be prevented.
With careful sample preparation and analysis,

this blank value can be minimized and
reliably determined. The blank value
consideration and the analysis of a system
blank value is only useful in very low
concentration ranges of < 1 mg/L.
Purified waters that have been produced
using highly complex water treatment
systems, have different water grades. The
DIN ISO 3696 standard specifies the
requirements and test methods for water for
analytical use and classifies these waters
according to 3 grades.
Parameter
Pure
water
TypIII
Pure
water
TypII
Ultra
pure
water
TypI
Ions,
resistance
(M.cm)
>0,05
>1,0
>18,0
Ions,
resistance
(S/cm)
<20
<1,0
<0,055
Organix,
TOC(ppb)
<200
<50
<10
Pyrogene
(EU/ml)
NA
NA
<0,03
Particle
>0,2m
(U/ml)
NA
NA
<1
Bacteria
(KBE/ml)
<1000
<100
<1
Tab 1: specification according to DIN ISO 3696
SCA-130-508
Blank value considerations

When, for instance, the NPOC is calibrated in
the lowest concentration ranges, a positive
area value for the zero value of the x-axis
generally results, as well as a positive value
of the y-axis where it intercepts the x-axis.
Both situations only describe the ratio

between the actual blank value and the blank
value when the calibration curve has been
created. To obtain an absolute concentration
value, there is the possibility of zero offset.
The zero offset is a parallel offset of the
calibration curve through the zero point.
Through this offset, the absolute term (b) of
the curve is set to zero and the blank value
(positive intercept) of the calibration is taken
into consideration in the sample analysis.
This positive area value reflects the blank

value. This blank value is, however, not
attributable to a specific factor or a specific
cause but appears as the sum of the various
blank value factors. This sum can consist of
the following:
Total blank value = of
+
Blank value of the instrument
+
Reagent impurity
+
Blank value of the standard
(ultrapure water)
+
Contaminations from the environment
(dust,
contaminations
on
the
glassware, etc.)
The calibration is evaluated according to the
general straight-line equation:
y=mx+b
y = Peak area
x = TOC concentration
m = slope of calibration
b = intercept
When a blank sample is now measured
against this curve, the concentration 0 mg/L
is obtained or, if the ultrapure water used is
slightly
cleaner,
even
a
negative
concentration value.
While the concentration in ultrapure water for

the preparation of standard includes a blank
value, the carbon concentration in an
ultrapure water sample only reflects the
actual TOC concentration of the sample.
In short: dilution water has a blank value, a
sample does not have a blank value.
SCA-130-508
Instrument blank value

Due to the ubiquity of certain compounds,
potential minute leaks in the instrument and
possibly persistent deposits or biofilms, can
lead to area values that originate from the
instrument itself and not from the measured
sample. To determine this value, the blank
check procedure can be performed:
For this purpose, the system (TOC-LCPH)
carries out an automatic analysis of
circulating ultrapure water. The resulting
condensation is collected in a suitable
container inside the instrument. As soon as
enough condensed water is available, the
water is circulated, i.e. it is injected again.
This procedure is carried out 50 times and it
can, therefore, be assumed that the final
determined area value corresponds to the
actual instrument blank value.
Reagents blank value

Reagents, such as hydrochloric acid, often
stand unobserved and unintentionally next to
the instrument for months and absorb vast
amounts of organic carbon from the
environment
(from
a
blank
value
perspective). For the determination of such
reagent blank values, the standard addition
method is suitable.
Contaminations from the environment
At last, the blank value is discussed that can
arise from everywhere in the environment
and can enter the analysis from various
sources. People and their industrial
landscapes are the source of a large variety
of organic carbon compounds. Humans
themselves consist of 18.2 % organic carbon
and lose, for example, 1 2 g skin particles
per day. These generally settle in the form of
house dust.
In addition to carbon originating from our
own bodies, carbon sources present in
cosmetics or toiletries such as soaps,
deodorants, perfumes, after-shaves skin
creams, ointments, plays an important role.
Also the laboratory harbors large sources of
organic carbon compounds.
Note: The determination of the instrument

blank value is also suitable for intensive
cleaning of the flow lines and for the breaking
in a newly built-in catalyst. As this is a very
time
consuming
method,
it
should
preferentially be carried out overnight.
Room air contains numerous pollutants that

can easily bind to dust particles and can
therefore also be present in house dust.
Finally, it should not be overlooked that room
air contains approximately 0.4 vol% / 0.06
mass% (400 / 600 ppm) CO2.
Sum Parameter Total Organic Carbon
TOC Measurement principle

Catalytic combustion at 680C
SCA-130-509
TOC-Measurement principle
The organic carbon compound is oxidized by
combustion to carbon dioxide. The carrier gas
(transporting the CO2) is cooled and
dehumidified and passed through a halogen
scrubber into the cell of the NDIR (Non
Dispersive Infrared) detector where the CO2
is detected. The NDIR outputs a detection
signal which generates a peak.
Salt interference at the detection cell from the

salt melt products may impact the quality and
accuracy of the data. Maintenance time is
also increased due to the extended cool
down and reheating time required based on
the higher combustion temperature.
Shimadzu TOC method
Shimadzu
developed
the
catalytically
oxidation at 680C and uses peak area for
integration. This temperature is lower as the
melting points of some salts:
Compound
NaCl
KCl
Na2SO4
MgCl2
CaCl2
Melting point
801 C
773 C
888 C
782C
782 C
Tab. Melting points of different salts
The deactivation of the catalyst and the

corrosion of the combustion tube are
minimized. In total the maintenance request
is lower as using higher temperature. On the
other hand the platinum catalyst ensures a
complete oxidation of all organic compounds.
Peak detection
In the past high temperatures (up to 1000C)
were necessary because the first TOC
instruments use the peak height for
integration. Due to this the conversion to CO2
must be instantaneous to keep the peak as
narrow and sharp as possible.
Disadvantage of high temperature
The very high combustion temperature has
the disadvantage of high levels of
maintenance (deactivation of catalyst,
corrosion of combustion tube and detector
cell) due to the salt melt products.
SCA-130-509
Recovery rates with 680C combustion

technique
Compound
Compound
Prepared
[mg/L]
Measured
[mg/L]
Recovery
[%]
Urea
200.0
203.0
101.5
Urea
2.000
1.986
99.3
Ethylurea
100.0
102.3
102.3
Thiourea
200.0
201.8
100.9
Thiourea
2.000
1.973
98.7
Prepared
[mg/L]
Measured
[mg/L]
Recovery
[%]
200.0
201.2
100.6
50.0
49.8
99.6
166.2
166.6
100.2
172.5
173.0
100.3
198.5
99.3
139.5
141.5
101.4
Nicotinic
acid
200.0
Dimethylformamide
1.932
96.6
200.0
200.4
100.2
Nicotinic
acid
2.000
Glucose
Sucrose
200.0
197.5
98,8
200.0
199.3
99.7
Sucrose
50.0
49.9
99.8
Sulfanilic
acid
Sucrose
2.000
1.968
98.4
Sulfanilic
acid
2.000
1.969
98.5
Fructose
50.0
49.9
99.8
53.0
100.6
55.0
56.0
101.8
Sulfosuccin
ic acid
52.7
Dodecylbenzene
sulfonic acid
10.10
10.55
104.5
L-glutamic
acid
50.0
Cyanuric
acid
8.36
8.61
103.0
Tartaric
acid
50.0
Acrylamide
200.0
197.1
98.6
Citric acid
50.0
49.6
99.2
Pyridine
hydrochloride
Tannine
47.0
47.4
100.9
2.000
1.983
99.2
Lignin
48.3
47.7
98.8
Pyridine
hydrochloride
Albumin
44.5
44.1
99.1
202.3
100.4
44.7
45.3
101.3
Caffeine
50.0
49.5
99.0
Quinine
hydrochloric
200.0
Humic acid
1,10Phenanthroline
50.0
49.7
99.4
Quinine
hydrochloric
2.000
2.008
100.8
Catechin
50.0
49.1
98.2
Cellulose
(insoluble)
100.0
98.6
98.6
1,4-Benzoquinone
100.0
100.4
100.4
3.00
2.99
99.7
Sodium
acetate
100.0
98.3
98.3
Polystyrene
(insoluble)
Nicotinamide
200.0
198.9
99,5
Nicotinamide
100.0
101.3
101.3
Nicotinamide
2.000
1.993
99.7
Ethanol
2-Propanol
1-Pentanol
1-Hexanol
50.1
49.8
100.2
99.6
Note: The recovery rate is effected by sample

preparation, instrument condition and surrounding
circumstances!
Detection and determination limit of

NPOC method with standard catalyst
SCA-130-510
Calculation of detection and
determination limit according to DIN 32645
Measurement parameters
System:
TOC-L CPN
Catalyst:
Standard catalyst
(Al-balls covered with Pt)
Method:
NPOC (removing of IC by
acidification and sparging)
Acidification: 1,5%
Sparge time: 2 min
Injection vol.: 150l
function
A 10 point calibration curve is carried out by
using the automatic dilution of a 2mg/L C
stock solution.
Characteristics
Slope a:
Intercept b:
Correlation coefficient r:
Result uncertainty:
Probability of error (a):
Number of measurements n:
Standard error of estimate Sy:
Standard error of procedure Sx:
Sum of squared deviations:
Quantile (one-sided):
Quantile (two-sided):
Limit of detection:
Limit of quantification:
7,226
0,544
0,9997
33,3%
5,00%
3
0,108
0,015
3,3
1,860
2,306
0,025mg/L
0,089mg/L
Note: The results depend on the selected

injection volume, the purity of the
vessels, water, chemicals and gases
used.
TOC determination with wet chemical UV-oxidation
SCA-130-511

used in TOC analysis: catalytic combustion
and wet-chemical oxidation.
In catalytic combustion, carbon compounds
are
converted
to CO2
using
high
temperatures and a catalyst, with subsequent
detection of the resulting CO2 using an NDIR
detector.
Wet-chemical oxidation uses a combination
of UV irradiation and persulfate oxidation.
Wet chemical UV-oxidation
In the wet chemical UV-oxidation, the
oxidation power of OH-radicals is used.
T
he UV (185nm) activates the H2O to
generate the [OH] radicals as
H2O + hv (185nm) OH + H+
The UV (185nm) also activates the persulfate
to generate the [OH] radicals as
S2O82- + h (254nm) 2 SO4SO4- + H2O HSO4- + OH
OH radicals are strong oxidants and oxidize
the carbon compounds to CO2.
Abb.: Peak graph of KHP standard

(NPOC = 5 mg/l)
Blue: Temperature / UV / Persulfate

Peak shape : 2.46 min.
Red: UV / Persulfate
(Peak shape: 3.54 min.)
Green: Temperature / Persulfate
(Peak shape: 4.13 min.)
The graph shows signal vs time for the
analysis of a 5 ppm KHP standard using the
different methods. The graph clearly
demonstrates that the combined method of
UV, persulphate and temperature has the
shortest analysis time and sharpest peak
shape.
{Organic compounds} + OH CO2 + H2O
In addition the temperature has an influence

to the oxidation reaction. The following figure
illustrates the influence of the different
parameter:
TOC-V WP
The key technique of the TOC-VWP analyzer
is the powerful oxidation via the combination
of sodium persulphate and UV oxidation at
80 C. A persulphate solution is needed for
the determination and it is therefore important
that this solution does not contain any
contaminants that could negatively affect the
measuring value.
SCA-130-511
The TOC-VWP contains an automatic reagent

preparation function that eliminates possible
contamination of the persulphate solution in
order to assure that the average TOC value
truly originates from the sample and not
from the reagent solution used.
The sample is added to the persulphate
solution in the TC reactor, which is heated
under UV illumination to convert the carbon
content to carbon dioxide.
Limitations
The wet chemical oxidation detects less
particles. To measure samples containing
particles the catalytic combustion with its
higher oxidation potential has to be used.
In
addition,
simultaneous
TOC/TNb
measurements can be carried out.
Application
The main domain of the wet chemical
oxidation is the analyses of ultra pure water
(pharma water, semiconductor industry,
condensate), because of the low detection
and good reproducibility in the ppb range.
Or in special applications, where the
combustion technique is not suitable.
Example of applications
205 TOC determination in ultra pure
water with wet chemical oxidation
309 TOC determination in phosphoric
acid (TOC-V WP)
Figure.: TC reactor with integrated UV lamp and heating
Advantage of the method

In the combustion oxidation the injection
volume is limited to 2000l (because of the
pressure impulse after injection). The wet
chemical oxidation can use injection volume
up to 20400l. This high injection volume
leads to higher sensitivity and therefore
enables high precision measurements in the
lower ppb range.
The detection limit of these systems is
0,5g/L.
Figue: TOC-V WP with ASI-V

TOC-VWP/WS
ASI-V (with 40ml or 125ml vials)
Silanisation of the syringe

TOC-determination of surfactants
SCA-130-512
The TOC determination of a surfactant
solution was not reproducible, nor did they
correspond with the theoretically calculated
values.
Subsequently,
TOC
direct
determination of the surfactant was executed
using the solid sampler SSM. The
measurement values obtained this way
corresponded well with the theoretical values.
This led to the conclusion that conversion of
carbon to CO2 was not the problem, rather
that the surfactant exhibits interactions with
the glass surface. Consequently, carbon is
being removed from the surfactant solution,
which explains the lower TOC measurement
values.
The main module of the TOC-L CPH is the
ISP module (integrated sample preparation
system). It consists of an 8-port valve and a
syringe with sparging connection. The syringe
is made of glass. In order to prevent
interaction of the surfactant with the glass
surface, the syringe is first silanized.
Required material for silanisation
1ml N-Methyl-N-(trimethylsilyl)trifluoroacetamide (for GC derivatization, 98.5%)
e. g.: von Fluka, No. 69479)
approx. 20ml methanol
1ml syringe with needle
Preparation and security notes

First the syringe has to be clean and dry.
Please refer to the warning remarks of the
used chemicals, wear protective clothing and
work under the extractor hood.
Procedure
Take the silanization reagent (1ml) and
put it into the syringe
Turn the syringe 5 10 minutes to coat
the complete surface
Drain the silanisation reagent

Remove the excess MSTFA by washing
two times with 10ml methanol.
Following this procedure, the syringe is
rinsed with water and dried (at 40C 50C in the dying cabernet)
After 24 hours, the syringe is ready for
use
Note
It is difficult to assume about the long-term
stability of this silanization. It depends of
different influences.
TOC determination with solid module

SSM-5000A
No.SCA-130-513
In addition to aqueous samples, TOC
determination can also performed on soil,
sludge, sedimentation and other solid
samples. By swabbing, the carbon in
attached residues can be measured for
cleaning validation.
In some regulation (e.g regulation for the
acceptance of waste at landfills pursuant) a
limit value for TOC is mentioned.
The modular design of Shimadzus TOC

series supports straightforward combination
with a solid sample module. In this way, the
instruments can also be employed for the
analysis of solids. The SSM-5000A module
can be used in combination with TOC-L a
TOC-V wet-chemical.
The solid module allows the separate
determination of TC (Total carbon) and the IC
(inorganic carbon). It has two different
sampling parts.
The module is fully integrated into the TOC
software (standalone and TOC-Control
software) which automatically calculates the
TOC-content.
TC Determination
For the TC determination, a subsample of the
dried solids is weighed into a ceramic boat
and combusted at 900 C in a stream of
oxygen. To ensure complete conversion to
CO2, the generated gases are passed over a

mixed catalyst (cobalt/platinum) for catalytic
post-combustion. The CO2 produced is
subsequently transferred to the detector in
the main unit.
The SSM-5000A solid sample module does
not have its own detector, but is coupled to
the NDIR detector of the main instrument
(TOC-V or TOC-L).
The NDIR detector of the main unit contains a
tandem cell consisting of a long cell and a
short cell the long cell is used for water
analysis and a short cell for solid sample
analysis.
This configuration assures that the system
can be employed for measurements of solids,
while retaining its complete flexibility and
switching functionality between water and
solid sample analysis without any additional
conversion.
IC Determination
The determination of the inorganic carbon is
carried out in a separate furnace of the
module. Phosphoric acid is added to the
sample and the resulting CO2 is purged at
200 C and measured.
SCA-130-513
Calibration
The SSM calibration can be carried out at
different manner. A solid (with known Ccontent) is weight in a ceramic boat or a
standard solution is added to a sample boat
filled with ceramic wool.
Example of a real solid sample (Bauxit)

TC determination
Result: 1.30 0.001% (CV: 0,11%)
In case of solid calibration, different weights

in of one compound (for example glucose)
are used. Based on the carbon content of the
compound (Glucose contains 40% carbon)
the absolute carbon content in the boat is
calculated (in g) and used for the calibration
graph (x-axis).
Kal. Kurve
2136,2
IC determination
Result: 0,94 0.009% (CV: 0,95%)
Flche
1500
1000
500
0
0
4000
8000
Abs C [ug]
12000
18101,6
Figure: TC-Calibration with Glucose
The IC calibration can be done with sodium

hydrogen carbonate (for instant).
Kal. Kurve
1234,2
TOC-Result: 0,36%
Flche
900

TOC-L or TOC-V wet chemical
SSM-5000A
600
300
0
0
2000
4000
6000
Abs C [ug]
8000
Figure: IC-Calibration with NaHCO3
10644,5
Example of Application
108
TOC determination in solids
203
TOC determination in cleaning
validation SWAB method
Comparison of different sum parameters

COD, BOD and TOC
SCA-130-514
Identification of organic pollutants in

wastewater is essential for performance
evaluation, construction and operation of a
wastewater
treatment
plant.
Several
parameters are currently used in wastewater
analysis applications. Some of these are
based on oxygen demand, for instance BOD
(biochemical
oxygen
demand),
COD
(chemical oxygen demand and TOD (total
oxygen demand). Using TOC analysis,
however, the total organic carbon content is
determined directly so the method is relatively
free from matrix effects. The advantages of
TOC analyses are apparent especially during
continuous monitoring.
BOD (Biochemical Oxygen Demand)

The BOD value indicates the amount of
oxygen in water needed for biological
decomposition
of
organic
compounds
dissolved
in
wastewater.
For
BOD
determination, microorganisms are added to
the water sample. After a predefined time
interval, usually five days, the oxygen
consumed by bacteria during decomposition
of organic compounds in the water sample is
determined. The BOD5 test is much too slow
to provide suitable information and the results
obtained are therefore not useful for

monitoring and controlling of wastewater
treatment procedures. For continuously
operated BOD analyzers, determination
within 5 -15 minutes has been attempted.
COD (Chemical Oxygen Demand)
The COD value indicates the amount of
oxygen needed to chemically oxidize organic
compounds present in wastewater. A
chemical oxidizing agent is added to the
sample and its consumption is subsequently
measured. In addition to the organic
compounds, other compounds (nitrites,
bromides, iodides, metal ions and sulfur
compounds) present in the water sample can
also be oxidized and have an influence on the
measuring value.
The COD determination is a subject of critical
discussion due to the use of environmentally
hazardous substances such as mercury and
chromium compounds.
TOD (Total Oxygen Demand)
This rather seldom parameter evolved from
the idea that chemical oxidation via COD
could be replaced by thermal oxidation,
whereby the amount of oxygen required for
high-temperature
combustion
of
all
contaminants is determined. This reduces the
measuring time when compared with COD
determination.
However,
during
TOD
measurements,
non-carbon
containing
compounds, for example sulfur and nitrogen
compounds, are also oxidized. This is
probably the reason why this parameter is not
used by most well-known regulatory
agencies.
SCA-130-514
TOC, total organic carbon

The TOC content is a measure of the
concentration of organically bound carbon
and is therefore a direct indication of the
pollution levels by organic compounds in
wastewater. For TOC determination, the
sample is typically first acidified in order to
convert the inorganic carbonate and
hydrogen carbonate compounds into carbon
dioxide. The dissolved CO2 is subsequently
removed from the sample via sparging with a
stream of carrier gas. The remaining organic
carbon compounds are then converted to
CO2 via high temperature (catalyst) or wetchemical oxidation. The amount of CO2
obtained is subsequently determined via
NDIR detection. NDIR is a specific detection
mode that renders TOC determination free
from the effects described above when using
other parameters. Based on this, the TOC
parameter is used in many environmental
regulations. Another advantage is the
relatively simple conversion of TOC
measurements into a continuous monitoring
procedure.
Correlation between COD and TOC
In recent years, COD measurements are
increasingly being replaced by TOC analysis.
However, as the threshold values for organic
pollution levels in wastewater are usually
described and determined as COD values,
efforts are underway to find a correlation
between the two parameters.
For single compounds the factor can be
calculated.
1. Example Glucose (C6H12O6) 1000mg/L
COD= 1067mg/L
TOC= 400mg/L
Correlation COD/TOC= 2,66
2. Example Acetone (C3H6O) 1000mg/L

COD=2207mg/L
TOC= 621mg/L
3. Example Ethanol (C2H6O) 1000mg/L
COD=2087mg/L
TOC= 522mg/L
The examples show the diversity of
correlation factors. In addition to the organic
compounds, other compounds like nitrites,
bromides, iodides, metal ions or sulfur
compounds may be oxidized and influenced
the factor.
Due to this, the correlation factor can be vary
between 2,5 and 4 depending of the
wastewater.
In order to simplify the determination of the
correlation factor, paragraph 6 of the German
wastewater law (AbwV) of June 17, 2004
includes the following: One of the values for
the chemical oxygen demand (COD) as
defined in the wastewater regulatory law is,
under compliance with paragraph 1, also
valid when the four-fold value of the total
organically bound carbon (TOC) in mg/L,
does not exceed this value.
In the European Union, the factor 3 is used
for conversion of TOC in COD.
The instrument software of Shimadzu TOC

systems (TOC-L standalone, TOC-Control L,
TOC-4200 standalone) enables the automatic
conversion of measured TOC values into
COD value (if the correlation is known).
COD and TOC correlation factor Conversion

examples
SCA-130-515
The determination of the chemical oxygen

demand (COD) is time-consuming and
complex. After the sample has been mixed
with various reagents, it is left to boil at 120C
(according to DIN regulation) under reflux (air
cooler), subsequently an aliquot of the
mixture is back-titrated or photometrically
measured (rapid test).
In addition, environmentally hazardous
substances, such as a mercury-containing
sulfuric acid and a potassium-dichromate
solution are used.
The determination of TOC (Total Organic
Carbon), on the other hand, is fast and easy
to perform. In addition, less than 1 mL of a
diluted hydrochloric acid solution is used for
each analysis.
COD and TOC in the German Waste
Water Ordinance (AbwV)
For decades, there have been efforts to
replace the COD by the TOC parameter.
However, to date the COD is laid down in the
German Waste Water Ordinance. In order to
still use the TOC parameter, Article 6
Compliance with the requirements of the
German Waste Water Ordinance states the
following:
(3) With due regard for paragraph (1) above,
a chemical oxygen demand (COD) level
specified in the water discharge permit shall
also be deemed to have been met provided
the quadruple amount of total organically
bonded carbon (TOC), specified in milligrams
per liter, does not exceed this level.
Theoretical COD/ TOC factor

If the TOC is used as an analytical parameter
to calculate the COD, a conversion factor is
required. The AbwV specifies the factor 4. A
theoretical factor is derived from the reaction
ratios between C and O2:

As the COD corresponds to the required
oxygen amount, the O2 consumption
corresponds to the COD value C represents
to the TOC value.
Since the COD or the TOC concentrations
must be expressed in terms of mass
concentration, the molar masses of the two
reactants are used here for the conversion.
The ratio of carbon concentration to oxygen
concentration corresponds to the TOC/COD
correlation. Based on the reaction equation
above, this means
for C: 1000
12
83.33
for O2: 1000
32
31.25
The COD factor is derived from the molar

ratio of C to O2:
88.33
31.25
2.667
In this case, the conversion from TOC to

COD is as follows:

2.667
SCA-130-515
The example above describes the oxidation

of carbon with oxygen. For organic
substances the ratio between carbon atoms
and oxygen atoms is different, which is of
direct influence on the conversion factors
from TOC to COD.
Methanol
Oxidation of methanol:
2
2 Carbons react with 3 oxygen molecules.

The calculation is as follows:
Here are a few examples.

Oxalic acid
Oxidation of oxalic acid proceeds as follows:
2
4 12
for O2: 1000
1 32
31.25
20.83
20.83
31.25
0.667
Benzene
The way oxidation of benzene proceeds:
2
15
12
for C: 1000
12 12
6.94
for O2: 1000
15 32
2.08
2.08
41.67
for O2: 1000
3 32
10.42
41.67
10.42
4.000
Real water samples

These examples show how the COD factor
can be calculated. They also illustrate why,
due to the composition of a sample, the COD
factor may vary so much.
In addition, real water samples usually
contain a large number of different organic
substances. This is why the bandwidth of the
conversion factors ranges from < 1 to > 5,
depending on the amount of oxygen that is
already bound in the organic compounds.
12 Carbons react with 15 oxygen molecules.

The calculation is as follows:
6.94
2 12
4 carbons react with an oxygen molecule.

This is the calculation:
for C: 1000
for C: 1000
3.34
Furthermore, COD determination also

measures oxidizable inorganic compounds,
such as nitrites, bromides, iodides, metal ions
and sulfur compounds and this may influence
the conversion factor.
The instrument software of Shimadzu TOC
systems (TOC-L standalone, TOC-Control L,
TOC-4200 standalone) enables the automatic
conversion of measured TOC values into
COD value (if the correlation is known).
Sum parameters Total Organic Carbon
TOC Control samples and control cards
SCA-130-516
Analytical quality assurance is an important
topic in many analytical application areas.
Various information leaflets as well as
appropriate quality standards provide tips or
guidelines on the most suitable measures to
attain high-level analytical quality.
Control samples
Control samples are important tools in
analytical quality control. Specially prepared
solutions of known concentration are used to
test the system and the validity of the specific
calibration. The control samples are treated
like unknown samples to determine the
concentrations or recovery. The users quality
management system specifies a tolerance
range the target value should be in.
The TOC Control software of the TOC-L and
TOC-V systems enable the definition of such
control samples.
Users can define their own parameters for

each control sample. The results can be
specified either in terms of concentration or
directly in terms of recovery.
Blind value controls can be defined as well.
The blind values are usually entered without
specifying a concentration (area).
Measures
The TOC autosamplers often run overnight
and process the samples sequentially until
the next morning. All the more annoying
when the analytical staff finds out the
following morning that the control samples
are outside of the specified tolerance limit. In
such cases, the software offers a solution.
When tolerance limits are exceeded, the
software can, for example, start an automatic
recalibration or repeat the run of the last
control sample within the tolerance limits.
When precious samples need to be
measured, or only very small amounts of the
sample material are available, the analytical
run can also be stopped.
Figure: Control sample parameters.
Control cards
In order to identify trends or system
deterioration in due time, the measurement
values of the control samples are
documented on a time axis. This leads to socalled control cards, in which the results are
listed on the Y-axis and the corresponding
dates on the X-axis.
SCA-130-516
Control card program

The TOC Control Software features an
integrated control card program. This way,
the user does not need to transfer values
manually. This is done automatically by the
system.
In the cards, control and warning limits are
defined that must not be exceeded. They can
be determined automatically by the program
(in a so-called pre-period) or manually
entered by the user.
With the software, the following control cards
can be generated and applied:
Mean value control cards

Blind value control cards
Recovery control cards
Span width control cards
Individual control cards
(target value control)

- TOC-V / L
- TOC-Control V / L
An editable cell also provides the option to

comment on the result entries.
Example of mean value control card

Pre-Period: 12 Samples
Mean value: 7,69mg/L
Control limit: 7,36mg/L and 8,02mg/L (green line)
Warning limit: 7,47mg/L and 7,91mg/L (blue line)
Out of control event: Sample 55 is over the control limit
Figure: Mean value control card

Measurements that lie outside of the control limits are automatically marked.

6.1. Continuous TOC/TN determination in wastewater
treatment plants
6.2. TOC process analysis in the paper industry
6.3. Continuous TOC determination in the chemical industry
6.4.
6.5.
6.6.
6.8.
Laboratory analysis yields comprehensive and detailed results

but, depending on circumstances, requires much time time
that is often not available during ongoing operations. For this
reason, operators of different types of plants increasingly use
sum parameters, which can also be determined continuously
during the actual process. Contrary to conventional laboratory
analysis, it is not an individual substance but an entire substance group that is determined here. In process waters from
the chemical industry, sum parameters serve as an indicator of
contaminations or all kinds of substance loads.
Various types of sampling systems as well as kits and options

for the many diverse applications are therefore essential. In addition to suitable equipment, robustness and service life of the
instrument (availability) are of major importance. After all, it is
important that the analyzer can measure autonomously and
transmit reliable analytical data.
Continuous condensate monitoring using the TOC-4200

TOC-4200 with high sensitivity option
Continuous TOC determination on airports
TOC-4200 measurement range up to 55,000 mg/L TOC
One of the most important chemical sum parameters is the

TOC. It is a measure of the organic pollution level or the organic constituents in the matrix.
With its TOC-4200 series, Shimadzu offers an online analyzer

that, with its various modules, kits and options, provides exactly the flexibility needed and can be equipped for the most
diverse applications. A selection of sampling techniques is
available: from a single-stream sampler to a sample exchanger
for six different sample streams, without or with homogenizer
for water containing particles.
Particularly during process control it is important to obtain

fast, continuous and informative data on the organic pollution
levels of waters. TOC process analysis offers this possibility.
The sample is fed continuously to the instrument for subsequent measurement. The instrument sends the analytical data
to the control room, which can react promptly to any possible
process changes.
The TOC-4200 stands out not only in terms of its robustness

but also by its reliability. The TOC-4200 already integrates the
most advanced communication channels to the control room.
In addition to the conventional communication modes, a Modbus communication protocol is available. An optional web
browser enables access to the instrument from any networkconnected computer.
One of the most important attributes of a TOC process analyzer

is its versatility. Since a TOC process system is not available
off-the-shelf, each measurement task must be customized to
the particular measuring problem, the matrix and the sampling
location. The analyzer must be tailored to the specific measuring task and not vice versa.
More information can be found in various application notes

(for instance TOC determination in the paper industry, sewage
treatment plants and power plants). In addition to TOC process analysis, information is also available on the application
areas Pharmaceutical industry, Chemical Industry, TOC special applications, TOC in daily practice and Environmental
analysis.
Continuous TOC/TN determination in

wastewater treatment plants
SCA-130-601
A uniform definition of wastewater does not
yet exist. Wastewater is often used as a
generic term for sludge, industrial wastewater
and infiltration water. The contents of
wastewater can vary widely depending on
their origin, and a distinction is made between
oxygen consuming compounds, nutrients,
harmful substances and contaminants [1].
Wastewater treatment is carried out to
eliminate wastewater contents and to restore
the natural water quality.
In municipal wastewater treatment plants,

biological processes are used in aerobic and
anaerobic wastewater treatment for the
degradation of organically highly polluted
wastewater. These plants use microbiological
degradation processes. A stable nutrient ratio
(carbon : nitrogen : phosphorus) is a
precondition for an optimal degradation
capacity of the microorganisms. Therefore, it
is important to continuously monitor the inflow
to the sewage plant. The treated effluent
leaving the sewage plant must also be
monitored continuously. Only when the limit
levels of the German Wastewater Ordinance
are reached, the water may flow back.
TOC determination in wastewater

used in TOC analysis:
catalytic combustion, where carbon
compounds are converted into CO2
using
a
catalyst
under
high
temperatures
with
subsequent
detection of the resulting CO2 using
an NDIR detector
wet chemical oxidation, which applies
a combination of UV irradiation and
persulfate for oxidation. The resulting
CO2 is either detected via an NDIR
detector or using a conductivity
detector.
For TOC determination in wastewater,
catalytic combustion has become the method
of choice based on its higher oxidation
potential, especially for particles. Regarding
TOC methods, the German Wastewater
Ordinance states the following: A TOC
system with thermal-catalytic combustion
(minimum temperature of 670 oC) must be
used.
TOC-4200
The TOC-4200 is a high-performance
analyzer with catalytic combustion at 680 C.
Depending on the sample characteristics,
three TOC analysis methods can be selected
(direct method, difference method, addition
method). The automatic dilution function
enables TOC analyses up to 20,000 mg/L. In
addition, the TOC-4200 can be extended with
a module for measuring the total bound
nitrogen (TN). An automatic dilution function
and the self-calibration option allow a virtually
independent operation of the measuring
system.
SCA-130-601
Sampling
An analysis system is only as good as the
sample preparation preceding it. Various
sample preparation systems are available for
the 4200 series, which can be optimally tuned
to the individual application area. When
sewage plant inlet and outlet are to be
measured using the same instrument, the
sample
stream
switcher
is
used.
Remote control
The measuring instruments can be started
and calibrated from a control station, and a
selection between the different measuring
streams is possible. Numerous alarm and
status signals simplify detection of exceeded
limit levels and indicate the need for
maintenance. In addition to the conventional
communication
modes,
a
Modbus
communication channel is available. An
optional web browser enables a view of the
instrument from any networked computer.
The software counts consumables such as
acids and pure water for dilution, and emits a
signal to the measuring station for refilling the
consumables.
TOC-4200
Multi-Stream suspended solids sampling unit
Acid Rinse option
Fig. Multi-Stream switcher
The sample enters the sample chamber via a

strainer, where it is homogenized through a
rotating knife before it is transferred to the
instrument for analysis. This way, even
samples containing large amounts of
particulate matter can be measured without
any problems. After sampling, the chamber
and the strainer are cleaned with rinsing
water. Depending on the application, the
rinsing water can be acidified in order to
prevent the growth of algae. The rinsing
function prevents any carry-over effects when
changing sample streams. The measuring
program can be individually selected for each
sample stream. In addition, the user can
freely choose the measuring sequence of the
sample streams.
[1] Source: Wikipedia
TOC process analysis in the paper

industry
SCA-130-602
Paper manufacturing requires the use of

water for various processes (suspension and
transport of the pulp, cooling water, sieve and
felt cleaning, system cleaning). Although the
water circulation in paper mills has been
systematically optimized in recent years due
to water conservation, the paper industry still
requires large quantities of fresh water for the
production of paper. Wherever fresh water is
consumed, large amounts of wastewater are
also produced and these must be
continuously monitored. The wastewater from
paper and pulp mills is usually highly polluted
with organic carbon compounds. The many
different products with various coatings, for
instance
specialty
papers,
produce
wastewater of widely varying compositions
and concentrations.
Fig.Example of four different sample streams in the

paper industry
The online analysis of these types of

wastewater is a major challenge for the
analyzer and for the sample preparation
TOC-4200
The TOC-4200 is a high-performance
analyzer with catalytic combustion at 680 C.
Depending on the sample characteristics,
three TOC analysis methods can be selected
(differential method, addition method, direct
method). The automatic dilution function
enables TOC analyses up to 20,000 mg/L. In
addition, the TOC-4200 can be extended with
a module for measuring the total bound
nitrogen (TN).
An automatic dilution function and the selfcalibration
option
allow
a
virtually
system. The measuring instruments can be
started and calibrated from one measuring
station and a selection between the different
measuring streams is possible. Numerous
alarm and status signals simplify detection of
exceeded limit levels and indicate the need
for maintenance.
In addition to the conventional communication
modes, a Modbus communication channel is
available. An optional web browser enables a
view of the instrument from any networked
computer.
SCA-130-602
Sampling
The sometimes highly fibrous wastewater can
clog tubes and pipes. Various mechanisms
and options are available to prevent clogging.
The wastewater streams are sequentially
transported to the analyzer using various
valves. Following each sample feed to the
analyzer, the valves and tubes are flushed
with fresh water and an acid rinse. This
prevents the formation of buildup in the
valves. The acid rinse and water rinse are
controlled by the TOC analyzer.
The rinsing function prevents any carry-over

effects when changing sample streams. The
measuring program can be individually
selected for each sample stream. In addition,
the user can freely chose the measuring
sequence of the sample streams.
Fig.: Multi-stream suspended solids pretreatment unit

Fig. Acid Rinse option to clean tubes and
sampling system
After the sample has passed the respective

valve, it enters the sample chamber via a
strainer where it is homogenized using a
rotating knife before it is transferred to the
instrument for analysis. This way, even
samples containing large amounts of
and the strainer are cleaned with acidified
rinsing water.
TOC-4200
Multi-stream suspended solid pretreatment
unit
Acid rinse system
Continuous TOC determination in the

chemical industry
SCA-130-603
The high demand for many different products
from the chemical industry and the required
efficiency of the manufacturing processes
often requires around-the-clock production.
This results in huge amounts of wastewater.
This water mostly originates from flowing
water bodies.
Industrial wastewaters must be pretreated

before being discharged into public sewage
treatment plants. Direct discharge into water
bodies requires an extensive cleaning
process. This is why many large companies
or industrial parks operate their own
wastewater treatment plants.
TOC determination in industrial
wastewater
The TOC content (Total Organic Carbon) is a
measure of the concentration of organically
bound carbon and is an indication of the
pollution level by organic compounds in
wastewater. This is why the TOC is often
used in sewage treatment plants as
measuring parameter to monitor and optimize
the treatment process and to calculate
pollution levels. The matrix in industrial
effluents can vary greatly and can prior to
sewage treatment
be polluted with high salt loads. For TOC

determination
in
wastewater,
catalytic
combustion has become the method of
choice based on its higher oxidation potential,
especially for particles.
Are high salt loads a problem?
During thermal catalytic combustion of the
test sample, the dissolved salts crystallize.
High salt loads can lead to pollution of the
catalyst, or even clogging of the system.
Maintenance
measures
(for
instance
exchanging the catalyst) would then be
required in order to render the instrument
operational again. Of course, it is desirable to
keep the maintenance intervals as long as
possible.
TOC-4200
The TOC-4200 offers various possibilities to
keep the maintenance needs for highly
polluted samples at a minimum. The TOC4200 with catalytic combustion at 680 C is a
high-performance analyzer. This temperature
is lower than the melting point of sodium
chloride and will, therefore, prevent
deactivation of the active centers of the
catalyst by a melt. The use of a platinum
catalyst ensures the complete conversion of
the organic compounds to CO2. The highly
sensitive NDIR detector allows small injection
volumes (typically 20 - 50 L) that reduce the
absolute sample input onto the catalyst. A
further reduction can be achieved using the
integrated dilution function.
SCA-130-603
This can take place when measurement

values are exceeded or can be applied
permanently. In this case, the user specifies
the desired dilution factor in the selected
method.
For the continuous TOC determination of
samples with high salt loads (> 10 g/L),
Shimadzu has developed a salt kit. The
combustion tube has a special shape and
uses two different catalyst beads. This
combination prevents crystallization that can
lead to clogging of the system.
TOC-4200 in daily practice
To verify the robustness and the reliability of
the TOC-4200 during practical operation, the
analyzer has been subjected to an endurance
test in a German chemical park. For three
months, the TOC-4200 had to stand the test
under the most difficult conditions at one
measuring station. The wastewater under
investigation was alkaline (pH 12) and
highly saline (conductivity 4 mS/cm).
The software enables planning of various

automatic maintenance and calibration tasks.
This way, automatic calibration of the
measuring method was programmed to take
place every 48 hours and automatic
regeneration of the catalyst twice a week.
Sampling took place in the counterflow mode
with backflushing in order to prevent clogging.
Results of the practice test
As described in the test, a sample was
collected every 4 minutes over a period of
three months, and subsequently diluted,
acidified and analyzed. After three months a
total of approximately 27,000 measurements
was achieved. . Within this period, the
instrument was automatically calibrated 45
times and the catalyst was regenerated
nearly 25 times. These functions can be
easily programmed via a calendar on the
touch screen. The calibration function
gradients remained stable over the entire
time period.
Fig. Diagram of 27.000 Measurement results (three

months)
The test did not require any catalyst

exchange or a single maintenance operation.
There was also no instrument or software
failure or any other component failure. In
short: the TOC-4200 has successfully passed
the endurance test.
Fig. TOC-4200 on site
This is why the instrument was equipped with

a kit for salt-containing samples. In addition,
the automatic dilution function was used to
dilute the samples (including the matrix).

TOC-4200
Continuous condensate monitoring using

the TOC-4200
SCA-130-604
When applying TOC determination to

condensates, few particles are usually
expected, but here as well, it is better to be
on the safe side with the higher oxidation
potential offered by catalytic combustion. It is
important to be able to quickly and reliably
detect every possible organic contamination.
Due to the low pollution level of the sample,
the catalyst remains stable over a long time
span, whereby the need for maintenance is
relatively low.
The chemical and petrochemical industry

uses superheated steam as energy carrier for
the supply of energy needed in various
thermal processing steps. Superheated
steam is usually generated from ultrapure
water, which prevents damage to the boilers.
In order to use as little water as possible, the
reflux condensate is redirected to the boiler. It
is, therefore, important to ensure that the
condensate is free from organic pollutants.
TOC determination in condensate
The TOC parameter provides information on
organic pollution. The TOC can be easily
determined and is easy to implement in
process analysis. Two oxidation techniques
are now commonly used in TOC analysis:
Catalytic combustion, where carbon
compounds are converted into CO2
using
a
catalyst
under
high
temperatures
with
subsequent
detection of the resulting CO2 using
an NDIR detector
Wet chemical oxidation, which uses a
combination of UV irradiation and
persulfate for oxidation. The resulting
CO2 is either detected via an NDIR
detector or a via conductivity detector.
TOC-4200
The high-performance TOC-4200 analyzer
applies catalytic combustion at 680 C. Three
TOC analysis methods can be selected
depending on the sample characteristics:
differential method, addition method, direct
method. Due to the automatic dilution
function TOC analyses up to 20,000 mg/L are
possible. In order to measure the total bound
nitrogen (TN), the TOC-4200 can be
extended with a specific module.
The self-calibration option and an automatic

dilution
function
enable
a
virtually
system which can be started and calibrated
from one measuring station. The different
measuring streams can be selected.
SCA-130-604
Numerous status and alarm signals simplify

detection of exceeded limit levels and
indicate the need for maintenance.
A
Modbus
communication
channel
complements
the
conventional
communication modes. An optional web
browser gives access to the instrument from
any networked computer.
Sampling
For the 4200 series, various sample
preparation systems are available, which can
be optimally tuned to the individual
application area. As condensates are
homogeneous samples (in contrast to
wastewater), an extra sample preparation
step is not necessary. Two sampling systems
are, therefore, suitable:
an overflow tube, from which the sample
is automatically drawn.
filling the sampling chamber through a
strainer (50 Mesh), in case the sample
does contain particles that need to be
removed
prior
to
measurement.
Compressed air empties the chamber and
cleans the strainer.
whereby the inorganic carbon content

(carbonates and hydrogen carbonates) is
removed prior to the actual analysis. For this
purpose, the sample is drawn from the
continuous sample stream into a syringe and
automatically acidified via the 8-port valve
(pH 2).
Using the sparging gas connection, the CO2
formed (from the carbonates and hydrogen
carbonates) is purged from the sample. The
remaining solution containing the organic
components
is
subsequently
injected
(septum-free) into the oxidation unit using the
sliding valve technique. The syringe and 8port valve allows automatic dilution and
creation of calibration curves.
TOC measurement in the condensate
The system is calibrated using a 2-point
calibration curve, blank water and 2 mg/L.
This is realized using a standard catalyst and
an injection volume of 200 L. Typical
measuring values are around 0.2 mg/L.
The measuring values of 275 consecutive
measurements of a condensate monitoring
are presented in the Figure below:
The mean value is 0.208 mg/L with a

standard deviation of 0.006 mg/L. The results
show that the required detection limit of 0.05
mg/L presents no problem.
Fig. Sampling
TOC measuring method

TOC determination is often carried out via the
NPOC method,

TOC-4200
Backwash Strainer Sampling unit
TOC-4200 High Sensitivity Measurement Option
SCA-130-605
Ultra pure water is one of the most widely
used reagents in industry and its quality is
therefore of utmost importance in all industrial
processes. Quality control has, for many
years, been carried out and documented via
conductivity measurements, which provide an
assessment of the concentration of all
inorganic species present in water. This
detection method does not take organic
pollutants into account, as they typically do
not contribute to conductivity. Organic
pollutants can, however, greatly influence
further industrial processes and it has
become increasingly more important to
include quantitative determination of all
organic species in quality control of water
samples.
When industrial processes require large

volumes of ultra pure water, it is
recommended to monitor its TOC content
continuously.
TOC-4200
The high-performance TOC-4200 analyzer

applies catalytic combustion at 680 C. Three
TOC analysis methods can be selected
depending on the sample characteristics:
difference method, addition method, direct
method. Due to the automatic dilution
function TOC analyses up to 20,000 mg/L are
possible. In order to measure the total bound
nitrogen (TNb), the TOC-4200 can be
extended with a specific module.
The self-calibration option and an automatic
dilution
function
enable
a
virtually
system which can be started and calibrated
from one measuring station. The different
measuring streams can be selected.
TOC (Total Organic Carbon)

The TOC value (Total Organic Carbon) can
be used as a sum parameter for organic
compounds. Similar to conductivity signals
composed of various ionic compounds, the
TOC value is a measure of the contribution of
the numerous organic compounds present in
a water sample.
Numerous status and alarm signals simplify

detection of exceeded limit levels and
indicate the need for maintenance.
A
Modbus
communication
channel
complements
the
conventional
communication modes. An optional web
browser gives access to the instrument from
any networked computer.
SCA-130-605
High Sensitivity Measurement Option

Adding the high-sensitivity measurement
option enables high-sensitivity measurements
in the 0 to 1 mgC/L range FS. This option
achieves high sensitivity by using a highly
sensitive catalyst and increasing the
maximum sample injection volume to 500 L
(standard specification is 150 L).
Calibration Curve Characteristics

Slope a:
Intercept b:
Correlation coeff r:
Result uncertainty:
Probability of error:
36.88
1.135
0.9997
33.33%
5%
Calibration Curve
Calibration
Point
1
2
3
4
Concentration
[mg/L]
0.250
0.500
0.750
1.000
Area counts
10.420
19.210
28.100
37.780

TOC-4200
High Sensitivity Measurement Option
Carrier Gas: High-purity air or
High-purity nitrogen,
(N2 Carrier Gas High
Sensitivity Measurement
Option required)
0,500
0,450
0,400
0,350
0,300
0,250
0,200
0,150
0,100
0,050
11:58
12:31
13:05
13:39
14:14
14:48
15:23
15:56
16:31
17:04
17:39
18:14
18:48
19:23
19:58
20:32
21:05
21:39
22:12
22:48
23:22
23:56
00:30
01:06
01:40
02:15
02:49
0,000
Fig. TOC-4200 Measurement results in mg/l of ultra pure water
Continuous TOC determination on airports
SCA-130-606
Ice and snow on the wings of airplanes
increase their total weight and have a
negative impact on their aerodynamics. For
reasons of safety, airplanes need to be deiced just before they are ready for takeoff.
The de-icing agent that is most frequently
used is a mixture of water, glycol and
additives. The exact composition depends,
among other things, on the outside
temperature.
After spraying the airplanes, the de-icing

agent enters the sewage system where it
leads to a significant increase of the organic
load. Even when the agent used is
biodegradable, the effluents must be
subjected to a controlled treatment process.
For the airport operator, it is therefore
important to know the organic load of the
airports wastewater. The TOC sum
parameter has been well established as an
assessment parameter for wastewater
analysis.
Continuous online NPOC monitoring
Important for TOC determination is the
differentiation between organic and inorganic
carbon.
Carbonates
and
hydrogen
carbonates are, after all, present in all natural
waters. The most widely used method for
TOC determination is the so-called NPOC
method. In this method, the sample is

acidified to convert the carbonates and
hydrogen carbonates present in the sample
to CO2. The resulting carbon dioxide is
subsequently purged using a gas stream
passed through the sample.
TOC (Total Organic Carbon) is a measure of
the concentration of organically bound carbon
and therefore reflects the pollution level of
organic substances in wastewater.
Depending on the use of the de-icing agent,
the TOC values can fluctuate significantly.
Tried and tested and powerful the
TOC-4200
The TOC-4200 process analyzer is perfectly
designed for this application. The TOC-4200
is a powerful analyser that uses catalytic
combustion at 680 C. After the analyser has
automatically removed the inorganic carbon,
a sub-quantity is injected onto a hot (680 C)
platinum
catalyst.
Here,
all
organic
components present are oxidized to carbon
dioxide. The resulting CO2 is transported by a
carrier gas stream to a highly sensitive and
CO2 selective NDIR detector, where it is
measured. The TOC concentration is
calculated using an external calibration.
SCA-130-606
The integrated dilution function enables TOC

analyses up to 20,000 mg/L as well as
automatic sample dilution when the
measuring range is exceeded. The measured
value is transmitted directly to a control room
that initiates suitable measures when a
threshold value is exceeded. The analyser
can also take direct action. For example, a
slider valve can be closed automatically to
prevent the discharge of contaminated water
into watercourses or stagnant water bodies.
Multiple sample streams in one
instrument
An airport may have several separate
wastewater collection systems. In this case,
multiple sample streams must be measured
using one instrument, requiring the use of a
multi-stream sampler. The sample is passed
through a strainer and reaches the sample
chamber where it is homogenised using a
rotating knife before being transferred to the
instrument for further analysis. In this way,
even samples containing large amounts of
and strainer are cleaned with rinsing water.
The rinsing water prevents carry-over effects
when switching sample streams. The

measuring parameter can be selected
individually for each sample stream. In
addition, the user can freely select the
sequence by which the sample streams are
to be measured.
Conclusion
The automatic dilution function, the selfcalibration check and the optimized sampling
process allow virtually independent operation
of the instrument at the airport. Numerous
alarm and status signals simplify detection of
exceeded threshold values or indicate
maintenance requirements. In addition to the
conventional
possibilities,
Modbus
communication is available. An optional web
browser enables access to the instrument
from any networked computer. This makes
the TOC-4200 the ideal instrument for
continuous TOC determination of wastewater
streams at airports, especially during the
winter period.
TOC-4200
Stand set
Multi-stream unit (for suspended samples)
The diagram represents measurement results of an airport wastewater stream in a period of 6

weeks. It shows the high fluctuation based on frosty or frost-free weather.
TOC-4200 Measurements up to 55,000mg/L TOC
SCA-130-608
TOC-process analyzers (TOC-4200) are used
in different applications from monitoring of
cooling water or condensate up to high
contaminated wastewater. For this, the TOC
analyzers have to provide a broad
measurement range.
ISP-Module in TOC-4200
The
TOC-4200
achieves
the
broad
measurement range by using the dilution
function of the ISP-module (integrated
sample pretreatment).
Figure: ISP-module in TOC-4200
The ISP module consists of an 8-port valve

and a syringe with sparging gas connector.
Sample and dilution water is taken in the right
ratio into the syringe. The solution is
homogenized by sparging (over the sparge
gas connector) with carrier gas.
Dilution factors from 2 to 50 can be used.
Normally the announced measurement range
of 20,000mg/L is sufficient for the controlling
of wastewater. But in some application (e. g.
de-icing process on airports) measurement
values up to 50,000mg/L are possible.
TOC-determination in the range of

55,000mg/L
The recovery and repeatability in the high
measurement range is proven with a Glucose
solution.
Calibration
Parameter: TC
Catalyst:
Standard
Std-Solution: 500mg/L (1-point)
Injection vol.: 20l
#Injection
Peak Area
768.6
1
784.2
2
762.1
3
771.6
Mean value
1,47%
RSD
Glucose standard
Std-Solution: 55,000mg/L
Dil. factor:
40
Injection vol.: 20l
Port:
Offline-Port
#Inj.
Area
Concentration
Recovery
1
2
3
MW
SD
RSD
2106
2137
2104
2116
18,51
0,87%
54,595 mg/L
55,399 mg/L
54,543 mg/L
54,854 mg/L
479 mg/L
99,3%
100,7%
99,2%
99,7%
SCA-130-608
TOC-Determination of a high
concentrated Glycol solution
TOC-determination on airports is one of the
applications where the TOC values can
fluctuate significantly depending on the use of
the de-icing agent. The de-icing agent that is
most frequently used is a mixture of water,
glycol and additives.
Due to this, the test is repeated with a glycol
solution in different concentration.
1. Glycol Solution
Parameter:
Concentration:
Dil. factor:
Injection vol.:
Port:
TC
45,250mg/L
40
20l
Offline-Port
#Inj.
Area
Concentration
Recovery
1
2
3
MW
SD
RSD
1734
1770
1720
1741
25,8
1,48%
44,951 mg/L
45,885 mg/L
44,588 mg/L
45,133 mg/L
669 mg/L
99,3%
101,4%
98,5%
99,7%
2. Glycol Solution
Parameter:
Concentration:
Dil. factor:
Injection vol.:
Port:
TC
55,340mg/L
40
20l
Offline-Port
#Inj.
Area
Concentration
Recovery
1
2
3
MW
SD
RSD
2087
2087
2027
2067
34,6
1,68%
54,102 mg/L
54,102 mg/L
52,547 mg/L
45,133 mg/L
898 mg/L
97,8%
97,8%
95,0%
96,8%
Function Auto Re-measurement

The previous measurements are done with a
fixed dilution factor of 40. But which
parameter should be set if the samples with
high concentration are exceptional cases
only?
In this case, the TOC-4200 provides the
function Auto RE-measurement.
This function allows setting of the parameters

for the normal measurement (lower
measurement range, un-diluted or low dilution
factor).
If the measurement value exceeds the
calibrated range, the injection volume and
dilution factor are automatically updated and
measurement is performed again.
Conclusion
The results show that the TOC-4200 can
handle samples with very high concentration
(up to 55,000 mg/L Carbon) without any
problems
TOC-4200
For information about Shimadzu, and to contact your local office, please visit our Web site at www.shimadzu.eu
Shimadzu Europa GmbH

Albert-Hahn-Str. 6-10 D-47269 Duisburg
Tel.: +49 - (0)203 - 76 87-0
Fax: +49 - (0)203 - 76 66 25
shimadzu@shimadzu.eu
www.shimadzu.eu
TOC Application Handbook
Founded in 1875, Shimadzu Corporation, a leader in the development of advanced technologies, has a distinguished history
of innovation built on the foundation of contributing to society
through science and technology. We maintain a global network
of sales, service, technical support and applications centers on
six continents, and have established long-term relationships
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Sum Parameter

1.7. Determination of particulate organic after filtration

2.4. TOC determination according to EP 2.2.44

3.7. TOC determination in ammonia or ammonium salt

4. TOC special application

4.3. Carbon dioxide determination in beer

5.10. TOC-L detection limit normal catalyst

6.5. TOC-4200 with high sensitivity option

1.6. TOC determination in particle-containing samples

A clean environment is the basis for a healthy life. Whether

Looking at the numbers of possible chemical contaminations

The sum parameter TOC (Total Organic Carbon) is one of the

Further details can be found in the individual application notes

Sum parameter Total Organic Carbon

TOC Determination in drinking water

European Drinking Water Directive

This list of indicator parameters also includes

TOC determination in drinking water

The organic fraction is only 1% of the total

Recommended analyzer / Configuration

Sum parameter Total Organic Carbon

TOC Determination in wastewater

Wastewater is water that has been

Sewage also includes the liquids that are

According to the German Water Resources

Example of wastewater measurement

Fig. Result of the wastewater

A TOC-LCPN was used for the analysis. To

In many cases, wastewater contains

Recommended Analyzer / Configuration

Fig. Combustion tube (of salt kit)

To test long-term stability, more than 300

Useful instrument parameters::

Sum parameter Total Organic Carbon

TOC Determination in surface and

exhibit high levels of TOC concentrations

Clean spring water

Weakly polluted rivers

Typical TOC-Concentrations (1)

Definitions according to WHG

Depending on the region, high TIC

The excellent particle tolerance of the

Example: River water

Recommended analyzer / Configuration

Sum parameter Total Organic Carbon

TOC Determination in seawater

TOC is an important indicator of the degree of

Are high salt loads a problem?

Kit for high-salt samples

Tab. Melting point of different salts

Simultaneous TN determination using

In this application, sample acidification is

Recommended analyzer / Configuration

Sum parameter Total Organic Carbon

TOC determination in solid samples

The TOC content in solids plays an important

To date, the established regulations describe

Approximately 200 mg of the dried and

The suspension is homogenized for several

1.7. Determination of particulate organic after filtration

2.4. TOC determination according to EP 2.2.44

3.7. TOC determination in ammonia or ammonium salt

4.3. Carbon dioxide determination in beer

5.10. TOC-L detection limit normal catalyst

6.5. TOC-4200 with high sensitivity option

1.6. TOC determination in particle-containing samples