5.

TOC in daily practice

5. TOC in daily practice
5.1. TOC determination methods according to EN 1484 5.10. TOC-L – detection limit normal catalyst
5.2. Determination of the purgeable organic carbon (POC) 5.11. TOC determination with wet chemical UV-oxidation
5.3. TNb – total bound nitrogen 5.12. Silanisation of syringe – TOC determination of surfactant
5.4. Kit for high-salt samples 5.13. TOC determination with solid module SSM-5000A
5.5. Kit for small sample volumes 5.14. Comparison of different sum parameters – COD, BOD
5.6. Kit for manual injections and TOC
5.7. Calibration with automatic dilution function 5.15. COD and TOC correlation factor – conversion examples
5.8. Blank value consideration in TOC analysis 5.16. TOC – control samples and control cards
5.9. TOC – measurement principle – catalytic combustion at
680°C

As market leader in TOC analysis, Shimadzu connects tradition This chapter also applies to the indi­vidual modules, kits or op-
with ex­perience. This enables users to profit from personal sup- tions of Shimadzu’s TOC analyzers. Useful functions are also
port or by attending seminars and user meetings organized by described.
Shimadzu. These application-oriented meetings serve for the
exchange of in­formation and experiences. Further details are available in the individual application notes
(for instance ‘TOC determination methods’, ‘Total nitrogen de-
In this particular field of application notes, specific sets of sub- termination’ or ‘Blank values’). In addition to the information
jects ‘TOC in daily practice’ are listed that are not covered by on ‘TOC in daily practice’, there are also application notes on
one of the special applications. These are subjects that are re- ‘Pharmaceutical industry’, ‘Chemical Industry’, ‘TOC special ap-
lated to the TOC parameter, independently of the matrix. plications’, ‘Environmental analysis’ and ‘TOC process analysis.’

The wealth of experience in TOC analysis naturally finds its way

into the development of our TOC systems. Whether online ana-
lyzers or laboratory TOC systems – they all impress by their
great flexibility, high availability, extreme robustness and sta-
bility, simple and intuitive operation and advanced operating
and evaluation software. Many additional functions facilitate
the user’s work and provide more freedom for other important
tasks.
 

 
Sum parameter – Total Organic Carbon
 

 
TOC – Determination methods according
  to EN 1484
 
SCA-130-501

The EN 1484 standard “Guidelines for the The following graph shows how the
determination of total organic carbon (TOC) parameters are linked:
and dissolved organic carbon (DOC)” defines
various terms and parameters.
TC
■ Definitions according to EN 1484
TC: Total carbon – the sum of organically
bound and inorganically bound carbon
TOC IC
present in water, including elemental carbon.
NPOC POC
TIC: Total inorganic carbon – the sum of
carbon present in water, consisting of ■ Determination methods
elemental carbon, carbon monoxide, carbon The TOC can be determined according to
three different methods:
dioxide (also carbonates and hydrogen
carbonates), cyanide, cyanate, and
thiocyanate. TOC instruments mainly detect
CO2, originating from hydrogen carbonates
and carbonates, just like TIC.

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 ■ Difference method

content that is purgeable under the conditions For the difference method, the parameters
of this method. TC and IC are measured. The TOC is then
determined by way of calculation.
NPOC: Non Purgeable Organic Carbon – the
TOC content that is not purgeable under the TC: The analysis of the total organic carbon
conditions of this method. is carried out via oxidation (thermal or wet-
chemical) 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 ■ Addition method

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

 
 

 
Sum parameter – Total Organic Carbon
 

 
Determination of the purgeable organic
  carbon (POC)
  SCA-130-502

According to EN 1484, which contains the Here, the volatile organic compounds are
instructions for TOC determination, the POC converted to CO2 and detected via NDIR
(purgeable organic carbon) is the TOC detector.
content that can be expelled under the
conditions of this method. This information is
very unspecific and should be described here TOC
in more detail.

The instruments in the TOC-L series can be

extended with an option to include NPOC POC
measurement of the POC parameter. The
core feature of this option is the LiOH trap,
Fig. The addition method (NPOC + POC)
which is placed in the flow line of the
analyzer. 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.

■ 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
For POC determination, the sample is is why IC standard solutions (prepared from
aspirated using the TOC-L injection syringe, carbonates and/or hydrogen carbonates) are
acidified with HCL and subsequently purged used for POC calibration. Sampling of the IC
using carrier gas. In this step, CO2 originating solutions for POC determination is carried out
from carbonates and hydrogen carbonates as using the TOC-L injection syringe. The IC
well as all volatile organic compounds (POC) solution is acidified in the syringe. The
are purged from the solution. The LiOH trap inorganic substances of the standard solution
binds the CO2 from the gas mixture are converted to CO2 and transferred to the
(originating from the TIC). The volatile NDIR detector using a carrier gas.
compounds pass the trap and reach the
catalyst.
 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:
Result:
An IC control solution (TIC = 1000 mg/L) is
prepared and analyzed as a POC sample. TOC=4,05mg/l
For efficient functioning of the LiOH trap, the
POC=4,05mg/l => 100%
POC measuring result must be < 0.1 mg/L.
NPOC=0mg/l

■ Example of a POC measurement

■ Recommended Analyzer / Configuration
Sample: Toluene in ultrapure water
TOC-LCXX
Toluene is a compound that is fully ASI-L
purgeable. In the addition method, the POC-Option
toluene sample is completely determined as
POC.

POC measuring method:

Injection volume: 800 µL

Purging time: 3 min

 
 

 
Sum parameter – Total Organic Carbon
 

 
TNb – total bound nitrogen
 
SCA-130-503  
 

Although nitrogen compounds are essential ■ Total nitrogen TNb

for nature and the environment, high nitrogen The variety of possible nitrogen compounds
depositions can lead to problems. Nitrogen necessitated the definition of a sum
compounds enter the environment primarily parameter that represents the total nitrogen
through agricultural processes. Nitrogen- compounds. For this purpose, the so-called
containing fertilizers constitute the largest TNb (total bound nitrogen) was defined and
proportion. But nitrogen compounds can also standardized.
enter the environment via chemical industrial
processes. The TNb is the total nitrogen content of a
sample in the form of ammonium, nitrite,
Excessively high concentrations of nitrogen nitrate, as well as organic compounds. The
compounds in the environment can cause TNb does not include dissolved or gaseous
eutrophication of water bodies. Eutrophication nitrogen (N2). A differentiation between
is the process of uninhibited growth of algae inorganic and organic nitrogen compounds is,
and other organisms due to an excess supply by definition, not possible.
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.

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

■ 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

It should be noted that an optimal injection

volume must be selected for both
Fig. TOC-L CSH with TNM-L Modul parameters.

The benefit is that no additional laboratory ■ Recommended Analyzer / Configuration

space is required.
TOC-L CXX with TNM-L
For the simultaneous determination, the ASI-L
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.

 
 

 
Sum parameter – Total Organic Carbon
 

 
Kit for high-salt samples
 
 
 
SCA-130-504

Samples with high-salt loads generally are a While NaCl has a melting point of 801 °C, the
problem for TOC analysis. The problem is melting point of Na2SO4 is higher (888 °C).
less the conversion of organic compounds to The potassium salts of sulfuric acid also have
CO2 than the effects of the salt on the a significantly higher melting point than those
catalyst. This leads to higher maintenance of hydrochloric acid. This has a positive effect
needs, as the salt can crystallize in the on the lifetime of the combustion tube.
combustion system.

In many applications for the instruments in Compound Melting point

the TOC-L and the TOC-4110/4200 series, NaCl 801°C
the kit for salt-containing samples is an
important component. It consists of a KCl 773°C
combustion tube of a special geometry and a
Na2SO4 888°C
unique mixture of catalyst beads.
MgCl2 708°C

CaCl2 782°C

K2SO4 1.069°C
Tab. Melting point of different salts

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
In this application, sample acidification is
carried out with sulfuric acid which is used to
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 µL.
■ Recommended Analyzer / Configuration
The following figure shows the excellent TOC-L CXX
reproducibilities and the stability of the ASI-L
measurement. Kit for high-salt samples
B-Type Scrubber
H i g h Sa l t　Conbuti uon　tube 　 28%N a Cl i n 5mg /LKH P[Inj :50uL A ci d:15%]
(At very high halogen concentrations in the
Concentratoin matrix, the B-type scrubber is recommended.
Area
50
10 This scrubber protects the detector cell of the
Concentration[mg/L]

40
8
30
NDIR detector.)
Area

6
4 20

2 10

0 0
0 50 100 150 200 250
Injections

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

 
 

 
Sum parameter – Total Organic Carbon
 

 
Kit for small sample volumes

  SCA-130-505  

The instruments of the TOC-L series are ■ Small sample volumes

designed to successively analyze many It can also occur, however, that only a few mL
different types of samples of different of sample are available. This is usually the
concentrations. For the autosampler, sample case when there is only little sample
trays for different sample numbers and available, the sampling process is complex or
sample volumes are available. 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 µL 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:

Measurement range: TC, IC: to 2,000 mg/L

TN: to 200 mg/L
Injection volume: 150µl maximal
Diameter: 0.2 mm
To eliminate cross-contamination between NPOC-Measurement: In ASI-L with external
analyses of the different samples, the number Sparge kit
of rinsing steps can be defined in the ASI-L: 9ml Rack
software. There is usually enough sample
volume available to rinse the tubing and the ■ Example
injection system of the TOC-L several times. 5 mL sample is sufficient for NPOC
Depending on the measuring method, determination using an ASI-L, 9mL vials
injection volume, measurement range and (3 injections with 150 µL injection volumes)
rinsing steps, 10 – 20 mL of the sample is
needed.
 

 
Sum parameter – Total Organic Carbon
 

 
Kit for manual injection
   

 
SCA-130-506

The manual injection kit enables the analysis For gas samples, a distinction can be made
of water samples and gases. The sample for between total carbon (for instance CO or
TC determination is directly injected into the CH4) and CO2.
combustion chamber using a µL syringe. This
is interesting for applications where only a The kit consists of two injection blocks, which
very small sample volume is available. 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.

The kit for small sample volumes is a module This conversion does not take longer than
for TOC analyzers that can be used for one minute.
automated sample preparation and analysis
■ Specification
of small sample amounts. The methods can
For liquid samples:
be optimized in such a way that only a few
Measurement range: TC, IC: to 20.000 mg/L
mL of the sample are required. Optimization
Injection volume: 150µl maximal
should, however, not be at the expense of the
Measurement time: TC, IC: 3 minutes
intermediate rinsing step.
Reproducibility: RSD: 2%
When even smaller amounts than the few (over 8.000mg/L: 3% )
milliliters are available, the TOC-L user can For gas samples:
fall back on the manual injection kit. Measurement range: 6ppm to 100% CO2
Injection volume: 20µl bis 10mL
Measurement time: 2 – 4 Minuten
Reproducibility: RSD: 2%
 

 
Sum parameter – Total Organic Carbon
 

 
Calibration with automatic dilution
  function
 
SCA-130-507

■ Calibration with automatic dilution

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 When filling the data of the calibration points,
8-port valve and a syringe with sparging gas the concentration of the standard solution
connector. In addition to acidification and (stock) is entered first, followed by the
sparging in the syringe, the system enables desired calibration curve point. The software
automated dilution. This allows for the wide calculates the required dilution factor:
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.

Since fractional factors are allowed, it is

Fig. ISP-Module of TOC-L possible to create a 10-point calibration curve
series with equidistant concentration intervals from
one standard solution.
 SCA-130-507

The following fgure shows the list of ■ Calibration with automatic dilution
calibration points of a 10-point calibration function over two decades
curve in the range of 1 to 10 mg/L: 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).

 
 

 
Sum parameter – Total Organic Carbon
 

 
Blank value consideration in TOC analysis
 
 
 
SCA-130-508

Water plays a dual role in TOC trace With careful sample preparation and analysis,
analysis. On one hand, it is applied as a this blank value can be minimized and
measuring medium and consumable in the reliably determined. The blank value
TOC analyzer. It is used to prepare standards consideration and the analysis of a system
and to rinse the instrument. The automatic blank value is only useful in very low
dilution function of the TOC-L uses ultrapure concentration ranges of < 1 mg/L.
water for dilution of the samples or the
standard solutions for multi-point calibration. Purified waters that have been produced
using highly complex water treatment
On the other hand, ultrapure water is a systems, have different water grades. The
sample type in TOC analysis. In ultrapure DIN ISO 3696 standard specifies the
water applications, including the analysis of requirements and test methods for water for
water for injection and cleaning validation, analytical use and classifies these waters
ultrapure water samples are analyzed to according to 3 grades.
determine their organic impurities.
Ultra 
Pure  Pure 
pure 
Parameter  water  water 
water 
Typ III  Typ II 
Typ I 
Ions, 
resistance  >0,05  >1,0  >18,0 
(M.cm) 
Ions, 
resistance  < 20  <1,0  <0,055 
(µS/cm) 
Organix, 
<200  <50  <10 
TOC (ppb) 
Pyrogene 
NA  NA  <0,03 
(EU/ml) 
For the determination of low concentrations at Particle 
the trace-level, knowledge on the blank value >0,2µm  NA  NA  <1 
is essential. The blank value is usually (U/ml) 
composed of several components. First, there Bacteria 
is the instrument blank, secondly residual <1000  <100  <1 
(KBE/ml) 
concentrations can occur in the solvent and in
Tab 1: specification according to DIN ISO 3696
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.
 SCA-130-508

■ Blank value considerations Both situations only describe the ratio

When, for instance, the NPOC is calibrated in between the actual blank value and the blank
the lowest concentration ranges, a positive value when the calibration curve has been
area value for the zero value of the x-axis created. To obtain an absolute concentration
generally results, as well as a positive value value, there is the possibility of zero offset.
of the y-axis where it intercepts the x-axis. 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 = Σ of

+ Blank value of the instrument While the concentration in ultrapure water for
+ Reagent impurity the preparation of standard includes a blank
+ Blank value of the standard value, the carbon concentration in an
(ultrapure water) ultrapure water sample only reflects the
+ Contaminations from the environment actual TOC concentration of the sample.
(dust, contaminations on the
glassware, etc.) In short: dilution water has a blank value, a
sample does not have a blank value.
The calibration is evaluated according to the
general straight-line equation:
y=m•x+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.

 
 SCA-130-508

■ Instrument blank value ■ Reagents – blank value

Due to the ubiquity of certain compounds, Reagents, such as hydrochloric acid, often
potential minute leaks in the instrument and stand unobserved and unintentionally next to
possibly persistent deposits or biofilms, can the instrument for months and absorb vast
lead to area values that originate from the amounts of organic carbon from the
instrument itself and not from the measured environment (‘from a blank value
sample. To determine this value, the ‘blank perspective’). For the determination of such
check’ procedure can be performed: reagent blank values, the standard addition
method is suitable.
For this purpose, the system (TOC-LCPH)
carries out an automatic analysis of ■ Contaminations from the environment
circulating ultrapure water. The resulting At last, the blank value is discussed that can
condensation is collected in a suitable arise from everywhere in the environment
container inside the instrument. As soon as and can enter the analysis from various
enough condensed water is available, the sources. People and their industrial
water is circulated, i.e. it is injected again. landscapes are the source of a large variety
This procedure is carried out 50 times and it of organic carbon compounds. Humans
can, therefore, be assumed that the final themselves consist of 18.2 % organic carbon
determined area value corresponds to the and lose, for example, 1 – 2 g skin particles
actual instrument blank value. 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.

Room air contains numerous pollutants that

can easily bind to dust particles and can
therefore also be present in house dust.
Note: The determination of the instrument Finally, it should not be overlooked that room
blank value is also suitable for intensive air contains approximately 0.4 vol% / 0.06
cleaning of the flow lines and for the ‘breaking mass% (400 / 600 ppm) CO2.
in’ a newly built-in catalyst. As this is a very
time consuming method, it should
preferentially be carried out overnight.

 
 

 
Sum Parameter – Total Organic Carbon
 

 
TOC – Measurement principle
  Catalytic combustion at 680°C
  SCA-130-509
 

■TOC-Measurement principle Salt interference at the detection cell from the

The organic carbon compound is oxidized by salt melt products may impact the quality and
combustion to carbon dioxide. The carrier gas accuracy of the data. Maintenance time is
(transporting the CO2) is cooled and also increased due to the extended cool
dehumidified and passed through a halogen down and reheating time required based on
scrubber into the cell of the NDIR (Non the higher combustion temperature.
Dispersive Infrared) detector where the CO2
is detected. The NDIR outputs a detection ■ Shimadzu TOC method
signal which generates a peak. Shimadzu developed the catalytically
oxidation at 680°C and uses peak area for
integration. This temperature is lower as the
melting points of some salts:

Compound Melting point

NaCl 801 °C
KCl 773 °C
Na2SO4 888 °C
MgCl2 782°C
CaCl2 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 1000°C)
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 680°C combustion Prepared Measured Recovery

technique Compound [mg/L] [mg/L] [%]
Compound Prepared Measured Recovery Urea 200.0 203.0 101.5
[mg/L] [mg/L] [%]
Ethanol Urea 2.000 1.986 99.3
200.0 201.2 100.6
2-Propanol Ethylurea 100.0 102.3 102.3
50.0 49.8 99.6
1-Pentanol Thiourea 200.0 201.8 100.9
166.2 166.6 100.2
1-Hexanol Thiourea 2.000 1.973 98.7
172.5 173.0 100.3
Nicotinic 200.0 198.5 99.3
Dimethyl- 139.5 141.5 101.4 acid
formamide
Nicotinic 2.000 1.932 96.6
Glucose 200.0 200.4 100.2 acid
Sucrose 200.0 197.5 98,8 Sulfanilic 200.0 199.3 99.7
acid
Sucrose 50.0 49.9 99.8
Sulfanilic 2.000 1.969 98.5
Sucrose 2.000 1.968 98.4
acid
Fructose 50.0 49.9 99.8
Sulfosuccin 52.7 53.0 100.6
Dodecyl- 55.0 56.0 101.8 ic acid
benzene
sulfonic acid Cyanuric 10.10 10.55 104.5
acid
L-glutamic 50.0 50.1 100.2
acid Acryl- 8.36 8.61 103.0
amide
Tartaric 50.0 49.8 99.6
acid Pyridine 200.0 197.1 98.6
hydro-
Citric acid 50.0 49.6 99.2 chloride
Tannine 47.0 47.4 100.9 Pyridine 2.000 1.983 99.2
Lignin 48.3 47.7 98.8 hydro-
chloride
Albumin 44.5 44.1 99.1
Quinine 200.0 202.3 100.4
Humic acid 44.7 45.3 101.3 hydro-
chloric
Caffeine 50.0 49.5 99.0
1,10-
Quinine 2.000 2.008 100.8
50.0 49.7 99.4 hydro-
Phenan-
throline chloric

Catechin 50.0 49.1 98.2 Cellulose 100.0 98.6 98.6

(insoluble)
1,4-Benzo- 100.0 100.4 100.4
quinone Poly- 3.00 2.99 99.7
styrene
Sodium 100.0 98.3 98.3 (insoluble)
acetate
Nicotin- 200.0 198.9 99,5 Note: The recovery rate is effected by sample
amide preparation, instrument condition and surrounding
circumstances!
Nicotin- 100.0 101.3 101.3
amide
Nicotin- 2.000 1.993 99.7
amide
 

 
 
 

 
Sum parameter – Total Organic Carbon
 

 
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.: 150µl Characteristics
Slope a: 7,226
■ Calibration with automatic dilution Intercept b: 0,544
function Correlation coefficient r: 0,9997
A 10 point calibration curve is carried out by Result uncertainty: 33,3%
using the automatic dilution of a 2mg/L C Probability of error (a): 5,00%
stock solution. Number of measurements n: 3
Standard error of estimate Sy: 0,108
Standard error of procedure Sx: 0,015
Sum of squared deviations: 3,3
Quantile (one-sided): 1,860
Quantile (two-sided): 2,306

Limit of detection: 0,025mg/L

Limit of quantification: 0,089mg/L

Note: The results depend on the selected

injection volume, the purity of the
vessels, water, chemicals and gases
used.
 

 
Sum parameter – Total Organic Carbon
 

  TOC determination with wet chemical UV-oxidation

 
 

 
SCA-130-511

Two oxidation techniques are now commonly

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 Abb.: Peak graph of KHP standard
of UV irradiation and persulfate oxidation. (NPOC = 5 mg/l)

■ Wet chemical UV-oxidation Blue: Temperature / UV / Persulfate

In the wet chemical UV-oxidation, the Peak shape : 2.46 min.
oxidation power of OH-radicals is used.
T Red: UV / Persulfate
he UV (185nm) activates the H2O to (Peak shape: 3.54 min.)
generate the [OH•] radicals as
H2O + hv (185nm) → OH• + H+ Green: Temperature / Persulfate
(Peak shape: 4.13 min.)
The UV (185nm) also activates the persulfate
to generate the [OH•] radicals as The graph shows signal vs time for the
S2O82- + hν (254nm) → 2 SO4- analysis of a 5 ppm KHP standard using the
SO4- + H2O → HSO4- + OH • different methods. The graph clearly
demonstrates that the combined method of
OH radicals are strong oxidants and oxidize UV, persulphate and temperature has the
the carbon compounds to CO2. shortest analysis time and sharpest peak
shape.
{Organic compounds} + OH • → CO2 + H2O
■ TOC-V WP
In addition the temperature has an influence The key technique of the TOC-VWP analyzer
to the oxidation reaction. The following figure is the powerful oxidation via the combination
illustrates the influence of the different of sodium persulphate and UV oxidation at
parameter: 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 ■ Limitations

preparation function that eliminates possible The wet chemical oxidation detects less
contamination of the persulphate solution in particles. To measure samples containing
order to assure that the average TOC value particles the catalytic combustion with its
truly originates from the sample – and not higher oxidation potential has to be used.
from the reagent solution used. In addition, simultaneous TOC/TNb
measurements can be carried out.
The sample is added to the persulphate
solution in the TC reactor, which is heated ■ Application
under UV illumination to convert the carbon The main domain of the wet chemical
content to carbon dioxide. 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 2000µl (because of the
pressure impulse after injection). The wet
chemical oxidation can use injection volume
up to 20400µl. This high injection volume
leads to higher sensitivity and therefore Figue: TOC-V WP with ASI-V
enables high precision measurements in the
lower ppb range. ■ Recommended analyzer / Configuration
The detection limit of these systems is TOC-VWP/WS
0,5µg/L. ASI-V (with 40ml or 125ml vials)

 
 
 

 
Sum parameter – Total Organic Carbon

Silanisation of the syringe –

TOC-determination of surfactants
 
SCA-130-512
The TOC determination of a surfactant ■Preparation and security notes
solution was not reproducible, nor did they First the syringe has to be clean and dry.
correspond with the theoretically calculated Please refer to the warning remarks of the
values. Subsequently, TOC direct used chemicals, wear protective clothing and
determination of the surfactant was executed work under the extractor hood.
using the solid sampler SSM. The
measurement values obtained this way ■ Procedure
corresponded well with the theoretical values.  Take the silanization reagent (1ml) and
This led to the conclusion that conversion of put it into the syringe
carbon to CO2 was not the problem, rather  Turn the syringe 5 – 10 minutes to coat
that the surfactant exhibits interactions with the complete surface
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.  Drain the silanisation reagent
 Remove the excess MSTFA by washing
■ Required material for silanisation two times with 10ml methanol.
 1ml N-Methyl-N-(trimethylsilyl)trifluoro-  Following this procedure, the syringe is
acetamide (for GC derivatization, ≥98.5%) rinsed with water and dried (at 40°C -
– e. g.: von Fluka, No. 69479) 50°C in the dying cabernet)
 approx. 20ml methanol  After 24 hours, the syringe is ready for
 1ml syringe with needle use

■ Note
It is difficult to assume about the long-term
stability of this silanization. It depends of
different influences.
 

 
 
 

 
Sum parameter – Total Organic Carbon
 

 
TOC determination with solid module
  SSM-5000A
 
No.  SCA-130-513
In addition to aqueous samples, TOC CO2, the generated gases are passed over a
determination can also performed on soil, mixed catalyst (cobalt/platinum) for catalytic
sludge, sedimentation and other solid post-combustion. The CO2 produced is
samples. By swabbing, the carbon in subsequently transferred to the detector in
attached residues can be measured for the main unit.
cleaning validation.
The SSM-5000A solid sample module does
In some regulation (e.g regulation for the not have its own detector, but is coupled to
acceptance of waste at landfills pursuant) a the NDIR detector of the main instrument
limit value for TOC is mentioned. (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
The modular design of Shimadzu’s TOC conversion.
series supports straightforward combination
with a solid sample module. In this way, the ■ IC – Determination 
instruments can also be employed for the The determination of the inorganic carbon is
analysis of solids. The SSM-5000A module carried out in a separate furnace of the
can be used in combination with TOC-L a module. Phosphoric acid is added to the
TOC-V wet-chemical. sample and the resulting CO2 is purged at
200 °C and measured.
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
 SCA-130-513

■ Calibration  ■ Example of a real solid sample (Bauxit)

The SSM calibration can be carried out at TC determination
different manner. A solid (with known C- Result: 1.30 ± 0.001% (CV: 0,11%)
content) is weight in a ceramic boat or a
standard solution is added to a sample boat
filled with ceramic wool.

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 µg) and used for the calibration
graph (x-axis).

Kal. Kurve
2136,2
IC determination
Result: 0,94 ± 0.009% (CV: 0,95%)
1500
Fläche

1000

500

0
0 4000 8000 12000 18101,6
Abs C [ug]

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%
900
■Recommended analyzer / Configuration
Fläche

600 TOC-L or TOC-V wet chemical

SSM-5000A
300

0
Example of Application
0 2000 4000 6000 8000 10644,5
Abs C [ug]
108 TOC determination in solids
203 TOC determination in cleaning
Figure: IC-Calibration with NaHCO3
validation – SWAB method

 
 

 
Sum parameter – Total Organic Carbon
 

  Comparison of different sum parameters –

COD, BOD and TOC
 

  SCA-130-514

Identification of organic pollutants in obtained are therefore not useful for

wastewater is essential for performance monitoring and controlling of wastewater
evaluation, construction and operation of a treatment procedures. For continuously
wastewater treatment plant. Several operated BOD analyzers, determination
parameters are currently used in wastewater within 5 -15 minutes has been attempted.
analysis applications. Some of these are
based on oxygen demand, for instance BOD ■ COD (Chemical Oxygen Demand)
(biochemical oxygen demand), COD The COD value indicates the amount of
(chemical oxygen demand and TOD (total oxygen needed to chemically oxidize organic
oxygen demand). Using TOC analysis, compounds present in wastewater. A
however, the total organic carbon content is chemical oxidizing agent is added to the
determined directly so the method is relatively sample and its consumption is subsequently
free from matrix effects. The advantages of measured. In addition to the organic
TOC analyses are apparent especially during compounds, other compounds (nitrites,
continuous monitoring. 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
■ BOD (Biochemical Oxygen Demand) high-temperature combustion of all
The BOD value indicates the amount of contaminants is determined. This reduces the
oxygen in water needed for biological measuring time when compared with COD
decomposition of organic compounds determination. However, during TOD
dissolved in wastewater. For BOD measurements, non-carbon containing
determination, microorganisms are added to compounds, for example sulfur and nitrogen
the water sample. After a predefined time compounds, are also oxidized. This is
interval, usually five days, the oxygen probably the reason why this parameter is not
consumed by bacteria during decomposition used by most well-known regulatory
of organic compounds in the water sample is agencies.
determined. The BOD5 test is much too slow
to provide suitable information and the results
 SCA-130-514

■TOC, total organic carbon 2. Example Acetone (C3H6O) 1000mg/L

The TOC content is a measure of the COD=2207mg/L
concentration of organically bound carbon TOC= 621mg/L
and is therefore a direct indication of the Correlation COD/TOC= 3,55
pollution levels by organic compounds in
wastewater. For TOC determination, the 3. Example Ethanol (C2H6O) 1000mg/L
sample is typically first acidified in order to COD=2087mg/L
convert the inorganic carbonate and TOC= 522mg/L
hydrogen carbonate compounds into carbon Correlation COD/TOC= 4,00
dioxide. The dissolved CO2 is subsequently
removed from the sample via sparging with a The examples show the diversity of
stream of carrier gas. The remaining organic correlation factors. In addition to the organic
carbon compounds are then converted to compounds, other compounds like nitrites,
CO2 via high temperature (catalyst) or wet- bromides, iodides, metal ions or sulfur
chemical oxidation. The amount of CO2 compounds may be oxidized and influenced
obtained is subsequently determined via the factor.
NDIR detection. NDIR is a specific detection Due to this, the correlation factor can be vary
mode that renders TOC determination free between 2,5 and 4 depending of the
from the effects described above when using wastewater.
other parameters. Based on this, the TOC
parameter is used in many environmental In order to simplify the determination of the
regulations. Another advantage is the correlation factor, paragraph 6 of the German
relatively simple conversion of TOC wastewater law (AbwV) of June 17, 2004
measurements into a continuous monitoring includes the following: “One of the values for
procedure. the chemical oxygen demand (COD) as
defined in the wastewater regulatory law is,
■ Correlation between COD and TOC under compliance with paragraph 1, also
In recent years, COD measurements are valid when the four-fold value of the total
increasingly being replaced by TOC analysis. organically bound carbon (TOC) in mg/L,
However, as the threshold values for organic does not exceed this value”.
pollution levels in wastewater are usually
described and determined as COD values, In the European Union, the factor „3“ is used
efforts are underway to find a correlation for conversion of TOC in COD.
between the two parameters.

For single compounds the factor can be The instrument software of Shimadzu TOC
calculated. systems (TOC-L standalone, TOC-Control L,
TOC-4200 standalone) enables the automatic
1. Example Glucose (C6H12O6) 1000mg/L conversion of measured TOC values into
COD= 1067mg/L COD value (if the correlation is known).
TOC= 400mg/L
Correlation COD/TOC= 2,66

 
 

 
Sum parameter – Total Organic Carbon
 

  COD and TOC correlation factor – Conversion

 
examples  

  SCA-130-515

The determination of the chemical oxygen ■ Theoretical COD/ TOC factor

demand (COD) is time-consuming and If the TOC is used as an analytical parameter
complex. After the sample has been mixed to calculate the COD, a conversion factor is
with various reagents, it is left to boil at 120°C required. The AbwV specifies the factor 4. A
(according to DIN regulation) under reflux (air theoretical factor is derived from the reaction
cooler), subsequently an aliquot of the ratios between C and O2:
mixture is back-titrated or photometrically
measured (rapid test). →
In addition, environmentally hazardous
substances, such as a mercury-containing As the COD corresponds to the required
sulfuric acid and a potassium-dichromate oxygen amount, the O2 consumption
solution are used. corresponds to the COD value – C represents
to the TOC value.
The determination of TOC (Total Organic
Carbon), on the other hand, is fast and easy Since the COD or the TOC concentrations
to perform. In addition, less than 1 mL of a must be expressed in terms of mass
diluted hydrochloric acid solution is used for concentration, the molar masses of the two
each analysis. reactants are used here for the conversion.
The ratio of carbon concentration to oxygen
■ COD and TOC in the German Waste concentration corresponds to the TOC/COD
Water Ordinance (AbwV) correlation. Based on the reaction equation
For decades, there have been efforts to above, this means
replace the COD by the TOC parameter.
However, to date the COD is laid down in the for C: 1000 ∶ 12 83.33
German Waste Water Ordinance. In order to
still use the TOC parameter, Article 6
“Compliance with the requirements” of the for O2: 1000 ∶ 32 31.25
German Waste Water Ordinance states the
following: The COD factor is derived from the molar
(3) “With due regard for paragraph (1) above, ratio of C to O2:
a chemical oxygen demand (COD) level
specified in the water discharge permit shall
88.33 ∶ 31.25 2.667
also be deemed to have been met provided
the quadruple amount of total organically
bonded carbon (TOC), specified in milligrams In this case, the conversion from TOC to
per liter, does not exceed this level.” COD is as follows:

∗ 2.667
 SCA-130-515

The example above describes the oxidation ■ Methanol

of carbon with oxygen. For organic Oxidation of methanol:
substances the ratio between carbon atoms
and oxygen atoms is different, which is of 2 3 → 2 4
direct influence on the conversion factors
from TOC to COD. 2 Carbons react with 3 oxygen molecules.
The calculation is as follows:
Here are a few examples.
for C: 1000 ∶ 2 ∗ 12 41.67
■ Oxalic acid
Oxidation of oxalic acid proceeds as follows:
for O2: 1000 ∶ 3 ∗ 32 10.42
2 → 4 2
41.67 ∶ 10.42 4.000
4 carbons react with an oxygen molecule.
This is the calculation:
■ Real water samples
These examples show how the COD factor
for C: 1000 ∶ 4 ∗ 12 20.83
can be calculated. They also illustrate why,
due to the composition of a sample, the COD
for O2: 1000 ∶ 1 ∗ 32 31.25 factor may vary so much.

In addition, real water samples usually

20.83 ∶ 31.25 0.667 contain a large number of different organic
substances. This is why the bandwidth of the
■ Benzene conversion factors ranges from < 1 to > 5,
The way oxidation of benzene proceeds: depending on the amount of oxygen that is
already bound in the organic compounds.
2 15 → 12 6
Furthermore, COD determination also
12 Carbons react with 15 oxygen molecules. measures oxidizable inorganic compounds,
The calculation is as follows: such as nitrites, bromides, iodides, metal ions
and sulfur compounds and this may influence
for C: 1000 ∶ 12 ∗ 12 6.94 the conversion factor.

The instrument software of Shimadzu TOC

for O2: 1000 ∶ 15 ∗ 32 2.08 systems (TOC-L standalone, TOC-Control L,
TOC-4200 standalone) enables the automatic
conversion of measured TOC values into
6.94 ∶ 2.08 3.34
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 Users can define their own parameters for
topic in many analytical application areas. each control sample. The results can be
Various information leaflets as well as specified either in terms of concentration or
directly in terms of recovery.
appropriate quality standards provide tips or
guidelines on the most suitable measures to Blind value controls can be defined as well.
attain high-level analytical quality. The blind values are usually entered without
specifying a concentration (area).
■ Control samples 
Control samples are important tools in ■ Measures
analytical quality control. Specially prepared The TOC autosamplers often run overnight
solutions of known concentration are used to and process the samples sequentially until
test the system and the validity of the specific the next morning. All the more annoying
calibration. The control samples are treated when the analytical staff finds out the
like unknown samples to determine the following morning that the control samples
concentrations or recovery. The user’s quality are outside of the specified tolerance limit. In
management system specifies a tolerance such cases, the software offers a solution.
range the target value should be in.
When tolerance limits are exceeded, the
The TOC Control software of the TOC-L and software can, for example, start an automatic
TOC-V systems enable the definition of such recalibration or repeat the run of the last
control samples. 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.

■ 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 so-
called control cards, in which the results are
listed on the Y-axis and the corresponding
Figure: Control sample parameters. 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: ■ Recommended analyzer / Configuration
- TOC-V / L
 Mean value control cards - TOC-Control V / L
 Blind value control cards
 Recovery control cards
 Span width control cards
 Individual control cards
(target value control)

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.