Total Organic Carbon Analysis - General Theory

Organic material as an environmental problem

Everything we eat, most of what we wear and many of the ordinary things that surround us are
made of organic material. All living creatures are themselves made of organic material.

Organic material is in itself normally not poisonous. Why, then, does it pose a problem for the
environment?

The answer is found in its decomposition. When organic material decomposes in an environment
where oxygen is available, an aerobic destruction process metabolises the organic material into
basic fragments, consisting mainly of water and carbon dioxide. Where oxygen is not available,
an anaerobic destruction process will release volatile methane gas instead of carbon dioxide.

When organic decomposition occurs in water, oxygen is drawn from the water to support the
aerobic breakdown. Oxygen is a limited resource in water. It is used by all living creatures. If an
extra load of organic material is mixed into the natural water environment, some, and sometimes
all, of the oxygen in the environment is consumed during the decomposition process of the
organic material.

Oxygen depletion of our natural waters leads to ecological imbalance. In severe cases, the
environmental damage can be permanent, resulting in dead water without fish, plankton, algae,
or other forms of aquatic life.

Oxygen depletion can occur when sewage outlets or effluents from any modern industry are let
out into a river or the sea with surplus organic material. Industries which present particularly
high risk to the environment would include the food processing, pulp & paper processing,
pharmachemical, petrochemical, and textile & dyeing industries.

The proper monitoring and control of all outlets of organic material to our natural waters will help
to maintain environmental balance and secure the future for our children.

Methods used for measuring organic pollution in water

The first method for measuring organic material in water was developed almost 100 years ago.
By measuring the oxygen consumption in a closed sample, the presence of organic material could
be indirectly quantified. Biological Oxygen Demand (BOD) analysis as originally developed is still
in use today, with only minor changes. BOD analysis, however, is time consuming and
inaccurate. The sample must be monitored for a period of 5-7 days and accuracy is at best ±
20%.

In the 1960s, a laboratory model of BOD analysis was developed which shortened the analysis
period by adding chemicals to the sample. Chemical Oxygen Demand (COD) analysis requires
only 3 hours and gives better results than BOD results. In more recent years, a number of on-line
methods for measuring correlation to COD have been developed.
Both the BOD and COD methods, however, only provide indirect measurements of organic
material. All organic material, no matter how complex, are basically made of organic carbon.
When organic matter is oxidized in water, it releases carbon which then bonds with oxygen to
form carbon dioxide. By monitoring the development of carbon dioxide, it is possible to obtain a
direct measurement of the organic material in the water. Total Organic Carbon (TOC) analysis
can give accurate results within just a few minutes.

TOC analysis can be automated for on-line applications. This gives it an inherent advantage over
the BOD and COD laboratory measurements. It is important, however, to ensure that any on-line
analysis method takes a truly representative sample, including small and large particulates and
colloidal material of the stream being monitored. For this reason, filtration of the sample should
be avoided.

The following equation exemplifies the difference as well as the correlation between BOD, COD
and TOC measurements:

C6H12O6 + 6O2 => 6CO2 + 6H2O

A comparison of BOD, COD and TOC

BOD COD TOC

Biological Oxygen Demand Chemical Oxygen Demand Total Organic Carbon

Measurement Base

Indirect measurement based Indirect measurement based Direct measurement of organic

upon oxygen consumption upon oxygen consumption carbon

Analysis Period

5 - 7 days 3 hours few minutes

Procedure

A sample in a closed system is A sample in a closed system is A sample is injected into a

saturated with oxygen. The
initial oxygen content is
measured. The sample is kept
under stable temperature
conditions for 5 to 7 days.
After this incubation period,
the oxygen content of the
sample is again measured.
The difference in the oxygen
concentration gives the BOD.
saturated with oxygen. The
initial oxygen content is
measured. Potassium
dichromate solution and
concentrated sulphuric acid are
added to the sample, which is
then boiled under pressure for
3 hours. The oxygen in the
sample is again measured. The
difference in the oxygen
concentration gives the COD.
reaction chamber. Acid is added
to the sample to remove the
inorganic carbon. When pH<2,
inorganic carbon, through a
natural chemical process, is
converted into carbon dioxide.
The carbon dioxide is purged
from the reaction chamber using
an inert carrier gas. The organic
material in the sample is then
oxidized. The carbon dioxide
produced during the oxidation
process is measured for TOC.

Drawbacks
- Low accuracy, being at best
± 20%, sometimes much
lower.
- Organic material requiring
longer oxidation periods than
5-7 days are not captured by
BOD measurement.
- Not suitable for on-line
analysis as the process
involves boiling sulphuric acid
and produces hazardous
waste.
- Accuracy is affected by
interference from inorganic
substances which are oxidised
and also consume oxygen in
the process.
- The sample volume used in
TOC analysis is so small that all
particles must, in principle, be
filtered out.
- TOC analysers are normally
strongly affected by Chlorine
(salt) in the sample.
<< The BioTector® uniquely
overcomes the above two
problems. >>

Oxidation methods used in TOC measurement

Three different oxidations methods are used in TOC measurement. Though a number of TOC
analyzers have been developed, each with their own design and varying characteristics, all
instruments can be categorized according to which oxidation method they employ to convert
organic carbon into carbon dioxide.

Thermal Oxidation
The Thermal Oxidation Method uses high temperature combustion to convert organic material
into carbon dioxide. When applied properly, it gives the best oxidation rate among the three
methods.
The sample is fed into a small oven, a few drops at a time, where it is oxidized at temperatures
of 600 to 800°C in the presence of a platinum catalyst. For complete oxidation, combustion must
be instantaneous.
The allowable sample volume is small, approximately 1/10 ml, and the pre-treatment of the
sample by homogenisation or filtration is vital to the success of the analysis.
Though thermal oxidation is a good laboratory method, it is less suitable for on-line applications
where the filtering requirement prevents the measurement of representative samples. Moreover,
this technology leads to a very high requirement for maintenance.

UV/Persulphate Oxidation
In the UV/Persulphate Oxidation Method, the sample is mixed with a solution of persulphate and
exposed to UV light. Large particulates are not completely oxidized and the oxidation rate varies
with the different organic compounds present in the sample.
UV light also generates tiny quantities of ozone. However, the quantities are so small as not to
effectively contribute to oxidization.
The variable and generally poor oxidation rate for this simplified oxidation method is regarded by
a number of experts as unsuitable for either laboratory or on-line applications. Despite this,
UV/Persulphate oxidation is in widespread use because the instruments are simple to design and
inexpensive to construct.

Advanced Oxidation
The Advanced Oxidation Method pioneered by the BioTector® uses hydroxyl radicals as its
oxydizing agent. By exposing high pH reagents to a heavy concentration of ozone, hydroxyl
radicals are created. Hydroxyl radicals are very unstable and highly corrosive. They are one of
the most reactive substances which can be found to oxidise organic material.
Because this oxidising chemical can be created within the reaction chamber from basic
components (oxygen and sodium hydroxide), it is possible to use larger sample volumes for the
analysis and thereby allow the introduction of particles into the sample. Filtering is not required.
This method is highly suitable for on-line applications