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Abstract
Many chemical measurements are subjected to international recommendations and rules. When applied to environment, they must also
respect national rules. In this paper, rules to measure TOC issued in the period 19732002 are presented. Over 20 rules and guidelines, both
national and international, are presented all aiming to increase the environmental monitoring capacity of ecologists and researchers through
the use of the best instruments commercially available and manufactured by the market farms.
The tracking of CO2, obtained by oxidative system, is the heart of TOC modern analysers. Practically, all the methods foresee the
determination of the CO2 produced by the degradation of the organic matter present in solution, often IR devices are used. Also, other
detectors can be used (conductivimeter, CO2electrode) but they must be characterised by mechanical resistance and stability, not interfered by
other gases, not easily corroded.
The thermal oxidation methods are distinguished in low-temperature method (below 100 8C) and high-temperature method (between 600
and 1200 8C) with the presence also of mixed oxidation systems.
In many countries, TOC determination is ruled in order to avoid that manufacturers of scientific equipment manage at their commercial
convenience on this field. Anyway, the rules imposed by internationally recognised organisms must be actually followed. They establish the
use of reference solutions, specific methods of measure and detection limits that must be respected by the analytical instruments.
Due to the wide field of application involving TOC measurements, especially related to water (drinking, surface, waste), this kind of
instruments is largely present everywhere.
At present, definitive rules about TOC measurement are not laid down by law; so, we consider it interesting to present the chronological
list of the rules with their content concerning the measurement method, the sensitivity and detection limit, and the matrices that must be
subjected to the control. Consideration about the measurement quality and the correspondence between rules and analytical power are out of
the interest of this work.
D 2004 Elsevier B.V. All rights reserved.
Keywords: Total organic carbon; TOC; Normative; Guidelines; Rules; Chronological; Water measurement; Review
1. Introduction
The presence of organic matter in water has always
attracted the attention of researchers. The variability of the
matrix must be taken into consideration with different
attention to the carbon in solution and suspension. In the last
year, the interest to apply the analysis by bglobal indicatorsQ
has got an increasing trend for both pollution and quality
* Corresponding author. Fax: +39 06 490631.
E-mail address: gnn.vsc@tiscali.it (G. Visco).
0026-265X/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.microc.2004.10.018
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Fig. 1. Carbons in water; summary of the typical definitions and their relations.
(3)
(4)
(5)
(1)
(2)
(6)
(7)
(8)
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(9)
(10)
(11)
(12)
(13)
(14)
(15)
4. CO2 detectors
A TOC measurement requires an instrumental apparatus
mainly consisting of two parts: the first must ensure the
mineralisation of the organic content in the sample while the
second (the detector) has to measure the produced CO2. The
same attention paid to obtain stoichiometric CO2has to be
spent to obtain its correct detection. The detector has to be
carefully chosen, according to the matrix under investigation, in order to ensure suitable values for the analytical
characteristics (reproducibility, accuracy, selectivity, sensitivity, and limit of detection).
Many analytical methods are available to detect carbon
dioxide; the most used are here listed.
4.1. IR detector
Infrared (IR) absorption (or reflection for solids) is a
widely used spectroscopic technique that can be successfully applied also for a continuous monitoring of chemical
processes.
The IR wavelength region ranges from 800 to 15,384 nm
but, generally, the commercially available instruments can
operate in the near IR (8002500 nm) or in the mid-IR
(250015,384 nm).
Among the detectors used in TOC analysers, the most
common is the non-dispersive IR analyser (NDIR), which
operates in the mid-IR where, at this high wavelengths,
interference from IR-absorbing gases (CO, NO, SO2 and
NH3) are minimised.
Carbon dioxide produced by the sample degradation
flows through the sample cell and absorbs the IR light.
The IR spectrum is shown in Fig. 3; the characteristic
wavelengths corresponding to the CO2 absorption and the
main possible interference (water vapour) can be seen [4].
IR detectors used for TOC analysers can differ from each
other: one or more wavelengths and single or double rays
can be used. In the last case, different reference gases are
filled in a sealed reference cell or flow through an open
cell. In order to avoid interference of IR absorbing gases,
a selective gas-permeable membrane is located between
the degradation and the detector chambers. In order to
remove as much water as possible prior to introducing
the gas stream into the IR analyser, air-cooled condensers
are generally used.
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5. Conclusion
Articles and reviews available starting from 1970 [6,7]
up today [8] have demonstrated a great interest in the TOC
analysis. An increasing attention is really turned to the TOC
measurements as important index to assess the water quality
[9]. For example, some industries producing semiconductors or drugs need extreme pure water.
At the present, a defined law on this topic does not exist,
probably due to the involved very complex issues; on the
contrary, many guidelines, by internationally recognised
organisms, are available. In the present communication, a
collection of the actually available rules, treating TOC
measurements, useful to deepen the subject and to allow a
rightly critical reading of the literature on this topic, is
presented. The last researches reveal that, among the
mineralisation methods, the photoassisted degradation is
actually the most studied [10] for both the remediation of
wastewater and for the production of the TOC analyser
devoted to the oxidation of the organic matter.
Generally inadequate attention is paid to the characterisation of catalysts (often TiO2) even if molecular formula
constitutes only one point of view since the surface area and
production method play principal role in the efficiency
improving.
References
[1] Canadian Water Quality Guidelines, Parameter-specific Background
Information, Canadian Council of Research and Environment
Ministers, 1996.
[2] F. Wolpers, Workshop of the Turkish Pharmaceutical Ind.; Istanbul
Hilton Hotel; 23 May 2002, http://www.ikev.org/haber/2002validpdf/
Sunum%20Wolpers.pdf.
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