I I.I.I (nat) 11.5.1 (waste) 11.6.1 (trade) 11.7.1 (sew)

Pyrol/sis gas High- HPLC-mass Ion-exchange Column coupled chromato- performance spectrometry chromato- ¡sot echography liquid chromato- graphy electrophoresis graphy (nat) (trade) (sew) (nat)

Organ oarsenic Organolead Orga no-mercury



Organosilicon Total halogen Organic phosphorus Total organic carbon (nat) (nat) (rain) (sea) (pot)

Table 1.13(d) Liquid chromatographic, superfluid chromatographic and thin-layer chromatographic methods for the determination of organic compounds in waters'

Ion Conventional Superfluid Thin-layer chromatography chromatography chromatography chromatography

Aliphatic hydrocarbons Aromatic hydrocarbons Poly aromatic hydrocarbons Mineral oils and petroleum spills

Aldehydes Esters

Carbohydrates Lactams Qui non es


Anionic detergents Non-ionic detergents Saturated aliphatic halogen compounds Haloforms Haloaromatics

Polychlorobipheny I s Chlorophenols (nat) Aliphatic amines

Nitrophenols Amides

Ethylene diamine tetraacetic acid Nitriloacetic acid Clorinated insecticides Mixtures of chlorinated insecticides and poly ch I o robi phe ny I s

Rationale, analysis of water samples 103

Table 1.13(a) Continued

Table 1.13(a) Continued

Note a Nat = natural waters, pot = potable waters, rain = rain/snow, sew = sewage effluents, trade = trade effluents.

Note a Nat = natural waters, pot = potable waters, rain = rain/snow, sew = sewage effluents, trade = trade effluents.

analysis are gas chromatography (77 types of organics) and highperformance and conventional liquid chromatography techniques (40 types HPLC, 26 types conventional column chromatography).

In a well-equipped laboratory it is mandatory that these techniques be coupled with a mass spectrometric detector in order to achieve a combination of resolution of mixtures, positive identification of separated organics and the high sensitivity that is essential when dealing with environmental water samples. The penetration of mass spectrometers in recent years is indicated by the fact that of the 77 types of organic compounds that have been determined by gas chromatography, in 19 cases mass spectrometric detection is discussed. This trend will, without doubt, continue into the future.

Another growing technique is supercritical fluid chromatography. Although recent references discuss only polychloroinsecticides, polychlorobiphenyl mixtures and mixtures of other types of organic compounds, there is no doubt that these applications will multiply in the future and that the range of supercritical fluids used (carbon dioxide, and methanol modified carbon dioxide, nitrogen dioxide, ammonia, fluorohydrocarbons) will increase as will the combination of this technique with mass spectrometric identification of separated compounds. For more volatile organic compounds such as aliphatic hydrocarbons, haloforms and saturated and unsaturated low-boiling aliphatic halogen compounds headspace gas chromatography and purge and trap gas chromatography are methods of choice.

A technique involving pyrolysis of the organic compound followed by gas chromatography of the pyrolysis products has, to date, found very limited application in the water laboratory (chlorolignosulphonic acids, chlorocarboxylic acids). It is, nevertheless the basis of a well-established method for determining total organic carbon in water.

Similarly, the technique of ion chromatography which has extensive application in the determination of anions and cations has very limited application in the determination of organics in water. The substances that have been determined include carboxylic acids, chlorophenols and sulphur-containing organic compounds.

Thin-layer chromatography has been applied extensively but is really only of value in preliminary scouting experiments or with types of samples such as sewage and trade effluents where the concentrations of organics present are relatively high, usually in the high milligram per litre range.

Regarding routine analysis, which in many cases is amenable to automation, a variety of techniques are available but, as always, in applying these methods the questions of interference effects and sensitivity must be borne in mind. These methods include:

1 Visible spectrophotometry (32 types of organic compounds), flow injection analysis (six types of organic compounds).

2 Ultraviolet spectroscopy (10 types of organic compounds): unsaturated hydrocarbons, PCBs, phenols, detergents, nitriloacetic acid; humic and fulvic acids, organolead, arsenic and antimony compounds, total organic carbon and dissolved organic carbon.

3 Fluorescence spectrometry (eight types of organic compounds): polyaromatic hydrocarbons, carboxylic acids, phenols, amino acids, carbamate herbicides, humic and fulvic acids, chlorophyll and organoantimony, tin and boron compounds.

4 Polarographic methods (15 types of organic compounds): polyaromatic hydrocarbons, carboxylic acids, aldehydes, esters, cations, PCBs, quinones, detergents, chlorophenols, amides, humic and fulvic acids, phosphorus-containing insecticides, ethylenediamine tetraacetic acid and nitriloacetic acid.

5 Titration methods (13 types of organic compounds): detergents, mercaptans, humic and fulvic acids and chlorine, iodine and organic nitrogen.

Other miscellaneous techniques which have found very limited application in water analysis include the following:

1 Infrared spectroscopy (seven types of organic compounds): hydrocarbons, cationic detergents, humic and fulvic acids, mixtures of organics, total organic carbon.

2 Raman spectroscopy (five types of organic compounds): polyaromatic hydrocarbons, phenols, lignosulphonates, phosphoruscontaining insecticides, mixtures of organics.

3 Nuclear magnetic resonance spectrometry (four types of organic compounds): nitrosamines, chlorine-containing insecticides, humic and fulvic acids, mixtures of organic compounds.

4 Neutron activaton analysis (four types of organic compounds): organomercury compounds, chlorine, bromine and iodine.

5 X-ray fluorescence spectroscopy: alkyl and aryl phosphates.

6 Isotope dilution analysis (four types of organic compounds): chlorocarboxylic acids, cobalamin, organic nitrogen and phosphorus.

7 Enzymic assay methods (eight types of organic compounds): carbohydrates, phenols, polychlorobiphenyls, adenosine triphosphate, chlorine and phosphorus-containing insecticides, carbamate herbicides and triazine herbicides.

8 Atomic absorption spectrometry, inductively coupled plasma atomic emission spectrometry and atomic emission spectrometry (13 types of organic compounds): detergents, ethylenediamine tetraacetic acid, nitriloacetic acid, organic compounds of arsenic, lead, mercury, tin, germanium, silica and sulphur.


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