152 Organic compounds in soils, sediments & sludges
6.5 SULPHUR CONTAINING COMPOUNDS
The analysis of organosulphur compounds has been greatly facilitated by the flame
photometric detector [148]. Volatile compounds can be separated by a glass capillary chromatographic column and the effluent split to a flame ionisation detector and
a flame photometric detector. The flame photometric detector response is proportional to the square of the concentration of the sulphate [149–152]. The selectivity
and enhanced sensitivity of the flame photometric detector for sulphur permits quantitation of organosulphur compounds at relatively low concentrations in complex
organic mixtures. The flame ionisation detector trace allows the organosulphur compounds to be referenced to the more abundant aliphatic and/or polynuclear aromatic
hydrocarbons.
Reliable flame photometric detector quantification of organosulphur compounds
requires careful optimisation of the gas chromatograph parameters. Although the
relative response of the flame photometric detector to various sulphur compounds
remains somewhat controversial [153], analysis of organosulphur compounds by flame
photometric detector is now relatively straightforward.
Trehey et al [154] used gas chromatography-mass spectrometry to determine alkyl
benzene sulphonates and dialkyltetralin sulphonates in sediments by this technique
with a detection limit of 0.5 g kg
−1 .
Shea and MacCrehan et al [155] determined hydrophilic thiols in sediment pore
water using ion-pair chromatography coupled to an electrochemical detector. Down
to 2 p mole absolute of these compounds could be determined including cysteine,
monothiogylcerol, glutathione, mercaptopyruvic acid, 3-mercaptopropionic acid and
2-mercaptopropionic acid. Dichloroethane extraction of the sediment, followed by
elimination of elemental sulphur, mercaptans, disulphide and dibenzothiophene on a
copper column is followed by a gas chromatographic analysis with flame photometric
detection of the organosulphur compounds. The detection limit is 1 ng as sulphur with
a precision of ±10% [156].
6.6 PHOSPHORUS CONTAINING COMPOUNDS
6.6.1 Alk yl and ar yl phosphates
Ishikawa et al [56] developed procedures to determine the trialkyl and triaryl phosphate esters in sediment, involving extraction with dichloromethane (for water) or
acetone (for sediment), followed by gas chromatography using a flame photometric
detector and gas chromatography-mass spectrometry after clean-up through a Florisil
column.
Sediments containing 50–1600 mg kg
−1 of triphenyl phosphate altered the drift
dynamics of benthic invertebrates invertebrates. Invertebrates exposed to contaminated sediments drifted almost immediately when threshold toxicity was reached [157].
6.6.2 Inositol phosphate
Inositol phosphate esters have been determined in sediments [158].
6.5 SULPHUR CONTAINING COMPOUNDS
The analysis of organosulphur compounds has been greatly facilitated by the flame
photometric detector [148]. Volatile compounds can be separated by a glass capillary chromatographic column and the effluent split to a flame ionisation detector and
a flame photometric detector. The flame photometric detector response is proportional to the square of the concentration of the sulphate [149–152]. The selectivity
and enhanced sensitivity of the flame photometric detector for sulphur permits quantitation of organosulphur compounds at relatively low concentrations in complex
organic mixtures. The flame ionisation detector trace allows the organosulphur compounds to be referenced to the more abundant aliphatic and/or polynuclear aromatic
hydrocarbons.
Reliable flame photometric detector quantification of organosulphur compounds
requires careful optimisation of the gas chromatograph parameters. Although the
relative response of the flame photometric detector to various sulphur compounds
remains somewhat controversial [153], analysis of organosulphur compounds by flame
photometric detector is now relatively straightforward.
Trehey et al [154] used gas chromatography-mass spectrometry to determine alkyl
benzene sulphonates and dialkyltetralin sulphonates in sediments by this technique
with a detection limit of 0.5 g kg
−1 .
Shea and MacCrehan et al [155] determined hydrophilic thiols in sediment pore
water using ion-pair chromatography coupled to an electrochemical detector. Down
to 2 p mole absolute of these compounds could be determined including cysteine,
monothiogylcerol, glutathione, mercaptopyruvic acid, 3-mercaptopropionic acid and
2-mercaptopropionic acid. Dichloroethane extraction of the sediment, followed by
elimination of elemental sulphur, mercaptans, disulphide and dibenzothiophene on a
copper column is followed by a gas chromatographic analysis with flame photometric
detection of the organosulphur compounds. The detection limit is 1 ng as sulphur with
a precision of ±10% [156].
6.6 PHOSPHORUS CONTAINING COMPOUNDS
6.6.1 Alk yl and ar yl phosphates
Ishikawa et al [56] developed procedures to determine the trialkyl and triaryl phosphate esters in sediment, involving extraction with dichloromethane (for water) or
acetone (for sediment), followed by gas chromatography using a flame photometric
detector and gas chromatography-mass spectrometry after clean-up through a Florisil
column.
Sediments containing 50–1600 mg kg
−1 of triphenyl phosphate altered the drift
dynamics of benthic invertebrates invertebrates. Invertebrates exposed to contaminated sediments drifted almost immediately when threshold toxicity was reached [157].
6.6.2 Inositol phosphate
Inositol phosphate esters have been determined in sediments [158].