194 Organic compounds in soils, sediments & sludges
applicability to wastewaters and marine samples (marine sediments and marine organisms). Typical analytical results for marine samples are tabulated. The determination
of extractable halogenated compounds was of greatest importance for marine samples.
8.1.4 Nitrogen containing organic compounds
Kido et al [30] determined basic organic compounds such as quinoline, acridine,
aza-fluorene, and their N-oxides in marine sediments found in an industrial area.
The sediments were extracted with benzene by using a continuous extractor for 12
hours. Hydrochloric acid (1N) was added to the benzene extracts, and the mixture
was shaken for 5 minutes; the acid layer separated from the benzene layer was made
alkalinc by the addition of sodium hydroxide and the alkaline aqueous solution was
extracted with diethyl ether; the ether extracts were then dehydrated with anhydrous
sodium sulphate and concentrated with a Kuderna-Danish evaporator. The concentrations were separated and analysed by gas chromatography-mass spectrometry and gas
chromatography high-resolution mass spectrometry.
Krone et al [31] used capillary column gas chromatography with nitrogen
specific detection and gas chromatography-mass spectrometry to determine nitrogencontaining aromatics originating from creosote oil in solvent extracts of sediments
taken in Eagle Harbour, Puget Sound and in uncontaminated areas. Organic sediment
extracts and the commercial creosote oil were fractionated by silica alumina column chromatography. No nitrogen-containing aromatics were detected in sediments
from a pristine reference area. Over 90 nitrogen-containing aromatics were identified
in the sediments from Eagle Harbour and in the creosote oil. The total nitrogencontaining aromatics concentration in Eagle Harbour sediments ranged from 200 µg to
1200 mg kg
−1 sediment (dry weight). Primarily, three ring and four ring nitrogencontaining aromatics were indentified, thought to originate from a wood creosoting
facility on the shores of the harbour.
8.1.5 Sulphur containing organic compounds
In a method described by Bates and Carpenter et al [32] for the characterisation of
organosulphur compounds in the lipophilic extracts of marine sediments these workers
shows that the main interference is elemental sulphur (S 8 ). Techniques for its elimination are discussed. Saponification of the initial extract is shown to create organosulphur
compounds. Activated copper removes S 8 from an extract and appears neither to create
nor to alter organosulphur compounds. However, mercaptans and most disulphides
are removed by the copper column. The extraction efficiency of several other classes
of sulphur compounds is 80–90%. Extracts are analysed with a glass capillary chromatograph equipped with a flame photometric detector. Detection limit is ng S and
precision ±10%. The recovery of 100ng of individual sulphur standards added the
pre-extracted sediment varied from 80-90% for sulphides, sulphonates and aromatic
sulphur compounds. Mercaptans and disulphides were not recovered since these classes
of compounds were retained in the copper column. The trace obtained by applying
this method to a sulphur containing sediment sample is shown in Figure 8.1.
applicability to wastewaters and marine samples (marine sediments and marine organisms). Typical analytical results for marine samples are tabulated. The determination
of extractable halogenated compounds was of greatest importance for marine samples.
8.1.4 Nitrogen containing organic compounds
Kido et al [30] determined basic organic compounds such as quinoline, acridine,
aza-fluorene, and their N-oxides in marine sediments found in an industrial area.
The sediments were extracted with benzene by using a continuous extractor for 12
hours. Hydrochloric acid (1N) was added to the benzene extracts, and the mixture
was shaken for 5 minutes; the acid layer separated from the benzene layer was made
alkalinc by the addition of sodium hydroxide and the alkaline aqueous solution was
extracted with diethyl ether; the ether extracts were then dehydrated with anhydrous
sodium sulphate and concentrated with a Kuderna-Danish evaporator. The concentrations were separated and analysed by gas chromatography-mass spectrometry and gas
chromatography high-resolution mass spectrometry.
Krone et al [31] used capillary column gas chromatography with nitrogen
specific detection and gas chromatography-mass spectrometry to determine nitrogencontaining aromatics originating from creosote oil in solvent extracts of sediments
taken in Eagle Harbour, Puget Sound and in uncontaminated areas. Organic sediment
extracts and the commercial creosote oil were fractionated by silica alumina column chromatography. No nitrogen-containing aromatics were detected in sediments
from a pristine reference area. Over 90 nitrogen-containing aromatics were identified
in the sediments from Eagle Harbour and in the creosote oil. The total nitrogencontaining aromatics concentration in Eagle Harbour sediments ranged from 200 µg to
1200 mg kg
−1 sediment (dry weight). Primarily, three ring and four ring nitrogencontaining aromatics were indentified, thought to originate from a wood creosoting
facility on the shores of the harbour.
8.1.5 Sulphur containing organic compounds
In a method described by Bates and Carpenter et al [32] for the characterisation of
organosulphur compounds in the lipophilic extracts of marine sediments these workers
shows that the main interference is elemental sulphur (S 8 ). Techniques for its elimination are discussed. Saponification of the initial extract is shown to create organosulphur
compounds. Activated copper removes S 8 from an extract and appears neither to create
nor to alter organosulphur compounds. However, mercaptans and most disulphides
are removed by the copper column. The extraction efficiency of several other classes
of sulphur compounds is 80–90%. Extracts are analysed with a glass capillary chromatograph equipped with a flame photometric detector. Detection limit is ng S and
precision ±10%. The recovery of 100ng of individual sulphur standards added the
pre-extracted sediment varied from 80-90% for sulphides, sulphonates and aromatic
sulphur compounds. Mercaptans and disulphides were not recovered since these classes
of compounds were retained in the copper column. The trace obtained by applying
this method to a sulphur containing sediment sample is shown in Figure 8.1.