Table Of ContentDetermination of Toxic Organic
Chemicals In Natural Waters,
Sediments and Soils
Determination of Toxic
Organic Chemicals In
Natural Waters,
Sediments and Soils
Determination and Analysis
T.R. Crompton
RetiredLaboratory Manager,NationalRiversAuthority,
Anglesey, United Kingdom
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Preface
This book is concerned with a discussion of methods currently available in
the world literature up to 2015 for the determination of organic and organo-
metalliccompounds innatural watersinsoils and sediments.
In the case of soils, the presence of deliberately added or adventitious
organic compounds can cause contamination of the tissues of crops grown
on the land or animals feeding on the land and, consequently, can cause
adverse toxic effects on man, animals, birds and insects and have a profound
effectontheecosystem.Drainageofthesesubstancesfromthesoilcancause
pollution of adjacent streams, rivers and eventually the oceans. Some of the
substancesincludedinthiscategoryarepesticides,herbicides,growthregula-
tors,organic fertilisers,crop sprays andsheep dip.
The presence of organic compounds in river sediments is due, in part, to
manmade pollution and monitoring the levels of these substances in the sedi-
ment and sediment cores provides an indication of the time dependence of
their concentrations over large time spans.
Another consideration is that fish, particularly bottom feeders and crusta-
cean pick up contaminants when sediments enter their gills and the contami-
nation of these creatures has definite toxicological implications both for the
creatures themselves, for man who eats them and, in the case of fish meal,
for animals.
Sediments have the property of absorbing organic contaminants from
water within their bulk (accumulation) and, indeed, it has been shown that
the concentration, for example, of some types of insecticide in river sedi-
ments is 10,000 times greater than occurs in the surrounding water. The sub-
sequent slow release of the substances will occur from sediment into the
surrounding water and, consequently, will continue to cause contamination
even after the sourceof pollutioninto the water has been stopped.
To date, insufficient attention has been given to the analysis of soils and
sediments and one of the objects of this book is to draw the attention of ana-
lysts and others concerned to the methods available and their sensitivity and
limitations.
Examination for organic substances combines all the exciting features of
analytical chemistry. First, the analysis must be successful and in many
cases, must be completed quickly. Often the nature of the substances to be
analysed for is unknown, might occur at exceedingly low concentrations and
xv
xvi Preface
might, indeed, be a complex mixture. To be successful in such an area
requires analytical skills of a high order and the availability of sophisticated
instruments.
The work has been written with the interests of the following groups of
people in mind: management and scientists in all aspects of the water indus-
try, river management, fishery industries, sewage effluent treatment and dis-
posal, land drainage and water supply; also management and scientist in all
branches of industry. It will also be of interest to agricultural chemists, agri-
culturalists concerned with the ways in which organic chemicals used in
crop or soil treatment permeate through the ecosystem, the biologists and
scientists involved in fish, plant, insects and plant life, and also to the medi-
cal profession, toxicologists and public health workers and public analysts.
Other groups or workers to whom the work will be of interest include ocea-
nographers, environmentalists and, not least, members of the public who are
concerned with the protection ofourenvironment.
Finally, it is hoped that the work will act as a spur to students of all sub-
jects mentioned and assist them in the challenge that awaits them in ensuring
that the pollution of the environment is controlled so as to ensure that we are
left with aworthwhile environment to protect.
Chapter 1
Hydrocarbons in nonsaline
waters
Chapter Outline
1.1 Aliphatichydrocarbons 1 1.2 Aromatichydrocarbons 17
Headspaceanalysis 3 Gaschromatography 17
Gasstrippingmethods 4 Columnchromatography 18
Gaschromatography 5 Spectrophotometricmethod 18
High-performanceliquid Infraredspectrometry 18
chromatography 7 Ultravioletspectroscopy 19
Infraredspectroscopy 7 Polycyclicaromatichydrocarbons 21
Thin-layerchromatography 10 Gaschromatography 22
Fluorescencetechniques 11 High-performanceliquid
Paperchromatography 12 chromatography 24
Sampling 12 Thin-layerchromatography 25
Oilspillages 13 Fluorescencespectrometry 26
Metalsinspillageoils 16 Miscellaneous 26
Continuousmonitoringofoil References 28
slicks 16
1.1 Aliphatic hydrocarbons
The identification procedure for oils in natural water samples can be divided
into three stages:
1. Isolationofthe hydrocarbon componentsfrom the pollutant sample.
2. Identification of the same in terms of the petroleum product, for example
crude oil,petroleum and gas oil.
3. Identification of the specific source of pollution, such as an individual
tanker, tank truck, factoryor domestic fuel tank.
Stage (2), a general classification of the oil is often satisfactorily
achieved by gas chromatographic techniques possibly coupled with mass
spectrometry or infrared spectroscopy applied to a sample of the oil pollut-
ant. Stage (3), the true identification, invariably requires samples from
potential sources for comparison with the pollutant.
DeterminationofToxicOrganicChemicalsInNaturalWaters,SedimentsandSoils.
1
DOI:https://doi.org/10.1016/B978-0-12-815856-2.00001-1
©2019ElsevierInc.Allrightsreserved.
2 DeterminationofToxicOrganicChemicals
This is often attempted again using gas chromatography, by comparison
of the resulting chromatograms, but in a less satisfactory and confident
manner. Generally, when the comparisons of chromatograms are reasonably
similar, the perpetrator of the pollution accepts liability in the case of
accumulatedcircumstantialandscientificevidence andintroduces therecom-
mendedremedial measures.
Existing gas chromatographic techniques can, in the majority of cases,
classify petrol, paraffin, light fuel oils, intermediate fuel oils and, with less
ease, lubricating, transformer and cutting oils. Higher boiling products with
little volatility are not amenable to conventional gas chromatographic
techniques, and recourse has to be taken to other techniques such as the use
of capillarycolumns ornon-gas liquid chromatography (GLC) techniques.
Techniquesotherthangaschromatographyor,morecommonly,combina-
tions of techniques have been used to characterise oil spills. These include
analytical determination such as the infrared spectra, asphaltene and paraffin
contents, that provide a general classification of the pollutants (crude oils,
fuel oils, oil sludges, etc.) and others, such as the Ni/V ratios, sulphur
content and chromatographic profiles, that permit, by comparison with refer-
ence samples, their precise identification.
However, another approach involving only one analytical technique, but
increasing the number of parameters considered, has been emphasised
recently for analysis, that is infrared spectroscopy(cid:1)gas chromatography. In
these cases a multiparametric profile is used for identification, instead of a
combination of different analytical determinations and pattern recognition
techniques have, often, been applied toimprove the diagnostic performance.
The main requirements that must fulfil these fingerprinting parameters
besides their specificity are that they must remain unaltered during the
weathering processes affecting the pollutant, namely by evaporation,
solution, photooxidation and biodegradation. In consequences, both condi-
tions, specificity and stability, need to be investigated in order to evaluate
the reliability andthe usefulness ofany proposedmethod.
Vos et al. [1] have carried out a detailed study of the analysis of oil-
contaminated groundwater to ascertain the rate of filtration of oil compo-
nents and the effects of their biodegradation under conditions very close to
those in a natural aquifer. Large-scale lysimeter experiments are reported in
a sand-dune area where the groundwater level could be adjusted with an
external overflow device. Details are given of hydrocarbon concentrations
determined by adsorption onto Amberlite XAD-4 resins and investigations
using chromatography, mass spectroscopy, high-resolution gas chromatogra-
phy, infraredspectroscopy andultraviolet spectroscopy.
Matsumoto and Hanya [2] compared the principal hydrocarbons from
polluted river water and unpolluted surface water in Japan. The presence of
aqualane, and unresolved mixture of hydrocarbons, and n-alkanes with an
even number of carbon atoms was related to the occurrence of artificial
Hydrocarbonsinnonsalinewaters Chapter | 1 3
hydrocarbons (fossil fuels and industrial products) while the occurrence of
n-alkanes with an odd number of carbon atoms in unpolluted waters was due
mainly tothe presence ofalgaeand higher aquatic plants.
Peitscher [3] detected and identified traces of oil on surface water.
Samples of oil films on surface water were collected with a cloth made of
polyester fabric. The cloth was fixed to telescopic rods, so that less accessi-
ble sites could be reached and it was kept on the oil interface for periods
ranging from several minutes to 1hour depending on the amount of oil.
The adsorbed oil was extracted and analysed by infrared spectroscopy.
Investigation by techniques including gas chromatography and mass spec-
troscopy facilitated identification of the sources of pollution, which could be
confirmed by direct comparison of infrared spectra. Differences between
spectra for five different types of oil were distinct for a film thickness of
0.2mm but lessdistinct for a film thicknessof0.1mm.
Various techniques for the determination of aliphatic hydrocarbons are
now reviewed.
Head space analysis
Khazal et al. [4] and Drodz and Novak [5] examined and compared the
methods of headspace gas and liquid extraction analysis, comparing the gas
chromatography of samples of gaseous liquid-extract phases withdrawn from
closed equilibrated systems and involving standard addition quantitation, for
the determination of trace amounts of hydrocarbons in water. The liquid
extraction method [6] is more accurate but it yields chromatograms with an
interfering background due to the liquid extractant. The sensitivity of deter-
mination of volatile hydrocarbons in water is roughly the same for each
method, and the concentration amenable to reliable determination amounting
to tens ofµgL21on a packed column with a flame ionisation detector.
Drodz et al. [7] examined the reliability and reproducibility of qualitative
and quantitative headspace analyses of parts per billion of various aliphatic
and aromatic hydrocarbonsinwater usingcapillarycolumngas chromatogra-
phy utilising a simple all-glass splitless sample injection system. They exam-
ined the suitability of the standard addition method for quantitative
headspace gas analysis for concentrations in the condensed phase up the
hundreds ofparts per billion.
The headspace method of analysis is less accurate but more sensitive
than methods based on liquid extraction. With this method an equilibration
time of10minutesis adequate for equilibrium betweenthe water sample and
the headspace tobeachieved.
Various other workers [8,9] have studied the application of headspace
analysis to the determination of hydrocarbons in water. McAucliffe [10]
determined dissolved individual hydrocarbons in 5mL aqueous samples by
injecting up to 5mL of the headspace. For petroleum oils, which contain
4 DeterminationofToxicOrganicChemicals
numerous hydrocarbons, very much larger aqueous samples are required.
The percentage of hydrocarbons in the gaseous phase, after water containing
the hydrocarbons in solution was equilibrated with an equal volume of gas,
was found to be 96.7%(cid:1)99.2% for most C (cid:1)C alkenes. In the case of
3 8
benzene and toluene the values were 18%, 5% and 21.0% respectively,
indicating that the lower aromatic hydrocarbons may be less amenable to the
technique.
Gas stripping methods
Swinnerton and Linnenbom [11] were the first to examine the applicability
of gas stripping methods to the determination of hydrocarbons in water.
They determined C (cid:1)C hydrocarbons by stripping them from water with a
1 6
stream of helium.
After gas stripping, the hydrocarbons can be passed directly to a gas
chromatograph or, to increase sensitivity, trapped in a cold trap and then
releasedintothegaschromatograph.Alternatively,thestrippedhydrocarbons
can be trapped in, for example active carbon then released into the gas chro-
matograph. This method offers the possibility of determining trace amounts
of organic compounds in water even below the parts per trillion (ppt) level
(1 part in 1012, w/w), particularly for the most volatile compounds [12].
Grob and coworkers [13(cid:1)16] reported an impressive improvement of the
method by using a closed-loop system, provided with a small-volume effec-
tive charcoal filter, but several precautions are necessary when working at
such low concentrations. The complication of the procedure and the
sophisticated equipment required results, in view of the absolute amounts of
pollutants involved, inoverall were excellent results.
Kaiser [17] has described a sensitive degassing technique for trace hydro-
carbons in which volatile hydrocarbons up to C are removed from aqueous
12
solution at 20(cid:3)C by a stream of dry nitrogen during 2(cid:1)10minutes, and
passed into a gas chromatographic column cooled in liquid nitrogen. After
the degassing period was completed, the column temperature was pro-
grammed at a rate of 7.5(cid:3)Cmin21 and the hydrocarbons eluted and detected
in the usual manner. The detection limit achieved for individual hydrocar-
bons inwater was 100ppb (1029wt.%).
Polak and Lu [18] have described a gas stripping method for the determi-
nation of the total amount of volatile but slightly soluble organic materials
dissolved in water from oil and oil products. Helium is bubbled through a
sample ofthe aqueous liquid, and the gas carriesthe organic vapours directly
to a flame ionisation detector. The detector response plotted against time
gives an exponential curve from which the amount of organic material is
derived with the aid ofan electrical digitalintegrator.
Colenutt and Thorburn [19] applied a gas stripping technique to various
synthetic and actual samples of hydrocarbons in water. Synthetic solutions of
