Org. Geochem.Vol. 18, No. 4, pp.

431-446, 1992
Printed in Great Britain.All rights reserved

0146-6380/92 $5.00+ 0.00

Copyright 1992Pergamon Press Ltd

Analysis of sedimentary organic materials by scanning electron

microscopy: the application of backscattered electron imagery and
light element X-ray microanalysis
A. N. BISHOP,l* A. T. KEARSLEYl and R. L. PATIENCE2t
t Department of Geology, Oxford Polytechnic, Gipsy Lane, Headington, Oxford OX3 0BP and
2Exploration Technology Branch, BP Research Centre, Chertsey Road, Sunbury-on-Thames,
Middlesex TWl6 7LN, U.K.
(Received 10 September 1991; returned for revision 31 October 1991; accepted 24 February 1992)

Abstract--Whole rock polished thin sections, from a variety of sedimentary environments (Carboniferous
and Jurassic coals, Toarcian and Kimmeridgian source rocks, Recent upwelling sediments) have been
examined using the scanning electron microscope techniques of backscattered electron imagery and light
element X-ray microanalysis. Backscattered images allow the recognition of variations in composition
between different materials and within individual particles. Light element X-ray analysis enables the
detection of carbon, oxygen, sulphur and chlorine contents within individual sedimentary organic
particles. The different types of sedimentary organic material have been distinguished on a morphological
basis. The conventional maceral classification is not applicable due to the lack of characteristics such as
reflectance and fluorescence in the SEM. Osmium tetroxide staining demonstrates that significant
concentrations of organic matter are present in some sediments adsorped by clay minerals. The results
show that backscattered electron imagery can be related to the composition of sedimentary organic matter,
revealing overall differences in elemental content. Qualitative light element X-ray microanalysis results
show that sulphur uptake is related to kerogen type, with a correlation between sulphur and oxygen
contents. The latter may be attributable to uptake of sulphur by oxygenated functional groups. The
concentration of organic sulphur between homologous particles varies millimetre by millimetre in source
rock samples, indicating a lamina scale control on diagenetic processes. This study demonstrates that
surface analytical techniques, such as backscattered electron imagery and light element X-ray microanalysis, can offer a new insight into the relationship between the optical petrology of a sample and its
geochemistry.
Key words--SEM, osmium tetroxide staining, sulphur, chlorine, diagenesis, particle classification

INTRODUCTION
A considerable volume of literature has been published on both the geochemistry and the petrology of
sedimentary organic materials. However, very few
attempts have been made to integrate these two
approaches. Coal petrologists originally determined
the chemical composition of the individual maceral
groups by analysing concentrates obtained by density
separation (e.g. van Krevelen, 1961). These early
studies still form the basis of much of our present
understanding of the chemistry of the visible organic
components of sedimentary rocks. But how these
results relate to conventional organic geochemical
analyses of whole rock samples is still unclear.
The use of scanning electron microscopy (SEM) in
the study of the inorganic components of sedimentary
rocks is well documented (Welton, 1984; Trewin,
*Present address: Newcastle Research Group in Fossil
Fuels and Environmental Geochemistry, Drummond
Building, University of Newcastle, Newcastle upon Tyne
NEI 7RU, U.K.
tPresent address: Statoil, Den norske stats oljeselkaap a.s.,
Forus, Postboks 300, N-4001 Stavanger, Norway.

1988; O'Brien and Slatt, 1990), but apart from palynological studies, previous applications of SEM to
the analysis of the organic components of sediments
are limited. Earlier electron microscopy based studies
of sedimentary organic materials have generally been
restricted to the examination of organic particles,
separated from the mineral matrix by treatment with
hydrofluoric acid, visualised using secondary electron
imagery. Such images convey detailed information
of the structure and morphology of 3-dimensional
objects (e.g. Scott and Collinson, 1978; Davis et al.,
1986), but give little indication of composition.
Backscattered electron imagery has the potential
to reveal differences in the composition of organic
materials, although to date its main use has been to
assess the distribution of organic matter in sediments
(e.g. Green et al., 1979; Bertrand et al., 1990).
Work has previously been conducted using energy
dispersive X-ray microanalysis (EDS) to directly
determine the elemental content of sedimentary
organic materials (Harvey et al., 1983; Harrison,
1991), in particular organic sulphur (van Swijgenhoven, 1984; Raymond, 1986; Tseng et al., 1986;
Bertrand et al., 1990). Most of these earlier EDS

431

432

A.N. BISHOPet al.

based studies of sedimentary organic materials have

used conventional X-ray mieroanalysis systems, fitted
with a beryllium window. This only allows detection
of elements of atomic number 10 (i.e. sodium) or
above. EDS systems fitted with an ultra thin window,
consisting of a thin foil of aluminium, allow passage
of X-rays from and hence detection of elements of
atomic number 5 (i.e. boron) and above. This enables
the detection and determination of carbon, oxygen
and nitrogen contents, elements of obvious importance with respect to the geochemistry of sedimentary
organic particles.
The aims of this study were to devise methods
based on scanning electron microscopy to (i) locate
sedimentary organic matter in whole-rock polished
thin sections; (ii) analyse it directly for elemental
content using backscattered electron imagery (BEI)
and light element energy dispersive X-ray microanalysis (LE-EDS).

THEORY

A thorough account of the operation of the scanning electron microscope is obviously outside of
the scope of this paper, but further details can be
found in Goldstein et al. (1981) and Goodhew and
Humphreys (1988). In the SEM, a sample is placed in
a chamber under vacuum, and exposed to a focused
beam of electrons which scans over the surface of the
specimen. These electrons, known as primary electrons, undergo a number of elastic and inelastic
collisions with the atomic nuclei of the surface of the
sample. The collisions result in the generation of a
number of different types of charged particle and
electromagnetic radiation, including secondary electrons, backscattered electrons and X-rays (Fig. 1).
Backscattered electron imagery

Following interaction with the atomic nuclei, some

of the primary electrons are scattered back out of the
surface of the material. These electrons are known as
backscattered electrons. The fraction of primary
beam electrons re-emitted in this way is known as
the backscattered coefficient 0/), which is largely
dependent on the atomic number of the specimen
(Goodhew and Humphreys, 1988). Therefore, backscattered electron imagery (BEI) can be used to
distinguish materials of differing elemental compo-

X- rayst
Cathodoluminescence~

Incident
beam

scattered
/ Back,
electrons
~ _/ ~ . . . . . ~ Secondary
electrons

Fig. 1. Types of charged particle and electromagnetic radiation emitted by materials exposed to a beam of electrons
(after Goodhew and Humphreys, 1988).

sition. A common misconception is that the backscattered coefficient of a material is directly related to
its average atomic number. Hermann and Reimer
(1984) showed that the backscattered coefficient of a
compound is actually related to the sum of the weight
fractions for each of the individual elements present,
multiplied by their respective backscattered
coefficients.
e.g. Backscattered coefficient of a compound XYZ:
?]compound= 2 (qx*wt frac,, ) + (q}*wt fra%)
+ (qz*wt frac:)
(wt frac = weight fraction of element in compound)
The backscattered electron detector generates a signal
proportional to the number of electrons detected.
Hence, the contrast of a backscattered image is a
function of the differing elemental compositions of
the various materials in view. Consequently, as
organic materials predominantly consist of lower
atomic number elements (i.e. carbon, hydrogen, oxygen etc.) than the co-existing inorganic mineral
content of sediments (i.e. silicon, aluminium etc.),
organic particles appear much darker in tone than the
surrounding minerals in BEI.
Light element X-ray microanalysis

X-rays are also emitted following the collisions of

the primary beam electrons with the atomic nuclei.
The distribution of the energies of the X-rays is
shown as a peak or series of peaks in an X-ray
spectrum which is characteristic for each individual
element. Whereas the tone of a backscattered electron
image reflects the overall composition of the material,
X-ray microanalysis allows distinction and quantification of the individual elements contained within
that material.
The X-ray detector of the SEM needs to be cooled
continuously using liquid nitrogen. In the presence of
even minute traces of water vapour, a film of ice will
quickly build up on the surface of the detector, thick
enough to seriously impair X-ray detection. To prevent the passage of contaminants such as water
vapour from the main SEM chamber to the detector,
a window is placed in between. Conventional EDS
X-ray detectors have a window of beryllium which
allows the passage of elements of atomic number 10
and above. The detector used in this study has an
additional "ultra thin" window consisting of a thin
foil of aluminium, which when used in place of the
beryllium allows passage of X-rays corresponding to
elements of atomic number 5 and above. By using an
"ultra thin" window, the contents of all the main
elements commonly found to occur within sedimentary organic material, with the exception of hydrogen, can be determined.
Polysulphone resin (PSR) is a polymer similar in
elemental composition to some sedimentary organic
materials. Comparison of a spectrum of PSR (Fig. 2)

Analysis of sedimentary organic materials by SEM

433

Osmium tetroxide staining

400 -

10

Fig. 2. LE-EDS spectrum of polysulphone resin.

with its composition as determined by elemental
analysis (i.e. carbon 74.1%, hydrogen 5.1%, oxygen
14.8% and sulphur 5.9%) shows that there is not a
simple relationship between peak height and elemental composition. In conventional X-ray microanalytical studies of silicate minerals etc., the spectra
are corrected for the effect of differences in atomic
number (Z), X-ray absorbence (A) and X-ray fluorescence (F) using a ZAF correction to give true
elemental weight percent (Goodhew and Humphreys,
1988). However, due to the complexity of the X-ray
background at the low energy end of the spectrum,
such a correction for light element spectra is much
more complex. But it may be possible to quantify
light element spectra empirically by comparison with
a range of polymer standards. Work along these lines
is currently in progress. At the moment, elemental
analyses using this technique are only qualitative.

Effect of mineral contamination

Care must be taken in the acquisition of spectra
to prevent misinterpretation of contamination by
neighbouring inorganic minerals as representing real
concentrations of these elements within the organic
material. This is largely avoided by assuring that the
area where the analysis is to be taken is completely
free of any potential contaminant, such as framboids
of pyrite or quartz grains etc. However, some organic
materials possess a porous structure, such as the walls
of Carboniferous megaspores, commonly infilled by
clay minerals (Petitt, 1966). The mineral matter may
be too finely disseminated to be visible in a backscattered image, its presence going unnoticed until an
analysis is taken.
Situations can also arise where the organic material
appears to be completely free of any potential contamination, but in fact only represents a thin veneer
on the surface of the section. Careful examination of
the spectrum should reveal serious contamination.
The presence of elements corresponding to common
minerals will quickly identify the contaminant. High
concentrations of aluminium and silicon are certainly
indicative of alumino-silicate contamination rather
than representing the presence of aluminium and
silicon organic complexes.

Osmium tetroxide (OsO4) staining is a standard

technique used in biology to enhance the contrast of
biological specimens in the transmission electron
microscope (Alberts et aL, 1989). OsO4 is a non-polar
molecule which is soluble in water and organic solvents. It reacts with unsaturated groups, e.g. double
bonds and phenols (Hayat, 1989). Tests conducted
during this study show that OsO4 does not react with
any of the minerals commonly found to occur within
sediments, only with organic material. By mapping
the distribution of osmium within a stained sample
of sediment it is possible to indirectly assess the
distribution of organic matter.
EXPERIMENTAL

Samples
A variety of lithologies have been chosen in order
to provide a range of different types of sedimentary
organic material (Table 1). Much of the work has
concentrated on samples of coal (Carboniferous
and Jurassic), petroleum source rocks (Jet Rock,
Toarcian, Yorkshire Basin; Kimmeridge Clay,
Dorset) and upwelling sediments from the Peru
Continental Margin (Pleistocene to Recent) Ocean
Drilling Program Leg 112.

Preparation of samples
Samples of sediment were vacuum dried for 36 h in
a Logitech 10-20 impregnator. Epotec 301 resin was
evacuated for 20 min and then released onto the dried
sediment. After a gradual return to atmospheric
pressure, the resin impregnates enough of the connected pore space to allow preservation of the original sedimentary fabric during polishing. The resin
was allowed to harden for 24 h. The impregnated
samples were then cut and lapped before being
polished using a single stage polishing technique
(Allen, 1984). All preparation had to be conducted in
a non-aqueous medium as many samples contained
large quantities of expandable clays. Paraffin was
used to minimize extraction of soluble organic
materials, which might occur with low molecular
weight alcohols. Polished samples were finally coated
with a thin layer of evaporated carbon in a Polaron
coater, to allow dissipation of electrons and prevent
charging of the specimen. These prepared specimens
were stored in an argon filled chamber when not in
use to prevent oxidation.

Osmium tetroxide staining

Samples of wet sediment were held above a solution of 4% osmium tetroxide solution, for a period
of 24 h. These samples were then prepared using the
same methods as detailed above.

Electron microscopy
The instrument used in this study was a Jeol
JSM840 SEM, fitted with a solid state backscattered

A. N. BISHOP et al.

434

Table I. Description of samples

Lithology

Sample

Rootlet Beds

PALl931
PAL1929
KE3
PALl957
PALl956
PALl886
PALl885
KE4
KE7
KEI
WHSP
HWMC
BOTR
CAUPME
HDMG
DOCK
PALl909
PALl904
PALl 887
KE2
PALl949
PALl921
KE6
PALl850
PALl851
Kimmeridge
JRI
JR2
JR4
JR3
JR5
680B

Coals

Lagoon Overbank
Silts

Nearshore Marine
Silts
Marine Mudstones

Upwelling Sediments

Locality
Cloughton Wyke, Yorkshire, England
Cloughton Wyke, Yorkshire, England
Upholland, Wigan, Lancashire, England
Cloughton Wyke, Yorkshire, England
Cloughton Wyke, Yorkshire, England
Whitby, Yorkshire, England
Whitby, Yorkshire, England
Scarborough, Yorkshire, England
Hayburn Wyke, Yorkshire, England
Swadlincote, Derbyshire, England
Swadlincote, Derbyshire, England
Swadlincote, Derbyshire, England
Donisborough, Derbyshire, England
Ayrshire, Scotland
Fife, Scotland
Beith, Ayrshire, Scotland
Hayburn Wyke, Yorkshire, England
Hayburn Wyke, Yorkshire, England
Whitby, Yorkshire, England
Whitby, Yorkshire, England
Cloughton Wyke, Yorkshire, England
Burniston Wyke, Yorkshire, England
Radstock, Somerset, England
Ravenscar, Yorkshire, England
Ravenscar, Yorkshire, England
Kimmeridge Bay, Dorset, England
Runswick Bay, Yorkshire, England
Runswick Bay, Yorkshire, England
Runswick Bay, Yorkshire, England
Whitby, Yorkshire. England
Whitby, Yorkshire, England
ODP Leg 112, Peru Continental Margin

detector, and linked to a Tracor Northern TN2000

X-ray microanalysis system. An acceleration voltage
of 20 kV was used at all times. Although this acceleration voltage may result in some local damage to the
specimen following prolonged exposure to high beam
current, the advantage of this voltage is that it
provides a satisfactory signal to noise ratio during
light element spectrum acquisition. Spectra were
acquired with a standard working distance (i.e. the
distance between the detector and the specimen) of
32mm and a probe current of 5 10-9A, precisely
adjusted using a Faraday cup. Each acquisition was
of 100s duration (live time). For backscattered
imagery, probe current and working distance were
adjusted as necessary to obtain optimum resolution
and contrast. Digital X-ray maps were obtained using
a digital beam control unit attached to the TN2000.
A matrix of 128 x 128 points is set up, with individual
spectra acquired for up to 4 s per point. Regions of
the spectrum are defined to allow characterisation of
a maximum of eight elements. The portion of the
spectrum selected as a "region of interest" for a
particular element is chosen so that only X-rays
corresponding to that specific atomic number will be
counted, and not from any other element which may
be present within the sample.
RESULTS AND DISCUSSION

Classification of Sedimentary Organic Material

The conventional maceral classification of sedimentary organic matter (Stach et al., 1982) is largely

Age
Middle Jurassic
Middle Jurassic
Upper Carboniferous
Middle Jurassic
Middle Jurassic
Middle Jurassic
Middle Jurassic
Middle Jurassic
Middle Jurassic
Upper Carboniferous
Upper Carboniferous
Upper Carboniferous
Upper Carboniferous
Middle Carboniferous
Lower Carboniferous
Lower Carboniferous
Middle Jurassic
Middle Jurassic
Middle Jurassic
Middle Jurassic
Middle Jurassic
Middle Jurassi
Upper Carboniferous
Middle Jurassic
Middle Jurassic
Upper Jurassic
Lower Jurassic
Lower Jurassic
Lower Jurassic
Lower Jurassic
Lower Jurassic
Quaternary

based on reflectance and fluorescence characteristics.

These are entirely different physical properties to
those which are responsible for the contrast of
backscattered images. Consequently, it was felt that
such a classification scheme would be inappropriate
for this study. In order to avoid confusion, a simple
scheme based solely on the actual morphology of the
different types of particle has been erected. Each class
may include materials derived from a number of
different biological sources. The following section
lists the most commonly noted morphological types,
together with the diagnostic features on which
each distinction is based, and speculative biological
origins.
Interfingering particles [Plate l(a, b)] are apparently structureless masses of organic matter, the
lateral margins of which interfinger with the sediment
matrix. They often contain inorganic clasts [Plate
1(b)], especially calcareous nanofossils, which suggest
that some of these particles may represent faecal
pellets. Other potential origins for this group include
pockets of migrated bitumen and fragments of
gelified terrestrial plant material (vitrinite) with no
observable cellular structure:
Vesiculate particles [Plate l(c, d)] are distinguished
by the presence of vesicles, which may be infilled by
clay minerals, carbonate or gelatinous organic
material. They are largely derived from terrestrial
vascular plants, the vesicles representing the remains
of cell lumen. Vesiculate particles often show deformation by plastic flattening [Plate l(c)], brittle fracture or a combination of the two. Small fragments of
vesiculate material are ubiquitous.

Plate I. (a) Intertingering, Kimmeridge Clay, Dorset; (b) Detail of interfingering particle showing inclusion
of calcareous bioclasts (C), detrital clay minerals (D) and pyrite (P). Jet Rock, Yorkshire; (c) Vesiculate,
Kimmeridge Clay, Dorset. Particle shows plastic flattening; (d) Vesiculate, Carboniferous coal, Ayrshire.
Individual vesicle labelled (v); (e) Capsulate (megaspore), Carboniferous coal, Derbyshire; (f) Detail of
wall structure of megaspore showing inftll by clay minerals. Carboniferous coal, Ayrshire.

435

Plate 2. (a) Ovoid (O), Carboniferous coal, Ayrshire; (b) Ovoid (a), Carboniferous coal, Derbyshire.
Particle represents an individual algal colony (Botryoccocus) which in this example shows zonation, centre
appears lighter in tone than margins; (c) Arched, Carboniferous coal, Ayrshire; (d) Blocky, Middle
Jurassic coal, Yorkshire; (e) Groundmass, Carboniferous coal, Derbyshire. Area marked (B) represents
beam damage due to prolonged electron beam exposure; (f) Microgranular, Carboniferous coal, Ayrshire.

436

Analysis of sedimentary organic materials by SEM

Capsulate particles [plate l(e)] consist of a single
continuous capsule which commonly surrounds a
sediment infill. Wall thickness is variable, and may
show the development of a sculptured surface. Particles with small walls or only simple surface sculpture
are likely to be terrestrial spores and pollen. Particles
with complex surface sculpture are probably organic
phytoplankton, freshwater or marine, such as dinoflagellate cysts. The walls of large capsulate particles,
e.g. Carboniferous megaspores [plate l(e)], commonly have a granular structure which may be infilled
by clay minerals [plate l(f)].
Ovoid particles [Plate 2(a, b)] are identified on the
basis of their simple oval outline. Although no
internal structure is visible, particles may show compositional zonation in backscattered [Plate 2(b)].
Groups of ovoid particles may fuse together to form
masses with triangular inclusion of sediment between
individual particles. Ovoids are likely to be derived
from plant cell infillings, resin bodies and algal
colonies (e.g. Botryoccocus).
Arched particles [Plate 2(c)] consist of a long and
narrow strip with arched protuberances on one or
both sides. Particles with simple arching are derived
from leaf cuticles, the arches representing cuticular
extensions downwards between epidermal cells.
Broken wall sections of organic phytoplankton may
also fall into this category.
Blocky particles [Plate 2(d)] are simple rectangular
blocks of organic matter with fracture outlines.
No internal structure is discernible. Size and shape
are very variable. Blocky particles include reworked
fragments of groundmass (see next paragraph)
broken into rectangular sections, and vesiculate particles with widely spaced vesicles. Hence, they are
ultimately terrestrial in origin.
Groundmass [Plate 2(e)] is a continuous sheet
of apparently structureless organic material. The
margins of groundmass sheets may preserve relict
cellular structure, attesting to its origin as compressed, gelified terrestrial vascular plant material.
It is a common constituent of coals.
Microgranular [Plate 2(f)] texture is an aggregation
of very small equant particles ( < 1 #m). It may result
from the breakdown of the granular wall structure of
some capsulate particles. Microgranular may also
represent poorly preserved bacteria.

Distribution of morphological groups between different

lithologies
The abundances of each of the morphological
groups is very variable between different sediment
types. In general, coals predominantly consist of
vesiculate, capsulate and groundmass types, with
lesser amounts of ovoid, blocky and arched types.
These correspond to spores, pollen, wood and other
vascular plant detritus associated with such terrestrial
environments.
The marine mudrock samples (e.g. Jet Rock, Kimmeridge Clay) predominantly consist of interfingering

437

particles, with a much lower concentration of terrestrial organic matter. Capsulate particles are common
in some samples (e.g. Jet Rock) but these are largely
represented by the remains of marine phytoplankton,
such as tasmanitids.
Rootlet beds, lagoon overbank silts and the
nearshore marine silts studied are dominated by
terrestrially derived organic matter such as vesiculate,
blocky, capsulate and ovoid. The Peru upwelling
sediments contain almost no recognisable organic
particles, the sole exceptions being occasional
fragments of vesiculate.

Effect of Composition on Backscattered Coefficient

As the backscattered coefficient of a material is
dependant on elemental content, this technique can
be used to reveal variations in composition within
individual particles [e.g. Plate 2(b)], and between
separate types of organic material.

Effect of sulphur
[Plate 3(a)i] shows a backscattered image of a
section of Carboniferous coal, with a capsulate particle towards the top, and a vesiculate particle beneath. Digital processing of the image reveals that the
backscattered coefficient of the capsulate is higher
than that of the vesiculate [Plate 3(a)ii]. Hence, the
elemental compositions of these two particles must be
different to give rise to this distinction. Plate 3(a)iii
shows the sulphur distribution, obtained by digital
X-ray mapping of the same field of view, clearly
showing the presence of sulphur within the capsulate,
with no evidence of any sulphur within the vesiculate.
The concentration of sulphur, in this example, is
sufficient to give rise to the difference in backscattered
coefficient observed in Plate 3(a)ii.

Effect of hydrogen
Interfingering particles, common constituents of
marine mudrocks [e.g. Kimmeridge Clay, Plate 3(b)i],
in some instances have a lower backscattered coefficient than coexisting vesiculate particles [Plate
3(b)ii]. The sulphur distribution [plate 3(b)iii] shows
the sulphur to be concentrated within the interfingering particles, and again not with the vesiculate. In the
coal, the higher backscattered coefficient of the capsulate particle, relative to the vesiculate, was associated with the higher sulphur content of the capsulate.
In this example the reverse is true, with the higher
sulphur concentration of the interfingering particle,
relative to the vesiculate particle, associated with the
lower backscattered coefficient of the former. This
can be accounted for by the difference in hydrogen
content between the capsulate particle in the coal and
the interfingering particle in the Kimmeridge Clay. In
Plate 3(a), the capsulate particle is a Carboniferous
megaspore, which corresponds to the maceral group
sporinite (type II kerogen) with a moderate hydrogen
content. The interfingering particles in Plate 3(b) are

438

A.N. BISHOPet al.

likely to correspond to the maceral group alginite

(type I kerogen) with a high hydrogen content. The
backscattered coefficient of hydrogen is zero, hence
it acts as a diluent on the overall backscattered
coefficient of a multielement material. Hence, the
presence of hydrogen within a material will be to
reduce the overall backscattered coefficient. In these
examples, the interfingering particle has a high hydrogen content which more than offsets the effect of
sulphur. In the coal, the capsulate particle has only
a moderate hydrogen content, which will have lowered the backscattered coefficient to an extent, but
not enough to compensate for the increase due to the
presence of sulphur.
Assessment of the Distribution of Organic Material
Using OsO ~ Staining

Samples of upwelling sediment from the Peruvian

continental margin (ODP Leg 112) were found to
have a negligible content of particulate organic
matter, despite having TOC contents of up to 10%
(Patience et al., 1990). The lack of identifiable organic
constituents is supported by palynological assessments of the same samples which show that on
average over 95% of the organic matter is present as
amorphous kerogen (Powell et al., 1990). To account
for the shortfall in organic content between the TOC
and the abundance of visible components in BEI,
OsO4 staining was used to determine the distribution
of the "missing" organic material. A similar approach, using OsO4 staining to locate organic matter
in sediments was documented by Green et al. (1979).
OsO4 reacts with organic material, itself being
reduced to osmium. By X-ray mapping the sample
for osmium, the distribution of sedimentary organic
matter can be indirectly assessed.
The sediments comprise a laminated sequence of
alternating diatom and clay rich layers [Plate 4(a)].
The osmium distribution map shows the osmium,
and consequently the organic matter, to be relatively
more concentrated within the clay rich laminae
[Plate 4(b)]. Fine scale geochemical studies, including
total organic contents, were also conducted on these
samples, the results of which confirmed that the
organic matter is relatively more concentrated in the
clay rich horizons (Patience et al., 1990; Aptin et al.,
1992). Osmium distribution maps taken at higher
magnifications [Plate 4(c)] show high levels of organic
matter associated with pyrite and clay minerals, with
high concentrations associated with detrital iron rich
clays.
Simple coatings of organic matter as a film on the
surface of mineral grains are unlikely to pick up
enough osmium to be detected with this technique.
Therefore, the organic matter must be intimately
associated with the minerals, within the grains rather
than just on the surface. The adsorptive properties
of clay minerals for organic material are well
documented (e.g. Rausell-Colom and Serratosa,
1987), with preferential adsorption by iron rich

phyllosilicates (Trabelsi, 1987). Adsorption of dissolved organic materials by clay minerals is likely to
take place in the water column during deposition
(Tissot and Weite, 1984, p. 59). The abundance of
organic matter in these samples associated with clays
suggests that this depositional mechanism may
account for a significant proportion of the organic
component of some sediments. On dissolution of the
mineral matrix, adsorped organic matter is likely to
form an amorphous mass. Hence, the high levels
( > 9 5 % ) of amorphous kerogen in these samples
(Powell et al., 1990) may be linked to the abundance
of organic materials adsorped by clays.
Test runs conducted as part of this study demonstrated that pure pyrite does not react with OSO4.
Framboids of pyrite in these samples are typically
surrounded by a thin film of organic material, however this is unlikely to account for the observed extent
of OsO4 uptake. Therefore, within this membrane
and surrounding the iron sulphide a significant
concentration of organic matter may be present.
Hence, in these samples it would appear that much
of the organic material is associated with mineral
constituents, typically clays. In fluorescence microscopy, a general background fluorescence of clay
and carbonate is often attributed to the presence of
organic matter on a scale too small to be resolved
clearly (Creaney, 1980), These results indicate
that such organic materials may be quantitatively
important in organic rich sediments.
Light Element X-Ray Mieroanalysis

Examples of light element spectra of a number of

different types of sedimentary organic material are
shown in Fig. 3. The elements commonly detected are
carbon, oxygen, sulphur and chlorine. Hydrogen
cannot be determined directly by this method, and
the nitrogen peak is overlapped by those of carbon
and oxygen. Carbon and probably oxygen are
elements inherited from the original biological composition of the organic material, but sulphur and
chlorine will be largely diagenetic in origin.
Due to the present difficulty in quantifying these
spectra as elemental weight percent, the data have
simply been processed to give number of X-ray
counts (X-ray yield) for each element. Hence, relative
elemental ratios based on X-ray yield can be calculated and the results plotted. It should be noted that
these are not true atomic ratios, though they do allow
an assessment of relative variations in elemental
content. However, some of these results are at variance with previously published maceral analyses.
Until the spectra can be quantified using polymer
standards, the results quoted here should be regarded
as preliminary.
Differences in the composition of particles analysed
are clearly shown by graphs of oxygen and sulphur
contents relative to carbon (Fig. 4). Compositions of
the separate morphological groups plot in distinct

"~ d .

~e~ 8
..,~,, N
~--,o

Nr~ o.~

~...

~ ~

~ ,

.~

NN~
~ISeNN

'

.,

..~ .=,

..,

-~.~

= ~

. ~

,~---

e.,

'N .N
.

~ , . - , ~ .~

8 4"" &~

439

Plate 4. Assessment of the distribution of sedimentary organic materials using osmium tetroxide staining:
(a) Low magnification backscattered image of osmium stained upwelling sediment (ODP Leg 112, 680B).
Backscattered tone is inversely proportional to porosity; dark bands correspond to diatom rich laminae
with high porosity, light band correspond to clay rich laminae with low porosity; (b) Osmium distribution
(digital x-ray map) shows highest levels of osmium to be associated with clay rich laminae [field of view
of this image corresponds to white box in plate 4(a)]; (c) Left--high magnification (ca x 1000) element
distribution maps. Same field of view: iron = red, sulphur = green osmium = blue, chlorine = yellow.
Chlorine distribution indicates location of impregnating resin, and hence porosity; Right--composite of
iron, sulphur and osmium distributions. Osmium, and hence organic matter, associated with the mineral
content. High levels of osmium associated with pyrite (P), an iron rich detrital clay (C) and a small organic
particle (O).

440

Analysis of sedimentary organic materials by SEM

441

8
.o
O

CO

C0

L~

I',-

~D

t~

uO

--LO

--tO

O.~

o94
--Od

Oal

O-

I
o

o
o
O
u5

o
o
o
0~

L)

. . o=

e~

II =
O
o

o.o

O'r.
oO

00

r-.

(D

~D

L0 ".-~

(0

--O
~fJ

co

00
O,I

t'M

e~

0
O

I
o

o
r-,.

i
O

I
o
c0

6~

442

A.N. BISHOP et aL

regions, although some groups show bimodal distributions, and/or considerable scatter.
Bimodal composition distributions
phological types

of individual

particles are likely to be derived from terrestrial plant

material, whereas those with higher oxygen and
sulphur concentrations are marine in origin. The
division of vesiculate compositions into two separate
groups [Figs 4(a, b)] may reflect the difference in
composition between sedimentary organic material
derived from land plants (vitrinite) and organic matter derived from land plants which has been oxidised
to a far greater extent (inertinite). Inertinites typically
have a lower oxygen content than vitrinites (van
Krevelen, 1961).

mor-

The plots of vesiculate and interfingering compositions are typically bimodal. The group of interfngering particles of lower oxygen and sulphur
content plots in the same general region as vesiculate
analyses [Figs 4(c, d)]. Hence, these interfingering

3.0

(a)

2.5

_~ 2.0

tr

I
X

(..)

1.5

1.0

o o

CO

oo
0

0.5

0.0
0.000

0.050

0.025

o
0

0.075

O/C

0.100

0.125

0.150

0.125

0.150

(X-Roy Yield)

Fig. 4(a)
3.0

(b)

2.5

_~ 2.0
@

>-

"

1.5

1.0
0

0.5

o
GO

0
0

0
0

% 4~8~

~oP~o~

0.0
0.000

0.025

0.050

0.075

O/C

0.100

( X - R a y Yield)

Fig. 4(b)

Analysis of sedimentary organic materials by SEM

3.0

(c)
X

X
X

2.5

>.
0
I
X
(..)

XX

~xX
XX X

o
>-

443

~x ~ xX ~

2.0
XX

X X

x~

X
X
X

1.5

XX

X
X
X

X
Xx

1.0

Oq

0.5
o

XX

xXx
X~

~IL d~.

0.0
0.000

0.025

0.050

0.075

O/C

(X-Ray

0.100

0.125

0.150

Yield)

Fig. 4(c)
3.0

(d)

2.5

~" 2.0
@
>.
0

1.5

X
0

03

1.0

0.5

0.0
0.000

0.025

0.050
O/C

0.075

0.100

0.125

0.150

( X - R a y Yield)

Fig. 4(d)
Fig. 4. Oxygen and sulphur compositions, relative to carbon, of visible organic materials.
X=interfingering, =vesiculate, C)=capsulate, =ovoid. (a) Carboniferous coal, Ayrshire;
(b) Carboniferous coal, Fife; (c) Kimmeridge Clay, Dorset and (d) Jet Rock, Yorkshire.

Effect of kerogen type on composition

Comparison of the distribution of vesiculate, capsulate and intertingering compositions show that the
various morphological groups plot in distinct regions
(Fig. 4). Vesiculate particles, and interfingering particles derived from terrestrial land plants (type III)
have low S/C and O/C values, capsulate particles
OG 18/~-D

(type II) are moderately higher, with the highest

observed levels of sulphur and oxygen being associated with the main field of the interfingering group
(type I). Therefore, it would appear that sulphur and
oxygen content are related to kerogen type.
This association of type and oxygen content is the
reverse of previously published data on maceral
compositions (e.g. van Krevelen, 1961). The reasons

444

A.N. BISHOPet al.

for this are presently not known, but future quantification of these results should resolve this apparent
contradiction.

O/C
0.00
2.5

( X - R a y Yield)

0.05

0.10
__m

0.15

~)

__

Cr

Correlation o f sulphur and oxygen concentrations

The graphs shown in Fig. 4 indicate a definite

correlation between sulphur and oxygen concentrations. This is demonstrated by the relative positions of the compositional fields, and the distribution
of the points within the fields themselves. Such a
correlation between sulphur and oxygen was noted by
Durand and Monin (1980) who reported elemental
analysis results for different kerogen types. However,
their data points show considerable scatter, which
may be related to impurity of the kerogen concentrates. In this study, by analysing individual organic
particles, this danger is avoided.
Sinninghe Damste et al. (1989) attribute the origin
of organic sulphur compounds to abiogenic incorporation of sulphur into functionalised lipids at an
early stage of diagenesis. This is supported by the
data presented here, showing that the highest concentrations of sulphur correspond with type I (i.e. lipid
rich) kerogen. But, the association of sulphur with
oxygen suggests that oxygenated moieties may be
responsible for sulphur uptake. A more detailed
discussion of the role of oxygen in sulphur uptake will
be possible with quantitative results.
Lamina scale rariations oJ" composition

Analyses of interfingering particles on a lamina

scale (Jet Rock, Yorkshire) show considerable variation in composition, but again demonstrate a strong
correlation between oxygen and sulphur contents
(Fig. 5). The wide variation in results may account for
the scatter observed in Fig. 4. The range of compositions noted is more probably related to control of
diagenesis and hence uptake of sulphur on a microscopic scale. Similar lamina scale variations of S/C
have been reported by Aplin et al. (1992). These
variations were attributed to differential uptake of
sulphur into organic matter due to variations in
concentration of inorganic sulphur species.
Chlorine

In some of the samples of coal studied, significant

concentrations of chlorine were detected in the
groundmass [Fig. 3(d)], and to a lesser extent in the
other morphological groups. The resin used to mount
the samples contains chlorine, but chlorine was also
detected in coal samples which were not resin impregnated or mounted. Inorganic analyses have previously identified chlorine as a constituent element of
some coals (e.g. Caswell et al., 1984).
Chlorine has typically been regarded as being
associated with inorganic salts deposited during diagenesis or derived from the initial biological composition of the coal (Francis, 1961; Stach et aL, 1982).
However, Harrison (1991) showed that the chlorine
content of coals is probably organic. The lack of any

3.0
Ct

3.5
.0 ~-4.0

E 4,5
E
I
5.0
o
i=
~,

\
"0

5.5
/

6.0

O
6.5

7.0

7.5
0.0

0.5

1.0

1.5

S/'C ( X - R a y Yield)

Fig. 5. Lamina scale variation of oxygen (

) and sulphur
(
) contents of interfingering particles: Jet Rock,
Yorkshire.

recognisable mineral contaminant, either visually or

from the presence of cation elements within the
spectrum, supports the view that this chlorine is
organically bound. The chlorine is likely to be derived
from circulating groundwater brines (Stach et al.,
1982; Caswell et al., 1984).
CONCLUSIONS

Sedimentary organic materials are readily distinguished using backscattered electron imagery.
However, the traditional maceral classification is
inappropriate to this method of study, due to the lack
of characteristic features such as reflectance and
fluorescence. By using a new classification scheme
based on simple morphological criteria, organic
materials can be distinguished with reasonable success and reproducibility. The contrast of a backscattered image reveals differences in composition
within single particles, and between different types of
material. These variations can be related to specific
elemental distributions using digital X-ray mapping.
Osmium tetroxide staining of organic rich sediments
suggests that adsorption of organic matter by clay
minerals during deposition may be an important
control on the location and distribution of sedimentary organic matter.

Analysis of sedimentary organic materials by SEM

445

Table 2. Summary of morphological and chemical characteristics of sedimentary organic matter as determined by SEM
Palaeoenvironmental
Morphology
Diagnostic features
restriction
Chemical characteristics
Interfingering

Structurelessparticles, lateral
margins of which "interfinger"
with the sediment matrix.

Vesiculate

Contains vesicles, or reeognisable

fragment of broken vesicle.

Capsulate

Single continuous capsule.

Ovoid

Massive, with no internal fine

structure discernible. Outline is
simple and ovoid.
Elongate, long and narrow with
arched protuberances on one or
both sides.
Simple rectangular or polygonal
areas of organic matter, with
simple fracture outline.

Arched
Blocky

Groundmass

Apparently structureless
groundmass of organic material.

Microgranular

Very small particles (<1/~ m)

equant in shape, and aggregated
into larger masses.

Very abundant in marine

mudstone anoxic environments.
Seldom found in terrestrial or
nearshore horizons,
Derived from terrestrial
environments. Commonly found in
marine mudstones. Small
fragments are ubiquitous,
Common in both terrestrial and
marine environments,
Largely terrestrial in origin, but
also found in marine sediments,

Low to high oxygen content.

Moderate to very high sulphur
content. Bimodal composition
distribution common.
Zero to moderate oxygen content.
Generally very low sulphur content.
Bimodal composition distribution
common.
Moderate to high oxygen and sulphur
contents.
Moderate to high oxygen and sulphur
contents.

Common in terrestrial sediments.

Uncommon in distal marine
environments.
Common in terrestrial
environments from which these are
derived. Smaller fragments may be
present in marine sediments.
Terrestrial only.

Moderate to high oxygen and sulphur

contents.

Rare in terrestrial. Unknown in

marine.

Light element analysis allows the qualitative assessm e n t o f c a r b o n , oxygen, sulphur a n d chlorine
c o n t e n t s o f individual sedimentary organic particles.
Quantification of these results should be possible
using a p p r o p r i a t e polymer standards, additionally
enabling resolution o f nitrogen contents. The analyses show t h a t u p t a k e o f sulphur is related to kerogen
type, with type I kerogen (e.g. interfingering particles)
representing the m a i n potential sink for organic
sulphur within m a r i n e sediments. Positive correlation
o f sulphur a n d oxygen c o n t e n t s suggest t h a t oxygenc o n t a i n i n g moieties m a y be directly involved in sulp h u r uptake. Series o f analyses t a k e n o n a l a m i n a
scale indicate t h a t diagenesis is controlled on a very
local scale, with wide variations in sulphur c o n t e n t
extending over only a few millimetres. A s u m m a r y of
the m a i n morphological features a n d typical elemental c o n t e n t s o f sedimentary organic m a t t e r is s h o w n
in T a b l e 2.
Overall, this study illustrates t h a t the scanning
electron microscopy techniques o f backscattered elect r o n imagery a n d light element microanalysis represent i m p o r t a n t new tools in the field o f organic
geochemistry. T h e results offer a new insight into
the relationship between the optical petrology o f a
sample a n d its geochemistry.

Acknowledgements--We would like to thank Chris Jones

and John Wells (Oxford Polytechnic) for the preparation of
samples and Paul Farrimond (NRG) for reading the
manuscript and for helpful suggestions. We also wish to
thank Yvonne Hall (NRG) for assistance with the final
preparation of the manuscript, and Christine Jeans (NRG)
for help with drafting. Samples were provided by Oxford
Polytechnic and BP, ODP samples were provided by Alan
Kemp, Department of Oceanography, Southampton University. The project was funded by BP Research.

Low oxygen, low to moderate sulphur

content.
Low to moderate oxygen, low sulphur
content. May contain significant
concentrations of chlorine.
Due to small particle size, almost
impossible to analyse without
significant contamination.

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