GEOCHEMISTRY / Sediment 181
Miscellaneous Techniques
Mineral identication may be performed using po-
larized light microscopy, but where possible single-
crystal or powder X-ray diffraction is the technique
of choice for determining mineral structure. Fourier
transform infrared spectrometry (FTIR) is also com-
monly used to identify mineral structure and deter-
mine crystal perfection in geological materials.
Standards and Standardization in
Geochemical Analysis
The performance of any analytical procedure must
be assessed through analysis of certied reference
materials. As geological materials are varied, often
with complex heterogeneous matrices, articially
produced standards are seldom sufcient. Homo-
genized, certied standard reference materials are
available for a wide range of rock, soil, mineral, and
biomaterial types and must be used to validate an-
alytical protocols. Interlaboratory comparisons of
measurements of the elemental and isotopic compo-
sition of reference materials are frequently published
in dedicated journals such as the Geostandards
Newsletter.
See also: Archaeometry and Antique Analysis: Dating
of Artifacts; Metallic and Ceramic Objects. Atomic Ab-
sorption Spectrometry: Principles and Instrumentation.
Atomic Emission Spectrometry: Inductively Coupled
Sediment
G E Millward, University of Plymouth, Plymouth, UK
& 2005, Elsevier Ltd. All Rights Reserved.
Introduction
This article covers general methods applicable to
the physical and chemical analysis of sediments
from lakes, rivers, estuaries, and coastal seas. The
material uxes from the land to the sea are domi-
nated by the sediment loads delivered by the global
rivers. Although the river sediment ux cannot be
predicted accurately, it is thought to be in a range
from 10 to 20 Gt a
1. Contributions by individual
rivers are conditional upon the geology, topography,
and climate of their drainage areas. Much of the
sediment transported by rivers is temporarily stored
Plasma. Atomic Mass Spectrometry: Laser Microprobe.
Environmental Analysis. Geochemistry: Sediment; Soil,
Organic Components. Infrared Spectroscopy: Overview.
Mass Spectrometry: Stable Isotope Ratio; Archaeological
Applications. Microscopy Techniques: X-Ray Micros-
copy. Quality Assurance: Reference Materials; Method
Validation. Sample Dissolution for Elemental Analysis:
Wet Digestion; Microwave Digestion. Sampling: Theory;
Practice. X-Ray Absorption and Diffraction: X-Ray Dif-
fraction Powder. X-Ray Fluorescence and Emission:
X-Ray Diffraction Single Crystal; Wavelength Dispersive
X-Ray Fluorescence; Energy Dispersive X-Ray Fluores-
cence; Synchrotron X-Ray Fluorescence.
Further Reading
Deer WA, Howie RA, and Zussman J (1966) An Intro-
duction to the Rock Forming Minerals. Harlow, Essex:
Longman.
Faure G (1986) Principles of Isotope Geology. New York:
Wiley.
Fenter PA, Rivers ML, Strurchio NC, and Sutton SR (eds.)
(2002) Applications of Synchrotron Radiation in Low-
Temperature Geochemistry and Environmental Science,
Reviews in Mineralogy and Geochemistry vol. 49.
Washington, DC: Mineralogical Society of America.
Gill R (ed.) (1997) Modern Analytical Geochemistry, Geo-
chemistry Series. Harlow, Essex: Longman.
Potts PJ, Bowles JFW, Reed SJB, and Cave MR (1995)
Microprobe Techniques in the Earth Sciences, The Min-
eralogical Society Series, vol. 6. Dordrecht: Kluwer.
in the lower part of the river basin and often only
reaches the ocean by slow migration through its
estuary. Although there are compositional differences
between sediments from these environments they
generally comprise highly variable and complex
mixtures of aluminosilicate particles, quartz grains,
terrestrial organic detritus, planktonic material, and
ferromanganese oxides. The surfaces of mineral
phases, such as clays, are modied by coatings of
organic matter and iron and manganese oxides. The
various particle types in a sedimentary assemb-
lage have unique surface properties that inuence
their chemical reactivity with dissolved constituents.
Thus, particlewater interactions, which are accen-
tuated in estuaries because of the sudden change in
reaction conditions across the freshwaterseawater
interface, give rise to complex array of adsorbed
and absorbed species of inorganic and organic
182 GEOCHEMISTRY / Sediment
constituents. Depending on their grain size, carbon
content, and the length of time deposited at the
site, consolidation of sediments may occur and
anaerobic conditions may also develop in the sedi-
ment column, as a consequence of the bacterially
moderated decomposition of particulate organic
matter. Consequently, the focus of analytical
methods for metals, radioisotopes (including metals,
nonmetals, and metalloids) and persistent organic
pollutants have become highly oriented to pre-
serving, detecting, and quantifying the concentra-
tions of particulate species in sediments and to
establishing their relationship with basic particle
properties.
From the applications viewpoint, chemical analy-
ses of aquatic sediments are essential in the assess-
ment of their contaminant loadings, in reconstructing
the history of contaminant deposition, and in quan-
tifying the rate at which sedimentwater exchange
processes contribute to recovery from contamina-
tion. The bioavailability of toxins in contaminated
sediments has also become a priority for managers of
aquatic systems. In an attempt to assess the impact
of sediment chemistry and toxicity on the health
of bottom-dwelling organisms a Sediment Quality
Triad has been developed.
Sediment Sampling and
Preservation
There is little point in undertaking complex chemical
analyses of sediment samples if they have been signi-
cantly modied during collection or contaminated
during subsequent laboratory manipulation. Thus,
sediment collection, preservation, and analysis re-
quire careful preplanning and execution, as shown in
the hierarchy of operations in Figure 1. Sediments
should be obtained in such a way as to retain their
natural integrity, although some disturbance and
losses of the ne fraction may occur because of the
application of relatively crude sampling methods.
These include heavy mechanical grabs and corers
that are deployed from a vessel and whose operation
requires them to impact with the seabed, causing
shock waves and sediment disturbance. Large
volume sediment samples, typically of 1 m depth,
can be obtained by a spade-box corer from which
undisturbed sediment subcores can be taken by
carefully inserting plastic tubes. Multicorers are
used to obtain several undisturbed samples at
the same site, allowing assessment of small-scale
variations in sediment composition to be made,
especially in areas of bioturbation or variable sedi-
ment texture. In shallow waters, in situ collection
Planning sediment analyses
Evaluation of the problem
Organization of physical and human resources
Sample strategy
Sample locations
Sampling frequency in time and space
(including replicates)
Logistics and implementation
Sample collection
Method to obtain undisturbed samples
Minimization of contamination and losses
Maintain integrity of anoxic sediments
Sample preservation
Manipulate anoxia sediments in an inert
atmosphere; separate pore waters
Short- to long-term storage under cryogenic
conditions, possibly after aliquotation
Determination of sediment properties
Drying and homogenization
Grain size and shape; surface area
Major elements
CHNS;
13C and
15N
Analytical methods
Extraction and analysis of metals
Direct and indirect methods for -, -, -
emitting radionuclides
Extraction and analysis of organic compounds
Analytical quality assurance
Quality assurance using certified reference
materials, in-house standards, and interlaboratory
calibration exercises for verification
of accuracy and precision
Checks that the data are within the set limits of
accuracy and precision
Data interpretation
Pollutant loadings; particulate speciation;
exchangeability; bioavailability
Figure 1 Hierarchy of operations when conducting a sediment
survey, sample preparation, and analysis.
by divers may involve less sample alteration,
although care should be taken to ensure that move-
ments near the seabed do not cause sediment
resuspension.

Oxic surface sediment samples should be trans-
ferred to a suitable container and stored in a freezer
as soon as possible after collection. Suitable contain-
ers will depend on the analyte, such that sediments
for metal and/or radiochemical analyses are stored in
acid-washed, plastic containers. Glass or metal con-
tainers should be used when storing sediments for
the analysis of organic molecules, since plastic may
contain similar organic compounds that may leach
into the sample. Prior to use, glass or metal contain-
ers are normally washed repeatedly in an organic
solvents, such as high-performance liquid chro-
matography (HPLC)-grade acetone and hexane and
then baked at high temperature (B4501C) overnight.
The preservation of the integrity of subsurface anoxic
sediments, normally retained in a plastic core tube, is
more taxing. Immediately on retrieval, the top of the
sediment core tube is enclosed within a plastic glove
bag lled with an inert gas, e.g., white spot nitrogen
and the core is extruded from the tube by applying a
piston to its base. The sample can be sectioned, into
slices of appropriate thickness, as the sediment core
is extruded into the nitrogen-lled glove bag. The
separation of pore waters from the sediments is
essential since they may contain signicant concen-
trations of redox-sensitive elements, which, if ex-
posed to the atmosphere, may precipitate on the
sediment particles thereby modifying their composi-
tion. Isolation of the pore waters is achieved by
centrifugation using sealed, plastic centrifuge tubes
ushed with an inert gas. After decanting the pore
water under nitrogen the centrifuge tubes containing
the anoxic sediments are stored in a freezer.
Determination of Sediment
Properties
The concentrations of adsorbed sedimentary consti-
tuents tend to increase with decreases in particle dia-
meter owing to an enhancement of the surface area
per unit weight. To account for regional diversity of
sediment grain size distributions, separation of a ne
fraction is undertaken by sieving through a mesh
(grain size commonly o63 mm) of plastic or metal,
appropriate to the analyte. However, the ne fraction
may form only a small part of the total sediment and
given that sieving is time-consuming and does not
always disperse aggregates, it may be preferable to
carry out chemical analyses of the bulk sediments.
Concentrations of the constituents can be normalized
with respect to a property of the ne fraction, such as
percentage weight, specific surface area (via BET
nitrogen adsorption on a freeze-dried sample), or
by reference to the total concentration of a major
GEOCHEMISTRY / Sediment 183
element, such as Al or Li. The grain sizes of cohesive
muds can be obtained from sedimentation tubes,
generally known as Owen Tubes, or by laser gran-
ulometry (operating in the range 21000 mm).
High-resolution scanning and transmission electron
microscopy yield details of particle morphology, in-
cluding size and shape. If the instrument is tted with
an element dispersive X-ray analyzer, major elements
(Al, Ca, Si, Fe) can be determined, thereby identify-
ing differences in the detrital (i.e., the underlying
solid phase) composition of individual particles as a
function of particle size. Where mineral phases have
been separated on the basis of density or magnetic
properties, their mineralogy can be examined by
X-ray diffraction methods.
The surfaces of sediment particles normally have
deposits of natural organic macromolecules, such as
humic and fulvic acids, and ferromanganese oxides.
The organic macromolecules have functional groups
that are effective sorbents for persistent organic pol-
lutants and, together with the oxides, they are sites
where metals undergo surface complexation reac-
tions. The proton and cation exchange capacities of
natural sediments have been obtained from acid
base titrations. Extraction of surface-bound humic
(molecular weight B10 000 Da) and fulvic (o5 000 Da)
compounds can be made using sodium hydroxide.
The extracts can be concentrated on a resin column,
separated by liquid chromatography, and detected by
ultraviolet (UV) spectrophotometry or Fourier trans-
form infrared spectrophotometry or by gas chro-
matographymass spectrometry (GCMS). Total
carbon, hydrogen, nitrogen, and sulfur analyses are
undertaken by using a commercially available com-
bustiometric technique and particulate organic
carbon can be similarly determined after removal of
inorganic carbon by acidication. Isotope ratio-mass
spectrometry (IRMS) has been used to determine the
mean d13C and d15N in sediments:
d13 C 13 C=12 Csample =13 C=12 CPDB
1  1000
d15 N 15 N=14 Nsample =15 N=14 Nair
1  1000
The equations give d13C values (per mil or per thou-
sand) using Chicago PDB carbonate as the standard
and d15N values (per mil or per thousand) with at-
mospheric nitrogen as the standard value. The d13C
values for individual compounds, albeit with some
loss of sensitivity, can be determined by coupling
IRMS with GC separation of sediment extracts. The
combination of C:N ratios and d13C and d15N values
give vital information on the provenance of sedi-
ments since the values are signicantly different for
various particle types (Table 1). The determination of
184 GEOCHEMISTRY / Sediment
Table 1 Examples of C:N ratios and d13C and d15N values for various particle types
Particle type C:N ratio
Soil organic mattera 1220
Sediments from stratied lakesa 614
Sediments from Forth Estuary, UKb 21.776.6
Marine sedimentb 11.3
Sewageb 12.6
Micro-phytoplanktonb 6.3
a
Last WM and Smol JP (eds.) (2002) Tracking Environmental Change Using Lake Sediments: Volume 2, Physical and Chemical
Methods. Dordrecht: Kluwer Academic.
b
Graham MC, Eaves MA, Farmer JG, Dobson J, and Fallick AE (2001) A study of carbon and nitrogen stable isotopes and elemental
ratios as potential indicators of source and fate of organic matter in sediments of the Forth Estuary, Scotland. Estuarine, Coastal and
Shelf Science 52: 375380.
18
O/16O and deuterium/hydrogen ratios in sedimen-
tary organic matter could be of advantage to
paleolimnological studies concerned with the re-
construction of paleoclimate. However, there are
considerable practical difculties in the analysis of
these stable isotopes and few laboratories currently
have the required level of analytical skills.
Chemical Analyses of Sediments
The determination of trace constituents in sediments
requires that contamination be minimized during
sample manipulation, which should be conducted in
a clean room, or, at least, in a laminar ow hood.
The laboratory-ware should be of good-quality boro-
silicate glass, polyethylene, or Teon and high-purity
reagents be used throughout to reduce the blanks.
Normally, the analysis of sedimentary constituents
involves a freeze-dried or air-dried sample that can be
accurately weighed. If appropriate, samples may be
homogenized by mortar and pestle and then sieved.
Drying and chemical treatment of anoxic sediments
should be undertaken in an inert atmosphere and
with reagents that are oxygen-free.
Metals
The analysis of metals by X-ray uorescence has
been widely used on geological and sediment sam-
ples, either deposited on lters or as thin lms. The
method can be made quantitative by using geological
standards and transition metals can be determined in
the 15 mg per g range. The surfaces of sediment par-
ticles can be examined by the direct use of electron
microprobe X-ray emission spectrometry and Auger
electron spectroscopy. Although these methods are
not particularly sensitive, they can allow the deter-
mination of a depth-prole of trace metals within a
sediment particle.
Determinations of total metals in sediments can be
achieved with electrothermal atomic absorption
d13C (per mil) d15N (per mil)

23 to
29 5

20 to
33
2 to 20

24.070.2 5.670.6

23.2 5.9

26.7 2.3

17.2 to
26.5 0.5 to 8.2
spectrometry or multielement inductively coupled
plasma-mass spectrometry (ICP-MS), following mi-
crowave assisted extraction (MAE) using concentrat-
ed HNO3 and HF in sealed Teon vessels. The
accuracy of the method can be veried by certied
reference sediments, such as MESS-3 and PACS-2
available from the National Research Council of
Canada (NRCC). High-resolution ICP-MS is also
used for determinations of isotopes, for example,
204
Pb, 206Pb, 207Pb, and 208Pb in studies of source
apportionment. Direct analysis of solid samples may
be possible and has a number of advantages, inclu-
ding reducing the preparation time, minimizing con-
tamination, retention of volatile elements, and
determination of highly refractory matrix-bound
elements. Methods involve slurry nebulization ICP-
MS using nely ground, uidized sediments and laser
ablation ICP-MS where solid samples are mixed with
a binder and pelletized. Determinations of total
metals allow geochemical normalization using con-
centrations of Al, since it is a major component of
aluminosilicate minerals and it is usually unaffected
by anthropogenic inputs. However, Li is a potentially
superior normalizer because, unlike Al, it is not usu-
ally present in feldspars. An added advantage of
geochemical normalization is that it allows estima-
tion of enrichment factors.
Metals associated with various binding sites on
sediments have been assessed using extraction pro-
cedures applied as single digests or as a set of se-
quential steps. Selective dissolution of trace metals
from the particle surfaces is followed by determina-
tion using atomic absorption spectrometry (AAS),
ICP-MS, or total reection X-ray uorescence. The
use of sequential extraction schemes for the opera-
tional definition of metal species in sediments has
proved contentious. They have been criticized on the
basis that the reactions are not sufciently phase
selective and labile phases could be transformed dur-
ing sample preparation, causing a marked reduction
 GEOCHEMISTRY / Sediment 185

Table 2 A sequential extraction scheme for trace metal speciation in sediments. The rst three steps relate to the standardized
sequential extraction method applicable to BCR CRM 601

Fraction Extractant Extracted component

Exchangeable and carbonatic
Moderately reducible
Suldic and organic
Residual

1
0.11 mol l HOAc Exchangeable ions and carbonates
0.1 mol l
1 NH2OHHCl acidify with HNO3 to pH 2 Amorphous iron and manganese oxides
8.8 mol l
1 H2O2 and 0.02 mol l
1 HNO3 at pH 2, Sulfides and organic matter
extracted with 1 mol l
1 NH4OAc at pH 2 with
HNO3
Concentrated HNO3/HF Detrital matrix

HOAc, acetic acid.

From Caruso J, Sutton KL, and Ackley KL (2000) Elemental Speciation: New Approaches for Trace Element Analysis. In: Barcelo D
(ed.) Comprehensive Analytical Chemistry, vol. 33. Amsterdam: Elsevier.

in selectivity, particularly for anoxic sediments. 120

Moreover, until recently there was no appropriate
100
certied reference material (CRM), allowing interna-

% Metal extracted
tional comparison of data. The Community Bureau 80
of Reference (BCR, now renamed as the Standards,
Measurements and Testing Programme) of the Euro- 60
pean Union has produced sediment reference material 40
CRM 601 which can be used in the validation of a
three-stage sequential extraction procedure (Table 2). 20
In the case of anoxic sediments, methods have been
0
developed for determination of acid volatile sulfides )
Ac H in sin (1

)
l
ps
C

(2
simultaneously with the extraction of metals, under O
HO yp d
H

Na e i

id
P Tr flu

flu
oxygen-free conditions. This combined approach is ut

ut
(A) G

G
useful in interpreting the data from bioassay tests of
metal toxicants on aquatic sediments. 120
Innovative methods to determine the bioavailability
100
of trace metal in estuarine sediments have been
% Metal extracted

developed recently using digests that are more re- 80

presentative of the digestive uids of aquatic organi-
60
sms. Studies with trypsin and pepsin (two of the most
important enzymes involved in the digestion of food 40
by marine organisms) and the intestinal uids ex-
tracted from codsh have shown signicant varia- 20
tion from mineral reagents used in sediment extrac- 0
tions. Figure 2 shows the proportions of Cu and Zn
)
l

(2
n

)
in
H
Ac
C

(1
si
aO

ps
H

released by single extractions by various reagents,

id
O

yp

id
Pe

flu
H

flu
Tr

relative to the concentration of total metal on estu-

ut
ut

(B)
G
G

arine sediments. Compared to Zn, Cu is associated

with particulate organic material as shown by the
amount released by the NaOH digest. Pepsin
removed more Zn than Cu, whereas the gut uids
(1 and 2) solubilized more Cu and Zn than the en-
zymes pepsin and trypsin. It appears that acetic acid
represents the best reagent with which to dene the
metals that are available under gastrointestinal con-
ditions. However, more research is required on the
extraction efciency of other enzymes, such as
proteinase-K, which targets metals associated with
proteinaceous material on sediments.
Butylated Sn compounds have been determined in
sediments by exploiting microwave technology to
simultaneously extract and derivatize Sn compounds
Figure 2 Percentage metal extracted, relative to the total con-
centration, from marine sediments by different reagents, enzymes,
and the gut uid from cod. HCl 1 mol l
1 HCl; HOAc 25% gla-
cial acetic acid; NaOH 0.1 mol l
1 NaOH; Pepsin Pepsin A pH
2; Trypsin Trypsin II-S pH 7.6; Gut uid (1) natural ltered in-
testinal uid, pH 7; Gut uid (2) natural ltered intestinal uid, pH
2. (A) Cu and (B) Zn. (Adapted from Turner A and Olsen YS
(2000) Chemical versus enzymatic digestion of contaminated es-
tuarine sediment: Relative importance of iron and manganese
oxides in controlling trace metal bioavailability. Estuarine, Coastal
and Shelf Science 51: 717728.)
(usually by ethylation) to give volatile tetra-substi-
tuted species, suitable for separation by GC. Methyl
mercury species have been released from sediments
by using KOH/methanol mixtures in sealed Teon
186 GEOCHEMISTRY / Sediment
reactors with an open focused MAE system. Subse-
quently, the methylated Hg species are extracted into
a suitable organic solvent, separated by HPLC and
the individual methylated compounds decomposed
by UV irradiation as they come off the column. The
pulses of inorganic Hg are then detected by cold
vapor-atomic uorescence spectrometry. The accuracy
of analytical methods for Sn and Hg can be veried
with certied reference sediments for mono-, di-, and
tributyl tin (BCR CRM 646) and for methyl mercury
(BCR CRM 580). Arsenic species on sediments (in-
cluding the methylated forms) have been determined
by coupled HPLCICP-MS following their extraction
in phosphoric acid using a low-power MAE system.
Radionuclides
Radionuclides such as 238Pu, 234U, and 232Th emit
a-particles that have a limited penetration in matter,
requiring a complex separation and preconcentration
of the individual elements from sediments. Alpha-
emitting radionuclides can be separated from sedi-
ments by a primary digestion with concentrated
mineral acids (e.g., aqua regia) followed by several
steps involving precipitation and ion exchange.
Chemical yields for the various elements can be ob-
tained using internal spikes that are not present in
natural sediments (e.g., 236Pu) and the accuracy of
the analyses can be veried with CRMs, such as In-
ternational Atomic Energy Agency (IAEA)-367 sedi-
ment for 239(240)Pu. Thin sources are prepared, for
example, by electrodeposition or by microprecipita-
tion with NdF3 onto polyethylene lters (pore size
0.1 mm), prior to a-spectrometry, using silicon surface
barrier detectors coupled with pulse height analysis
by a multichannel analyzer. More progress has been
made in the use of nonradiometric methods for
a-emitting radionuclides at natural concentrations
(e.g., 232Th, 235U, 239Pu, 240Pu) using acid digests of
sediments followed by ICP-MS determination.
Pure b-emitters such as tritium (3H), 14C (radio-
carbon widely used in geochronology), 35S, 63Ni, and
Table 3 Mean activity concentrationsa of gamma-emitting radionuclides in sediments from the coastal region of Cumbria, UK
Location Sediment type Activity concentrations (Bq kg
1)
241
Am
St. Bees Sand 180
Sellaeld Sand 230
Ravenglass Mud 1500
Ravenglass Mud and sand 500
a
Becquerels per kilogram dry weight.
From Centre for Environment, Fisheries, and Aquaculture Science (2002) Radioactivity in Food and the Environment, 2001. London:
Food Standards Agency and Scottish Environment Protection Agency.
90
Sr are chemically separated from the sediments
before liquid scintillation counting. Tritiated mole-
cules and 14C compounds have been separated from
freeze-dried sediment samples using a computer-con-
trolled, combustion technique with a CuO catalyst.
The radioactive gases, 14CO2 and 3HHO, are separat-
ed by selective trapping and each isotope is determined
by liquid scintillation counting. Limits of detection for
a 20 g sample are B20 mBq g
1 for both isotopes.
Activity concentrations for b-emitters can be deter-
mined, using thin sources with a 40K standard, or for
solutions via a liquid scintillation counter or for low
levels using a gas-ow multicounter.
Gamma rays from some radionuclides, such as
137
Cs, 241Am, and 106Ru, have a specific energy that
can be detected by nondestructive gamma spect-
rometry using sensitive hyper-pure germanium de-
tectors, with relative efciencies of 2025%. The
homogenized, freeze-dried sediment is normally
placed in a Marinelli beaker, shaped to surround
the detector, and of 0.8 l capacity. Sediment geo-
chronology may be determined from the gamma
emission of 210Pb (half-life 22 years) and 226Ra, from
which the excess 210Pb can be calculated and the
sediments dated. Dating of sediment cores is also
assisted by peaks in the activity concentration of
137
Cs, e.g., the peak generated by deposition from
the Chernobyl accident in 1986. The gamma-emit-
ters 7Be (half-life 53 days) and 234Th (half-life 24
days) are both particle-reactive and, since they have
different source functions, they can be applied to the
tracing of sediment migration in estuaries.
Activity concentrations for various gamma-emitting
radionuclides in coastal marine sediments from the
Irish sea are given in Table 3. A major source of
radionuclides to the Irish Sea is the Sellaeld nuclear
reprocessing plant and the distribution of radionucli-
des shows that higher concentrations may be found
away from the source, thereby emphasizing the point
concerning particle properties because the higher
activity concentrations are associated with the ner
sediments either side of the source.
60 137 106
Co Cs Ru
4.5 87 o4.0
5.2 90 o4.6
64 610 190
26 210 51

Organic Compounds
Polychlorinated organic compounds Polychlorinated
biphenyls (PCBs) comprise a family of 209 individual
compounds, referred to as congeners, and to make
identication easier systematic numbering was intro-
duced by the International Union for Pure and
Applied Chemistry (IUPAC). For example, toxicologic-
ally important PCB congers notably 3,3,4,40 -tetra-
chlorobiphenyl, 2,3,30 ,4,40 -pentachlorobiphenyl, and
3,30 4,40 ,5-pentachlorobiphenyl have the IUPAC num-
bers 77, 105, and 126, respectively. Polychlorinated
dibenzodioxins (PCDDs) have 75 congeners and poly-
chlorinated dibenzofurans (PCDFs) have 135 conge-
ners, although there is no numbering system. PCBs and
PCDDs/PCDFs are found at low concentrations in se-
diments (in the range ng per g to pg per g) and co-con-
taminants have to be eliminated from the samples prior
to analysis, which requires considerable analytical
expertise to identify the compounds on a congener-
specific basis.
Due to the wide range of organic compounds in
sediments, a three-stage analytical protocol is gene-
rally adopted:
1. Extraction of the organic compounds from a dried
sediment sample: Prior to extraction an internal
standard mixture of 13C-labeled compounds is added
to the sediments. The extraction is normally carried
out in a Soxhlet apparatus with an azeotropic mixture
of organic solvents such as hexane and acetone or
benzene and toluene. The extract is then concentrated
using rotary evaporation and dried if appropriate.
2. Cleanup of the extract: This step involves the
removal of other organic components that have been
coextracted in stage (1) and would interfere with sub-
sequent analyses. This stage is usually carried out by
using column chromatography, thereby allowing the
various homologs to be eluted and separated. This
process may need to be repeated on an iterative basis
to ensure complete removal of interfering compounds.
3. Separation, identication, and quantication:
Using GCMS with internal quantication standards
that are added as spikes at the extraction stage. If the
subsequent GCMS analyses reveal that accurate de-
termination of PCDDs and PCDFs is not possible
owing to the presence of interfering peaks then liquid
chromatography separation may be employed.
Developments in high-resolution GC and/or MS
allow the detection of ultralow concentrations,
B10
15 g, on-column. However, any increased sen-
sitivity brings additional problems and empha-
sizes the need to control contamination in reagents
and glassware. Considerable improvements have
been made in the precise quantication of many
GEOCHEMISTRY / Sediment 187
compounds by isotope dilution-MS because of the
availability of a wider range of 13C and deuterated
compounds of organic molecules. Advances are
being made in the coupling of instrumental tech-
niques such as HPLC with MS, which will yield a
highly sensitive method for the detection and quan-
tication of more polar and water-soluble com-
pounds. A novel approach to the determination of
broad classes of chlorine-, bromine-, and iodine-con-
taining organic compounds in sediments, extracted
into a mixture of methylene chloride and hexane,
involves monitoring the gamma-ray emissions of
38
Cl, 80Br, and 128I, following neutron activation of
the extracts.
Determinations of polyaromatic hydrocarbons
(PAHs) in freeze-dried sediments (sample mass of
the order 1020 g) has been carried out where hexa-
methylbenzene added as a standard to the sediment
prior to extraction. The sediments were extracted
sequentially with methanol followed by methylene
chloride and substituted and unsubstituted were de-
termined by GCMS. The accuracy of the method
was veried using the marine reference material HS6
(NRCC). The technique allowed the determination
of 17 unsubstituted and 33 substituted PAHs with
detection limits in the range 50200 ng per g. An ex-
ample of the results from the sediment core from a
Canadian fjord contaminated with PAHs derived
from an aluminum smelter is shown in Figure 3. The
PAH concentration illustrates the wide concentration
range available to this analytical method and also
show the variation of PAH concentrations with
depth. Each PAH has an increase in concentrations
PAH concentration (ng per g)
0.1 1 10 100 1000
0
10
20
Depth (cm)
30
40
50
60
70
80
Figure 3 Concentrations of PAHs in a sediment core from
Kitimat Arm, Douglas Channel, British Columbia. J total
unsubstituted PAHs; m unsubstituted perylene; & phenan-
threne;  uoranthrene; } 2-methylphenanthrene. (Adapted
from Simpson CD, Harrington CF, Cullen WR, Bright DA, and
Reimer KJ (1998) Polycyclic aromatic hydrocarbon contamination
in marine sediments near Kitimat, British Columbia. Environmen-
tal Science and Technology 32: 32663272.)
188 GEOCHEMISTRY / Soil, Major Inorganic Components
between 20 and 45 cm depth, indicating the beginn-
ing of Al smelting.
Surfactant compounds that sorb onto sediments
after discharge from sewage works are thought to be
endocrine disrupters and are, therefore, of consider-
able interest to environmental managers. One of the
largest classes of commercially available nonionic
surfactants are the nonyl phenol-n-ethoxylates de-
ned by the abbreviation NpnEO, where n is the
number of ethoxylate groups that normally reach a
maximum of 9, giving rise to a large number of iso-
mers. Biodegradation of NpnEOs takes place during
sewage treatment and the more lipophilic and per-
sistent alkylphenols are formed. Current methods
involve the extraction of freeze-dried sediments,
ground to a free-owing powder, with hexane/ace-
tone mixtures, using an accelerated solvent extrac-
tion system where the sample is held at 1001C and
1500 psi. After the extract is reduced to dryness, it is
reconstituted with hexane and the extract cleaned up
on a solid-phase extraction cartridge. The nal ex-
tracts can be analyzed by coupled normal liquid
phase chromatographyelectrospray mass spectro-
metry. Detection limits are in the low ng per g range.
Shang et al. in 1999 found that the average concen-
trations for total NpEO in the sediments
of the Straits of Georgia, Canada were 15007
130 ng per g; whereas in the Venice Lagoon the range
was 5006700 ng per g (total of Np, Np1EO, and
Np2EO), and in marine sediments near a Barcelona
sewage outfall the range was 1006600 ng per g.
Concentrations of the breakdown product octylphe-
nol were typically o20 ng per g.
See also: Analytical Reagents: Purication. Arsenic.
Atomic Absorption Spectrometry: Electrothermal. Atomic
Mass Spectrometry: Inductively Coupled Plasma. Dioxins.
Elemental Speciation: Overview. Endocrine Disrupting
Chemicals. Geochemistry: Sediment. Humic and
Fulvic Compounds. Isotope Dilution Analysis. Mass
Soil, Major Inorganic Components
H van der Jagt, KIWA Water Research, Nieuwegein,
The Netherlands
& 2005, Elsevier Ltd. All Rights Reserved.
Introduction
Major inorganic compounds, such as trace elements,
are of concern as contaminants of terrestrial and
Spectrometry: Overview. Mercury. Microscopy Tech-
niques: Scanning Electron Microscopy; X-Ray Micros-
copy. Particle Size Analysis. Polychlorinated Biphenyls.
Polycyclic Aromatic Hydrocarbons: Environmental Appli-
cations. Radiochemical Methods: Overview. Sample
Handling: Sample Preservation. Sampling: Theory. Sur-
face Analysis: Auger Electron Spectroscopy. Tin. X-Ray
Absorption and Diffraction: Overview. X-Ray Fluores-
cence and Emission: Energy Dispersive X-Ray Fluores-
cence; Particle-Induced X-Ray Emission.
Further Reading
Chapman PM and Wang FY (2001) Assessing sediment
contamination in estuaries. Environmental Toxicology
and Chemistry 20: 322.
Evans EH, Dawson JB, Fisher A, et al. (2001) Atomic spectro-
metry update. Advances in atomic emission, absorption,
and uorescence spectrometry, and related techniques. Jour-
nal of Analytical Atomic Spectrometry 16: 672711.
Gill R (ed.) (1997) Modern Analytical Geochemistry. Har-
low, UK: Pearson Education.
Jickells TD and Rae JE (eds.) (1997) Biogeochemistry of Inter-
tidal Sediments. Cambridge: Cambridge University Press.
Jones KC and de Voogt P (1999) Persistent organic pollu-
tants (POPs): State of the science. Environmental Pollu-
tion 100: 209211.
Morrow RW and Crain JS (eds.) (1998) Applications of
Inductively Coupled Plasma-Mass Spectrometry to
Radionuclide Determinations. Chelsea, MI: American
Society for Testing and Materials.
Pawliszyn J (2002) Sampling and Sample Preparation for
Field and Laboratory. In: Barcelo D (ed.) Comprehensive
Analytical Chemistry, vol. 37. Amsterdam: Elsevier.
Shang DY, MacDonald RW, and Ikonomou MG (1999)
Persistence of nonylphenol ethoxylate surfactants and
their primary degradation products in sediments from
near a municipal outfall in the Strait of Georgia, British
Columbia, Canada. Environmental Science and Tech-
nology 33: 13661372.
Turner A and Millward GE (2002) Suspended particles:
their role in biogeochemical cycles. Estuarine, Coastal
and Shelf Science 55: 857883.
aquatic systems because of their persistence and toxi-
city at low concentrations. There is considerable evid-
ence that the bioavailability and toxicity of such trace
elements are markedly inuenced by the physico-
chemical forms in which they are present in waters, in
sediments, and in soils. Specifically, concerns about
trace elements relate to utilization, disposal, and dis-
charge of sewage and wastes. With regard to aquatic
systems, complexation reduces the toxicity of