War. Res. Vol. 29, No. 1, pp.

165-177, 1995
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SEDIMENT PORE WATER COLLECTION METHODS FOR

TRACE METAL ANALYSIS: A REVIEW

STEVEN E. BUFFLAPand HERBERT E. ALLEN*~

Department of Civil Engineering, University of Delaware, Newark, DE 19716, U.S.A.

(First received June 1993; accepted in revised form April 1994)

Abstract--Collection and analysis of pore water has become an important aspect of many environmental
programs. Pore water analyses are used for toxicity identification, sediment quality assessment and
diagenetic studies. This paper reviews the four commonly used methods for collection of pore water and
potential artifacts from their use, particularly in the preparation of samples for trace metal analysis. Two
of the methods, centrifugation and squeezing, are ex situ, requiring the removal of sediment from the
natural environment. The other two, dialysis and suction filtration, are used in situ. Each method has its
advantages and disadvantages, and usage must be determined by the individual researcher. The handling
of most samples should be conducted in an inert atmosphere until pore water samples are acidified because
oxidation has been shown to significantly alter sample speciation. Significant errors have also been found
to result from temperature alteration. Sample contamination by fine particles is important in all methods
as differentiation of particulate and soluble components is based on membrane pore size.

Key words--pore water, trace metals, centrifugation, squeezing, suction filtration, dialysis, sediment
quality criteria, oxidation

INTRODUCTION ation of the contribution of sediments to the pol-

lution of the overlying water column (Aggett and
Bottom sediments in natural systems are formed by
O'Brien, 1985). Knowledge of pore water chemical
sedimentation of particles from the overlying water
concentrations is also important in dredging oper-
column. During this process, water will be trapped
ations, as these chemicals will potentially be released
and entrained in the sediment, forming the interstitial
into the water column and/or mobilized after
or pore water (Batley and Giles, 1979). During the
sediment disposal as sediment is removed from
sedimentation process, chemical species that were
the natural environment (Adams and Darby,
found in the water column and adsorbed to the
1980; Brannon et al., 1980; Brannon and Patrick,
suspended sediment will also be trapped in the
1987).
bottom sediment. As a result of this process, sedi-
More recently, it has been suggested that sediment
ments serve as a valuable sink for pollutants, elimi-
pore water may be used for determination and assess-
nating them from the water column and reducing
ment of Sediment Quality Criteria (SQC) (U.S.
the potential toxicity to aquatic organisms
Environmental Protection Agency, 1989; DiToro
(Ramamoorthy and Rust, 1978; Salomons et aL,
et al., 1991). Current methods of assessing SQC are
1987). Within the sediment system, chemical species
indirect and use normalization techniques. One such
will tend toward equilibrium between the pore water
method involves the use of Acid Volatile Sulfide
and solid phase. However, due to diagenetic processes
(AVS) and Simultaneously Extracted Metals (SEM)
such as precipitation, adsorption, sulfide formation,
(DiToro et aL, 1990; Ankley et al., 1991; Carlson
remobilization, biological degradation, and biologi-
et al., 1991; DiToro et al., 1992; Allen et al., 1993).
cal uptake, the concentrations of chemical species in
It has been shown that if the ratio SEM/AVS is less
the pore water and the overlying water will not
than or equal to one, a sediment is not toxic due to
necessarily be the same (Elderfield et al., 1981; Oakley
the presence of trace metals. However, if SEM/AVS
et aL, 1981; Graybeal and Heath, 1984; Sakata, 1985;
is greater than one, there is potential for a sediment
Salomons et aL, 1987).
to be toxic. There are binding phases in addition to
Pore water has been collected and analyzed for
sulfide, such as organic matter and metal oxides,
studies of diffusion of chemical species into the water
which can also remove trace metals from the pore
column (Sayles, 1979; McCaffrey et al., 1980).
water (Nissenbaum and Swaine, 1976; Elderfield,
Knowledge of pore water concentrations is useful in
1981; Oakley et al., 1981; Luoma and Davis, 1983;
determining sediment contamination and in evalu-
Davis, 1984; van den Berg and Dharmvanij, 1984;
Douglas et al., 1985; Jenne et al., 1985; Salomons
*Author to whom all correspondence should be addressed. et al., 1987; Tessier and Campbell, 1987; Morrison,

165
166 STEVENE. BUFFLAPand HERBERTE. ALLEN
1989; U.S. Environmental Protection Agency, 1989;
F6rstner, 1990; Fu and Allen, 1992; Fu et al., 1992;
Allen, 1993). In fact, Bennett and Cubbage (1992)
found no significant correlation between the cop-
per/AVS ratio and toxicity when analyzing sediments
from Steilacoom Lake, Washington, where copper
was determined to be the major pollutant. Sediment
with a copper/AVS ratio of only 0.6 showed signifi-
cant effects for Hyalella azeteca and Hexagenia lim-
bata. However, sediment with a ratio of 27 did not
exhibit any significant effects for the species tested.
They suggested that for copper, organic matter is a
more important binding phase than AVS. This theory
has also been suggested by others (Nissenbaum and
Swaine, 1976; Davis, 1984; Douglas et al., 1986). It
has also been shown that iron and manganese oxides
can be important binding phases for copper (Swallow
et al., 1980; Lion et al., 1982; Tessier et al., 1985; Fu
et al., 1991). These observations provide evidence
that binding phases other than AVS can play an
important role in removing trace metals from pore
water.
An alternative to normalization techniques is the
direct assessment of sediment quality. It has been
established that the fraction of trace metals that cause
the most significant biological effects is the free metal
ion (Sunda and Guillard, 1976; Sunda et al., 1978;
Allen et al., 1980; U.S. Environmental Protection
Agency, 1989; F6rstner, 1990; DiToro et al., 1992).
This fraction is often referred to as the bioavailable
fraction (U.S. Environmental Protection Agency,
1989). It should be noted that free metals does not
refer to soluble metal because soluble metal includes
complexed, as well as free metals. For example,
metals that are bound by organic matter, such as
humic materials, can be soluble in natural waters, but
because they are in a complexed state, they will not
be bioavailable. Because the fraction of soluble
metals that is free is not constant, the concentration
of soluble metal will not always correlate to a biologi-
cal effect. This effect is substantially more important
in interstitial waters than it is in overlying waters
because interstitial organic matter concentrations are
10--50 times those of overlying waters (Lyons et al.,
1979a; Neubecker and Allen, 1983; Douglas et al.,
1986). Thus, if an interstitial water sample and an
overlying water sample contained the same soluble
concentration of a metal, we would expect there to be
less metal bioavailable in the interstitial water sample
because it is in an environment with greater complex-
ing capacity than the overlying water.
Additional tests have shown a correlation between
the total trace metal concentrations in pore water and
organism mortality (Swartz et al., 1985; DiToro et al.,
1990). If one were to sample the sediment pore water
and analyze for trace metal concentrations (or prefer-
ably free metal concentrations), these numbers could
be compared to the established Water Quality
Criteria (WQC) in order to evaluate potential sedi-
ment toxicity. However, because the established
WQC are based on total recoverable metals, this
approach would provide a conservative measure of
sediment contamination until WQC are developed
that do account for metal speciation (Allen, 1993).
The assessment of pore water metal concentrations
could provide a more direct means of assessing
sediment toxicity than do the present normalization
methods. Thus problems associated with determining
partition coefficients in complex equilibrium parti-
tioning modeling schemes to predict pore water con-
centrations would be eliminated.
In general, there are four means of extracting
sediment pore water. Two of the methods, squeezing
and centrifugation, are ex situ and require the re-
moval of the sediment from the natural system, and
the other two, vacuum filtration and dialysis, are in
situ. In addition to each method having its own
advantages and disadvantages, there are several gen-
eral sources of error that can alter pore water chemi-
cal concentrations. This paper reviews the four
methods of extraction and the potential artifacts that
may result from the usage, focusing on obtaining
pore water for trace metal analysis. Methods of
analysis of the isolated pore water were not discussed.
SOURCES OF ERROR
TO better understand why some methods of pore
water sampling may produce incorrect results, it is
helpful to first look at the various sources of error
that may alter the trace metal concentrations in the
pore water.
Oxidation
One of the primary sources of error is the oxidation
of anoxic pore waters. Sediment-water systems can
be divided into three distinct parts: the oxic layer, the
anoxic layer and the oxic-anoxic interface (Salomons
et al., 1987). The oxidative state of the sediment
system is determined by the primary electron receptor
in each constitutive layer. In the oxic layer the
primary electron receptor is oxygen. Once the oxygen
supplies are exhausted, the oxic-anoxic boundary
layer is created. At this layer, nitrate acts as the
electron receptor. The extent of this reaction is
usually limited due to the generally small amount of
available nitrate. In the anoxic layer sulfate ions are
converted to sulfides. Once the supply of sulfate ions
is exhausted, methanogenesis becomes the primary
redox reaction. In marine environments, this reaction
will generally occur only at great depths in the
sediment due to the large supply of sulfate available
in sea water (28 mM = 2700 mg/l) (Stumm and Mor-
gan, 1981). In freshwater, methanogenesis can be
more significant because there is a much smaller
supply of sulfate in the water (0,12 m M = 11.5 rag/l).
Bray et al. (1973) and Troup et al. (1974) were
among the first researchers to notice the problems
associated with pore water oxidation. In their studies
of phosphate in pore waters, they encountered several
 Collection and analysis of pore water
problems while squeezing sediments in a nitrogen
atmosphere. First, as the volume of pore water
passing through the squeezer increased, the concen-
tration of Fe(II) also increased. They determined that
this trend was due to the oxidation of Fe(II) to Fe(III)
by oxygen trapped in the squeezer. Second, they
noticed significant losses of phosphate in pore water
samples that were intentionally exposed to the lab-
oratory atmosphere. These losses were caused by
direct precipitation of the phosphate with ferric iron
and also by ferric hydroxide scavenging of the phos-
phate. In later studies, Loder et al. (1978) and Lyons
et al. (1979b) analyzed silicate, phosphate and iron
concentrations in pore water. In each study, samples
were handled both in a nitrogen atmosphere and in
the laboratory atmosphere. Loder et al. found that
75% of the Fe(II) in the pore waters was lost during
a 12 rain exposure to air and Lyons et al. found an
81% loss of Fe(II) during a 10 min exposure. Both of
these groups also found significant losses of silicate
and phosphate in the pore waters when the samples
were handled outside of a nitrogen atmosphere.
Stumm and Lee (1961) and Eary and Schramke
(1990) have computed the oxidation kinetics of
ferrous iron solutions and have found a strong depen-
dence on both pH and oxygen concentration. At pH
less than 3.5, the oxidation rate is independent of pH.
At higher pH values, the oxidation rate has a second
order dependent on the hydroxyl concentration.
Calculated half-lives for ferrous iron range from
years at pH less than 3.5, but decrease to minutes at
pH greater than 6.5 (Eary and Schramke, 1990).
The above observations provide significant evi-
dence for the need to prevent oxidation when hand-
ling anoxic sediments and pore waters. If the samples
are allowed to oxidize, the speciation of iron and
other trace metals will be altered. In addition, when
ferrous iron oxidizes, it forms ferric (oxy)hydroxides
which precipitate from the aqueous phase (Stumm
and Morgan, 1981; Belzile and Tessier, 1990). These
solids have the ability to scavenge other trace metals,
removing them from the aqueous phase (Davis and
Leckie, 1978; Swallow et al., 1980; Benjamin and
Leckie, 1982; Benjamin, 1983; Tessier et al., 1985).
Data on this process have been compiled and a model
to predict trace metal sorption on ferric hydroxides
has been developed by Dzombak and Morel (1990).
It is important that anoxic sediments can be
handled in an inert atmosphere, usually nitrogen or
argon, within a glove bag or glove box when extract-
ing pore water. The glove bag or glove box must be
flushed several times with the inert gas being used in
order to remove the air that is originally present.
Glove boxes offer more room for equipment than do
glove bags, but it is often difficult to manipulate
equipment in the glove boxes due to the bulky gloves.
Additionally, they are not as transportable for field
use as glove bags. Also, it is more difficult to flush the
air from glove boxes due to the larger volume. It is
also important that any sampling apparatus, such as
167
centrifuge tubes or squeezers, be flushed with the inert
gas before sediment samples are processed; otherwise,
any residual oxygen will react with the extracted pore
water. However, once the samples are acidified, they
can be exposed to air without chemical losses (Loder
et al., 1978; Batley, 1989).
Sediment sampling
A second source of error can result from improper
sampling of the sediment from the natural environ-
ment for ex situ analyses. If oxic and anoxic sedi-
ments are allowed to mix during sampling, the trace
metal speciation in the sediment and pore water will
be altered due to oxidation. In general, there are three
different methods of sampling sediments: dredging,
grab sampling, and coring. Several authors have
summarized the various samplers that are available
and the advantages and disadvantages of each
(Plumb, 1981; Batley, 1989; Baudo, 1990; ASTM,
1991; Burton, 1991; Mudroch and MacKnight, 1991).
Dredges only sample the surface sediment and pro-
duce the most disturbance. Grab samplers, such as
the Ponar and Ekman, obtain samples at greater
depths and provide larger volumes than dredges.
However, they too can produce mixing sediments.
Corers produce the least disturbance of the sediment.
They come in two types--box and cylindrical. Box
corers provide a larger volume of sample, but are
bulky and difficult to handle. Cylindrical corers
provide less sediment, but are easier to handle, es-
pecially in deep waters. They also provide samples
that may be sealed to prevent oxidation of anoxic
sediments if core liners are used.
M e t a l contamination
An important consideration when sampling sedi-
ments and pore waters for trace metal analysis is to
avoid contact by the samples with metal parts which
may potentially contaminate the samples. This prob-
lem is another reason why dredge and grab samples
are less appropriate for sediment sampling as most
are made of stainless steel or aluminium. PVC liners
should be used in core samplers to prevent contami-
nation. These liners can then be removed from the
sampler and capped to prevent oxidation. The pore
water samplers should also be made from inert
materials if trace metal analyses are to be performed.
For example, squeezers should be made from ma-
terials such as nylon, PVC, or Teflon and centrifuge
tubes should be polycarbonate, polysulfonate, or
Teflon. These particular considerations are discussed
in following sections.
Temperature artifacts
Another source of error can result from changes
in composition due to temperature changes
(Mangelsdorf et al., 1969; Bischoff et aL, 1970; Fan-
ning and Pilson, 1971). Mangelsdorfet al. (1969) were
the first to mention possible changes due to squeezing
168 STEVENE. BUFELAPand HERBERTE. ALLEN

at temperatures higher than the in situ temperature in section squeezers (often referred to as filter presses)
their analysis of potassium enrichments in oceans. are the more widely used (Lusczynski, 1961; Siever,
They suggested that the warming of the samples from 1962; Hartman, 1965; Manheim, 1966; Presley et al.,
the ocean bottom to room temperature, an increase 1967; Reeburgh, 1967; Sasseville et al., 1974). The
of approximately 25C, may shift the ion exchange squeezers designed by Manheim (1966), Sasseville
equilibria of the sediment, thus causing a release of et al. (1974), and Siever (1962) all employ a mechan-
ions from the sediment into the pore water. However, ical means of pressurizing the sediment. In all three,
they did caution that not all composition changes a rod is forced against a piston, which in turn
observed in sediments are due to thermal effects. pressurizes the sediment sample, forcing the pore
Fanning et al. (1971) squeezed sediments at 2C and water through an exit port. Siever's sampler used a
21-23C found a 40-60% increase in silica concen- turn-screw to apply 100-200 psi of pressure;
trations at the higher temperatures. However, phos- Saseville's squeezer also used a turn-screw, however,
phate concentrations were the same at the two no pressures were reported. Manheim's squeezer uti-
different temperatures. Although the data in these lized a standard 10-ton laboratory press to push the
papers demonstrate that there can be changes in the ram which squeezed the sediment at a pressure of
concentrations of some chemical constituents in pore 5000 psi.
water when the water is extracted at temperatures The samplers designed by Harman (1965),
other than in situ there is no direct evidence that Lusczynski (1961), Presley et al. (1967), and
extraction temperature plays a significant role in trace Reeburgh (1967) all extract the pore water by means
metal concentrations in pore water. of gas pressure. A typical squeezer is shown in Fig. 1.
Most employed an inert gas such as nitrogen or argon
Filtration in order to avoid oxidation artifacts. Carbon dioxide
If samples are not filtered during or after extrac- is not recommended, as it can dissolve in the pore
tion, the residual particles in the pore water can cause water and lower the pH of the samples. Hartman,
errors in two ways. First, the particles can cause
interferences in analytical procedures in a number of
ways including clogging tubing or scattering light in
spectroscopic measurements. Second, if particles are
allowed to remain in solution, trace metals could
adsorb to or be released by the particles, thus altering
the trace metal concentrations in the pore water.
Therefore, it is recommended that filtration be a step
in the processing of pore water samples in order to
avoid the potential problems that not filtering may
cause. It is important to note that the accepted
definition for dissolved phases being that material
which will pass through a 0.45/~m pore size filter is
an operational one and not an absolute parameter
(Stumm and Bilinski, 1973; A P H A et al., 1989). This
fact leaves room for potential discrepancy when
comparing data from different laboratories and in
comparison of experimental results to theoretical
calculations.

EX MTU METHODS

E x situ techniques are the oldest and currently the

most widely used methods for obtaining pore waters.
These methods include squeezing and centrifugation.
Because the sediment must be removed from the
natural environment in order to be processed, hand-
ling of the sediment and pore water samples should
be conducted in an inert atmosphere in order to avoid
oxidation artifacts.

Squeezing
There are various apparatus to pressurize a sedi-
ment sample in order to force the pore water through
an exit port. These samplers can be classified into two
types: core section and whole core squeezers. Core
Fig. 1. Core section squeezer: I--bolt: 2----cap;3--gas inlet
compression fitting; 4---rubber diaphragm; 5 ~ - r i n g seal;
6---sample chamber; 7--filter; 8--base; 9--compression
fitting with sample outlet tubing.
 Collection and analysis of pore water
Fig. 2. Whole core squeezer: l--top plunger; 2--sample
outlet chamber; 3--tubing; 4---squeezing stand; 5--sedi-
ment core; 6--O-ring seal; 7--bottom plunger.
Lusczynski, and Reeburgh used pressures up to
200 psi, while Presley reported squeezing pressures up
to 1000 psi. The use of gases for squeezing at press-
ures this high is not recommended because of possible
"channeling effects" that may be created while
squeezing the sediment.
The squeezer designed by Reeburgh (1967) has
been widely cited for its favorable features (Duchart
et al., 1973; Weiler, 1973; Robbins and Callender,
1975; Bricker et al., 1977; Chapman, 1981; Andrews
and Hargrave, 1984; Gibiln and Howarth, 1984). This
inexpensive sampler, constructed of nylon and Del-
rin, is simple to operate and compact, thus making it
an ideal sampler for use on board sampling vessels.
The unique feature of this squeezer is that pressure is
applied to the sediment sample by means of a rubber
diaphragm compressing the sediment instead of
direct gas pressure. This allows the pressure to be
distributed across the surface of the sediment sample
and prevent channeling in the squeezed sample. This
sampler is also ideal for extracting pore water
samples for trace metal analysis because of its non-
metallic construction, although adsorption onto the
rubber diaphragm has not been tested. Other core
section squeezers have been fitted with nonmetallic
linings when trace metal analysis was conducted
(Presley et al., 1967).
Core section squeezers are an inexpensive and
simple means of extracting sediment pore water. They
also offer immediate filtration of the water samples,
thus eliminating a handling step which may introduce
contamination to the samples. The disadvantage of
core section squeezers is that their use requires hand-
ling the sediment which may introduce artifacts re-
sulting from oxidation or temperature differences.
This potential for artifacts can be decreased by the
use of whole-core squeezers (Kalil and Goldhaber,
1973; Bender et al., 1987; Jahnke, 1988) (Fig. 2).
169
When using these samplers, the sediment remains in
the core liner with which it was removed from the
natural environment. All three samplers apply press-
ure to the sediment by the use of plungers. The
samplers designed by Kalil and Goldhaber (1973) and
Bender (1987) employ a specially designed piston on
the top to allow the water to exit. One problem with
these samplers is that they do not allow for the depth
resolution which is often desired. Jahnke's (1988)
sampler is designed with tapped holes at various
depths along the side of the core liner. These holes are
sealed with nylon screws until extraction is begun.
The sediment is pressurized by pistons on both ends
of the sediments. When pore water is desired at a
certain depth, the screw is removed and a specially
designed syringe, fitted with an in-line filter, is in-
serted into the hole and the pore water is extracted.
One unique feature included in the Kalil squeezer
is a cooling jacket. The jacket allows the sediment to
be squeezed at the in situ temperature, thus, avoiding
potential artifacts due to temperature differences.
However, Kalil cites no data illustrating the effective-
ness of the sampler to control sediment temperatures
or eliminate temperature artifacts.
One problem with whole core squeezers for trace
metal analysis is caused by solid-solution interactions
(Bender et al., 1987). Bender states that as pore
waters travel through the sediment in a whole core
squeezer, they come into contact with sediment par-
ticles that have previously been in equilibrium with
waters of different compositions. Therefore, if ex-
change kinetics between the sediment and water are
more rapid than the rate of squeezing, reequilibration
with the sediment will occur and the trace metal
concentrations will be altered. This problem can be
lessened in one of two ways. Either the pressure of
squeezing must be increased, which is sometimes
physically impossible, or the size of the sample must
be small enough to allow for complete extraction
before reaction kinetics override.
Centrifugation
Centrifugation of sediment is another widely used
and simple technique to obtain pore water. Extracted
samples have been used for trace metal analysis in
such studies as toxicity testing (Giesy et al., 1988;
Swartz et al., 1989; Ankly et al., 1990; Hoke et al.,
1990; Swartz et al., 1990; Ankley et al., 1991;
Schubauer-Berigan and Ankley, 1991), mobilization
studies (Sakata, 1985), and speciation studies (Iver-
son et al., 1990). Centrifugation is a fairly rapid
technique--times of 30 min or less are generally
sufficient. The speed and time necessary may vary for
different sediments and should be tested on an indi-
vidual basis. Samples may be processed at the in situ
temperature in a refrigerated centrifuge in order to
avoid potential temperature artifacts.
As with squeezing, centrifugation requires hand-
ling sediment samples to extract the pore water.
These manipulations should be conducted in an inert
170 STEVENE. BUFFLAPand HERBERTE. ALLEN
atmosphere in order to avoid oxidation artifacts.
The tubes or bottles used should be air-tight to
preclude reaction with oxygen once the tubes are
removed from the inert atmosphere and are placed
in the centrifuge.
One problem that is avoided in squeezing but
encountered in centrifugation is that of sample
filtration. When samples are centrifuged, some fine
particulates may still be suspended in the pore water
especially if the sediment is disturbed while decant-
ing the extracted water from the tube. Therefore, an
extra handling step is required, adding another po-
tential source of error.
There are two modified approaches that help to
avoid this problem. The first means is a centrifuge
tube that employs a built-in filter (Edmunds and
Bath, 1972; Saager et al., 1990) (Fig. 3). These
modified centrifuge tubes, often referred to as basal
cups, use a detachable cup on the bottom for collec-
tion of the pore water. A filter is seated on top of the
cup and the sediment placed on top. This method
has found success for extraction from coarse, sandy
sediments and for sandstone aquifer samples.
The second alternative to filtration is displacement
of the pore water in the sediment by an inert solvent
(Batley and Giles, 1979). In this method, a dense,
inert fluorocarbon, FC-78, is placed in the tube on
top of the sediment. During centrifugation, the more
dense solvent replaces the pore water in the spaces
between the particles, forcing the less dense pore
water to the top. This method provides a greater
percentage of pore water removal than conventional
centrifugation and should alleviate the need for
filtration of the water because the solvent provides a
barrier between the sediment and water. Addition-
ally, the investigators found no significant loss of
trace metals into the solvent in extraction studies,
which validates the use of this method for trace
metal analysis.
IN SITU METHODS
The two in situ techniques, suction filtration and
dialysis, eliminate many of the potential sources of
artifacts present in the ex-situ methods. For
example, because sediment samples are not required,
potential contamination from the sampling devices is
decreased. Any artifacts that may arise due to tem-
perature or pressure differences are also eliminated.
The changes of oxidation can be decreased by using
these devices if the extracted samples are handled
carefully and rapidly.
Suction filtration
There are a wide variety of suction filtration
apparatus available for pore water extraction. The
simplest of these devices is a glass volumetric pipette
modified for sampling purposes by closing the deliv-
ery end and blowing two small holes opposite each
7 f'-]
0---' II
Fig. 3. Basal cup centrifuge tube: 1---centrifuge tube; 2--
filter; 3--filter support; 4--sample cup.
other 1 or 2 centimeters from the tip (Makemson,
1972). The holes are covered with a nylon mesh
screen held in place with epoxy cement. The sample
is withdrawn by placing a pipette filler on the open
end and suctioning the pore water through the mesh
covered holes. This device proved to be successful
for the sandy beaches that Makemson was studying;
however, its use is probably limited to these types of
sediments because finer particles would pass through
the mesh that covered the holes and produce turbid
samples. <
There are other devices that offer the simplicity
of Makemson's sampler, but produce cleaner
samples. One employs a fused glass air stone
(Winger and Lasier, 1991), and the others use
porous tetrafluoroethylene (TFE) (Zimmermann
et al., 1978; Howes et al., 1985). Air stones with
metal stems are not appropriate for trace metal
analysis due to possible contamination. This prob-
lem can be avoided by using an inert porous
medium such as TFE. The primary difference be-
tween Howes' sampler and Zimmermann's sampler
is that the porous medium is attached to a glass tube
in Howes' and a section of PVC pipe in Zimmer-
mann's.
The main problem with these in-situ samplers is
that they do not offer the depth resolution in
sampling in which some researchers are interested.
This problem can be solved by using multi-level
samplers. Two such devices employing TFE inserts
to filter the pore water were designed by Mont-
gomery et al. (1981) and Watson and Frickers (1990)
(Fig. 4). When using these samplers, a vacuum is
applied through the porous TFE inserts, withdraw-
ing the pore water sample into an acrylic (or other
solid plastic) sample chamber. Both can be used
with in-line filters in order to assure particle free
samples. Samples can then be withdrawn from the
sampler body and collected directly into sample
bottles in an inert atmosphere in order to avoid
oxidation artifacts.
Two other devices employ spring driven pistons in
order to provide the suction necessary for sample
 Collection and analysis of pore water 171

Fig. 4. Suction filtration sampler: l--sample tubing; 2--compression fittings: 3--porous filtering media;
4--in-situ probe; 5--sample chamber; 6---in-line filter; 7--vacuum valve; 8--inlet valve; 9--anaerobic jar;
10--sample collection tube.

extraction (Barnes, 1973; Sayles et al., 1973; Sayles
et al., 1976). Pore water samples are drawn through
mesh screen and filter paper covered sample ports
into storage tubing within the sampler. Sample collec-
tion is accomplished by inserting a syringe into the
port and withdrawing the sample.
These sampling devices avoid many of the prob-
lems associated with using the ex situ methods. In
addition, some devices may be placed in the sediment
for repeated monitoring at one location. The main
disadvantages of these samplers is their complexity
and expense of construction. In addition, their usage
can be limited by the depth of the body of water due
to the suction pressures that would be required to
draw the pore water to a surface vessel. Finally, it is
important to consider the fact that there may be some
sediment disturbance or compacting as the samplers
are placed into the sediment. The placement of the
samplers may require the removal of a sediment plug
to facilitate easy placement. Therefore, it may be
necessary to allow the sediment to reequilibrate be-
fore pore water samples are extracted.
Dialysis
The second in situ method for collecting sediment
pore water is dialysis. The general principle of these
samples involves allowing a volume of deionized,
distilled water to come to equilibrium with the sedi-
ment pore water in order to determine chemical
concentrations. The dialysis sampler most often used
is known as a "peeper" (Fig. 5). It is based on the
design of Hesslein (1976), and has been modified by

(3------

Fig. 5. Peeper: l--sample chamber; 2--plexiglass body; 3--plexiglass top.

WR 29/1--L
172 STEVENE. BUFFLAPand HERBERTE. ALLEN
Table 1. Advantageand disadvantagesof pore water samplingmethods
Method Advantages
Squeezing Simple, inexpensive,
Immediate filtration
Centrifugation Rapid, simple
Suction filtration Limitedpotential for artifacts,
continuous monitoring
Dialysis Limited potential for artifacts
others (Carignan, 1984; Carignan et al., 1985; Gillard
et aL, 1986; Belzile et al., 1989; Belzile and Tessier,
1990; DiToro et aL, 1990). The body is constructed
of clear acrylic plastic with a bottom piece drilled
with holes to hold the samples and a top piece to hold
down the membrane. Sample chambers in Hesslein's
sampler were spaced one centimeter on center and
were less than 1/2 in. deep. The sample chambers
were filled with distilled water and a dialysis
membrane was placed over the chamber to retain
the distilled water. A second piece of plastic was
placed over the first and the two were held together
with nylon screws. Nylon screws were used to prevent
contamination. The samplers were then placed
into the sediment and the chemical species in the
pore water diffused across the membrane until equi-
librium was achieved. Equilibration times reported
have varied anywhere from 3 to 20 days (Carignan,
1984).
A dialysis sampler that is similar to Hesslein's was
designed by Bottomley and Bayly (1984). The sam-
pler consisted of a perforated Lexan tube which
contained small vials called stackers. Each stacker
(vial) had three side ports of 2 cm diameter which
were covered with a 0.45/~m polysulfone membrane
and could hold a 10-12 ml sample. The stackers were
emptied by inserting a syringe through a rubber
septum attached on one end. The equilibration time
for these samplers was tested in anoxic sediments for
1 to 27 days and it was determined that the samplers
reached equilibrium within l0 days.
Dialysis bags have also been used to sample sedi-
ment pore water (Mayer, 1976). The sampler con-
sisted of a perforated Lucite tube which was
separated into chambers by rubber washers fitted
over an inserted Lucite rod. One dialysis bag per
chamber was wrapped around the Lucite rod and the
rod was inserted into the perforated Lucite tube.
Equilibration times for unconsolidated clay and silt
sediments were found to be 100 h.
Another dialysis technique, which employs a thin
layer of ion exchange resin in a membrane "sand-
wich", has been developed in our laboratory and is
undergoing further evaluation (Desnoyers et al.,
1993). The resin equilibrates with the free metal ions
in the pore water phase in order to determine the
bioavailable fraction of trace metals in the sediment.
A similar technique has also been developed which
uses a thin layer of gel instead of ion exchange resin
(Davidson et al., 1991; Davidson and Zhang,
Disadvantages
Potential for oxidationand
temperature artifacts
Potential for oxidationand
temperature artifacts
Expensive,
depth limitations
Equilibration time,
placement and retrieval
1994). Diffusive equilibration in a thin-film (DET)
has been found to reach equilibrium with the pore
water in less than one hour.
One important problem in the use of dialysis
samplers is the production of oxidation artifacts.
Carignan (1984) conducted a study on the effect of
deoxygenating the water in the sample chambers and
found that when the samplers were not deaerated
initially (8.32 mg/l 02 present), there were noticeable
losses of Fe, Mn, and phosphate when compared to
samplers that had been deaerated. Not only can the
dialyzer water contribute to the oxidation of reduced
species, but the sampler body itself can contribute to
the reaction because all plastics are more or less
permeable to oxygen. Plexiglas samplers produced
less artifacts than did polycarbonate samplers (Carig-
nan, 1984). Dialysis samplers must be deaerated
before insertion into anoxic sediments and they need
to be stored in airtight containers when not in use in
order to minimize possible oxidation artifacts.
Another important consideration when using di-
alysis samplers is the type of membrane material
used. The membrane must be able to exclude sedi-
ment particles, allow the chemical species in the pore
water to diffuse into the sampler, retain the dialysis
water in the sampler, and maintain its integrity while
in the sediment. Hesslein only mentioned the use of
a dialysis membrane in his samplers. Brandl (1991)
recommended the use of cellulose membranes; others
have shown that cellulose membranes biodegrade
while in the sediment, thus causing the physical
breakdown of the membrane and rupturing of the
ports (Martens and Van Klump, 1980; H6pner, 1981;
Carignan, 1984). Several authors have found success
with polysulfone filtration membranes (Gelman HT-
450) (Carignan, 1984; Carignan et al., 1985; Belzile
et al., 1989; Belzile and Tessier, 1990).
The final consideration when using dialysis pore
water samplers is the equilibration time for the
samplers in the sediment. This time will be dependent
upon a number of factors including the porosity of
the sediment, diffusion coefficient of the species
of interest, temperature, and the area/volume ratio of
the sample compartment.
The primary advantage of dialysis pore water
samplers is that they sample the pore water at in situ
conditions. Potential artifacts that can result from
removing the sediment from its natural environment
are avoided by using these samplers as long as they
are deaerated properly. However, the volume of
 Collection and analysis of pore water
sample obtained is limited and the equilibration times
for these samplers can be as long as 20 days. This is
a much longer period of time for obtaining pore
water samplers than for other methods, Finally, the
use of these samplers often requires their placement
and retrieval by SCUBA divers, thus increasing the
costs of a study.
COMPARISONSTUDIES
As can be seen from the preceding discussions,
there are several different means of extracting sedi-
ment pore water and various ways of applying some
of the techniques. Because of the variety of extraction
techniques, it is often difficult to compare data from
different studies. This predicament raises the question
of which method provides pore water samples that
best represent the natural system.
This question has been addressed by a few re-
searchers. Adams et al. (1980) compared sediment
squeezing with centrifugation. All samples were
handled under a nitrogen atmosphere to avoid oxi-
dation artifacts and were filtered with a 0.4#m
Nuclepore membrane filter before storage. Squeezing
produced lower concentration of calcium, manganese
and phosphate but higher zinc concentrations than
those for centrifugation. Iron concentrations were the
same for each. No reasons were stated for the differ-
ences between the two methods. One possible expla-
nation might be the temperature at which the samples
were processed. Centrifugation was conducted at
4C; we assume that the squeezed samples were
processed at room temperature because no tempera-
ture was stated. The differences might be due to
shifting ion exchange equilibria as suggested by
Mangelsdorf et al. (1969) and Bischoff et al. (1970).
Carignan et aL (1985) compared in situ dialysis
with centrifugation for Ca, Mg, Fe, Mn, Cr, Co, Ni,
Cu, Zn, Cd and organic carbon. Within the study,
Carignan also compared different dialysis membranes
and different membranes for filtering the centrifugate.
The dialyzers (peepers) used were similar to those of
Hesslein (1976). The membranes compared were
Nuclepore polycarbonate (0.03 ~m pore size),
Amicon PM-10 (0.002/zm pore size), and Amicon
YM-2 (0.001/zm pore size). The Nuclepore mem-
branes were used in conjunction with Gelman HT-
450 polysulfone membranes (0.45/~m pore size) to
help provide a seal. Two different centrifugation
experiments were run. The first was conducted at
5000 rpm and was followed by filtration with a
0.45/zm filter. This procedure produced results simi-
lar to dialysis for Co, Ni, Cr, Fe, and Mn but gave
higher and more variable results for Cu, Zn, and
organic copper. When the centrifugation speed was
raised to 11,000 rpm followed by filtration with 0.2
or 0.03 lam membranes, similar results were found
for centrifugation and dialysis. Decreasing the
dialysis membrane pore size had little effect until
the 0.001 pm membrane was used. For this mem-
173
brane, slightly lower concentrations were found com-
pared to the other membranes. This observation
indicates either incomplete equilibration or exclusion
of certain metal-organic complexes with this pore
size.
The study of Schults et aL (1992) consisted of two
parts. The first was a comparison of different hard-
ware materials. They compared stainless steel and
Teflon (FEP) centrifuge tubes, glass fiber and Nude-
pore (polycarbonate) filters, dialysis membranes, and
fritted glass tubing with glass fiber filters using sea
water samples dosed with known concentrations of
Cd, Cr, Cu, and Pb. Very little change was seen in the
Cd and Cr concentrations for the different materials.
However, significant losses were seen for Cu for all
the materials except the Teflon tubes. Significant
losses were also seen for Pb in the stainless steel tubes,
glass fiber filters, and the fritted glass tubing, while
significant increases were seen for the polycarbonate
filters and dialysis bags. The losses with the stainless
steel and glass based materials were in agreement
with the findings of Batley (1989).
The second part of the study consisted of a com-
parison of different pore water extraction methods.
Schults et al. (1992) tested centrifugation within
Teflon (FEP) tubes followed by vacuum filtration,
basal cup centrifugation using a Pyrex tube with a
glass fritted disk and a Teflon cup, vacuum filtration
using a fritted glass sampler (Pittinger et al., 1988),
squeezing with a Teflon squeezer (Reeburgh, 1967),
and dialysis with Spectrapor 3 cellulose based dialysis
bags. All sample filtration was done with glass fiber
filters. A test sediment was prepared by adding
solutions of Cd, Cu, Cr, and Pb to a silty-sand
sediment and rolling the sediment for 2 days. Pore
water samples were extracted at this time using the
various methods except dialysis, which required a 6
day equilibration period. Centrifugation produced
the lowest coefficient of variance (8-23%) while
dialysis produced the highest variance (93-123%) for
the replicates. However, it is difficult to say which
method actually produced the most accurate results
because the expected concentrations for the different
metals were not reported.
Ankley et al. (1991) conducted studies comparing
trace metal concentrations in pore water samples
extracted by centrifugation (2500 and 10,000g, with
and without filtration through a glass fiber filter),
squeezing (with a Teflon lined press using a glass-fiber
filter), and dialysis (5 ml cups with 0.45/~m Nucle-
pore membranes) from two different sediment
samples.
At the first site (Saginaw River, MI), only centrifu-
gation and squeezing were compared for Cr, Cu,
Ni, Pb, and Zn. They found that low speed centrifu-
gation produced the highest concentrations of trace
metals, followed by high speed centrifugation, then
squeezing. When the centrifuged samples were filtered
after extraction, they lost 85-98% of the original
trace metal concentrations. Refiltering the squeezed
174 STEVENE. BUFFLAPand HERBERTE, ALLEN
samples that had previously been filtered did not
change the concentrations.
At the second site (Keweenaw Waterway, MI), all
four methods were compared for Cu, Pb, and Zn.
Results similar to the first site were found, with low
speed centrifugation having the highest concen-
trations and dialysis having the lowest concentrations
of trace metals. Again, all samples showed significant
losses (35-63%) of trace metals when filtered.
Ankley suggests that the loss of trace metals during
filtration may be due to removal of particle associated
chemicals, filtration of oxidized metal-ligand com-
plexes or sorption to the filter. These are all reason-
able assumptions. Because no precautions were taken
against oxidation, ferric (oxy)hydroxide precipitates
may have formed, sorbing trace metals and removing
them from the aqueous phase. During filtration, these
precipitates would be removed from the samples.
Sorption by the glass fiber filters is also a possibility.
In his reviews of sampling and storage of water
samples for trace metals analysis, Batley (1977; 1989)
explains that glasses have been shown to function as
weak ion exchangers, with the negatively-charged
silicic acid groups permitting cation exchange. Thus
it is distinctly possible that the glass fibers themselves
removed some of the trace metals that were originally
present.
SUMMARY AND C O N C L U S I O N S
With the increasing concern for developing Sedi-
ment Quality Criteria, much debate has been encoun-
tered concerning the best means of developing and
assessing the criteria. Current proposals for develop-
ing SQC for trace metals suggest equilibrium parti-
tioning models or other normalization techniques to
determine the criteria. However, many problems exist
in determining an overall partition coefficient for
trace metals. Unlike organic molecules, there are
numerous means by which trace metals may be
removed from solution. The predominant binding
site will depend upon the redox conditions in the
sediment. In anoxic sediments, sulfides are the pri-
mary binding phase. However, other sites, such as
humic acids, may also be important for certain
metals. In oxic sediments, humic acids are again
important, along with metal oxides. A better alterna-
tive would be the direct measurement of pore water
concentrations. Research has shown a correlation
between trace metal concentrations in the pore water
phase of sediments and organism mortality. Thus if
one were to sample the pore water from the sediment
and measure the total trace metal concentrations (or
preferably the free metal), these values could be
compared to the existing WQC in order to assess the
potential toxicity of the sediment.
The primary concern with obtaining sediment pore
water is finding an extraction technique that will
produce samples that best represent the natural en-
vironment. To accomplish this goal, the technique
that is used should have the lowest potential for
producing sampling artifacts. The e x situ techniques,
centrifugation and squeezing, require the removal of
sediment samples from the natural environment. Of
the two, squeezing has the lower potential for arti-
facts because all handling steps can be conducted in
an inert atmosphere contained in a glove bag in order
to avoid oxidation artifacts. In addition, pore water
filtration can be conducted in-line, thus eliminating a
handling step that is required in centrifugation, and
lowering the potential for artifacts, l n - s i t u tech-
niques, such as dialysis and vacuum filtration, have
less potential for producing sampling artifacts than
e x situ techniques because pore water samples are
extracted directly from the natural environment. Di-
alysis has limitations because equilibration times can
last several weeks. In addition, the volume of sample
is limited by the size of the sample chambers, not by
the physical features of the sediment. Vacuum
filtration has the best potential for producing artifact
free samples. The primary limitation for this tech-
nique is its usage in waters of great depth because of
the pressures that would be required for extracting
the samples. The advantages and disadvantages of
each technique are summarized in Table 1.
Because there are different techniques available for
extracting sediment pore water, it is often difficult to
compare data from different laboratories. What is
needed to eliminate these discrepancies is to compare
the existing techniques and to develop a sampling
methodology that will produce pore water samples
that best resemble the in-situ conditions and can be
easily utilized by all researchers. Until such time,
individual researchers must determine which method
best suits their needs based on the characteristics of
their particular study,
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