Integrated Environmental Assessment and Management — Volume 3, Number 1—pp.

18–31
18
2007 SETAC

Predicting Metal Toxicity in Sediments: A Critique of

Current Approaches
Stuart L Simpson* and Graeme E Batley
Centre for Environmental Contaminants Research, CSIRO Land and Water, Private Mailbag 7, Bangor, NSW 2234, Australia

(Received 25 October 2005; Accepted 17 February 2006)

Review

ABSTRACT
The ability to predict metal toxicity in sediments based on measurements of simple chemical parameters is not possible
using currently available sediment-quality guidelines (SQGs). Past evaluations of available SQGs for metals indicated little
difference in their predictive abilities; however, the scientific understanding of cause–effect relationships is progressing
rapidly. Today, it is clear that they can be protective of benthic ecosystem health, but single-value SQGs will be ineffective for
predicting the toxicity of metals in sediments. Recent exposure–effects models and the sediment biotic ligand model both
indicate that a better approach would be to have SQG concentrations, or ranges, that are applied to different sediment
types. This review indicates that significant improvements in laboratory and field-based measurements, better recording of
parameters that influence metal toxicity in sediments, as well as quantification of the metal exposure routes and the relative
contribution of dissolved and particulate sources to toxic effects are needed to improve the power of predictive models and
the overall effectiveness of SQGs for metals. Simply exposing benthic organisms to contaminated sediments and reporting
effects concentrations or thresholds based on particulate metal concentrations will provide little information to aid future
SQG development. For all tests, careful measurement and reporting of concentrations of particulate metal-binding phases
(e.g., sulfide, organic carbon, and iron phases), metal partitioning between porewater and sediments, and porewater pH are
considered as minimum data requirements. When using metal-spiked sediments, much better efforts are required to achieve
sediment properties that resemble those of naturally contaminated sediments. Our current understanding of metal toxicity
indicates that considerably greater information requirements will be needed to predict sublethal and chronic effects of
metals, because the toxic, metabolically available concentration of metals within an organism will fluctuate over time. Based
on the review of exposure and effects models, along with improved measurement of metal exposure-related parameters, the
measurement of the short-term uptake rate of metals into organisms is likely to improve future models.

Keywords: Metals Toxicity Exposure pathway Predictive model Sediment-quality guideline

INTRODUCTION burrowing and feeding behavior of benthic organisms varies

The toxicity of metal contaminants in sediments to benthic
organisms is dependent on the bioavailability of metals in
both the water (via exposure to porewater, burrow water, or
overlying water) and sediment phases (via ingestion of
particles) and on the sensitivity of the organism to these
metal exposures (Lee et al. 2000a; Eriksson-Wiklund and
Sundelin 2002; Besser et al. 2003; Riba et al. 2003; Di Toro et
al. 2005; Simpson 2005). Although the bioavailability of
metals in the overlying water may be predicted using models
such as the biotic ligand model (BLM; Paquin et al. 2002;
Niyogi and Wood 2004), the bioavailability of metals in
sediments is more complex. The latter is controlled by the
following: 1) speciation (e.g., metal binding with particulate
sulfide, organic carbon, and iron hydroxide phases); 2)
sediment–water partitioning relationships; 3) organism phys-
iology (e.g., uptake rates from waters and assimilation
efficiencies [AEs] from particulates); and 4) organism feeding
and other behavior (e.g., feeding selectivity and burrow
irrigation; Luoma and Rainbow 2005; Simpson 2005).
To predict the toxic effects of metals in sediments, it is
important to consider the relative importance of the sediment
and water-column compartments as sources of metals to
benthic organisms (Warren et al. 1998; Hare et al. 2003;
Luoma and Rainbow 2005; Simpson 2005). Because the
* To whom correspondence may be addressed: stuart.simpson@csiro.au
greatly, the importance of dissolved and particulate metal
exposure routes also varies. For benthic organisms that
irrigate their burrows with the oxygenated water overlying
the sediment and that feed on particles in this burrow
irrigation water, their metals are more likely to come from the
water column than from sediments (Munger and Hare 1997;
Hare et al. 2001). For many polychaete worms, ingestion of
sediments is the major pathway of metal exposure (Selck et
al. 1998; Wang et al. 1999; Lee et al. 2001; Yan and Wang
2002). Amphipod and bivalve species may deposit-feed and/
or suspension-feed and are exposed to metals associated with
ingested particles as well as with porewater, burrow water,
and overlying water (Luoma et al. 1992; Fan and Wang 2001;
Eriksson-Wiklund and Sundelin 2002; Griscom and Fisher
2002, 2004; King et al. 2005). Consequently, a one-size-fits-
all approach to assessing species sensitivity to metals generally
is not appropriate, and careful consideration of metal
exposure routes is necessary. The relative contribution by
each exposure route to metal toxicity will depend on both the
metal concentration in each compartment (e.g., overlying
water, porewater, and sediment) and the relative importance
of each compartment for the individual organism.
The ability to predict sediment metal toxicity is becoming
increasingly important for the assessment of contaminated
sediments and for the development of sediment-quality
guidelines (SQGs) (Wenning et al. 2005). The most common
approach has been to interpret metal toxicity only in terms of
Predicting Metal Toxicity in Sediments—Integr Environ Assess Manag 3, 2007 19

dissolved metals, namely those present in the porewater, with

porewater–sediment partitioning models being used to predict
sediment effects concentrations for various metals that can be
related to water-quality guidelines (Batley et al. 2005). The
equilibrium partitioning (EqP) model based on acid-volatile
sulfide (AVS)/simultaneously extracted metals (SEM) is
widely regarded as being accurate for predicting the lack of
toxicity of the metals cadmium (Cd), copper (Cu), nickel
(Ni), lead (Pb), and zinc (Zn) in laboratory-contaminated,
metal-spiked sediments and in field-contaminated sediments,
and it now forms the basis for EqP sediment benchmarks for
metals proposed by the US Environmental Protection Agency
(USEPA 2005). Di Toro et al. (2005) recently extended the
AVS/SEM-based EqP approach by coupling it to a BLM with
more explicit consideration of particulate organic carbon
(POC) as a metal-binding phase. This sediment BLM (sBLM)
was demonstrated to have considerable potential for predict- Figure 1. Generalized concentration–response relationship for contaminated
ing metal toxicity associated with metal-spiked sediments. sediments. (Adapted with permission from Batley et al. 2005. Copyright 2005
Society of Environmental Toxicology and Chemistry.)
The EqP approach can be contrasted with multiphase
exposure and effects models, which explicitly consider toxic
effects from both porewater and sediment-ingestion exposure
tion rates and to understand how these parameters influence
routes (Simpson 2005). The exposure–effects model (EEM)
the MAC and the various chronic effects being assessed. No
approach described by Simpson (2005) is derived from a
current models appear to address these issues adequately.
bioenergetic-based kinetic model that describes the rate of
The purpose of the present review is to critique current
assimilation of metals by benthic organisms from the
approaches for predicting sediment metal toxicity. Limita-
dissolved and particulate phases. Toxicity occurs when the
tions of both the data sets used for model development and
metal exposure exceeds a threshold value. Like the sBLM, the
the predictive ability of the approaches are discussed. A good
EEM uses an EqP approach to predict the exposure to
predictive model should predict the influence of sediment
dissolved metals; however, the EEM also considers metal
properties and organism physiology on toxic effects and,
assimilation from ingested particles.
hence, how these factors will influence derived SQGs.
The development of both the sBLM and EEM relies
Whereas many modeling approaches appear to be suitable
predominantly on sediment toxicity data compiled from
for progressing this science, the major current limitation is the
studies using metal-spiked sediments (Di Toro et al. 2005;
Simpson 2005). Today, it is well recognized that inadequate availability of good data sets. The requirements for generating
sediment-spiking procedures will accentuate the partitioning data sets that will be applicable for evaluating a range of
of metals to the dissolved phase and shift the pathway for modeling approaches are outlined.
metal exposure from particulate to dissolved metals (Lee et
al. 2000b, 2004; Simpson et al. 2004; Simpson 2005). In CONCENTRATION–RESPONSE MODELS FOR
naturally contaminated sediments, porewater metal concen- PREDICTING SEDIMENT METAL TOXICITY
trations typically are in the sub- or low-lg/L range (especially Ideally, SQGs should unequivocally distinguish between
in marine sediments), and exposure to particle-bound metals sediments that cause biological effects and those that do not.
may be the major metal-exposure pathway (Luoma and However, in reality, the occurrence of biological effects does
Rainbow 2005; Simpson 2005). For metal-spiked sediments not show such a clearly delineated relationship (Batley et al.
that have porewater and/or overlying water metal concen- 2005). A generalized concentration–response model (Figure
trations that greatly exceed those of metal-contaminated 1) has 3 distinct zones, comprising concentrations below the
sediment environments (e.g., mg/L vs lg/L concentrations), threshold for effects, above the probable effects limit, and in a
toxicity thresholds determined in laboratory tests of these transition zone (TZ) between the two (Batley et al. 2005).
sediments will not be widely applicable for developing SQGs. Currently, greater confidence exists regarding our ability to
Rainbow (2002) proposed that toxicity will occur when the define the probable effects limit and threshold for effects
rate of metal uptake into the body of an organism exceeds the zones; however, the TZ is poorly defined and may span more
combined rate of excretion and detoxification of metabol- than an order of magnitude of metal concentrations. This level
ically available metal. Luoma and Rainbow (2005) showed of uncertainty needs to be reduced, because the TZ also
that the dynamic multipathway bioaccumulation model encompasses the concentration range of many contaminated
(DYM-BAM) could provide a unified explanation of chronic sediments that are of concern to regulators.
metal bioaccumulation by a wide range of benthic organisms Effects data from toxicity tests are defined as statistically
in a range of sediment environments. During chronic significant relative to suitable control responses; consequently,
exposures, the metabolically available concentration (MAC) the output is indicative of either effects or no effects. Factors
of a metal will fluctuate over time (not reaching a steady that cause the overlap between effects and no-effects data are
state) as uptake rates (exposure sources) and efflux rates numerous and include unaccounted for contributions from
(excretion and detoxification) vary over time. Consequently, uncharacterized chemicals or stressors, differences in bio-
considerably greater information will be needed to predict availability, differing responses among organisms, and errors in
sublethal and chronic effects of metals because of the need to measurement of chemical and biological response parameters.
predict, for all exposure sources, the uptake and detoxifica- Procedures exist for normalizing some of these factors (e.g.,
20
AVS and organic carbon), but no normalization procedures
have yet been successful for complete discrimination.
Outlined in the following sections are modeling approaches
currently being pursued for interpreting cause–effect data for
metals in sediments.
AVS/SEM, SEM-AVS/fraction of organic carbon,
and sBLM approaches
The AVS/SEM EqP theory predicts that when a molar
excess of AVS over SEM (Rsilver [Ag], Cd, Cu, Ni, Pb, Zn)
exists, then these metals should not cause direct toxicity to
benthic organisms (Di Toro et al. 1990, 1992; Ankley et al.
1996; Berry et al. 1996; USEPA 2000, 2005). Criticism of the
AVS/SEM approach has been widespread regarding measure-
ment-associated artifacts (Cooper and Morse 1998; Simpson
et al. 1998; O’Day et al. 2000; Simpson, Apte, et al. 2000).
For example, in the 1 M HCl extraction used, CuS is almost
insoluble, NiS is only partially soluble, and PbS solubility is
kinetically slow (Cooper and Morse 1998; Simpson et al.
1998; Simpson, Apte, et al. 2000). The presence of
particulate iron(III) phases (e.g., FeOOH and Fe(OH)3) that
dissolve during the AVS/SEM extraction procedure results in
the oxidative release of Cu from CuS, whereas the associated
sulfide is oxidized and not measured in the AVS fraction
(Simpson et al. 1998). Nevertheless, because these metals will
be bound predominantly as sulfide phases when AVS/SEM .
1, the theory is sound.
It was recognized that rather than a ratio, the difference
between SEM and AVS, which is indicative of the maximum
expected porewater metal concentrations, more accurately
reflects the magnitude of metal bioavailability (Hare et al.
1994). The inability of this difference ([SEM
AVS]) to
predict toxicity was attributed to metal binding by other
sediment components (e.g., organic carbon; Chapman et al.
1998; Correia and Costa 2000; Besser et al. 2003). To account
for binding by POC, the difference between SEM and AVS
can be normalized to the fraction of organic carbon (foc) in the
sediment when no toxicity is expected when [SEM
AVS]/
foc , 1 (USEPA 2000).
The most recent extension of this procedure was the
sBLM (Di Toro et al. 2005), in which a BLM was coupled
with a porewater–sediment partitioning model (based on
WHAM V) (Tipping and Hurley 1992). It was used to
predict the sediment concentration that is in equilibrium
with the biotic ligand effects concentration (Di Toro et al.
2005). The sBLM model assumes that the residual metals of
the SEM fraction that are in excess of the AVS metal-binding
capacity are predominantly bound to the POC phases and
that other metal-binding phases in the sediments (e.g., iron
hydroxide phases) can be ignored. The initial application of
the sBLM to existing data sets indicated that the effects of
water hardness, salinity, dissolved organic carbon (DOC),
and competing ligands other than Hþ (pH) should have very
little effect on the computed median effects concentration
on a sediment organic carbon (OC)–normalized basis
(SEMoc ¼ [SEM
AVS]/foc, lmol/g OC). Only the
porewater pH is important. Because the amount of metal
bound to DOC and other ligands in the porewater is small
relative to the amount of metal bound to POC, the DOC
and other porewater ligands are ignored in the sBLM model.
The reason for the minor effect of competing cations (e.g.,
Ca2þ) other than Hþ is because of saturation of the POC-
cation binding sites (Di Toro et al. 2005). The result of this
Integr Environ Assess Manag 3, 2007—SL Simpson and GE Batley
is that detailed computation of the porewater chemistry
could be bypassed.
The sBLM model assumes that the exposures from dietary
sources (food and sediment ingestion pathways) do not
contribute to toxicity (Di Toro et al. 2005). This is the most
contentious area with regard to metal toxicity in sediments
(Munger and Hare 1997; Eriksson-Wiklund and Sundelin
2002; Lee et al. 2004; Meyer et al. 2005; Simpson 2005;
Simpson and King 2005) and will be discussed further later. A
discussion of iron hydroxides as metal-binding phases and
implications for the sBLM by ignoring this phase also is given
later.
The initial development and application of the sBLM relied
almost entirely on data from metal-spiked sediment studies,
for which porewater pH generally was not measured. On a log-
concentration basis, the fit between measured acute and
chronic effects and the SEMoc computed for the pH 6 to 9
range (estimated) appears to be encouraging (Di Toro et al.
2005). However, few data generally were available in the TZ
(Figure 1), because the metal-spiked sediments generally had
either an excess of AVS and negligible porewater metal
concentrations relative to the organism’s water-only effects
concentration or very high (mg/L) porewater metal concen-
trations as a consequence of [SEM
AVS] . 0 and inadequate
metal-spiking procedures resulting in low sediment–pore-
water pH, possibly as low as pH 5 (Carlson et al. 1991; Casas
and Crecelius 1994; Pesch et al. 1995; Berry et al. 1996;
DeWitt et al. 1996, 1999; Sibley et al. 1996; Han et al. 2005).
Bioaccumulation and critical body residues
For nonessential and nonregulated metals, the expression of
toxicity on a body concentration basis often has been a better
indicator of biological effects than the use of total sediment
concentrations (Borgmann 2000, 2003; Borgmann, Norwood,
et al. 2001). The critical body residue (CBR)/lethal body
concentration (LBC) approach assumes that toxicity occurs
when a threshold body concentration (accumulation) is
exceeded (regardless of the exposure pathway). For Cd, Ni,
and Pb, relationships between sediment toxicity and CBRs of
these metals were useful for predicting toxicity to the
freshwater amphipod Hyalella azteca (Borgmann 2003). With
H. azteca caged above the sediments and porewater, and with
overlying water Cd, Ni, and Pb concentrations comparable to
water-only effects concentrations, the results indicated that
the toxicity was caused by dissolved metals, not by metals in
the solid phase (Borgmann, Neron, et al. 2001). Copper and
Zn appeared to be regulated by H. azteca, and toxicity could
not be related to body concentrations (Borgmann and
Norwood 1997; Borgmann, Norwood, et al. 2001; Borgmann
2003). There remain many difficulties associated with relating
body concentration to the observed toxicity because of the
dynamics of metal accumulation and associated removal
processes (Rainbow 2002; Luoma and Rainbow 2005;
Simpson and King 2005). Rainbow (2002) reviewed metal
accumulation strategies of aquatic invertebrates and con-
cluded that body concentrations would be of limited value in
explaining metal toxicity. The deficiencies of the CBR/LBC
approach arise because 2 metal pools exist within organisms,
1 that is metabolically active and 1 that is metabolically
inactive. The internal sequestration of metals within organ-
isms may rapidly change the bioavailability of ‘‘accumulated’’
metals. Processes that detoxify the metabolically active metal,
such as metal–metallothionein binding or metal granule
Predicting Metal Toxicity in Sediments—Integr Environ Assess Manag 3, 2007
Figure 2. Body concentrations of copper in the amphipod Melita plumulosa and bivalve Tellina deltoidalis following short-term water and sediment exposures.
Symbols represent the copper body concentrations measured at the end of the toxicity tests: 1 and 3 are results for individual organisms (in replicate tests),
and  is the mean of the replicate results for each test. Sediment tests were 10 d for both species. Water-only tests were 10 d for M. plumulosa and 4 d for T.
deltoidalis. Animals were depurated in clean seawater for 24 h before analyses. (Adapted with permission from Environ Sci Technol 2005, 39:837–843.
Copyright 2005 American Chemical Society.)
formation (Ahearn et al. 2004; Vijver et al. 2004; Amiard et
al. 2006), greatly complicate the use of body concentration
data for predicting effects.
Body concentrations of Cu in the amphipod Melita
plumulosa and the bivalve Tellina deltoidalis following 10-d
water and sediment exposures are shown in Figure 2
(Simpson and King 2005). Although the mean body concen-
trations (10 individuals, 3–4 replicates) provided good
relationships with the Cu exposure concentration and could
be used to define LBCs, the variability among individuals was
high. Past studies of metal accumulation using different
benthic species and other metals have observed a similar high
degree of variability between individuals in laboratory-based
studies (Borgmann and Norwood 1999; Borgmann, Neron,
and Norwood. 2001; Borgmann 2003; Kahle and Zauke 2003)
and for field-collected organisms (Tessier et al. 1984, 1993;
Warren et al. 1998; Hare et al. 2001; Luoma and Rainbow
2005). For M. plumulosa and T. deltoidalis, 10-d whole-
sediment LC50 values for Cu were 1,300 and 1,020 lg/g,
respectively, indicating median LBC values of approximately
120 and 300 lg/g, respectively (Figure 2). Consequently, the
respective median LBC values were observed in individuals
present in sediments having a wide range of whole-sediment
Cu concentrations, making the use of LBCs for SQG purposes
inappropriate. Furthermore, at high metal concentrations,
increased mortality results in fewer organisms in sediments
and decreases the precision of body concentration data. This
variability and increased uncertainty associated with body
concentration data cause difficulties in using these data for
defining the TZ region of Figure 1.
As for the AVS/SEM and sBLM model data sets (Di Toro et
al. 2005), most of the data sets from which significant CBR–
effects relationships have been derived are from metal-spiked
sediments in which porewater or overlying water metal
concentrations are very high and provide the major contribu-
21
tion to toxic effects (Borgmann and Norwood 1997, 1999;
Borgmann, Neron, et al. 2001).
Multipathway EEMs
With increasing evidence that exposure and effects can vary
with dietary pathways, efforts are being made to develop and
test multiphase EEMs (Luoma and Rainbow 2005; Simpson
2005). Simpson and King (2005) demonstrated that median
lethal concentration (LC50) data for short-term (4- to 10-d),
water-only and whole-sediment exposures could be combined
with bioenergetic-based kinetic models of exposure pathways
(6- to 12-h metal uptake rate data) to explain the cause of Cu
toxicity in whole-sediment toxicity tests using the amphipod
M. plumulosa and the bivalve T. deltoidalis. In the lethal
exposure concentration (LEC) approach, toxicity occurs
when the organism’s internal exposure to bioavailable copper
(net uptake) exceeds a threshold value (e.g., LEC50, internal
exposure concentration that causes 50% lethality). For these
organisms, the LEC50 of copper was effectively the same for
both water-only and whole-sediment toxicity tests (Figure 3).
For metals that are not regulated by organisms, the LEC is
equivalent to the LBC (i.e., all the internal exposure is
accumulated). The LEC approach of Simpson and King
(2005) was used to develop an exposure-effects model
(EEM) for calculating metal effects concentrations for benthic
organisms in sediments with varying metal-binding properties
(Simpson 2005). In the EEM, an organism’s internal exposure
to metals was calculated as the sum of the internal exposure
from all dissolved and particulate exposure routes. The
dissolved-phase exposure was calculated using an EqP-Kd
approach, and the particulate (ingestion)-phase exposure was
calculated using a relationship between the AE and the
ingestion rate of the particulate material (Simpson 2005).
Simpson (2005) developed EEMs for 9 benthic organisms
and used these to predict the effects of sediment–water
22
Figure 3. Calculated copper exposures of Melita plumulosa and Tellina deltoidalis during 10-d water-only and whole-sediment toxicity tests. The exposure was
calculated as the organism’s internal exposure to copper (net assimilation, net uptake) in lg/g tissue dry weight. Diagonal lines represent the calculated
exposure for water-only (dashed) and whole-sediment (solid) toxicity tests. LEC50 ¼ internal exposure concentration that causes 50% lethality. The 10-d effects
concentrations for sediments had Kd (Cu) ¼ 5 3 104 L/kg, and dissolved copper concentrations were below the lowest observable effects concentration (LOEC)
of the 10-d water-only exposures. (Adapted with permission from Environ Sci Technol 2005, 39:837–843. Copyright 2005 American Chemical Society.)
partitioning (Kd) and Cu assimilation from ingested solids
(AE) on toxic effects and to determine how these factors will
influence derived SQG concentrations. For sediments with
high Kd values, the contribution of the dissolved metal
exposure pathway to the observed toxicity becomes negli-
gible, and calculated LC50 values are mostly influenced by
the sediment exposure route. For sediments with low Kd
values, the uptake rates and LC50 values are influenced most
by a water exposure route and were similar to those
determined for water-only exposures. The modeling indicated
that effects concentrations will be dependent on metal
exposure from both water and particulate-ingestion exposure
routes and that improved mechanistic models of contaminant
exposure, as influenced by both organism physiology and
sediment properties, are needed to predict toxic effects in
sediments.
The major difficulties associated with the EEM approach
are those of model calibration and prediction of effects on
organisms in the field. Varying filtration and feeding rates
because of water conditions or food availability will affect the
rate of exposure from water and food sources (Tran et al.
2002; King et al. 2005). Although suitable methods exist for
estimating Kd, methods for estimating AE and the organism’s
ingestion rate require development (Simpson 2005). It also is
to be expected that for some organisms, metals assimilated
through dissolved and particulate exposure pathways will
cause toxic effects of different magnitudes, which need to be
considered in future models.
Biodynamic models and predicting chronic effects
Biodynamic-based models (also known as bioenergetic- and
toxicokinetic-based models) show great promise for inter-
preting metal accumulation by organisms with multiple
exposure pathways (Thomann 1981; Wang and Fisher
1999a; Vink 2002; Kahle and Zauke 2003; Luoma and
Rainbow 2005). Luoma and Rainbow (2005) showed that the
DYM-BAM could provide a unified explanation of metal
bioaccumulation by a wide range of benthic organisms in a
range of sediment environments. The DYM-BAM uses metal
concentration data for dissolved and food (including sedi-
ments) exposure sources and a biodynamic model for key
physiological parameters that describe the metal influx and
efflux rates for each organism from each metal and exposure
source to predict steady-state metal concentrations in benthic
organisms. Whereas model predictions of metal bioaccumu-
lation were in close agreement with those in nature, extension
Integr Environ Assess Manag 3, 2007—SL Simpson and GE Batley
of the DYM-BAM for predicting toxic effects has the same
challenges as the EEM described by Simpson (2005), such as
determining metal uptake and efflux rates from each
exposure source. As discussed, for metals that are regulated
by organisms (e.g., Cu and Zn), the rate of metal uptake
(internal exposure) appears to be more important than the
net accumulation in determining effects thresholds (Simpson
and King 2005).
Rainbow (2002) proposed that toxicity will occur when the
rate of metal uptake into the body exceeds the combined rates
of excretion and detoxification of metabolically available
metal. For the soil isopod Porcellio scaber, van Straalen et al.
(2005) found that the rate of Zn accumulation was a superior
predictor of toxicity compared to the Zn body concentration.
Zinc toxicity to the isopod was attributed to dietary Zn
exposure, with mortality determined by the total Zn in the
hepatopancreas, and growth reduction by the rate of Zn
accumulation in the body. The authors reviewed applicable
toxicokinetic models, analyzing uptake rate data, and pro-
posed the initial slope of the accumulation rate as a useful
indicator of bioavailability, but they acknowledged that the
dynamics of metal bioavailability greatly complicated pre-
dictions.
To use metal uptake rate data to predict toxic effects, the
dynamics of the external metal exposure (e.g., depletion or
fluctuation of the dissolved and particulate exposure sources),
the dynamics of the concentration of metabolically available
metal (internalized within the organism), and the site and
mode of toxicity within the organism (e.g., specific cellular
function effects) need to be understood. The rate of metal
detoxification of the accumulated metal within the organisms
(e.g., metal–metallothionein binding and metal granule
formation) cannot yet be quantified. Without knowledge of
metal detoxification rates, it is not possible to determine or
model the effects of the true MACs of metals within an
organism. It also is likely that metal detoxification rates will
vary for metals assimilated via different exposure routes (e.g.,
dissolved vs particulate).
In the EEM approach, the total metal assimilated during
acute exposures (the short-term internal exposure) was
considered as metabolically available, regardless of whether
it was subsequently rendered nonmetabolically available
through excretion and detoxification processes. During
chronic exposures (as might be expected for steady-state
metal accumulation), the MAC of metals will fluctuate as
organisms move within their environment and, hence, as the
Predicting Metal Toxicity in Sediments—Integr Environ Assess Manag 3, 2007
influx rates vary over time. A chronic effects threshold will
depend on the specific chronic effects being assessed; for
example, the chronic effects threshold for growth rate effects
may be greater than the chronic effects threshold for
reproductive effects. A chronic exposure and effects model
should determine if the chronic effects threshold is exceeded
during any stage of the chronic exposure. Because the
organism’s exposure history seldom will be known for chronic
exposures, some estimates will be needed. Extensive data sets
currently are not available for better development of kinetic-
based exposure and effects models.
Based on the above discussion, the extension of the DYM-
BAM and EEM to the prediction of chronic effects appears to
be very challenging. Because of the dynamics of the MAC of
metals, the flux of metals into organisms (uptake rate data
from short-term exposures) rather than total concentrations
in organisms currently appears to be the best approach for
quantifying the toxic effects of metals in benthic organisms
(Rainbow 2002; Simpson 2005; van Straalen et al. 2005).
In contrast to the data used for the AVS/SEM and CBR
models (Borgmann 2003; Di Toro et al. 2005), the data sets
used for developing the DYN-BAM were based on naturally
contaminated sediments, and the EEM used metal-spiked
sediments with low (lg/L range) dissolved (porewater and
overlying water) metal concentrations. Consequently, for the
DYN-BAM and EEM, the effects of the porewater metal
exposure were not exaggerated to the same extent as the data
used for the AVS/SEM, sBLM, and CBR models, and the
important contribution of ingested sediment as an exposure
pathway is clear.
Empirical models
Most current SQGs are based on empirical models derived
from matching chemistry and toxicity data. They typically
define concentrations associated with low and high proba-
bilities of biological effects (Long, Field, et al. 1998; Long,
MacDonald, et al. 1998; Field et al. 1999, 2002; Long et al.
2000; MacDonald et al. 2000; Smith et al. 2003). A full
discussion of these approaches is provided by Batley et al.
(2005). A major limitation of empirical models is that the
data are confounded by the co-occurrence of contaminants for
which the observed toxicity typically is ascribed equally to all
contaminants. In natural settings, metal contamination often
co-occurs with other contaminants, such as hydrocarbons
(Long et al. 2000; Field et al. 2002; Smith et al. 2003;
Spadaro et al. 2006). The use of logistic regression models for
predicting toxicity is an improvement on earlier empirical
models (Field et al. 1999, 2002; Smith et al. 2003). In the
logistic regression models approach, rather than specifying
threshold values below which sediment toxicity is unlikely to
occur, concentration–response relationships are used to
estimate the extent to which the probability of toxicity
increases as the contaminant concentrations increase. In
assessment terms, co-occurrence of contaminants is not an
issue if the same contaminants always co-occur; however, it
will mean that at least some of the derived guidelines will be
conservative. In principle, this might be good, but the
consequences for management in overestimating hazard can
be costly.
Several studies have evaluated the effectiveness of SQGs
for predicting effects (Long, Field, et al. 1998; Long,
MacDonald, et al. 1998; O’Conner et al. 1998; MacDonald
et al. 2000; Shine et al. 2003). Shine et al. (2003) used
23
receiver operating characteristic curves, which statistically
assess the discriminatory power of diagnostic tests, to evaluate
the effectiveness of a range of SQGs for metals. The receiver
operating characteristic curves were used to evaluate the
extent to which the SQG threshold could classify a toxic
sample as toxic and a nontoxic sample as nontoxic. With
respect to specificity and sensitivity, the SQG approaches did
not differ in overall effectiveness. This analysis indicated that
significant improvements in SQG approaches (predictive
models) would be needed to enhance overall SQG effective-
ness.
EFFECTS DATA FOR METAL-CONTAMINATED
SEDIMENTS
Because, as discussed above, the interacting effects of
multiple co-occurring contaminants complicate the interpre-
tation of the observed organism response for each contami-
nant, the preferred approach for developing cause–effect
based SQGs is determining species sensitivity to an individual
metal or specific groups of metals (in isolation from nonmetal
contaminants; Borgmann 2003; Di Toro et al. 2005; Simpson
2005). Consequently, artificially metal-contaminated sedi-
ments, created by spiking single or multiple metal salts into
sediments, form the majority of sediment metal toxicity data
sets used for developing predictive models (Borgmann 2003;
Di Toro et al. 2005; Simpson 2005).
The introduction of metals into sediments initiates a
plethora of transformations to existing sediment chemistry,
and equilibration times are slow and dependent on a large
variety of different sediment properties (Simpson, Rosner, et
al. 2000; Simpson et al. 2004). For determining species
sensitivity to metals, possibly the most important factor in
determining the valid use of data is the partitioning of metals
between the porewaters and the sediment particles (Kd ¼
[sediment metal]/[porewater metal]). Added metals will
displace iron(II) and other cations into the porewaters, and
both the residual added metal and the displaced metals
hydrolyze, resulting in decreased pH and increased redox
potential (Simpson, Rosner, et al. 2000; Simpson et al. 2004).
The greater the concentration of added metal, the greater
these effects will be, and it is not uncommon to measure
iron(II) concentrations of more than 100 mg/L in the
porewaters of metal-spiked sediments (Simpson et al. 2004;
Han et al. 2005), whereas in natural sediments, iron(II)
concentrations often are in the range of 1 to 20 mg/L (Krom
et al. 2002; Simpson et al. 2004).
Spiking of sediments in an inert atmosphere (e.g., under
nitrogen) can minimize oxidation of iron(II) displaced from
FeS (AVS) and other phases, but the displaced iron(II) may be
oxidized during mixing with other sediment phases (e.g.,
MnO2) (Simpson and Batley 2003). For sulfidic sediments,
added metals that bind to sulfide (AVS) will not be hydro-
lyzed. However, once the sulfide phase is exhausted (i.e.,
SEM/AVS . 1), considerable hydrolysis of added metals
occurs, and the pH decreases (Simpson, Rosner, et al. 2000).
The relatively large pH-buffering capacity of seawater or
highly alkaline freshwaters is insignificant compared to the
buffering capacity of the sediment solid phase. The extent of
pH decrease thus will depend on the buffering capacity of the
sediment and the properties of the metal that is added (e.g.,
Cu will cause greater effects than Zn; Simpson et al. 2004).
For large metal additions, the pH may drop below 5 (Simpson
et al. 2004).
24
The final concentrations of metals in porewaters will
depend on a large number of factors, with the most important
being the types and concentrations present in the sediments of
metal-binding phases, such as particulate sulfide (AVS),
organic carbon, and iron, and on the porewater pH (Besser
et al. 2003; Lee et al. 2004; Simpson et al. 2004). Particle size
will affect the accessibility of the different metal-binding
phases, and high DOC concentrations may lead to an increase
in porewater concentrations (although not necessarily in
biologically available forms; Besser et al. 2003). It is well
accepted that with an excess of AVS over SEM, metal
concentrations in porewaters will remain low (Di Toro et al.
1990, 1992; Casas and Crecelius 1994; Ankley et al. 1996;
Berry et al. 1996; Lee et al. 2000b; Simpson, Rosner, and Ellis
2000; USEPA 2005). When [SEM
AVS] . 0, sediment
phases other than AVS will become important in metal
binding (Oakley et al. 1981; Lion et al. 1982; Millward and
Moore 1982; Luoma and Davis 1983; Tessier and Campbell
1987; Tessier 1992; Stumm and Morgan 1996; Tessier et al.
1996; Rivera-Duarte and Flegal 1997; Markwiese and Colberg
2000; Trivedi and Axe 2000). Metal binding by POC and iron
hydroxide phases is very pH-dependent, with the pH
dependence of metal-adsorption isotherms being greatest in
the pH 5 to 7 range (Lion et al. 1982; Millward and Moore
1982; Stumm and Morgan 1996), and Kd values typically
decreasing substantially as pH decreases (Tessier 1992;
Mahony et al. 1996; Stumm and Morgan 1996; Tessier et
al. 1996; Trivedi and Axe 2000). Consequently, in metal-
spiked sediments for which no precautions are taken to
neutralize the pH effects associated with the hydrolysis of
added metals by the addition of base, the metal-binding
capacity of POC and iron phases often is easily exceeded. As
discussed above, in natural metal-contaminated sediments,
porewater metal concentrations generally are in the sub- to
low-lg/L range (Tessier 1992), but poor metal-spiking
procedures frequently result in high-mg/L metal concentra-
tions once SEM/AVS . 1 (Kemp and Swartz 1988; Carlson et
al. 1991; Casas and Crecelius 1994; Pesch et al. 1995; Berry et
al. 1996; DeWitt et al. 1996; Bat et al. 1998; Borgmann and
Norwood 1999; Simpson, Rosner, and Ellis 2000; Höss et al.
2001; Kuhn et al. 2002; Han et al. 2005).
Equilibration rates of metal-spiked sediments vary consid-
erably and are dependent on sediment and metal properties
(Lee et al. 2004; Simpson et al. 2004). Results of both short-
term laboratory experiments and long-term field experiments
indicate that following metal spiking, porewater metal
concentrations decline slowly and may take many months to
reach equilibrium with the sediments (Hare et al. 1994;
Warren et al. 1998; Hare et al. 2001; Lee et al. 2004; Simpson
et al. 2004). Schlekat and Luoma (2000) used the bivalve
Macoma baltica to illustrate how short equilibration times for
metal-spiked sediments may erroneously overemphasize the
porewater exposure route. Porewater metals equilibrate faster
in sediments with high concentrations of metal-binding sites
(e.g., particulate sulfide, organic matter, and iron hydroxide
phases) and large surface areas (e.g., fine, silty sediments) than
in sandy sediments with low binding capacities. Equilibration
rates are faster at higher pH and slower at cooler temperatures
(Simpson et al. 2004). The equilibration rate for porewater
metals is faster than that observed for weak acid-extractable
metals (i.e., those metals weakly bound to the sediments)
(Simpson et al. 2004). Very long equilibration times may be
required to reduce the bioavailability of particulate metals
Integr Environ Assess Manag 3, 2007—SL Simpson and GE Batley
(that may be ingested by organisms) because of the slow re-
equilibration rates for adsorbed metals or metal precipitates.
However, regardless of equilibration time, if the pH decreases
significantly because of metal-spiking procedures, porewater
metals concentrations will remain unrealistically high in
metal-spiked sediments.
Using concentration–response models (Figure 1) for the
prediction of toxicity, sediments with [SEM
AVS] , 0 have
metal concentrations less than the threshold for effects. For
metal-spiked sediments with [SEM
AVS] . 0, the vast
majority of the available data are well into the probable
effects limit zone because of the high porewater metal
concentrations (Figure 4). This is quite evident in the sBLM
model, in which the onset of toxicity occurs at SEMoc ’ 100
lmol/g OC, regardless of the metal (Di Toro et al. 2005). In
other words, the porewater metal toxicity threshold is
exceeded so greatly that the differences in toxicity of the
various metals (Cd, Cu, Ni, Pb, and Zn) are lost. Data in the
TZ (see TZ in Figure 1) are the most relevant for the
development of models that accurately predict the onset of
metal toxicity. The threshold for effects concentrations will
exist for both porewater and sediment-bound metals, and
according to the EEM of Simpson (2005), toxicity may occur
in the TZ because of exposure from both these sources. Based
on most of the currently available data, the probable effects
limit zone will be dominated by porewater exposure effects.
However, as better data sets become available, effects caused
by sediment-bound metals are expected to be observed more
commonly at lower concentrations near the TZ (Simpson
2005).
Figure 4 is compiled from the data sets used for the sBLM
development, in which effects were reported for single metals
spiked into sediments and in which both porewater metal
concentrations and AVS/SEM were reported (Carlson et al.
1991; Casas and Crecelius 1994; Pesch et al. 1995; Berry et al.
1996; DeWitt et al. 1996, 1999; Sibley et al. 1996). Except
for sediments affected by low acidity, porewater metal
concentrations rarely exceed 100 lg/L (Carignan et al.
1985; Tessier 1992; Brumbaugh et al. 1994; Ingersoll et al.
1994; Tessier et al. 1996; Rivera-Duarte and Flegal 1997;
Simpson, Rochford, et al. 2002; Simpson, Pryor, et al. 2002;
Teasdale et al. 2003). In region A, porewater metal concen-
trations are in the region of environmental realism. In region
B, porewater metal concentrations range from high to very
high and are at the limit of environmental realism. In region
C, porewater metal concentrations are extremely high and are
well beyond the limits of environmental realism. In region C,
the low porewater pH (caused by hydrolysis of unbound
metals) greatly decreases metal binding to sediment particles,
and pH is the major factor controlling metal partitioning.
Because the porewater pH was either not measured or not
reported in any of the studies from which the sBLM data were
collated, it is difficult to judge the state of equilibrium
between the spiked metals and the sediments. Regardless of
the use of the AVS/SEM-based models, region C in Figure 4
would be expected to be classified as toxic because of the very
high and easily measurable porewater metal concentrations.
Like the AVS/SEM (sBLM) data sets, most of the better
relationships between CBRs and sediment metal concentra-
tions were based on metal-spiked sediment data sets with very
elevated porewater metal concentrations. For example,
reduced survival of H. azteca in metal-spiked sediments was
a result of high dissolved metal concentrations in porewaters
Predicting Metal Toxicity in Sediments—Integr Environ Assess Manag 3, 2007
Figure 4. Concentration–response data used as the basis for acid-volatile sulfide (AVS)/simultaneously extracted metals (SEM) and sBLM model development.
Symbols represent sediments in which AVS/SEM . 1 (filled symbols) and AVS/SEM , 1 (open symbols) for the metals cadmium ( and ¤), copper (n and m),

nickel ( and *), lead (n and u), and zinc (n and u). Data are from Carlson et al. (1991), Casas and Crecelius (1994), Berry et al. (1996), DeWitt et al. (1996,
1999), Pesch et al. (1995), and Sibley et al. (1996).
and overlying waters (typically hundreds of lg/L of Cu, Ni,
Pb, or Zn; Borgmann and Norwood 1997, 1999; Borgmann,
Neron, and Norwood 2001) rather than of effects from the
sediment particles. For much of this literature, effects
thresholds were derived in terms of particulate metal
concentrations. However, this is unreasonable, because the
toxic effects almost certainly resulted from dissolved metals in
the porewater and overlying water that were beyond the
region of environmental realism.
Fortunately, because of the exaggerated porewater expo-
sure route, SQGs for metals derived from both the AVS/SEM
and CBR data sets probably are quite conservative, unless it is
shown that the exposure from particulate metal sources
causes toxic effects at very low concentrations. To confuse
matters, however, several studies indicate that effects from
particulate metals may occur at very low total metal
concentrations (Costa et al. 1998; Marsden and Wong 2001;
Marsden 2002). For the amphipod species Gammarus locosta,
Costa et al. (1998) determined an LC50 for Cu of 6.8 mg/kg
dry weight for sediments in which porewater concentrations
of Cu were still less than half the LOEC in the water-only
exposure (50 lg/L).
DIETARY EXPOSURE
The most significant difference between the models used
for predicting metal toxicity in sediments is the treatment of
the exposure from dietary sources (food and sediment
ingestion pathways). The sBLM model assumes that dietary
sources do not contribute to toxicity (Di Toro et al. 2005), and
the CBR/LBC approaches do not consider exposure routes
(Borgmann 2003). However, the EEM approach explicitly
considers dietary exposure and effects (Simpson 2005).
The significance of the dietary exposure pathway in
contributing to metal exposure, accumulation, and toxic
effects has been highlighted for many years (Luoma 1989;
Luoma et al. 1992; Luoma and Fisher 1997; Munger and Hare
1997; Lee and Luoma 1998; Schlekat and Luoma 2000;
Eriksson-Wiklund and Sundelin 2002; Fan et al. 2002; Yan
25
and Wang 2002; Hare et al. 2003; Griscom and Fisher 2004;
Besser et al. 2005; King et al. 2005; Meyer et al. 2005).
Luoma et al. (1992) showed that whereas exposure from
dissolved selenium was insufficient to explain selenium
accumulation by the deposit-feeding bivalve Macoma balth-
ica, ingestion and assimilation of selenium from sediment
particulates could explain the accumulation. In a study of the
relative importance of water and food as Cd sources to the
predatory insect Chaoborus punctipennis, Munger and Hare
(1997) found that direct uptake from water probably was
unimportant. Chen and Maher (1999) observed that metal
solubilization in the organism’s gut generally is biphasic,
initially rapid, then slower, and that steady-state equilibrium
is unlikely to be reached within the gut passage time of
ingested sediment particles. Chen et al. (2002) proposed that
metal contaminants solubilized in digestive fluids may inhibit
digestive enzyme activities in the guts of marine benthic
invertebrates. For the estuarine amphipod Monporeia affinis,
Eriksson-Wiklund and Sundelin (2002) showed that metals in
the sediments (food), rather than metals in the porewaters,
were the main source of metal accumulation. Fan and Wang
(2003) found that the extraction of metals by gut digestive
fluids from 3 contaminated coastal sediments was not
correlated with either SEM or [SEM
AVS].
The metal AE from different sediment phases will depend
on the organism’s physiology (e.g., gut passage time and gut
chemistry) as well as on the properties of the sediment phase
(Wang et al. 1995; Wang and Fisher 1999b; Fan and Wang
2001; Fan et al. 2002; Griscom et al. 2002; Griscom and
Fisher 2004; Simpson and King 2005). For the 2 bivalves M.
balthica and Mytilus edulis, the AEs of Ag, Cd, and Co
associated with particles of differing geochemistry (e.g.,
sulfide, organic carbon, and iron) varied by greater than an
order of magnitude (Griscom and Fisher 2004). For metal-
contaminated sediments with varying sediment properties,
Fan et al. (2002) found no statistically significant relationships
between the AEs for Cd, Cr, and Zn of the clam Ruditapes
philippinarum and the concentrations of SEM or [SEM

26
AVS]. The metal uptake for sediment particles is greatly
influenced by food quality, with metal uptakes rates from
sediments increasing in the presence of algae (Lee and Luoma
1998; King et al. 2005). For sediments with low porewater
metal concentrations, the importance of the AE of different
sediment components becomes increasingly important, and
incorporating this information in predictive EEMs is very
challenging (Simpson 2005).
A substantial amount of literature highlights the signifi-
cance of dietary exposure routes, but it still is commonly
observed that the significance is missed when organism
sensitivity is assessed using metal-spiked sediments. Although
Kemp and Swartz (1988) found that Cd bioavailability to
amphipods was predictable by EqP approaches, close exami-
nation of their data reveals that the porewater Cd concen-
trations were more than 1,000-fold those found in
contaminated estuarine waters and, consequently, that the
relative importance of the sediment exposure pathways was
diluted. As exemplified in Figure 4, this overexaggeration of
the water exposure route is very common.
NONSULFIDE BINDING INFLUENCING METAL
TOXICITY
Both POC and iron oxyhydroxide phases are well
recognized for their strong binding of metals in sediments
(Luoma and Davis 1983; Tessier and Campbell 1987; Tessier
1992; Tessier et al. 1993; Trivedi and Axe 2000). Numerous
studies have shown the importance of POC at reducing metal
toxicity in sediments, with normalization of metal effects
concentrations to the fraction of organic carbon in sediments
improving the predictions of metal toxicity (Mahony et al.
1996; Correia and Costa 2000; Höss et al. 2001; Besser et al.
2003). Few studies directly implicate iron as the major metal-
binding phase that reduces metal toxicity in sediments,
because the chemistry of metal-binding iron oxyhydroxide
phases is considered to be much more complex than that of
metal-binding POC phases (Burdige 1993; Tessier et al. 1993;
Stumm and Morgan 1996; Williamson et al. 1999; Simpson
and Batley 2003).
The chemistry of particulate and dissolved forms of iron in
sediments is both complex and dynamic (Burdige 1993;
Canfield et al. 1993; Tessier et al. 1993; Williamson et al.
1999; Kristensen 2000; Simpson and Batley 2003). In many
sediments, the cycling between reduced and oxidized forms
of iron strongly influences metal partitioning (Burdige 1993;
Kristensen 2000; Simpson and Batley 2003). The oxic
fraction of silty sediments usually extends to depths of 2 to
5 mm (Williamson et al. 1999; Kristensen 2000). At greater
depths, the sediment becomes suboxic, containing mixtures
of oxic solid phases (e.g., iron and manganese (hydr)oxides)
in equilibrium with reduced dissolved phases (e.g., iron(II)
and manganese(II)) (Simpson and Batley 2003). Once the
easily reducible iron and manganese (hydr)oxide phases have
been depleted, bacteria reduce sulfate to sulfide, and the
solubility of many metals is controlled by the solubility of
metal sulfide phases (Di Toro et al. 1992; Burdige 1993). In
many sediments, redox zonation is not clear, and oxic
(oxyhydroxides) and anoxic (sulfide) phases coexist (Burdige
1993; Williamson et al. 1999; Simpson, Apte, et al. 2000).
Depth distributions indicate that iron(III) hydroxide phases
and porewater iron(II) coexist in most surface sediments and
that an individual iron atom typically is oxidized and reduced
hundreds of times before ultimate burial (Canfield et al.
Integr Environ Assess Manag 3, 2007—SL Simpson and GE Batley
1993; Williamson et al. 1999). The burrowing activity of
benthic organisms can cause sediment resuspension and
mixing of previously redox-stratified sediments with oxy-
genated overlying waters, thereby altering metal sediment–
water partitioning and speciation in the dissolved phase
(Riedel et al. 1997; Simpson et al. 1998; Williamson et al.
1999; Kristensen 2000; Simpson, Rosner, et al. 2002; Ciutat
and Boudou 2003). As discussed above, the AE of metals,
including iron, from particulate phases will vary greatly with
particle geochemistry (Fan and Wang 2001; Fan et al. 2002;
Griscom and Fisher 2004).
In many sediments, it might be expected that the
concentrations of POC, particulate iron, and the fractions of
fine particles may be correlated and, therefore, that only 1 of
these parameters may need to be included in an EEM.
However, data for natural sediments (Figure 5) indicate that
this commonly is not the case (Spadaro et al. 2006). The
distribution of metal contaminants among the different
particle size fractions may be similarly heterogeneous.
It is expected that both POC and iron oxyhydroxide phases
play an important role in metal binding in most sediments,
particularly the more oxic surface sediments with which
organisms interact and feed (Tessier et al. 1993, 1996; Hare et
al. 1994; Simpson and Batley 2003), and sediment particle
size also influences the bioavailability of these metal phases.
Careful measurement of both these parameters is expected to
improve interpretation and allow more accurate modeling of
effects data.
Porewater metal complexation and dynamics
The initial sBLM model calculations of Di Toro et al.
(2005) indicated that DOC and competing ligands, other than
Hþ (pH), should have very little effect on the computed
median effects concentration on a POC-normalized basis
(SEMoc). Besser et al. (2003) observed that the toxicity of Cd
and Cu in porewater to Hyalella organisms decreased with
increasing humus concentrations in the sediments, and this
effect was attributed to the formation of nonbioavailable Cu–
organic complexes. Höss et al. (2001) observed that the
toxicity of Cd in porewater to the nematode Caenorhabditis
elegans increased as POC concentrations in the sediments
increased, and they attributed this finding to increased
concentrations of Cd–organic complexes that were bioavail-
able in the gut of the nematodes. These contrasting results
indicate that further research is needed to understand better
the nature of POC and porewater DOC.
As discussed earlier, metal-spiking of sediments often
causes high concentrations of iron(II) in the porewaters
(often .100 mg/L; Simpson et al. 2004; Han et al. 2005). To
our knowledge, no studies have reported the effects that high
porewater iron(II) concentrations on the bioavailability of
other porewater metals. For sediment-dwelling organisms,
exposure pathways become even more complicated when the
relative importance of exposure from overlying water, pore-
water, and burrow water needs to be considered (Griscom and
Fisher 2002). Because of varying irrigation and respiration
rates of organisms in sediment burrows, concentrations of
dissolved oxygen and oxygen-sensitive ions (e.g., iron(II))
within the burrow water and surrounding porewater will
fluctuate according to the organism’s behavior (Kristensen
2000; Wenzhöfer and Glud 2004). Consequently, in the
suboxic waters of organism burrows and the surrounding
porewaters, the dissolved concentrations of metal ions that
Predicting Metal Toxicity in Sediments—Integr Environ Assess Manag 3, 2007
Figure 5. Concentration of particulate iron, organic carbon, and percentage of particles less than 63 lm in size for 60 marine sediments from Sydney, Australia.
Analyses were as follows: Particulate organic carbon (POC) by a high-temperature total organic carbon (TOC) analyzer, loss-on-ignition (LOI) at 3758C following
inorganic carbon removal, Total iron (u) by hot microwave digestion in 2:1 HCl:HNO3, and SEM-iron (¤) by 1 M HCl (30 min, cold). SEM-Fe ¼ the iron concentration
in sediment determined by a 30-min extraction with 1 M HCl. (Adapted with permission from Spadaro et al. (2006). Copyright 2005 CSIRO Australia.)
bind to iron hydroxide phases will fluctuate as the equilib-
rium position of the iron(II)/iron(III)–(oxy)hydroxide redox
couple shifts (Kristensen 2000; Simpson and Batley 2003).
Equilibrium partitioning theories do not account for the
dynamics that affect metal bioavailability in suboxic sedi-
ments. Although many metal sulfide phases are relatively
stable in the presence of oxygen (Simpson, Apte, et al. 1998,
2000), a better understanding is needed of how organism
activity within sediments (including burrows) affects concen-
trations of dissolved metals in the associated waters. Few
studies have considered the importance of porewater colloids,
but a significant amount of metal present in the filterable
porewater fraction (typically, ,0.45 lm) likely is colloidal
(Wang and Guo 2000; Cantwell and Burgess 2001).
DEVELOPING BETTER EFFECTS MODELS AND SQGS
The literature contains numerous examples of situations in
which the existing models and SQGs appear to be suitable for
predicting toxic effects of contaminants to benthic organisms
(Shine et al. 2003; Word et al. 2005). However, as the
emphasis of sediment-quality assessment moves further
toward prediction of chronic effects, the effects models will
require better treatment of the sediment factors that modify
toxicity and better distinction between effects from a range of
different exposure pathways. The sBLM proposed by Di Toro
et al. (2005) is elegant in its simplicity, and its initial
application indicates great improvement compared with past
EqP models for predicting the effects of metals in sediments.
The EEM developed by Simpson (2005) illustrates a novel
attempt at modeling the exposure and effects of metals from
both dissolved and particulate exposure pathways on sedi-
ment biota. However, predictions based on the EEM indicate
that changes in metal uptake rate from the various exposure
27
routes are influenced greatly by organism behavior (e.g.,
feeding) and that adequate parameterization of the EEM is
difficult. Both the sBLM and EEM indicate that the develop-
ment of greatly improved SQGs will be dependent on
improved measurement and reporting of key parameters
affecting causality.
Measurement parameters
Poor documentation of procedures and the omission of
carefully measured sediment parameters greatly limit the use
of most current data sets for wider modeling applications. A
number of physicochemical parameters are crucial for
modeling metal partitioning and metal toxicity in sediments,
and a larger number of parameters may be useful for
improving the accuracy of predictive models. Parameters that
are considered to be crucial for development of the sBLM are
AVS, SEM, POC, and pH. However, if values for parameters
such as pH and porewater metal concentrations are outside
the realms of environmental realism, then the data sets may
be of little relevance. To support the development of EEMs,
then along with those 4 parameters, the porewater metal
concentrations (including iron and manganese) and the
particulate iron and manganese concentrations of the sedi-
ment should be reported as well. Furthermore, recent
literature should be reviewed regularly to consider any
‘‘new’’ parameters that are being used in model develop-
ment. For organisms that ingest sediments, sediment particle
size, the metal concentrations associated with the fine-
particle-size fraction, and the accessibility of the metal in the
organism’s gut (i.e., the metal AE) also will be key
parameters. However, beyond the use of radiotracer experi-
ments, methods for determining AEs for metals associated
28
with different food sources remain to be developed (Wang
and Fisher 1999b).
Measurement of the metal uptake rates by benthic
organisms for short-term exposures will provide useful data
for refining biodynamic models to predict effects (Rainbow
2002; Simpson 2005; van Straalen et al. 2005). Measurements
of internal metal sequestration will improve our under-
standing of the dynamics of the MAC of metals within
organisms and of how the impairment of specific cellular
function leads to quantifiable effects (Ahearn et al. 2004;
Vijver et al. 2004).
Future challenges for effects models
The influence of organism behavior provides further
difficulties for predictive models, and perhaps the most
challenging is selective feeding that depends on the nutritional
value of the sediment. Selective feeding behavior of benthic
organisms (feeding rate and particle selection) influences the
uptake and toxic effects of metals in sediments (Munger and
Hare 2000; Lee et al. 2001; de Haas et al. 2004; King et al.
2005). For the amphipod M. plumulosa, the presence of algae
increased the rate of uptake of both Cu and Cd from
sediments and indicated that M. plumulosa fed more rapidly,
but not necessarily selectively, when algae were present with
sediments (King et al. 2005). The effect of varying feeding
behavior was not considered in the current models, but in
natural sediments, many organisms may selectively ingest, for
example, organic-rich fine particles that have higher contam-
inant concentrations than nonselected particles (e.g., the sand
component of the sediment).
Sediments are heterogeneous, and the speciation of
particulate metals varies greatly over small spatial scales.
Therefore, partitioning of contaminants is easily disrupted by
animal activity (Zhang et al. 2002; Ciutat and Boudou 2003;
Simpson and Batley 2003). The spatial variability, hetero-
geneity, and localized partitioning of metals within micro-
environments, which exist in most sediments, eventually may
limit the accuracy of EqP relationships for predicting pore-
water metal concentrations (Besser et al. 1996; Grabowski et
al. 2001; Zhang et al. 2002; van Griethuysen et al. 2003). The
existence of thermodynamic EqP may be rare in sediments
that are continually disrupted by animal activity at small
spatial (lm to mm) and temporal (s to min) scales (Forbes
1999; Simpson and Batley 2003). Understanding how these
factors affect species sensitivity requires further study to
determine whether assumptions of heterogeneity and con-
taminant dynamics can be ignored or require greater consid-
eration (Forbes 1999).
Although the additivity of the effects of metals appears to
be accounted for in the AVS/SEM and CBR approaches,
multiple-metal effects are not always additive (Hagopian-
Schlekat et al. 2001). Dealing with the effects additivity of
metals from multiple exposure pathways adds greater
complexity to effects prediction (Simpson 2005). However,
for the development of better EEM, these issues probably are
minor compared to those regarding the dynamics of metal
partitioning to POC and iron hydroxide phases.
Developing better SQGs
Despite the uncertainties discussed above, using SQGs as
screening or trigger values ensures that they serve some useful
purpose in sediment-quality assessment, particularly in
Integr Environ Assess Manag 3, 2007—SL Simpson and GE Batley
Figure 6. Conceptual species sensitivity distributions (SSDs) based on a
cumulative frequency model representative of toxic effects in sediments with
varying sediment properties. Symbols represent different classes of sediment-
dwelling biota, such as bacteria (diamond), algae (circle), mysids (hexagon),
amphipods (cross), bivalves (4-sided star), polychaete worms (triangle), snails
(5-sided star), and crabs (square).
association with other lines of evidence as part of a weight-of-
evidence approach (Chapman et al. 2002). Better models will
simply assist in refining the trigger thresholds. Using suitable
data for a range of benthic test organisms, it will be possible to
use species sensitivity distributions to derive SQGs that are
protective of a given percentage of sediment species, as
currently is done for water-quality guidelines. The difference,
however, will be that because the exposure concentration will
be dependent on sediment characteristics that control
contaminant binding, such species sensitivity distributions
will need to be derived separately for a range of sediment
types, as indicated in Figure 6. As discussed by Simpson
(2005), EEMs indicate that the ‘‘position’’ of species within
these distributions may move as the relative importance of
exposure pathways changes with varying sediment properties.
How well cumulative frequency distributions (e.g., those
shown in Figure 6) will collapse to form a single distribution
when normalized on the basis of sediment properties (e.g.,
AVS, SEM, POC, iron, and pH) may depend on the organism
sensitivity to metals from each exposure pathway and on
changes in the relative importance of each exposure pathway
for different sediment types. Regardless of the SQG approach
that is used, careful scrutiny should be given to all
experimental procedures used in estimating toxicity thresh-
olds or effects concentrations before such values are adopted
in SQGs.
Acknowledgment—We would like to thank Jenny Stauber
(CSIRO), Kay Ho (USEPA), and 2 anonymous reviewers for
constructive comments on this manuscript.
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