Environmental Toxicology and Chemistry, Vol. 32, No. 1, pp.
7–9, 2013
ET&C Impact Papers
THE INTERPLAY OF ENVIRONMENTAL TOXICOLOGY AND CHEMISTRY
IN THE DEVELOPMENT OF SEDIMENT QUALITY CRITERIA
DOMINIC M. DI TORO*
University of Delaware, Newark, Delaware, USA
(Submitted 25 September 2012; Returned for Revision 15 October 2012; Accepted 15 October 2012)
The search for rational methods to develop criteria for
various media—water, sediment, and tissue—and various
receptors—aquatic, terrestrial, and human—has been a con-
sistent and continuous enterprise from the beginning of environ-
mental toxicology. Many of the 100 most frequently cited
papers in Environmental Toxicology and Chemistry directly
or indirectly address topics relevant to criteria. Subsets of these
papers are concerned with the interaction between environ-
mental toxicology and environmental chemistry.
The first aquatic criteria were based on what today would be
called best professional judgment applied to the toxicity experi-
ments available at that time. Very little, if any, environmental
chemistry was considered. The transition came with the devel-
opment of the technical guidelines for water quality criteria [1],
which provided an explicit methodology for the toxicological
component of the criteria: a required minimum data set
(tests using eight species from specific groups of organisms),
a method of analysis to produce the acute criteria (the
5th percentile from the species sensitivity distribution), and
an acute to chronic ratio derived from paired experiments. The
criteria developed in the early 1980s, and those that continue to
be developed, employ either this framework or closely related
frameworks.
The criteria recognized that, in addition to the concentration
of the toxicant, there are environmental chemical factors that
need to be considered. Examples include water hardness
(Ca þ Mg concentrations) affecting the toxicity of certain diva-
lent cations and pH affecting ammonia toxicity. Both of these
were included in the criteria. An example of a chemical factor
that was recognized but not included is dissolved organic matter
concentration. Nevertheless, these water quality criteria marked
the transition from judgment-based criteria to scientifically
based criteria—compare the pre technical guidelines ‘‘Blue
Book’’ [2] and ‘‘Red Book’’ [3] to the post technical guidelines
‘‘Gold Book’’ [4].
The development of sediment quality criteria followed a
different path. The methods that have been, and are being,
developed are either mechanistic criteria or empirical criteria
that consider, or do not consider, the chemical factors in sedi-
ments that affect toxicity [5]. For the most part, the water
quality criteria that excluded the effects of other water quality
All Supplemental Data may be found in the online version of this article.
See Table S1 for the number of citations and rank of all the ‘‘Top 100’’
papers, which in this essay are references [8–10,15,21,24,27].
* To whom correspondence may be addressed
(dditoro@udel.edu).
Published online 12 November 2012 in Wiley Online Library
(wileyonlinelibrary.com).
7
# 2012 SETAC
Printed in the USA
DOI: 10.1002/etc.2049
parameters were reasonably successful, particularly for organic
chemicals, where the effects due to other chemical constituents
in the water were not large. By contrast, the toxicity of
chemicals in sediments can vary by factors of 10- to 100-fold
depending on sediment characteristics. This problem can be
thought of as a variation in the bioavailability of the total
quantity of the chemical in sediments—that is, that fraction
of the total concentration that can interact with the target that
causes the toxicity.
In view of this dramatic variability, it was clear that under-
standing the reason(s) for the variability in bioavailability was
necessary to develop successful mechanistic sediment quality
criteria. The key experiment was reported by Adams et al. [6],
who tested the toxicity of kepone in four quite different
sediments. Their insight was to relate the toxicity to the pore
water concentration rather than to the sediment concentration.
Equally important was their noting that the pore water median
lethal and effective concentration (LC/EC50) and the LC/EC50
derived from exposures to water only were essentially equal.
They rationalized this observation by hypothesizing that the
route of exposure was exclusively via the pore water.
This rationale was consistent with their findings, but it
suggested that the use of pore water concentration to understand
the toxicity variation across sediments would apply only to
organisms that were primarily exposed via the pore water.
Another rationale, which implied a much wider applicability
of their important findings, was suggested as part of the
equilibrium partitioning (EqP) model proposed by Di Toro
et al. [7]. It was based on the idea that the pore water and
sediment solids were in partitioning equilibrium and that the
toxicity of the chemical was determined by the chemical
activity or fugacity of the equilibrium mixture (hence the name
equilibrium partitioning). For kepone, the mortality and growth
dose-response curves for the different sediments overlapped to
within a factor of approximately 2 using either pore water
concentration (CPW) or organic carbon normalized sediment
concentration (CSed/fOC) as the dose metric, where CSed is the
sediment concentration per unit dry weight and fOC is the weight
fraction of organic carbon [7]. This would be expected if the
partitioning equilibrium between pore water and sediment
follows the partitioning model
CSed ¼ fOC KOC CPW
where KOC is the organic carbon/water partition coefficient.
The EqP model reduced the problem of predicting the
bioavailability of chemicals in sediments to the problem of
predicting the partitioning of chemicals between the particulate
phases that made up the sediment and the pore water. It also
8 Environ. Toxicol. Chem. 32, 2013
suggested that the EqP model was applicable to sediment-
ingesting and water-ingesting animals because the chemical
activity was the same in each phase.
A number of issues needed to be investigated to validate and
clarify the applicability of the EqP model. Whether sediments
and pore water are in equilibrium was being investigated prior
to the development of the EqP model. It was found by Karickh-
off and Morris [8] that the time to reach equilibrium can be quite
long for hydrophobic chemicals. Also, as found by Pignatello
[9] and Cornelissen et al. [10], a fraction of the chemical sorbed
to particles becomes fixed in the particle and resists desorption.
This problem would not be apparent in laboratory spiked
sediments but would be evident in field-collected sediments,
where contact time between contaminants and sediments is
much longer. Finally, the partitioning model may not be entirely
appropriate for the particular sediment in question. The sorption
to black carbon has been found to be important [11]. These
mechanisms make the original EqP criteria for organic chem-
icals conservative because they increase the extent of partition-
ing. Such problems do not invalidate the chemical activity basis
for EqP criteria but signal a need for direct measurement of
chemical activity in sediments [12]. The EqP model is the basis
for the U.S. Environmental Protection Agency (U.S. EPA)
sediment benchmark for certain pesticides [13,14], for a model
that deals with mixtures of polycyclic aromatic hydrocarbons
(PAHs) by Swartz et al. [15], and for the U.S. EPA benchmark
for mixtures of PAHs [16,17].
The application of the EqP model to potentially toxic metals
required that their partitioning in sediments be understood.
Metal speciation in sediments involves a number of distinct
phases, as demonstrated by sequential extractions [18]. In terms
of EqP, the problem was predicting the chemical activity of the
toxic form of the metal in pore water. The free ion activity
model [19], based on the work of Sunda [20], suggested that the
concentration of the divalent cation (e.g., Cd2þ) was the species
of interest.
It was known that very insoluble solid phase metal sulfides
(e.g., CdS) were present in sediments. What had not been
realized is that most sediments, including freshwater sediments,
contain a pool of reactive iron monosulfides (FeS), quantified by
the acid volatile sulfide (AVS) extraction, that could react
rapidly to precipitate the metals (Cd, Cu, Ni, Pb, Zn, Ag) that
form insoluble metal sulfides, thereby reducing the concentra-
tion of the cation to very low concentrations, well below toxic
levels. This observation was derived from cadmium toxicity and
subsequent chemical experiments by Di Toro et al. [21]. The
accompanying idea—that the proper extraction to determine if
excess AVS was present relative to metal in a sediment—was to
measure the metal concentration in the same extraction used to
measure AVS [22]. The simultaneously extracted metal (SEM)
was compared to the AVS to determine if metals in sediments
were bioavailable. An excess of AVS served as a sink for the
metal, precipitating it as an insoluble metal sulfide and render-
ing it unavailable to the biota. The necessary analytical methods
were evaluated by Allen et al. [23], and extensive testing was
conducted by Berry et al. [24] of laboratory-spiked sediments
and by Hansen et al. [25] of field-collected sediments.
The original partitioning model applied only to the situation
where AVS exceeded SEM. When the situation was reversed,
however (e.g., in oxic sediments), the SEM–AVS model made
no prediction. It had been found subsequently that normalizing
SEM–AVS by the organic carbon fraction in the sediment
extended the limits of no observed toxicity to the region of
positive SEM–AVS. A sediment biotic ligand model which
D.M. Di Toro
considered both the AVS and organic carbon partitioning
supported this empirical approach [26]. The EqP and SEM–
AVS models were the basis for a proposed sediment quality
criteria for metals by Ankley et al. [27] and for the sub-
sequent U.S. EPA sediment benchmark for metals and metal
mixtures [28].
The two approaches—the mechanistic criteria derived from
EqP and the empirical approaches typified by the Long and
Morgan effects range–low (ER-L) and effects range–medium
(ER-M) [29] and subsequent threshold effect level (TEL),
probable effect level (PEL), and consensus criteria [30]—have
different objectives. The EqP-based criteria aim to establish a
direct relationship between a chemical or mixture of chemicals
and sediment toxicity. The empirical criteria aim to predict the
probability that a sediment is toxic based on the total chemical
concentrations in that sediment. It is a remarkable and disturb-
ing observation that for most of the toxic sediments in large
existing field-collected data sets, neither method can identify
the chemical(s) causing the toxicity, nor can they predict that
the sediment is toxic [31]. Thus, there is much remaining work
to be done in understanding the causes and extent of sediment
toxicity. In particular, within the EqP framework, partitioning
models are necessary for many classes of compounds, such as
oxyanions and charged organic chemicals.
The EqP models are examples of the interplay of environ-
mental chemistry and environmental toxicology. The need to
consider both in the risk analysis and the solution of environ-
mental problems is more apparent now than in previous dec-
ades. A good example is the use of additives to sediments
to decrease the toxicity of contaminated sediments [32]. The
success of these methods depends on their ability to decrease the
chemical activity of the toxicants by increasing the sorption to
the added particles. The total concentration of toxicant does
not change, only the chemical speciation is changed, with the
resulting change in toxicity. As the problems become more
complex from both the toxicological and chemical sides, it is
critical that both disciplines are employed in their solution. Our
Society of Environmental Toxicology and Chemistry (SETAC)
is appropriately named.
SUPPLEMENTAL DATA
Table S1. (45 KB PDF).
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