Aquatic Toxicology 84 (2007) 292298

Science, policy, and trends of metals risk assessment at EPA:

How understanding metals bioavailability has
changed metals risk assessment at US EPA
Mary C. Reiley
US Environmental Protection Agency, Ofce of Water, MC-4304T, 1200 Pennsylvania Avenue, NW, Washington, DC 20460, USA
Received 8 December 2006; received in revised form 8 May 2007; accepted 8 May 2007

Abstract
The US Environmental Protection Agency (EPA) and the Office of Water have made significant changes in the approaches taken to assessing
metals in the aquatic environment. Over the last 20 years, the Office of Water has progressed through a variety of metals assessment tools from total
recoverable metal to the biotic ligand model. These changes were initially driven by the recognition that the total metals criteria were out of date and
that emerging science would make it possible to address bioavailability more thoroughly. More recent drivers are expectations that the agency ensure
the criteria are protective of endangered species and that the agency can bring the best available science to conducting total maximum daily loads
(TMDLs) for waters not meeting uses because of metal contamination. Changes have included: moving from total recoverable metals concentration to
dissolved metals and the development of dissolved metal to total metal translator guidance, the development of water effect ratios (WERs) guidance,
and most recently incorporation of the biotic ligand model (BLM) into criteria derivation for aquatic life protection (USEPA, 2007a. Aquatic Life
Ambient Freshwater Quality Criteria-Copper 2007 Revision. EPA-822-R-07-001. http://www.epa.gov/waterscience/criteria/copper/index.htm.).
On March 8, 2007, the agency published its Framework for Metals Risk Assessment (USEPA, 2007b. Framework for Metals Risk Assessment. EPA
120/R-07/001. http://www.epa.gov/osa/metalsframework.) discussing the state of the science for the persistent bioaccumulative, and toxic nature
of metals and the considerations of this science that will impact many programs. This paper provides a brief insight to these agency activities.
2007 Elsevier B.V. All rights reserved.
Keywords: Metals; Biotic ligand model; Water quality protection

1. Introduction
Over the last 20 or more years the US Environmental Protection Agency (EPA) and the EPA Office of Water have progressed
through a variety of increasingly rigorous approaches to protect
aquatic life from the potential effects of metals contamination
of surface waters. The approaches have moved from total metals to dissolved metals and have been most recently refined to
more effectively address bioavailability of metals through use
of the biotic ligand model (BLM). These changes were initially
driven by the recognition that the total metals criteria approach
was out of date and that emerging science would make it possible to address bioavailability and uncertainties more thoroughly.
More recent drivers for the agency to change its approach are
expectations that the agency ensure endangered species will be

Tel.: +1 202 566 1123; fax: +1 202 566 1140.

E-mail address: reiley.mary@epa.gov.

0166-445X/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.aquatox.2007.05.014

protected, that the best available science is used to develop total

maximum daily loads (TMDLs) for waters not meeting designated uses, and to achieve strategic environmental goals by
returning waters to the quality goals set by states and tribes.
2. Why is EPA so active in metals science, research, and
policy for aquatic systems?
EPA has mandates under a number of different statutes to
either directly regulate, or inform those entities that regulate
metals in aquatic systems or track or monitor metal discharges
in some manner. The Comprehensive Environmental Response,
Compensation, and Liability Act (CERCLA) requires EPA to
specify the concentrations of contaminants that may remain at
superfund sites at the completion of clean-up (US Code, 1980);
the Clean Water Act (CWA) obligates EPA to provide guidance
(Section 304a) to states and Indian tribes on the concentrations
of metals that will not harm aquatic life or human health for

M.C. Reiley / Aquatic Toxicology 84 (2007) 292298

293

use in their regulatory actions and to identify waters that do not

meet water quality goals (US Code, 1977); the toxics release
inventory (TRI) requires reporting total loadings of metals to
ambient environments (US Code, 1986).
The chemistry of metals provides unique challenges that
must be resolved in order to successfully address the potential for adverse effects of metals on water quality and aquatic
life, wildlife, and human health (USEPA, 2007b). How to
appropriately account for natural background, trace nutrient
requirements, and the relationship between speciation, toxicity, and bioavailability are ongoing research and water quality
protection questions. The decisions of regulators and their implementation must be based on vetted science and transparent to
stakeholders. The objective within EPA is to incorporate the
latest science, sufficiently vetted, to ensure our decisions and
guidance is well founded. This is done through extensive peer
review, public review, and both expert and public workshops
as outlined in the agency peer review handbook and agency
strategic plan (USEPA, 2006a,b).

has held or participated in a number of expert and public

workshops, peer reviews, and public comment opportunities
as well as having published a variety of technical memos and
guidance to capture and address the evolving science and technology. EPA has progressed through a number of methods, each
improving our ability to approximate the bioavailable fraction
of metalthe amount of the total that is toxic to aquatic life.
We started with total recoverable metals and moved on to
acid soluble metals. Total recoverable metal was recognized at
the time (pre-1985) as not optimal, but that it would provide
a stable and reproducible method that could be reliably implemented (USEPA, 1985). In 1985, the Office of Water moved to
acid soluble metals, an acknowledged improvement over total
recoverable.

3. How has, is, and will EPA assess the risks of metals in
aquatic systems?

(For a comparison of total recoverable to acid soluble to dissolved to BLM as tools to account for the bioavailability of
metals to aquatic organisms, see Table 1.)
Starting in 1993, the Office of Water once again refined its
guidance to states and tribes to accommodate the latest science and moved to dissolved metal concentration as an even

Since the early 1980s, EPA has acknowledged that measuring metals concentrations and accounting for metals toxicity is
an imperfect science. EPA, in particular the Office of Water,

Because of the variety of forms of copper and the lack

of definitive information about their relative toxicities, no
analytical measurement is known to be ideal for expressing aquatic life criteria for copper.. acid-soluble copper. . . is
probably the best measurement. (USEPA, 1985).

Table 1
Comparison of total recoverable to acid soluble to dissolved (with hardness corrections) to BLM as tools to account for the bioavailability of metals to aquatic life
Tool type

Description

Why the switch?

Total recoverable

Dissolved metals plus that portion of solid metals that can

easily dissolve under ambient conditions. Intended to measure metals in the effluent that are or may easily become
environmentally active, while not measuring metals that are
expected to settle out and remain inert (USEPA, 1984a,b).

Though the analytical method for quantifying total recoverable metal, hard mineral acid digestion provided a known,
simple, and consistent tool, it was also conservative. Many
stakeholders and scientists were concerned that it was likely
to be overly conservative in many situations potentially leading to high rates of false positive findings of impairment. A
more accurate method was needed for determining concentrations that may be used in regulations (USEPA, 1995).

Acid soluble

Same as total recoverable but using a less aggressive digestion

procedure (USEPA, 1992).

The acid soluble method used a less rigorous digestion and

was expected to measure less of the particulate metal than
the total recoverable method. It was believed that the acid
soluble method would more accurately measure bioavailable
metal. Data from ambient and effluent sampling demonstrated that acid soluble results were nearly identical to total
recoverable results but different from dissolved results. These
findings indicated that the acid soluble method will not significantly improve the correlation between measured metal
and bioavailable metal (USEPA, 1992).

Dissolved

Metal that passes through a 0.45-mu membrane filter, pH

between 6.5 and 9.0 and both TOC and TSS below 5 mg/L.
Water quality hardness corrections were established to better reflect the quality of the water under investigation and
improve correlation between dissolved concentration measured and effects (USEPA, 1995).
A metal bioavailability model accounting for the variety of
water chemistry characteristics that can interact with metals to affect their interactions with an organisms biological
receptors and thus a metals ability to cause adverse effects
to the organism (USEPA, 2007a).

Dissolved metal concentrations were adopted as the standard

to provide an improved approximation of the biologically
available fraction of waterborne metals for aquatic organisms
than total recoverable metal (USEPA, 1995).

BLM

Comparisons of BLM adjusted criterion maximum concentrations (CMCs) to hardness adjusted demonstrate the
accuracy gained using the BLM (See Fig. 4).

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M.C. Reiley / Aquatic Toxicology 84 (2007) 292298

Fig. 1. Top 10 causes of impairment (CWA 303D list as of 29.03.2007).

closer approximation of bioavailable metal (Prothro, 1993). But

even in 1993, we knew that we were still working with coarse
approximations and that to reach the goal of regulating metals
on bioavailability to aquatic organisms, there was a fair amount
of research to be actualized (Prothro, 1993).
Metals criteria for ambient waters should be based on
bioavailable metals rather than either total or soluble concentrations. This will achieve the desired goal of protection of
aquatic life without over-regulation of dischargers (USEPA,
1993).
Water effect ratios (WERs) filled the toxicity gap between
lab water and ambient water (Davies, 1994). Because dissolved
metals criteria were established using lab water with few binding
agents, whereas site-waters have a variety of chemistries due to
the geology of a given aquatic system, the water effect ratiothe
ratio of the toxicity of a metal in lab water to the toxicity of
the metal in site-water, is used to adjust a national criterion to
reflect site-specific concerns. The WER was a stop-gap (time
consuming, and expensive option) until EPA could come up
with a more directly applicable tool.
What the Office of Water, industry and academic scientists, and other interested stakeholders identified 20 years ago
in 1985 (and confirmed at a state-of-the-science public meeting in Annapolis, MD, January 1993, USEPA, 1993) through
research, collaboration, and dialogue, as necessary for appropriately assessing metals impact on aquatic life is coming to fruition
through the BLM. The first use of the BLM, which accounts

for the variety of water chemistry parameters that impact the

bioavailability of metals rather than hardness alone, was the proposed (2003) criteria for the protection of aquatic life-copper.
The copper-BLM document (USEPA, 2007a) was released in
February 2007. A number of other metals-BLM criteria are
under development (zinc, nickel, silver, lead).
4. What are the current program implementation and
research activities in water for metals?
Part of the implementation of EPAs water quality program is through the development of total maximum daily loads
(TMDLs). A TMDL is the concentration of a chemical, or other
pollutant, that can be added to a water body without causing
the water body to exceed the concentrations needed to maintain
its uses (e.g., swimming, fishing, drinking, aquatic life habitat, etc.). This concentrationthe TMDLis then partitioned
among all of the sources of the chemical to determine how much
each source can discharge to the water body in question.
TMDLs must be developed for all waters determined to be
impaired. Metal is one of the principle reasons for water bodies in
the US to be listed as having impaired water quality. Other contaminants in the top 10 include: mercury, pathogens, sediment,
metals (not Hg), nutrients, oxygen depletion, pH, biological
integrity, temperature, habitat alteration (see Fig. 1). The ranking
specifically for metals (not Hg) puts copper, lead, selenium, and
zinc in the top tier of water impairments due to metals. (Fig. 2)
(USEPA, 2006c). The research conducted in the bioavailability

Fig. 2. Top 10 causes of metals impairment (CWA 303D list as of 29.03.2007).

M.C. Reiley / Aquatic Toxicology 84 (2007) 292298

295

Biotic ligand model: a bioavailability model is used to adjust

the LC50 values for each tested species to reflect the competing water quality characteristics of a site and the biological
receptor for the metal(s) on the organism. The CMC is calculated using the normalized LC50 values. (USEPA, 2007a).

Fig. 3. Ranked freshwater genus mean acute values (GMACs) from 2007 copper
criteria update. (USEPA, 2007a).

of copper to aquatic life is a response to its ongoing appearance

in the top 10 metals impairments.
Taken directly from the 2007 copper criteria update (USEPA,
2007a), Fig. 3 displays the BLM normalized species sensitivity distribution of genus mean acute values. Fig. 4 and Table 2
demonstrate the ability of the BLM to account for changes in
water chemistry that could not be accounted for by a simple
hardness based value. In the past, only hardness would have
been used to normalize the data (USEPA, 1984a,b).
The three normalization approaches Office of Water has used
for derivation of acute criteria for freshwater aquatic life are:
hardness, WER, BLM. The foundation for using each of these
normalizing factors is the same, the 1985 aquatic life guidelines (Stephan et al., 1985). Each is simply a more rigorous
adjustment than its predecessor.
Hardness: the criterion maximum concentration, CMC, is
expressed as a function of waters hardness (mg/L). For
copper, the hardness equation is: CMC = e (0.9422 [ln(H)] 1.7)
(USEPA, 2007a).
Water effect ratio: the CMC is adjusted by the ratio of the
site water metal toxicity concentration to the lab water metal
toxicity concentration (or upstream to downstream) (USEPA,
1994).

Fig. 4. Comparison of criterion maximum concentrations (CMC) calculated by

biotic ligand model or hardness equation [from 2007 copper criteria update.
(USEPA, 2007a)].

The Office of Water is also preparing implementation guidance

for bringing the new BLM based copper criterion into state and
tribal water quality standards and providing training to states
and tribes on how to use the software to generate criteria and
permit limits.
As noted above, the Office of Water is examining the use
of the BLM with other metals (namely silver, zinc, lead, and
nickel). Over the last several years, Office of Water has stayed
connected with the ongoing industry and academic research to
develop and refine the models and parameters for the use of BLM
with these metals. Research is also ongoing into a number of
outstanding biological availability concerns for metals. Understanding and addressing the potential for toxicity to aquatic life
and aquatic dependent wildlife from dietary metals exposure is
one of these. In particular, the development of a tissue-based
criteria for metals, such as selenium, which are trace nutrients
but can cause adverse effects when consumed and bioaccumulated to higher concentrations. There is also the need to continue
to understand metals fate, transport, time-dependency, sequestration, and release as it relates to changes in environmental
chemistry and the impact on aquatic life and aquatic dependent
wildlife.
During the development of the draft Framework for Metals Risk Assessment, peer reviewers, white paper authors, and
public commenters identified a significant number of potential
research areas and activities. Those research suggestions are
captured in the draft Framework (USEPA, 2004) and include
the areas of environmental chemistry, bioaccumulation and
bioavailability, human health effects, characterization of ecological effects, and the unit world model.
5. What is the future for metals assessment
agency-wide?
The agency has just concluded the documentation of a
broader cross program initiative, The Framework for Metals
Risk Assessment, Metals Framework or Framework (USEPA,
2007b), of which BLM is also a part. The Framework is the result
of both interest generated by agencys toxics release inventory
rule making of January 2001 (USEPA, 2001a,b) and the longstanding efforts of the agency to improve the understanding of
metals and metal compounds as toxics in the environment. Many
EPA programs are faced with deciding whether and how to regulate toxic metals. These decisions range from setting regulatory
standards for environmental releases, to establishing safe levels
in different environmental media, to setting priorities for regulatory or voluntary efforts. A basic input to the decision-making
process for most EPA programs is an assessment of potential
risks posed by the metal(s) to human health and the environment.
The Metals Framework is designed around three pillars
in order to address the issues of environmental chemistry,

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M.C. Reiley / Aquatic Toxicology 84 (2007) 292298

Table 2
Copper water quality values using the BLM [from 2007 copper criteria update (USEPA, 2007a)]
pH

Hardness
(mg/L) CaCO3

6.5

40

80

159

317

7.0

40

80

159

317

DOC (mg/L)

Hardness equation based

water quality criterion
for Cua (g/L)

BLM based instantaneous

water quality criterion for
Cu (g/L)

2
4
8
16
2
4
8
16
2
4
8
16
2
4
8
16

5.9
5.9
5.9
5.9
11.3
11.3
11.3
11.3
21.7
21.7
21.7
21.7
41.5
41.5
41.5
41.5

1.6
3.3
6.8
14.3
1.9
3.8
7.7
16.0
2.3
4.5
9.2
18.9
2.8
5.6
11.4
23.1

2
4
8
16
2
4
8
16
2
4
8
16
2
4
8
16

5.9
5.9
5.9
5.9
11.3
11.3
11.3
11.3
21.7
21.7
21.7
21.7
41.5
41.5
41.5
41.5

3.9
8.0
16.4
34.3
4.4
8.8
18.0
37.0
5.1
10.3
207
42.4
6.2
12.4
24 9
50.6

Appendix G: representative water quality criteria values using the BLM and the hardness equation approaches for waters with a range in pH, hardness, and DOC
concentrations. The BLM calculation assumed that alkalinity was correlated with pH, and that other major ions were correlated with hardness based on observed
correlations in EPA synthetic water recipes.
a Notes: hardness equation: CMC = e(0.9422 [ln(H)] 1.7) , where: H is the water hardness of CaCO (mg/L).
3

exposure, human health effects, ecological effects, bioavailability, and bioaccumulation presented by commenters on the
TRI lead rule1 (USEPA, 1999, 2001a,b) and the variety of
workshops, peer reviews, and stakeholder discussions that
informed the direction of the water program which included the
following:
1. consistent application of state-of-the-science principles for
assessing hazard and risk for metals;
2. transparency in analysis, process, and decision-making;
3. flexibility to address regulatory program-specific mandates.

1 The TRI lead rule of 1999 added lead to the list of persistent, bioaccumulative, and toxic chemicals to be reported under the toxic release inventory.
Commenters were concerned about metals receiving high hazard ranking scores
for persistence when they are elements and for bioaccumulation when they
are often trace essential nutrients or purposefully bioaccumulated as a toxic
sequestration adaptation.

Assessments of metals and metal compounds raise issues

not generally encountered with organic chemicals. For
example:
metals are neither created nor destroyed by biological and
chemical processes; rather they are transformed from one
chemical species to another;
metal elements and some inorganic metal compounds are not
readily soluble and as a result toxicity tests based on soluble salts may overestimate the bioavailability and potential
toxicity for these substances;
some metals are essential elements at low levels (e.g., copper,
chromium, and zinc) but toxic at higher levels; while others which are non-essential (e.g., lead, arsenic, and mercury)
bioaccumulate and are toxic;
many organisms have developed mechanisms to regulate
accumulation of some metals to some extent, especially for
essential metals;

M.C. Reiley / Aquatic Toxicology 84 (2007) 292298

each environmental form of the metal has its unique

fate/transport, bioavailability, bioaccumulation, and toxicity
characteristics.
These complexities put limits on the generalizations that can
be made about the hazard and risk that a metal and its compounds
pose to humans and ecological systems. (USEPA, 2007b).
At the heart of the Metals Framework is the unit world model:
similar in concept to the European Unions EUSES (European
Unions uses for the evaluation of substances) though the application of EUSES is specific to organics. In simplification: as a
hazard ranking and screening tool the unit model is run for a
number of metals under the same generic environment to determine the critical load for each and thus be able to classify and
rank them against each other. This resolves many of the outstanding concerns for metals hazard ranking scenarios, since many of
the fate processes that effect metals and organic compounds are
similar, a common modeling framework for both could be developed with the ability to turn on or off the appropriate processes
(e.g. biodegradation) depending on the substance under consideration. As the unit world model is the core of the Framework, the
BLM is central to the unit world model metals modeling component. Implementing a unit world model approach using the BLM
will address many of EPAs and its stakeholders desire for both
intra-agency consistency and individual program flexibility.
6. Conclusion
The difficulties mentioned before:
applying a hazard ranking process for organics to metals;
the unique characteristics of metals which do not work well
in the application of traditional agency tools;
the sheer number of waters with metals impairments that have
to be addressed while incorporating the unique characteristics
of metals, and
using strong, vetted science and transparent decision making,
have facilitated the development of the agency Metals Framework and brought the Office of Water into the forefront of metals
research and implementation.
EPA and Office of Water had to either refine the tools it
was using or develop new ones to achieve their goals. From
total recoverable through dissolved to the BLM-EPA has made
significant strides in developing and implementing the most
appropriate and increasingly accurate metals criteria.
7. Where can I get more information?

www.epa.gov.water/waterscience: copper criteria;

www.epa.gov.water/watersheds: TMDL information;
www.epa.gov.ord: EPA home page;
http://cfpub.epa.gov/ncea/raf/recordisplay.cfm?deid=51736:
action plan for the development of a Framework for Metals
Assessment and Guidance for Characterizing and Ranking
Metals (metals action plan).

297

Disclaimer
The views, positions, and information presented in this article
are those of the author and do not represent the views or positions of the US environmental protection agency or the Office
of Water.
Acknowledgements
Though I have played a personal role in the development of
a variety of the materials used to prepare this manuscript, my
sincerest appreciation goes to all of those who have spent the last
20 years, or more, bringing this science to fruition. There are far
too many of you, both inside and outside of EPA and the Office
of Water, to name. Dr Rick Playles work opened the door to a
significant improvement in our efforts to protect the chemical,
physical, and biological integrity of the Nations waters from
the potential adverse effects of metals.
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