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EC number: 231-072-3
CAS number: 7429-90-5
The aluminium (Al)
toxicity studies compiled in this section represent tests with aquatic
organisms conducted over a pH range from 6
– 8 as being representative of conditions in most European surface
waters as evaluated in a preliminary exposure assessment (EURAS 2007). Most
of the short-term studies included were only those used for purposes of
characterization and to evaluate potential effects of water quality on
Al toxicity. The
long-term chronic studies represent all known studies of sufficient
reliability according to Klimisch criteria levels one (reliable without
restriction) and two (reliable with restriction; Klimisch et al. 1997). These
data are being assessed with a view towards developing a Probable No
Effect Concentration (PNEC) principally for use in setting Environmental
Quality Standards (EQS) values. We
point out that aluminium chloride was not classified for the aquatic
environment by the EU Classification and Labeling Committee, therefore
other less soluble forms of Al such as the oxides, powders, and massive
metal would also not classify for the aquatic environment (see reference
below). Therefore, no PNEC is required for REACH purposes. The
long term goal of the industry is to develop an aquatic PNEC that covers
the pH range of < 6, 6-7, and > 7. These
pH ranges reflect that the form of Al present in water changes
significantly as a function of pH. PNEC
values calculated in this dossier are preliminary and reflect the state
of the science to date. Scientists
around the world have worked towards a PNEC for Al for the past 30 years. The
aluminum industry over the past 3 years has utilized several decades of
work to develop a biotic ligand model (BLM) fish,
invertebrates and algae for pH values across the range of 5.5-8.0. The
state of the model is summarized in this CSR. It
is recognized that there is a need to demonstrate that this model
applies to a broader range of aquatic organisms. Efforts
to date have focused on salmonids, fathead minnows, daphnids and algae. Studies
are on-going at pH 6.0 with a wider range of species to achieve a data
base that has 8-10 chronic PNEC values as recommended in the London PNEC
The extent of this work to date is presented in this dossier. Studies
that are on-going and envisioned for the future were provided to ECHA,
July 2, 2010 for their notification.
For all of the aquatic
toxicity studies, endpoints are expressed as a function of total Al,
rather than as dissolved or monomeric Al. This is because for most test
solutions with pH from 6 – 8, Al will be largely insoluble, and so
dissolved and monomeric concentrations remain relatively constant even
with large increases in total or nominal Al. Thus, dose-dependent
responses observed by aquatic organisms can only be reliably quantified
using total Al across the full pH range from 5.5-8.0.
of Data Leading to Development of an Aluminium Chronic BLM: Toxic
effects of aluminium have been observed in several types of aquatic
organisms under certain exposure conditions. Factors
that influence aluminium toxicity are consistent with the factors that
(discussed in Section 4.2). These
factors include pH, dissolved organic matter concentration (DOC), and
water hardness (see Roy and Campbell 1997; and Gensemer and Playle 1999
for relevant reviews). Fluoride
has also been shown to influencealuminiumtoxicity
(Hamilton and Haines 1995), though fluoride is not commonly found at
elevated levels in the environment. Several
studies have demonstrated that some forms ofaluminiumare
only bioavailable and potentially toxic in freshly prepared solutions,
and that this toxicity declines or is eliminated after several minutes
of aging (e.g. Exely et al. 1996 [others too]; Witters et al. 1996;
Teien et al. 2006). Toxicity
in these cases may depend on short-lived transient chemical forms of
aluminium hydroxide whose environmental relevance would be restricted to
mixing zones where aluminium-rich acidic waters mix with a more alkaline
biotic ligand model (BLM) was developed to address the bioavailability
and toxicity of dissolved, particulate, and transient forms of aluminium. Application
of the BLM framework to understanding aluminium
toxicity was reasonable because many
of the factors that influence aluminium
bioavailability are consistent with
the factors that influence aluminium
speciation or forms in the environment. As
with BLMs for other metals, the Al BLM combines information about
chemical speciation and interaction with gill surfaces to explain and
bioavailability and toxicity (DiToro
et al, 2001; Santore et al 2001; Paquin et al 2002). Factors
that affect aluminium
bioavailability by altering the
chemical speciation of the metal (such as DOC, pH, and fluoride) are
directly considered by the speciation model (Tipping 1994; Santore and
Driscoll, 1996). Other
factors (such as hardness cations), affect aluminium bioavailability by
competing with gill binding sites in a manner similar to what has been
observed for other metals (Playle et al 1992; Meyer et al, 1999) and are
considered by including interactions for these cations with the BL sites
on the gill. The
detailed speciation within the aluminium BLM allows the model to predict
bioavailability for a number of different aluminium fractions. Depending
on available input data, the model can be run with monomeric, dissolved,
or total aluminium as the primary input parameter, and the distribution
among dissolved species and precipitated forms can be simulated by the
model. Comparison of
predicted and measured distribution of aluminium fractions in waters
where aluminium toxicity has been extensively studied typically shows
very good agreement (Figure7.1.1-1).
Factors that are known to affect speciation
have also been shown to affect bioavailability and toxicity in both
acute and chronic exposures, and the consistency of these affects in
different exposure durations allows a common model framework for
prediction of both acute and chronic affects. Acute
data were useful in model development due in part to the large amount of
available data that combined coincident measurement of detailed
speciation measurements, measures of Al accumulation in gills, and
observation of lethal and sub-lethal effects over wide ranges of water
chemistry. Data for
development of the Al BLM included Atlantic salmon (Salmo salar)
and brown trout (Salmo trutta) from studies performed by NIVA and
collaborators from UMB (Kroglund et al. 1997; Kroglund et al.
1998a,b,c,d; Erstad et al. 2002; Teien et al. 2004a,b; Teien et al.
2006; Andren et al. 2006). These
studies typically investigated the effects of water chemistry on the
accumulation of Al on/in the gills of S. salar and S. trutta,
but in some cases, mortality was reported. Many
of these studies purposefully investigated the effects of water
chemistry on the level of Al accumulation in S. salar and S.
trutta gills. The
pH conditions varied from approximately pH 5 (Andren et al. 2006) to pH
10 (Erstad et al. 2002). The
total organic carbon concentrations (TOC) ranged from approximately 0.5
mg/L to 16 mg/L (Kroglund et al. 1998a,b, and Erstad et al. 2002,
concentrations ranged from approximately 1 mg/L to 11 mg/L (Kroglund et
al. 1998a,b, and Erstad et al. 2002, respectively).
From these data it was clear that observed
toxicity was strongly related to aluminium accumulation on the gill
(Figure 7.1.1.-2). The
calibrated Al BLM was able to reasonably predict the level of Al
accumulation on the gills of S. salar and S. trutta, with
one consistent set of BLM parameters (Figure 7.1.1.-3) over a range of
approximately 2 orders of magnitude. This
wide range in gill accumulation was primarily due to the diverse water
chemistry conditions tested, and suggests that the BLM is relatively
robust over this wide range of conditions. These
data were also used to estimate critical Al accumulation levels for
those datasets that reported associated mortality data (i.e. Suldal Fall
1997 – Kroglund et al. 1998a). For
example, from Figure 7.1.1-2, critical accumulation levels corresponding
to the LC10 and LC50 values for mortality could b derived as 2995 and
4225 nmol/g wet weight, respectively.
Although data from acute exposures were
extensively used to parameterize the prediction of gill-accumulation
over a wide range of conditions, the goal in model development is the
evaluation of the ability of the Al BLM to predict effects in chronic
exposures. The use
of data from both acute and chronic exposures in model development is
justified by the consistency of the observed effects of changing water
chemistry (such as pH, NOM, and hardness) in both acute and chronic
of the Al BLM for different exposure durations (acute versus chronic)
and endpoints (lethal or sub-lethal) is primarily accomplished by
adjustment of the critical accumulation level for each endpoint and
exposure condition. Application
to chronic data will be further discussed in the sections that follow
Reason: Soluble aluminium salts are not classified; therefore
less soluble forms of aluminium are not classified.
Available data indicate that aluminium salts are relatively non toxic in
most waters with circumneutral pH and this was sufficient for the EU
Classification and Labelling Committee (1999) to determine that there
was no need for classification of aluminium chloride. Therefore it was
also concluded that aluminium massive and sparingly soluble forms of
aluminium are highly insoluble and non-hazardous. Studies reported in
the literature have extensively used test solutions (soluble salts) with
aluminium concentrations above that of its solubility limit. Due to
physical effects of precipitated material most of these studies are
meaningless for the investigation of intrinsic toxicity. Aluminium ions
released to surface waters quickly form insoluble aluminium hydroxides
in mixing zones. These colloids can sorb to fish gills resulting in
asphyxiation and mortality in rare circumstances. Formation of the
complex hydroxide causes the aluminium to drop out of solution very
rapidly in neutral and alkaline waters. The accumulation of aluminium on
fish gills or other organism respiratory membranes may result in
physical effects. These conditions however are not typical of most
ambient conditions and are more representative of specific mixing zones.
The dissolved natural background concentrations of aluminium, in most
cases, are at equilibrium therefore an addition of aluminium would lead
to the precipitation of aluminium compounds from solution and not result
in effects to aquatic life. We
conclude that a PNEC is not required for REACH. However,
the aluminium industry is continuing its efforts to develop a PNEC for
freshwater ecosystems for purposes of the Water Framework Directive. See
the PNEC discussion below.
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Information on Registered Substances comes from registration dossiers which have been assigned a registration number. The assignment of a registration number does however not guarantee that the information in the dossier is correct or that the dossier is compliant with Regulation (EC) No 1907/2006 (the REACH Regulation). This information has not been reviewed or verified by the Agency or any other authority. The content is subject to change without prior notice.Reproduction or further distribution of this information may be subject to copyright protection. Use of the information without obtaining the permission from the owner(s) of the respective information might violate the rights of the owner.
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