Aluminium tri-sec-butanolate

Short-term toxicity to fish

Link to relevant study record(s)

Reference

Reference 1

Endpoint:

short-term toxicity to fish

Type of information:

experimental study

Adequacy of study:

weight of evidence

Reliability:

2 (reliable with restrictions)

Rationale for reliability incl. deficiencies:

comparable to guideline study with acceptable restrictions

Guideline:

OECD Guideline 203 (Fish, Acute Toxicity Test)

Deviations:

yes

Remarks:

exposure period 48 hours

Principles of method if other than guideline:

10 fish per concentration were exposed to 0, 1.25, 2.5 and 12.5 mg/L (as Al) AlCl3 during 48 hours. Next to mortality, tissue concentrations of aluminum, effects on gill morphology, Na+, K+ -ATPase (NKA) activity, and global gene expression patterns were examined.

GLP compliance:

no

Remarks:

Information on GLP is not reported. Quality of the report implies that GLP conditions were met.

Analytical monitoring:

yes

Details on sampling:

from the middle of the exposure tank

Vehicle:

no

Details on test solutions:

No data

Test organisms (species):

Danio rerio (previous name: Brachydanio rerio)

Details on test organisms:

TEST ORGANISM
- Common name: Zebra fish
- Source: Ekk-Will (Gibsonton Florida UDA) wild caught

QUARANTINE (wild caught): kept at University of Florida Aquatic Toxicology Facility
- Duration:no data
- Health/mortality: no data
- conditions; in dechlorinated water (under conditions similar as during the test)

FEEDING DURING TEST; no data

Test type:

static

Water media type:

freshwater

Limit test:

no

Total exposure duration:

48 h

Hardness:

142 mg/L as CaCO3

Test temperature:

no data

pH:

6.73 , 6.72, 6.08, 5.99 and 4.34 at 0, 0.5, 2.5, 5 and 12.5 mg/L

Dissolved oxygen:

8.5-8.9 mg/L

Conductivity:

395 uS

Nominal and measured concentrations:

nominal 0. 0.5, 2.5, 5 and 12.5 mg/L as Al
measured total Al: 0.55-0.65 mg/L at 0.5 mg/L, 2.4-2.6 mg/L at 2.5 mg/L, 10-14 mg/L at 12.5 mg/L (values taken from a figure in the publication)
measured dissolved Al: ca 0.15 mg/L at 0.5 mg/L, ca 0.1 mg/L at 2.5 mg/L, ca 0.1 mg/L at 12.5 mg/L (values taken from a figure in the publication)

Details on test conditions:

TEST SYSTEM
- Test vessel: no data
- No. of organisms per vessel: 10

TEST MEDIUM / WATER PARAMETERS: dechlorinated water

OTHER TEST CONDITIONS
- Adjustment of pH: no
- Photoperiod: no data

EFFECT PARAMETERS MEASURED: mortality, tissue concentrations of aluminum, effects on gill morphology, Na+, K+ -ATPase (NKA) activity, and global gene expression patterns

Duration:

48 h

Dose descriptor:

LC100

Effect conc.:

12.5 mg/L

Nominal / measured:

meas. (not specified)

Conc. based on:

element

Basis for effect:

mortality (fish)

Duration:

48 h

Dose descriptor:

LC0

Effect conc.:

5 mg/L

Nominal / measured:

nominal

Conc. based on:

element

Basis for effect:

mortality (fish)

Details on results:

- tissue concentrations of aluminum: 0.51 and 0.67 ng Al/g ww at 0.5 and 2.5 mg/L (no treatment related effect)
- effects on gill morphology: thickening of the interlaminar regions and swelling of the lamellae at 2.5 mg/L
- Na+, K+ -ATPase (NKA) activity: increased at 0.5 mg/L and sign decreased (almost zero) at 2.5 mg/L (compared to controls)
- global gene expression patterns: significantly changed compared to controls at 5 mg/L

see executive summary

Reported statistics and error estimates:

ANOVA with Tukey's test; Shapiro Wilk test

Sublethal observations / clinical signs:

The pH seems to influence the toxicity of Al significantly. The author postulates that much of the effects may be related to insoluble Aluminium hydroxides, as the soluble concentrations do not differ much with increasing concentrations.

Conclusions:

Based on the outcome of the current test the LC50 in fish is between 5 and 12,5 mg Al /L
Effects on the gills are expected at concentration of 2.5 mg Al /L and above

Executive summary:

In freshwater fish, aluminum is a well-recognized gill toxicant, although responses are influenced by pH. Aluminum nanomaterials are being used in diverse applications that are likely to lead to environmental release and exposure. However, it is unclear if the effects of nanoparticulate aluminum are similar to those of other forms of aluminum or require special consideration. To examine the acute toxicological effects of exposure to aluminum nanoparticle (Al-NP)s, adult female zebrafish were exposed to either Al-NPs or aluminum chloride for up to 48 hours in moderately hard fresh water. Al-NPs introduced into test water rapidly aggregated and up to 80% sedimented from the water column during exposures. No mortality was caused by concentrations of Al-NP up to 12.5 mg/L. After exposure, tissue concentrations of aluminum, effects on gill morphology, Na+, K+ -ATPase (NKA) activity, and global gene expression patterns were examined. Exposure to both aluminum chloride and nanoparticulate aluminum resulted in a concentration dependent decrease in sodium potassium ATPase activity, although Al-NP exposure did not alter gill morphology as measured by filament widths. Decreased ATPase activity coincided with decreases in filamental NKA staining and mucous cell counts. Analysis of gill transcriptional responses demonstrated that exposure to 5 mg/L Al-NP only resulted in significant changes in expression of two genes, whereas aluminum chloride exposure significantly affected the expression of 105 genes. Taken together, these results indicate that nanoparticulate aluminum has little acute toxicity for zebrafish in moderately hard freshwater.

Reference 2

Endpoint:

short-term toxicity to fish

Type of information:

experimental study

Adequacy of study:

weight of evidence

Study period:

Not reported

Reliability:

2 (reliable with restrictions)

Rationale for reliability incl. deficiencies:

study well documented, meets generally accepted scientific principles, acceptable for assessment

Reason / purpose for cross-reference:

reference to same study

Qualifier:

no guideline followed

Principles of method if other than guideline:

Fish were exposed under flow-through conditions to solutions containing 5 concentrations of inorganic Al (Al–RSW) for 96 hours at pH 5.0. Basin volumes and flow rates were adjusted to ensure >99% molecular replacement of the basin volume (7 or 8 L) within 24 h. Mortality was observed for a calculation of an LC50.

GLP compliance:

not specified

Analytical monitoring:

yes

Details on sampling:

- Concentrations: all test concentrations and control
- Sampling method: samples taken daily using acid-washed pasticware
- Sample storage conditions before analysis: samples for analysis of total Al were acidified to pH 1.0 with concentrated trace-metal-grade HNO3 and were left at room temperature for at least 24 h before spectrophotometric analysis

Vehicle:

no

Details on test solutions:

PREPARATION AND APPLICATION OF TEST SOLUTION
- Controls: RSW water
- All other template details: Not reported

Test organisms (species):

Salmo salar

Details on test organisms:

TEST ORGANISM
- Common name: Atlantic salmon
- Source: provincial fish hatchery (Ministe`re de Loisir, Chasse et Pêche, Gaspe´, QC, Canada) and from a commercial aquaculture establishment (La Pisciculture Saukeb, Nouvelle, Gaspé, QC, Canada). The stocks of salmon originated from rivers of the Gaspé (MLCP) and North Shore (La Pisciculture Saukeb) regions of Québec.
- Age at study initiation (mean and range, SD): juvenile
- Weight at study initiation (mean and range, SD): average wet weight 1.8 ± 0.8 g

ACCLIMATION
- Acclimation period: at least 2 weeks
- Acclimation conditions: same as test
- Type and amount of food: trout chow pellets ad libitum
- Feeding frequency: fish were not fed for 24 hours prior to the experiment
- Health during acclimation (any mortality observed): not reported

QUARANTINE (wild caught): Not reported

Test type:

flow-through

Water media type:

freshwater

Limit test:

no

Total exposure duration:

96 h

Post exposure observation period:

Not reported

Hardness:

Not reported

Test temperature:

10 degrees C

pH:

Nominal: 5.0
Measured: 4.96 ± 0.06, n=54

Dissolved oxygen:

> 85% saturation

Salinity:

Not applicable

Nominal and measured concentrations:

Measured (μM): 0.4 (control), 1.1 ± 0.1, 2.2 ± 0.1, 3.4 ± 0.1, 3.2 ± 0.1, 3.9 ± 0.1

Details on test conditions:

TEST SYSTEM
- Test vessel: 7 or 8 L tanks
- Renewal rate of test solution (flow rate):>99% molecular replacement of the basin volume (7 L) within 24 hr
- No. of organisms per vessel: 7
- No. of vessels per concentration (replicates): 4
- No. of vessels per control (replicates): 4

TEST MEDIUM / WATER PARAMETERS
- Source/preparation of dilution water: RSW was prepared by the addition of salts to deionized water
- Total organic carbon: 1-3 mg C/L

OTHER TEST CONDITIONS
- Photoperiod: 12 hr light : 12 hr dark

EFFECT PARAMETERS MEASURED: mortality observed every 3 hours during the day and 7 hours at night

Duration:

96 h

Dose descriptor:

LC50

Effect conc.:

>= 0.078 - <= 0.108 mg/L

Nominal / measured:

meas. (not specified)

Conc. based on:

element

Basis for effect:

mortality (fish)

Remarks on result:

other: 95% CL 2.5-3.2 µmol/L: RSW experiment

Remarks:

based on inorganic Al concentration

Details on results:

Not reported

Results with reference substance (positive control):

Not applicable

Reported statistics and error estimates:

The LC50 values and their 95% confidence limits were determined using the Spearman–Karber method.

Conclusions:

The 96 hr LC50 for Salmo salar exposed to Al in solution was 2.9 µM Al (0.075 mg/l).

Reference 3

Endpoint:

short-term toxicity to fish

Type of information:

experimental study

Adequacy of study:

weight of evidence

Study period:

1978

Reliability:

2 (reliable with restrictions)

Rationale for reliability incl. deficiencies:

other: Not GLP. According to guideline. Although some details (concentrations, light period, pH and O2 measurement, controls, and replicates) are not reported, the study meets generally accepted scientific principles

Qualifier:

according to guideline

Guideline:

other: Deutsche Einheitsverfahren zur Wasser-, Abwasser- und Schlammuntersuchung. L 15: Fischtest (Bestimmung der Wirkung von Wasserinhaltsstoffen auf Fische). Pre-print in Vom Wasser 46:291-295 (1976). Later: DIN 38412-15

GLP compliance:

no

Specific details on test material used for the study:

Details on properties of test surrogate or analogue material:
Aluminium tri-sec-butylate reacts instantaneously with water to form 2-butanol and Al3+ species. The resulting pH being weakly alkaline indicates according to Langmuir et al. 2004 that Al3+ species formed are mainly Al(OH)4-, Al(OH)3 and Al(OH)2+ at pH 8.5.
Thus, aluminium tri-sec-butylate is abiotically degradable and forms 2-butanol being readily biodegradable as shown in the registration dossier of 2-butanol submitted by the same lead registrant. Thus, 2-butanol is the ideal surrogate for testing toxicity effects on fish posed by the organic moiety of the reference substance.

Analytical monitoring:

no

Vehicle:

no

Test organisms (species):

Leuciscus idus melanotus

Details on test organisms:

TEST ORGANISM
- Common name: Golden orfe
- Length at study initiation: 5-7 cm
- Weight at study initiation: 1.5 ± 0.3 g
- Method of breeding: 5 fish/L. Fed with dry fish-food (10-20 mg). Mortality < 1% per week
- Feeding during test: none

ACCLIMATION
- Acclimation period: at least 3 days
- Acclimation conditions: same as test
- Type and amount of food: 2 days before test no food
- Feeding frequency: normally 3 times/week

Test type:

static

Water media type:

freshwater

Limit test:

no

Total exposure duration:

48 h

Hardness:

15 ± 3 ° dH

Test temperature:

20 ± 1 °C

pH:

7-8

Dissolved oxygen:

> 5mg/L

Details on test conditions:

According to guideline
TEST SYSTEM:
- Test vessel: aquaria
- Type: open
- Material: glass; size: 24x32x22 (17L); fill volume: 10 L
- Aeration: glass pipette (1-3 blows/s)
- No. of organisms per vessel: 10

TEST MEDIUM / WATER PARAMETERS
- Source/preparation of dilution water: dechlorinated water
- Ca/Mg ratio: 2.7 ± 0.5 mmol/L

EFFECT PARAMETERS MEASURED: mortality (daily)

Duration:

48 h

Dose descriptor:

LC0

Effect conc.:

3 120 mg/L

Nominal / measured:

nominal

Conc. based on:

test mat.

Basis for effect:

mortality (fish)

Duration:

48 h

Dose descriptor:

LC0

Effect conc.:

2 400 mg/L

Nominal / measured:

nominal

Conc. based on:

test mat.

Basis for effect:

mortality (fish)

Duration:

48 h

Dose descriptor:

LC50

Effect conc.:

3 520 mg/L

Nominal / measured:

nominal

Conc. based on:

test mat.

Basis for effect:

mortality (fish)

Duration:

48 h

Dose descriptor:

LC50

Effect conc.:

3 540 mg/L

Nominal / measured:

nominal

Conc. based on:

test mat.

Basis for effect:

mortality (fish)

Duration:

48 h

Dose descriptor:

LC100

Effect conc.:

3 600 mg/L

Nominal / measured:

nominal

Conc. based on:

test mat.

Basis for effect:

mortality (fish)

Duration:

48 h

Dose descriptor:

LC100

Effect conc.:

4 000 mg/L

Nominal / measured:

nominal

Conc. based on:

test mat.

Basis for effect:

mortality (fish)

Validity criteria fulfilled:

not specified

Conclusions:

The LC50(48 h) of 2-butanol in the Golden orfe acute toxicity test from two different laboratories is: 3520-3540 mg/L

Executive summary:

Aluminium tri-sec-butylate reacts instantaneously with water to form 2-butanol and Al3+ species. The resulting pH being weakly alkaline indicates according to Langmuir et al. 2004 that Al3+ species formed are mainly Al(OH)4-, Al(OH)3 and Al(OH)2+ at pH 8.5.

Thus, aluminium tri-sec-butylate is abiotically degradable and forms 2-butanol being readily biodegradable as shown in the registration dossier of 2-butanol submitted by the same lead registrant. Thus, 2-butanol is the ideal surrogate for testing toxicity effects on fish posed by the organic moiety of the reference substance. 2-butanol showed a low aquatic toxicity towards golden orfe and an LC50 (48h) of 3520 mg/l is taken forward for classification and risk assessment in this dossier for the organic moiety.

Description of key information

Aluminium tri-sec-butanolate dissociates instantaneously when exposed to water forming butan-2-ol and aluminium(III) species.

The inorganic moiety shows LC50 values between 0.078 mg Al/L (Roy_Campbell 1997) and > 800 mgAl/L (Kovriznych 2013). These values strongly depend on the Al species tested, pH and the life-stage of the fish. Effects on the gills are expected at concentration of 2.5 mg Al /L (Griffith 2010)

In a worst case approach the LC50 in fish has been set at 0.078 mg Al/L.

For butan-2-ol the LC50(48 h) in the Golden orfe is 3520 mg/L (Juhnke 1978). Indicative of a very low toxicity.

Key value for chemical safety assessment

Fresh water fish

Fresh water fish

Effect concentration:

0.078 mg/L

Additional information

Aluminium tri-sec-butanolate reacts instantaneously with water to form butan-2-ol and Al3+ species. The resulting pH being weakly alkaline indicates according to Langmuir et al. 2004 that Al3+ species formed are mainly Al(OH)4-, Al(OH)3 and Al(OH)2+ at pH 8.5.

Thus, aluminium tri-sec-butanolate is abiotically degradable and forms sec-butanol being readily biodegradable as shown in a publication by Bridie (1979).

The inorganic moiety that forms in aqueous systems are insoluble Al3+ species. These were investigated by testing the more soluble aluminium chloride at pH 5 -7 for acute toxicity. The 48 hr LC50 for juvenile Danio rerio exposed to Al as AlCl3 was between 5 and 12.5 mg Al/L (Griffith 2010). Testing of aluminium phosphate tested in adult Salmo salar gave an LC50 of 0.078 mg/L (Roy-Campbell 1997), while aluminium oxide seemed much less toxic with an LC50 > 800 mg/L in adult Danio rerio (Kovriznych 2013).

Sec-butanol is of very low acute toxicity to fish.

Hence, both sec-butanol and aluminium species will be present in aqueous media. Based on its toxicity, aluminium species seem to represent a worst case surrogate for assessing toxicity to aquatic species exposed to the substance, aluminium tri-sec-butanolate.