Registration Dossier

Ecotoxicological information

Long-term toxicity to fish

Currently viewing:

Administrative data

Link to relevant study record(s)

Reference
Endpoint:
long-term toxicity to fish
Type of information:
other: Secondary source
Adequacy of study:
key study
Reliability:
2 (reliable with restrictions)
Rationale for reliability incl. deficiencies:
other: Study summarised in ICD and EU RAR. Methodologcial data for individual studies are incomplete, however the studies have been assessed as part of the EU RAR and are therefore considered to be suitably reliable.
Reason / purpose for cross-reference:
read-across: supporting information
Qualifier:
equivalent or similar to guideline
Guideline:
other: no guideline stated
Principles of method if other than guideline:
21-day fish toxicity study
GLP compliance:
no
Specific details on test material used for the study:
Details on properties of test surrogate or analogue material (migrated information):
No further details
Analytical monitoring:
yes
Details on sampling:
No further detials in review
Vehicle:
not specified
Details on test solutions:
No further details in review
Test organisms (species):
Oncorhynchus mykiss (previous name: Salmo gairdneri)
Details on test organisms:
No further details
Test type:
static
Water media type:
freshwater
Limit test:
no
Total exposure duration:
21 d
Post exposure observation period:
Not relevant
Hardness:
soft water (12 mg CaCO3/l)
Test temperature:
Not reported
pH:
Not reported
Dissolved oxygen:
Not reported
Salinity:
Not reported
Nominal and measured concentrations:
Measured concentration
Details on test conditions:
The test was conducted in very soft (12 mg CaCO3/l) natural water with daily renewal of the test water.
Reference substance (positive control):
no
Duration:
21 d
Dose descriptor:
NOEC
Effect conc.:
4 mg/L
Nominal / measured:
meas. (not specified)
Basis for effect:
mortality
Details on results:
In a 21 day test with Oncorhynchus mykiss a LC5 value of 4 mg/L was reported (actual concentration). This value is considered to be equivalent to the NOEC for mortality. The test was conducted in very soft (12 mg CaCO3/L) natural water with daily renewal of the test water.
Results with reference substance (positive control):
No results reported.
Reported statistics and error estimates:
No results reported.

In a 21 day test with Oncorhynchus mykiss a LC5 value of 4 mg/L was reported (actual concentration). This value is considered to be equivalent to the NOEC for mortality. The test was conducted in very soft (12 mg CaCO3/L) natural water with daily renewal of the test water.

Conclusions:
In a 21 day test with Oncorhynchus mykiss a LC5 value of 4 mg/L was reported (actual concentration). This value is considered to be equivalent to the NOEC for mortality. The test was conducted in very soft (12 mg CaCO3/L) natural water with daily renewal of the test water.
Executive summary:

In a 21 day test with Oncorhynchus mykiss a LC5 value of 4 mg/L was reported (actual concentration). This value is considered to be equivalent to the NOEC for mortality. The test was conducted in very soft (12 mg CaCO3/L) natural water with daily renewal of the test water.

Description of key information

Calcium fluoride is the main constituent of the substance, so its worst case value was chosen for the registered dossier. The 2 others constituents of the substance, calcium sulfate and calcium carbonate, are ubiquitous in the environment and essential to living organims : no long-term studies are available and no hazards are expected for both constituents.

As no studies are available for calcium fluoride, two data have been found for long term toxicity of flluorides on fish. One LC5 (21d,Onchorhynchus mykiss) value of 5 mg/L (Sloof, 1988) has been mentioned in the review of HF of the EU RAR (2001). Unfortunately, this value has not been found in litterature and it can’t be considered as reliability Klimish 2 due to the lack of informations : this data should be considered as reliability 4. Another fish long-term data from the RIVM document (1989, written by Sloof et al.) has been found : field data with healthy populations of trout in surface waters containing up to 14 mg/L of fluoride ions which corresponds to a NOEC value. This value has been used for calcium fluoride as worst case value :

NOEC =14 mg/L (based on concentrations of fluoride ions) which is equivalent to an NOEC of 28.8 mg/L for CaF2

As calcium fluoride is present at 47.5% in the reaction mass of calcium fluoride, calcium sulfate and calcium carbonate, the NOEC used for the registered substance is equal to 60.5 mg/L.

The water solubility of calcium fluoride is lower (15 mg/L) than the NOEC value (60.5 mg/L based on fluoride equivalent for the reaction mass), no toxiciy of the registered substance is expected on fishes at long term.

Long term toxicity data for marine fish are not available.

References :

EU RAR Hydrogen Fluoride, Volume 8, (2001)

Integrated Criteria Document Fluorides. Sloof W, Eerens HC, Janus JA & Ros RPM. (1989) National Institute of Public Health and Environmental Protection, Netherlands

Key value for chemical safety assessment

Fresh water fish

Fresh water fish
Effect concentration:
60.5 mg/L

Additional information

The substance is a reaction mass of calcium fluoride and calcium sulfate and calcium carbonate. No studies are available on the substance itself, nor on calcium fluoride. However, two data have been found for long term toxicity of fluorides on fish. One LC5 (21d,Onchorhynchus mykiss) value of 5 mg/L (Sloof, 1988) has been mentioned in the review of HF of the EU RAR (2001). Unfortunately, this value has not been found in litterature and it can’t be considered as reliability Klimish 2 due to the lack of informations : this data should be considered as reliability 4. Another fish long-term data from the RIVM document (1989, written by Sloof et al.) has been found : field data with healthy populations of trout in surface waters containing up to 14 mg/L of fluoride ions which corresponds to a NOEC value (equivalent to 28.77 mg/L). This value has been used for calcium fluoride as worst case value.

Regarding the 2 others constituents of the substance, calcium sulfate and calcium carbonate, they are known to be ubiquitous in the aquatic environment and essential constituents to living organims, including invertebrates. Aquatic organisms (eg : fish) are constantly exposed to calcium carbonate and calcium sulfate without suffering from any adverse or detrimental effects. No chronic studies are available for both constituents. Based on acute toxicity test available, calcium sulfate and calcium carbonate are considered not acutely toxic to fishes and hence long term testing is considered to be unnecessary.

Using a weight of evidence approach for the 3 constituents of the substance, calcium fluoride is the main constituent and is used as a worst case, with a NOEC of 28.77 mg/L. Regarding the 2 others constituents of the substance, calcium, sulfate and carbonate ions are extremely common in all natural surface waters and are therefore ubiquitous in the environment. Seawater contains approximately 400 ppm calcium and rivers generally contain 1-2 ppm calcium but in lime areas rivers may contain calcium concentrations as high as 100 ppm (Lenntech, 2010). One of the main reasons for the abundance of calcium in water is due to its natural occurrence in the Earth’s crust. These calcium-rich rocks undergo physical and/ or chemical weathering in the environment. The calcium sediments are then carried by water from the mountains to oceans or lakes as well as to the land portion of the Biosphere and thereby become part of the calcium and carbon cycles. This natural abundance of calcium, sulfate and carbonate ions in the environment means that aquatic organisms including fish are constantly exposed to calcium sulfate and/or calcium carbonate without suffering from any adverse or detrimental effects. Furthermore, calcium, sulfate and carbonate are essential constituents of living organisms, including fish.

Because of its widespread occurrence in rocks and soils, and its ready solubility, calcium is present in nearly all waters (Hem 1967). Sulfates are also ubiquitous in the aquatic environment, occurring largely in the completely oxidized form (S6+) as sulfate (SO42-).  According to GEMS/Water, a global network of water monitoring stations, typical sulfate levels in freshwater are in the vicinity of 20 mg/litre and range from 0 to 630 mg/litre in rivers (the highest values are found in Belgium and Mexico), from 2 to 250 mg/litre in lakes (the highest value is found in Mexico) and from 0 to 230 mg/litre in groundwater (the highest values are found in Chile and Morocco) (UNEP 1990). Levels of sulfate in rivers in western Canada ranged from 1 to 3040 mg/litre, most concentrations being below 580 mg/litre (WHO 2004). Levels of sulfate in groundwater in the Netherlands were below 150 mg/litre (van Dijk-Looijaard and Fonds 1985). In 1970, the US Public Health Service measured sulfate levels in the drinking-water sources of nine geographic areas. Sulfate was found to be present in 645 of 658 groundwater supplies and in all of the 106 surface water supplies sampled. Sulfate levels ranged from <1 to 770 mg/litre, with a median of 4.6 mg/litre. Only 3% of the water supplies sampled had sulfate levels in excess of 250 mg/litre (US EPA 1999). Furthermore, sulfate concentrations in rain in Canada ranged between 1.0 and 3.8 mg/litre in 1980 (Franklin et al. 1985). An annual mean value of about 6 mg/litre in precipitation over central Europe has been reported (WHO/UNEP 1989). Levels of sulfate in rainwater and surface water correlate with emissions of sulfur dioxide from anthropogenic sources (Keller and Pitblade 1986). Seawater is reported to contain around 2700 mg of sulfate per litre (Hitchcock 1975). In conclusion, if the calcium and sulfate ions are ubiquitous in water, then long term exposure of fish to calcium sulfate should not be a cause for concern

 Calcium carbonate is also directly applied to lakes to mitigate the effects of surface water acidification and to ensure the survival of aquatic species (Driscoll et al 1987). This use therefore implies that calcium carbonate is not toxic to fish following long term exposure. A 6 year study by Popp et al (1996) demonstrated that the addition of calcium carbonate to a slightly acidic lake did not adversely affect the integrity of the fish community and in fact may have increased the abundance and biomass of the forage fish community and indirectly increased the survival, abundance and growth of brook trout.

NOEC value (28.77 mg/L) of calcium fluoride has been used, as worst case, for the registered dossier of the reaction mass of calcium fluoride and calcium sulfate and calcium carbonate.

As calcium fluoride is present at 47.5% in the reaction mass of calcium fluoride, calcium sulfate and calcium carbonate, the NOEC used for the registered substance is equal to 60.5 mg/L.

The water solubility of calcium fluoride is lower (15 mg/L) than the NOEC value (60.5 mg/L based on fluoride equivalent for the reaction mass), no toxicity of the registered substance is expected on fishes at long term.