Reaction mass of copper oxide and manganese dioxide

Ecotoxicological Summary

Hazard for aquatic organisms

Freshwater

Hazard assessment conclusion:

PNEC aqua (freshwater)

PNEC value:

7.8 µg/L

Assessment factor:

1

Extrapolation method:

sensitivity distribution

PNEC freshwater (intermittent releases):

7.8 µg/L

Marine water

Hazard assessment conclusion:

PNEC aqua (marine water)

PNEC value:

0.78 µg/L

Assessment factor:

10

Extrapolation method:

sensitivity distribution

PNEC marine water (intermittent releases):

0.78 µg/L

STP

Hazard assessment conclusion:

PNEC STP

PNEC value:

0.14 mg/L

Assessment factor:

100

Extrapolation method:

assessment factor

Sediment (freshwater)

Hazard assessment conclusion:

PNEC sediment (freshwater)

PNEC value:

87 mg/kg sediment dw

Assessment factor:

1

Extrapolation method:

sensitivity distribution

Sediment (marine water)

Hazard assessment conclusion:

PNEC sediment (marine water)

PNEC value:

8.7 mg/kg sediment dw

Assessment factor:

10

Extrapolation method:

sensitivity distribution

Hazard for air

Air

Hazard assessment conclusion:

no hazard identified

Hazard for terrestrial organisms

Soil

Hazard assessment conclusion:

PNEC soil

PNEC value:

45.6 mg/kg soil dw

Assessment factor:

1

Extrapolation method:

sensitivity distribution

Hazard for predators

Secondary poisoning

Hazard assessment conclusion:

no potential for bioaccumulation

Additional information

Hazard assessment for the aquatic environment

FRESHWATER, PNEC aqua (freshwater)

Reliable long-term studies used for hazard assessment of reaction mass of copper oxide and manganese dioxide covered three trophic levels, i.e. algae, daphnia and fish. Key values were derived based on bioavailable copper, because it was the more hazardous element compared to manganese, which are both components of the registration substance. The most sensitive species was fish with endpoint juvenile growth. i.e. 60d-NOEC (Salvelinus fontinalis, fry growth) = 5 µg Cu/L.

In the EU assessment report on copper oxide (Directive 98/8/EC concerning the placing of biocidal products on the market, Copper (II) oxide, 2011, France), PNEC derivation for freshwater was based on a species sensitivity distribution (SDD). The most sensitive species in the data set was fish, concerning the endpoint growth (NOEC = 2.2 µg Cu/L). Comparing the most sensitive NOECs reported here and in the EU assessment report, results were similar (i.e., fish, endpoint growth, concentration range 2.2 – 5 µg Cu/L).

Based on SSD, a HC5-50 (HC5-50: hazardous concentration (HC) of median fifth percentile of the SSD) of 7.8 µg Cu/L was derived in the EU assessment report. The HC5-50 was used as PNEC freshwater of 7.8 μg Cu/L (assessment factor, AF = 1) in a generic context in absence of site-specific information on bioavailability parameters (such as pH, DOC, hardness). Therefore, the officially recommended PNEC freshwater for constituent copper oxide was adopted for the reaction mass of copper oxide and manganese dioxide. The same PNEC was applied for PNEC freshwater, intermittent release, i.e. 7.8 µg Cu/L.

 

MARINE, PNEC aqua (marine water)

As explained above, aquatic PNEC derivation for freshwater was based on a species sensitivity distribution (SDD) (EU assessment report on copper oxide from 2011, Directive 98/8/EC concerning the placing of biocidal products on the market, Copper (II) oxide, 2011, France). The HC5-50 was used to derive a PNEC freshwater of 7.8 μg Cu/L (AF = 1). In order to account for uncertainties with regard to the marine environment, an additional assessment factor of 10 was applied. Therefore, the PNEC marine water was 0.78 μg Cu/L. The same PNEC was applied for PNEC marine water, intermittent release, i.e. 0.78 µg Cu/L.

 

SEWAGE TREATMENT PLANT, PNEC stp

Reliable toxicity studies on microorganisms used for hazard assessment of reaction mass of copper oxide and manganese dioxide were available for both metal oxides. The PNEC stp was based on element copper, because it was the more hazardous element compared to manganese. Microorganism toxicity was assessed in reliable activated sludge respiration inhibition studies (n=225) acc. to OECD 209. The determined average 3h-EC50 of the lower valid range was 14 mg Cu/L. The derived PNEC stp with the applied assessment factor of 100 was therefore 0.14 mg Cu/L.

In the EU assessment report on copper oxide (Directive 98/8/EC concerning the placing of biocidal products on the market, Copper (II) oxide, 2011, France), the lowest reliable NOEC for respiration inhibition of STP microorganisms was 0.23 mg/L dissolved copper. The value was used for the derivation of PNEC stp of 0.23 mg Cu/L. Both derived PNECs were comparable, i.e. 0.14 mg Cu/L vs. 0.23 mg Cu/L. For the reaction mass of copper oxide and manganese dioxide, the more sensitive PNEC stp of 0.14 mg Cu/L was chosen.

 

SEDIMENT freshwater, PNEC sediment (freshwater)

There are no data requirements on sediment toxicity data according to REACH Annex VIII. Therefore, the available PNECs presented in the EU assessment report on copper oxide were adopted (Directive 98/8/EC concerning the placing of biocidal products on the market, Inclusion of active substances in Annex I or IA to Directive 98/8/EC Assessment Report, Copper (II) oxide, 2011, France). The derived PNEC sediment for freshwater was 87 mg Cu/kg dry weight for sediment with 5% OC based on SSD. The PNEC sediment was adopted for reaction mass of copper oxide and manganese dioxide. A PNEC sediment based on element copper was considered protective, because it was the more hazardous element compared to manganese.

 

SEDIMENT marine, PNEC sediment (marine water)

There are no data requirements on sediment toxicity data according to REACH Annex VIII. Therefore, the available PNECs presented in the EU assessment report on copper oxide were adopted (Directive 98/8/EC concerning the placing of biocidal products on the market, Inclusion of active substances in Annex I or IA to Directive 98/8/EC Assessment Report, Copper (II) oxide, 2011, France). The derived PNEC sediment for freshwater was 87 mg Cu/kg dry weight for sediment with 5% OC based on SSD. The PNEC sediment was adopted, and in order to account for uncertainties with regard to the marine environment, an additional assessment factor of 10 was applied. Therefore, the PNEC sediment, marine water for reaction mass of copper oxide and manganese dioxide was 8.7 mg/L sediment dw. A PNEC sediment, marine water based on element copper was considered protective, because it was the more hazardous element compared to manganese.

 

Hazard assessment for the terrestrial environment

SOIL, PNEC soil

There are no data requirements on soil toxicity data according to REACH Annex VIII. Therefore, the available PNECs presented in the EU assessment report on copper oxide were adopted (Directive 98/8/EC concerning the placing of biocidal products on the market, Copper (II) oxide, 2011, France). The derived PNEC soil was 45 mg Cu/kg dry weight in absence of site-specific information on soil properties. The PNEC soil was adopted for the reaction mass of copper oxide and manganese dioxide. A PNEC soil based on element copper was considered protective, because it was the more hazardous element compared to manganese.

Hazard assessment for the secondary poisoning

According to the evaluation of the EU assessment report on copper oxide (Directive 98/8/EC concerning the placing of biocidal products on the market, Copper (II) oxide, 2011, France), bioaccumulation and biomagnification did not apply for the constituent copper oxide of the submission substance, because bioavailable copper was an essential micronutrient and molecular mechanism of copper homeostasis exist in organisms.

For the constituent manganese dioxide, the OECD SIDS report on manganese dioxide (NIER, Republic of Korea, 2007) reported that manganese significantly bioconcentrated in lower organisms, e.g. marine plants (10-20000) and invertebrates (10-40,000), but showed small bioconcentration in fish (100-600), indicating that manganese has very low potential to accumulated in the food chain (Manganese and its compounds, International Programme on Chemical Safety (Concise International Chemical Assessment Document 12), WHO, Geneva, Switzerland).

In conclusion, no hazard due to secondary poisoning for the submission substance was anticipated.

Conclusion on classification

Classification according to Regulation (EC) No 2008/1272 (CLP)

The submission substance was classified according to the criteria set out for classification of a mixture, i.e. the summation method was applied to all components of the submission substance. Harmonised classifications acc. to Annex VI of the CLP Regulation were available for the main constituents manganese dioxide (not classified) and copper oxide (classified as Aquatic Acute 1 (H400, M-factor = 100), Aquatic Chronic I (H410, no M-factor).

 

Acute hazard category

The submission substance was classified as Aquatic Acute 1 (H400) for the environment according to Regulation No (EC) 2008/1272.

 

Chronic hazard category

The submission substance was classified as Aquatic Chronic 1 (H410) for the environment according to Regulation No (EC) 2008/1272.

 

In conclusion, the submission substance was classified as Aquatic Acute 1 (H400) and Aquatic Chronic 1 (H410).