Diphosphoric acid, copper salt

Ecotoxicological Summary

Hazard for aquatic organisms

Freshwater

Hazard assessment conclusion:

PNEC aqua (freshwater)

PNEC value:

29.4 µg/L

Assessment factor:

1

Extrapolation method:

sensitivity distribution

Marine water

Hazard assessment conclusion:

PNEC aqua (marine water)

PNEC value:

19.6 µg/L

Assessment factor:

1

Extrapolation method:

assessment factor

STP

Hazard assessment conclusion:

PNEC STP

PNEC value:

866.8 µg/L

Assessment factor:

1

Extrapolation method:

sensitivity distribution

Sediment (freshwater)

Hazard assessment conclusion:

PNEC sediment (freshwater)

PNEC value:

327.9 mg/kg sediment dw

Assessment factor:

1

Sediment (marine water)

Hazard assessment conclusion:

PNEC sediment (marine water)

PNEC value:

2 547.8 mg/kg sediment dw

Assessment factor:

1

Extrapolation method:

equilibrium partitioning method

Hazard for air

Air

Hazard assessment conclusion:

no hazard identified

Hazard for terrestrial organisms

Soil

Hazard assessment conclusion:

PNEC soil

PNEC value:

245 mg/kg soil dw

Assessment factor:

1

Hazard for predators

Secondary poisoning

Hazard assessment conclusion:

no potential for bioaccumulation

Additional information

Approach for PNEC derivation

 

The derived PNECs for Copper (II) pyrophosphate (CuPP) are based on the PNECs for copper and copper compounds published in a voluntary risk assessment report of copper and copper compounds which has been submitted to the European Chemicals Agency by the European Copper Institute. This report is based on the industry initiative to perform a voluntary risk assessment on a substance according to the mechanisms of the implementation of the Existing Substance Regulation (EEC) No 793/93 (ESR). The procedure was agreed by the 11th Joint Meeting of the Competent Authorities for the Implementation of Directive 67/548/EEC and ESR Regulation.

 

All high quality and ecological relevant chronic data (NOECs and EC10s) (also from non-standard protocols) were retained for the PNEC derivation. This resulted in a large amount of reliable and relevant environmental effects data of soluble copper compounds for a broad range of relevant species, covering key ecological compartments (freshwater, marine waters, freshwater sediments, terrestrial, and sewage treatment plants).

The assessment of the environmental hazard recognises that copper is a natural element and an essential nutrient and therefore important additional information of relevance for the PNEC derivations for the freshwater and marine compartments are also taken into account. Effects due to copper deficiency in addition to the effects of copper excess are reported. Information from scientific studies designed to elucidate the mechanism of action of Cu-ions are also reported. Toxicity from waterborne and dietary exposure routes is evaluated. Single species as well as multi-species laboratory or field test set-ups are assessed. As both the natural background copper concentrations and the additional added amounts by producing and using CuPP contribute to the observed effects, the present risk assessment implements the total risk approach. Information on background variability (in culture media and natural European environments (water, sediments, soils)) and its influence on a number of biological/ecological processes (e.g. optimal concentration ranges, acclimation/adaptation, field community responses) is nevertheless crucial for the derivation of ecological relevant PNEC values and are therefore also considered in the chemical safety report.

 

For the freshwater PNEC derivation, a weight of evidence approach is applied using the information from the different environmental compartments: (1) using the freshwater PNEC in an equilibrium partitioning approach; (2) using the high quality freshwater sediment NOECs and (3) comparison with soil NOECs. For the estuarine and marine PNEC derivations, the equilibrium partitioning approach is applied.

 

Derivation of PNECs for CuPP

 

For CuPP (Cu.xH4O7P2; SMILES: [Cu+2].[O-]P(O)(=O)OP([O-])(O)=O) the PNECs derived for copper were corrected as follows:

 

PNEC (CuPP) = PNEC (Cu) x (M(CuPP) / (M(Cu))

 

The molecular weight for CuPP is 239.5 g/mol.

The atomic weight for Cu is ca. 63.546 g/mol, and should be multiplied where > 1 Cu molecule is present, which is not necessary for CuPP.

 

PNEC (CuPP) = PNEC (Cu) x (239.5 / 63.546)

 

Table 1 provides an overview of PNECs derived for copper as published in the voluntary risk assessment report and CuPP.

 

Table 1 Overview of derived PNECs for Cu and CuPP.

Compartment	Hazard conclusion for Cu	Hazard conclusion for CuPP
PNEC aqua (freshwater)	7.8 µg/L	29.4 µg/L
PNEC aqua (marine water)	5.2 µg/L	19.6 µg/L
PNEC sediment (freshwater)	87 mg/kg sediment dw	327.9 mg/kg sediment dw
PNEC sediment (marine water)	676 mg/kg sediment dw	2547.8 mg/kg sediment dw
PNEC STP	230 µg/L	866.8 µg/L
PNEC soil	65 mg/kg soil dw	245 mg/kg soil dw
Air	Dicopper is non-volatile and as such is not considered to be a hazard for the air.	Dicopper is non-volatile and as such is not considered to be a hazard for the air.
Secondary poisoning	No potential for bioaccumulation	No potential for bioaccumulation

 

 

Conclusion on classification

Approach for Environmental classification

 

The high quality short term toxicity data for the hazard classification of copper, discussed by the competent authorities for EU classification and labelling have been included in the IUCLID database. 

 

For the acute and chronic classification of copper, information on acute (short term EC50 values) and chronic (long term NOEC/EC10 values) effects of soluble copper compounds to freshwater organisms (fish, invertebrates, algae and aquatic plants) are included in the IUCLID. Considering the large amount of information available, only high quality data derived from standard testing protocols and species were retained. Further considering the data-richness of the copper database, data summaries were carried out: when 4 or more acceptable L(E)C50 /NOEC values are available for the same species, the geometric mean of the toxicity values was used as representative toxicity value for that species instead of the lowest value for the species.

Considering the crucial importance of pH of the test media on the copper solubility and ecotoxicity, for the acute and chronic toxicity endpoints, 3 pH categories were distinguished within the acute and chronic ecotoxicity database: pH 5.5-6.5, >6.5-7.5 and >7.5-8.5. The lowest species-specific acute L(E)C50 and chronic NOEC values at the three pH levels and across pHs were selected as final environmental classification reference values.

 

For classification purposes, these are to be translated to the respective soluble copper compounds using a molecular weight translation. They are translated to the classification of sparingly soluble copper compounds, copper powders and copper massives using the results of the transformation/dissolutions.

 

All data and a synthesis of the species mean/lowest acute ecotoxicity data are given in Table 1 and Annex 2 (Table 2A) of the document attached at IUCLID section 6.1 Endpoint summary for aquatic toxicity (“Acute & chronic ecotoxicity of soluble copper species in view of hazard classification of copper and copper compounds and classification of copper in massive and powder form”; Update of EU RA Appendix K1; P. Van Sprang, Arche Belgium, K. Delbeke, ECI Belgium).

 

Acute reference values for classification

After data selection, as discussed above, 451 high quality acute data points were retained. For the algae 66 individual data points were selected for 3 standard species (Pseudokirchnerella subcapitata, Chamydomonas reinhardtii and Chlorella vulgaris). For the invertebrates 123 individual data points were selected for 2 standard species (Ceriodaphnia dubia and Daphnia magna) and for the fish 262 individual data points were selected for 5 standard species (Oncorhynchus mykiss, Pimephales promelas, Lepomis macrochirus, Brachydanio rerio and Cyprinus carpio).

 

Chronic reference values for classification

After data selection, 90 high quality chronic data points were retained. For the algae/aquatic plants, 33 individual data points were selected for 4 standard species (Raphidocelis subcapitata, Chlorella vulgaris, Chlamydomonas reinhardti and Lemna minor). For the invertebrates 23 individual data points were selected for 3 standard species (Ceriodaphnia dubia, Daphnia magna, Daphnia pulex). For the fish, 34 individual data points were selected for 3 standard species (Oncorhynchus mykiss, Pimephales promelas and Salvelinus fontanilis).

 

The lowest species-specific acute L(E)C50 and chronic NOEC values at the three pH levels and across pHs were selected as final environmental classification reference values. The derived values acute and chronic reference values are provided in Table 1.

 

Table 1: Acute and chronic reference values for soluble copper ions

pH range	Acute reference L(E)C50 (mg Cu/L)	Chronic reference NOEC (mg Cu/L)
pH 5.5-6.5	0.025	0.02
pH >6.5-7.5	0.035	0.074
pH >7.5-8.5	0.0298	0.0114
Across pHs	0.0344	0.0149

 

 

Environmental classification justification

 

The ecotoxicity database and reference values, agreed by the EU classification and labelling group and used for the ANNEX IV entries have been largely retained. For the environmental classification of copper metal, the reference effects data obtained with soluble copper compounds (section ecotoxicity) are compared to the copper releases as observed from transformation/dissolution tests (IUCLID section: physico-chemical properties: water solubility). Please see attached document for details on how the data are used to determine the classification for copper compounds.

 

The strategy for determining the classification was taken from: Annex IV: Metals and Inorganic Metal Compounds’ from the revised ‘Guidance on the Application of the CLP Criteria’ document. The strategy relies on the solubility of the metal compounds and evidence of rapid removal of the metal ion from the water column (see attachment).

In order to determine the classification of a ‘soluble’ copper compound using the available guidance, both the acute and chronic ERVs and solubility data are required. The ecotoxicity reference values for a metal compound can be calculated by:

 

Acute ERV compound= acute ERV of Cu ion x (Mwt of Cu compound /Awt of Cu)

Chronic ERV compound= chronic ERV of Cu ion x (Mwt of Cu compound /Awt of Cu)

 

The atomic weight for Cu is ca. 63.546, and should be multiplied where > 1 Cu molecule is present, which is not necessary for CuPP.

 

The reference values for Cu are included in the attached document and the molecular weight of CuPP is: 239.5.

 

Acute ERV Copper (II) pyrophosphate = 0.034 mg/L × (239.5/63.546) = 0.128 mg/L

Chronic ERV Copper (II) pyrophosphate = 0.015 mg/L × (239.5/63.546) = 0.057 mg/L.

 

According to the Guidance on the Application of the CLP Criteria, Version 4.1 as of June 2015 “a metal compound will be considered as readily soluble if the water solubility (measured through a 24-hour Dissolution Screening test or estimated e.g. from the solubility product) is greater or equal to the acute ERV of the dissolved metal ion concentration.

 

As data from a T/D test with CuPP show that the dissolved copper concentration after 24 h (0.2169 mg Cu/L molecular weight corrected for CuPP: 0.817 mg/L) is greater than the acute ERV of the test item (0.128 mg/L) CuPP is considered “readily soluble” for the purpose of classification.

 

Since CuPP is considered readily soluble and the acute ERV compound is > 0.1 mg/L and < 1 mg/L CuPP is classified for acute aquatic hazard as category Acute 1, with M factor of 1 according to Regulation (EC) No 1272/2008.

 

Since there is evidence that CuPP rapidly transformed in the environment and the ERV chronic is > 0.01 mg/L and < 0.1 mg/L the test item is classified for long-term aquatic hazard: category Chronic 2 according to Regulation (EC) No 1272/2008.