Scale (coating), copper

Toxicological Summary

Workers - Hazard via inhalation route

Systemic effects

Acute/short term exposure

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Local effects

Acute/short term exposure

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Workers - Hazard via dermal route

Systemic effects

Acute/short term exposure

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Additional information - workers

Human Health classification of B10 Scale, copper

 

1.     Introductionand approach

 

The copper intermediate is identified as follows

 

Intermediate B10 - Scale (coating), Copper   “Residue produced by melting or treating at a high temperature metallic copper (metal, alloy, scrap). The intermediate consist mainly of copper metal and oxides from copper (I) or zinc. It may contain silicates.”
EC names	EC number/ EINECS No.	CAS No.
Scale (coating), copper*	273-744-9	69012-45-9
Waste solids, copper-refinery*	273-718-7	679012-18-6
Waste solids, copper-casting*	273-717-1	69012-17-5
Copper, dross*	305-408-5	94551-59-4
Scale (coating), mill, copper*	305-427-9	94551-81-2

 

Copper scale is considered as a complex metal bearing material.

The substances are complex metal bearing substance. Their toxicity and classification will depend on

-         the % of metals present,

-         the speciation of the metals,

-         the solubility of the metals in media of relevance to oral, inhalation (in case the substance is not a massive material) and dermal exposure routes

-         the mixture classification toxicity rules defined in theguidance (2009).

For complex metal bearing substance, the self-classification of the UVCB substance (in accordance to the EU hazard classification system (CLP, 2009) was performed based on below outline:

 

Characterization: the material is accurately described from its elemental composition typical concentrations and concentration ranges across production sites), and the specific speciation data (mineralogical information) obtained from representative samples. This information is enough to initiate the classification process.

Classification by the Mixture Approach: the UVCB is treated as a complex metal containing substance with a number of discrete constituting compounds (metals, metal compounds, non-metal inorganic compounds). The hazard classifications of each compound is then factored into a combined classification of the UVCB as a whole. For human health endpoints, additivity and/or summation algorithms are applied to quantitatively estimate the mixture’s toxicity to human health. These concepts and rules are incorporated in easy to use IT tools, which can be used to classify the UVCB.

Bridging or Read-Across: toxicological data are not available for the specific UVCBs being evaluated. Considering the knowledge and variability in composition, read-across and bridging is done by using  a "representative" mineralogical/speciation analysis"  combined with the  "worst case" metal concentration (across companies)  as a basis for the classification of the UVCB substance (chemical and mineralogical surrogates with similar origin/production process and physical/chemical properties).

Eventual correction: correction for (bio)availability was not made for B10 Scale (coating), copper

2.     Summary of the chemistry and metal releases

 

The chemistry and mineralogy of Scale, copper B10 intermediate was assessed by Liippo et al, 2010 (see IUCLID Section 1.4 Analytical information & Section 4.23). In this assessment, samples of scales corresponding to different types of materials were characterized. Samples were selected as representative for the production processes, and the origin of the raw material (e.g. scale coating and dross-like materials). Sampling and sample preparation was performed according to the “ECI sampling protocol REACH B10” (see IUCLID Section 1.4 Analytical information):

 

Representative samples analysed:

• Type I: from cable producer 1: scale (coating)

• Type I: from cable producer 2 (=downstream user): copper scale

• Type II: from cable producer 1: slag as produced from a melting furnace (= dross)

• Type II: from cable producer 2 (downstream user): copper dross, from copper melting (a mix of copper dross and slags, with pieces up to 5cm diam)

• Type II: from (secondary) smelter: fines and parts were collected separately, resulting in two samples of copper dross (= two extremes); (sample 1) more oxidic fines, (sample 2) more metallic particulates

  

The studied six (6) copper scale and dross samples contains between 23.6 and 86.8% copper. Zinc and lead contents ranges from below detection limits to 19.1 and 1.6%, correspondingly. The chemistry and mineralogical data demonstrated that all tested samples correspond to the identity described above, although the mineralogical composition of the UVCB may vary slightly (see composition IUCLID Section 1.2). Most samples consist mainly of copper ( in some samples alloyed by zinc or aluminium), and copper oxides (cuprite and tenorite forms). Zincite (Zn oxides and Zn alloy) is present in two samples. In lead –bearing samples, lead is carried completely by metallic lead or mainly by metallic lead (61.5%), amorphous lead glass (32.1%) and lead oxides (6.3%).

 

For each type of scale, a characteristic distribution pattern for each constituting element was observed:

For type I (Scale-type materials):

Copper is in the form of Cu metal/alloys (massive, 46.09% from Total Cu) + oxides (WC Cu2O/Cu(I), 53.91% from total Cu)

Lead, if present, is in the form of Pb metal (massive, 100% from total Pb)

Iron, if present, is mainly in the form of amorphous glass

Other minor metal elements are, if present, following the same distribution pattern than Copper (= assumed Worst Case), i.e. metal/alloys (massive, 46.09% from Total Element) + oxides (WC , 53.91% from total Element)

For type II (Dross-type materials):

Copper is in the form of Cu metal/alloys (WC powder, 85.23% from Total Cu) + oxides (WC Cu2O/Cu(I), 14.77% from total Cu)

Lead is in the form of Pb metal/alloys (WC powder, 61.54% from Total Pb) + Pb compounds (38.46% from Total Pb)

Zinc is in the form of oxides (WC ZnO, 93.82% from total Zn) + metal/alloy (WC powder, 6.08% from Total Zn)

Nickel is in the form of oxides (WC NiO, 14.77% from total Ni) + Ni metal/alloy (WC powder, 85.23% from total Ni)

Iron is present mainly in the form of intermetallic inclusion, alloys, silicates, and/or amorphous glass.

Other minor metal elements are, if present, following the same distribution pattern than Cu , i.e. in the form of oxides (14.77% from total element) + metal/alloy forms (WC powder, 85.23% from Total element)

 

For classification purposes, these two distribution patterns were retained as Reasonable Worst Case (RWC). The two types of materials are mainly differentiated from each other based on their respective Fe content, closely linked to their Cu oxide content (i.e. higher % Fe( as in dross) = high %Cu metal/alloy forms and thus low %CuO content)

 

Considering the chemical compositions across industry, 4 grades were derived in order to cover the worst cases for key drivers of the classification:

 

	Grade 1	Grade 2	Grade 3	Grade 4
RWC pattern	Type I: scale(coating)-like materials	Type II : dross-like materials (Ni max <1%, Pb max <2%)	Type II : dross-like materials (Ni ≥1%, Pb max <2%)	Type II : dross-like materials  (Ni max <1%, Pb > 2%)
Cu	70 ≤ Cu < 90 % (typ: ca 75%)	20 ≤Cu ≤ 80% (typ: ca 70%)	20 ≤Cu ≤ 80% (typ: ca 70%)	20 ≤Cu ≤ 80% (typ: ca 70%)
Pb	Max ≤0.15%	Max < 2%	Max < 2%	Max < 10%
Ni	Max < 0.1%	Max < 1%	1 ≤ Ni < 10%	Max < 1%
Co	Max < 0.1 %	Max < 0.1%	Max < 0.1%	Max < 0.1%
Zn	Max ≤1%	Max < 40%	Max < 40%	Max < 40%
Cd	Max < 0.1%	Max < 0.1%	Max < 0.1%	Max < 0.1%
Sn	Max < 0.1%	Max < 10%	Max < 10%	Max < 10%
Fe	max ≤ca. 0.3%	Ca 0.1 ≤ Fe ≤ ca 15%	Ca 0.1 ≤ Fe ≤ ca 15%	Ca 0.1 ≤ Fe ≤ ca 15%
SiO2, Al2O3, etc	Max < 15%	Max < 30%	Max < 30%	Max < 30%

 

 

3.     Tier 1 (Lower Tier LT) classification

The Archetool (MeClas precursor, Verdonck and d’Have, 2010) was used to automatically calculate the classification of the intermediates (with varying typical characteristics as defined by the consortium members, using typical and maximum across industry). The tool is based on a database containing the human (and environmental) classification for each component of relevance to classification.

The information on the representative elemental and mineralogical composition (RWC distribution patterns for each constituent of the UVCB substance) is furthermore incorporated into the tool, so that the elemental composition (in % Total element) is automatically converted into % w/w of compounds that are relevant for applying the concentration limits.

Major constituents for Human health classifications were identified as follows:

 

Ø Pb (compounds): triggeringrepro toxicant cat 1(if max ≥ 0.1% from Total Pb); STOT-re cat 2 (if max ≥ 0.5%)

Ø Ni (oxide, WC): triggeringcarc cat 1A(if max ≥ 0.1%); andskin sensitizer cat 1 H317(if max Ni ≥ 1%), but notSTOT-re cat 1(because max Ni across industry is <10%)

Ø Cu (oxide, WC Cu2O): if oxide forms are above 10% from Total Cu(CLP, but cut off 20% if DSD), triggeringEye damage, and if above 25%Acute toxicity (oral and inhalation).

 

From the tool, the following classifications are derived:

 

HH Hazard derived by CLP Mixture toxicity rules (Arche tool/MeClas)
	Grade 1	Grade 2	Grade 3	Grade 4
acute toxicity	Cat 4 H302 (oral) Cat 4 H 332 (inhalation)			Cat 4 H332 (inhalation)
irritation/corrosion
eye damage	Cat 2 H319	Cat 2 H319	Cat 2 H319	Cat 2 H319
Respiratory sensitization
skin sensitization			Cat 1 H317
Germ cell mutagenicity
Carcinogenicity		cat 1A H350i	cat 1A H350i	cat 1A H350i
Reproductive toxicity		cat 1A H360	cat 1A H360	cat 1A H360
STOT Single Exposure
STOT Repetitive Exposure		cat 2 H373	cat 2 H373	cat 2 H373
Aspiration hazard

 

 

HH Hazard derived by DSD Mixture toxicity rules (Arche tool/MeClas)
	Grade 1	Grade 2	Grade 3	Grade 4
acute toxicity	Xn; R20/22			Xn; R20/22
corrosion
irritation	Xi; R26
Respiratory sensitization
skin sensitization			R43
Germ cell mutagenicity
Carcinogenicity		Car cat 1; R49	Car cat 1; R49	Car cat 1; R49
Reproductive toxicity		Repr Cat 1; R60/61	Repr Cat 1; R60/61	Repr Cat 1; R60/61

 

 

Classifications were derived using max concentrations across industry for each grade and are therefore precautionary.

See attached document

General Population - Hazard via inhalation route

Systemic effects

Acute/short term exposure

DNEL related information

Local effects

Acute/short term exposure

DNEL related information

General Population - Hazard via dermal route

Systemic effects

Acute/short term exposure

DNEL related information

General Population - Hazard via oral route

Systemic effects

Acute/short term exposure

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