Speiss, copper

Toxicological Summary

Workers - Hazard via inhalation route

Systemic effects

Long term exposure

Hazard assessment conclusion:

high hazard (no threshold derived)

Acute/short term exposure

Hazard assessment conclusion:

low hazard (no threshold derived)

DNEL related information

Local effects

Long term exposure

Hazard assessment conclusion:

no hazard identified

Acute/short term exposure

Hazard assessment conclusion:

low hazard (no threshold derived)

DNEL related information

Workers - Hazard via dermal route

Systemic effects

Long term exposure

Hazard assessment conclusion:

high hazard (no threshold derived)

Acute/short term exposure

Hazard assessment conclusion:

no hazard identified

DNEL related information

Local effects

Long term exposure

Hazard assessment conclusion:

high hazard (no threshold derived)

Acute/short term exposure

Hazard assessment conclusion:

no hazard identified

Workers - Hazard for the eyes

Local effects

Hazard assessment conclusion:

no hazard identified

Additional information - workers

The hazard assessment of inorganic UVCBs for the purpose of classification and derivation of safe effect thresholds (i.e. DN(M)EL) is a cumbersome and complex process. Due to the intrinsic variability of the composition of an UVCB, it is difficult to select a sample that would unambiguously be representative for the (eco)toxicological hazard profile of the UVCB and could subsequently be used for testing. Instead of direct testing, a precautionary approach is taken where the UVCB is treated as a complex metal containing substance containing a number of discrete constituents (metals, metal compounds, non-metal inorganic compounds etc.). For each of these constituents, the hazard profile is used for deriving the proper classification of the UVCB (using the mixture rules) and/or for the derivation of the DN(M)ELs of the constituent (forwarded to the risk assessment). Using the DN(M)EL of all individual constituents circumvents indirectly the issue of varying composition of an UVCB as it implicitly assumes that each time the UVCB substance consists of the pure substance, i.e. that each constituent would be present and bioavailable at a 100% concentration in the UVCB substance. This can be considered a conservative approach. A main outcome of the constituents’ based assessment is the selection of all the constituents for which any human health hazard is identified. This selection defines the scope of the further exposure and risk assessment (CSR, Ch. 9&10).

 

The actual hazard profile of the inorganic UVCB substance and the individual constituents is dependent on the speciation of each and every constituent andhence this information needs to be collected in order to obtain a robust classification or DNEL value used for risk assessment purposes. Different scenarios can be encountered.

·      When the speciation of a constituent is known, this is used as such for the human health hazard assessment.

·      When the speciation is unknown or few metal species co-exist, the worst-case speciation for the purpose of human health hazard assessment is selected, i.e. the speciation that would lead to the most severe effects and thus the lowest DN(M)EL

 

Please note that dependent on the exercise (i.e, classification versus risk assessment) different speciation forms could be utilized (see below).

 

Selection of the toxicological information for the purpose of classification

 

The UVCB classification is calculated by applying the CLP mixture rules based on the classification of the known or worst-case speciation for each constituent and worst-case constituent concentration in the UVCB (i.e. maximum of the legal entity typical value), using the MeClas tool. Depending on the availability of information, the UVCB classification can be refined following MeClas Tiered approach.

 

Selection of the toxicological information for the purpose of risk assessment

 

For the purpose of the human health risk assessment for the UVCB, the hazards of each constituent will be assessed and DNEL/DMEL values for all the constituents for which a hazard has been identified are compiled. As indicated above, workers can be exposed on the work floor to different speciation forms than those present in the mineralogical composition of the UVCB. Hence the information onthe intrinsic properties of the UVCB constituents relevant for the hazard assessment (classification) can be refined if it is known which chemical speciation is present in the work place.

 

For the sake of readability of the CSR and the IUCLID, the below sections therefore outlinetoxicity effects derived for the UVCB itself. Information on hazards linked to speciation occurring in case individual constituing species of the UVCB (see CSR 3.0 Introduction to Classification) are released during production/use of the UVCB are reported in a separate annex of this CSR, if deemed relevant for the risk assessment.

Hazard conclusions for the purpose of classification

 

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 are then factored into a combined classification of the UVCB as a whole. For health endpoints, UVCB classifications are based on the combined hazards of the compounds whereby additivity or key cut off levels, specified in look-up tables are used, depending on the endpoint and amount of information available for the constituting compounds. The classification was derived using Meclas (MEtals CLASsification tool - see www.meclas.eu), a calculation tool that follows classification guidance and implementation in accordance to legal rules and technical guidance from ECHA and CLP see IUCLID section 13 attachment for MeClas Classification conclusions.

 

Table27:Summary of the information on toxicological information for the purpose of classification

UVCB constituent		Variabiliy of elemental composition	Classification according each relevant endpoint
Element	Speciation* taken forward for Tier 1 classification
Cu	66% Cu massive, 34% covellite	Maximum of typicals	Self-classification of the speciation, see MECLAS report in CSR Annex I
Ag	Ag compounds	Maximum of typicals	Self- classification of the speciation, see MECLAS report in CSR Annex I
Al	Al silicate	Maximum of typicals	Not classified
As	As metal	Maximum of typicals	Harmonised classification of the speciation, see MECLAS report in CSR Annex I
Ba	Ba	Maximum of typicals	Self- classification of the speciation, see MECLAS report in CSR Annex I
Co	CoS	Maximum of typicals	Harmonised classification of the speciation, see MECLAS report in CSR Annex I
Fe	Fe compounds	Maximum of typicals	Not classified
Mg	Mg/Mg compounds	Maximum of typicals	Not classified
Mn	MnSO4	Maximum of typicals	Harmonised classification of the speciation, see MECLAS report in CSR Annex I
Ni	Ni massive	Maximum of typicals	Harmonised classification of the speciation, see MECLAS report in CSR Annex I
Pb	Pb massive	Maximum of typicals	Self- classification of the speciation, see MECLAS report in CSR Annex I
Sb	Sb metal	Maximum of typicals	Not classified
Sn	Sn	Maximum of typicals	Not classified
S	Sulfide		Taken into account in corresponding metal sulfides already
Zn	Zn sulphate	Maximum of typicals	Harmonised classification of the speciation, see MECLAS report in CSR Annex I
Minors: Au, Bi, C, Ce, Pd	Metallic	Maximum of typicals	Below 0.1% and/or the speciation not impacting classification, see MECLAS report in CSR Annex I
oxides	SiO2, CaO, etc	Maxiumum of typicals	Below 4% and/or the speciation not impacting classification, see MECLAS report in CSR Annex I

 

* see IUCLID/CSR section 1.2 composition and IUCLID 4.23 additional Physico-chemical Information

 

Selection of the DNEL(s) for the purpose of risk assessment

 

The UVCB is an intermediate, with a very limited life cycle (manufacturing and industrial uses only). Testing the UVCB is difficult because of the large uncertainty involved when selecting representative samples due to the variable elemental concentrations in the composition of the UVCB.Derivation of a DNEL for the UVCB as such is therefore difficult to interpret and to extrapolateresults of testing to the entirety of variations of the UVCB because of the uncertainty related to the representativeness of the testing. Also, exposure to the UVCB cannot be measured or modelled because of the multi-constituent character of the UVCB. For these reasons, the UVCB toxicological assessment is driven by the assessment of the individual UVCB constituents.

 

The human health assessment is based on all hazardous constituents for human health of the UVCB.

 

The scope of the exposure assessment and type of risk characterization required for workers for each constituent is described in section 9 of this CSR.

 

Table28:Summary of the information on toxicological information for the purpose of risk assessment

 

UVCB constituent		Variability in chemical composition	DNELs for systemic and local effects, inhalation and dermal route, short term and long term.
Element	Speciation used for occupational exposure assessment
Cu	Cu ion is toxic driver	Hazard assumed as if UVCB consists of 100% worst-case speciation	See respective DNEL summary in IUCLID and table below
S	SO2(gas)	Hazard assumed as if UVCB consists of 100% in this speciation	See respective DNEL summary in IUCLID and table below
Fe	Fe ion is toxic driver	Hazard assumed as if UVCB consists of 100% worst-case speciation	See respective DNEL summary table below
Ni	Ni ion is toxic driver except NiSO4for systemic acute inhalation and NiS for local acute inhalation	Hazard assumed as if UVCB consists of 100% worst-case speciation	See respective DNEL summary in IUCLID and table below
Pb	Pb ion is toxic driver	Hazard assumed as if UVCB consists of 100% worst-case speciation	See respective DNEL summary in IUCLID and table below
As	As ion is toxic driver	Hazard assumed as if UVCB consists of 100% worst-case speciation	See respective DNEL summary in IUCLID and table below
Zn	Soluble Zn compounds	Hazard assumed as if UVCB consists of 100% worst-case speciation	See respective DNEL summary in IUCLID and table below
Co	Speciation (CoCl2, CoCO3, Co) with worst-case DNEL	Hazard assumed as if UVCB consists of 100% worst-case speciation	See respective DNEL summary table below
Al	Al ion is the toxic driver	Hazard assumed as if UVCB consists of 100% worst-case speciation	See respective DNEL summary table below
Ag	Ag ion is the toxic driver	Hazard assumed as if UVCB consists of 100% worst-case speciation	See respective DNEL summary table below
Ba	Ba ion is the toxic driver	Hazard assumed as if UVCB consists of 100% worst-case speciation	See respective DNEL summary table below
Sb	Sb ion is the toxic driver	Hazard assumed as if UVCB consists of 100% worst-case speciation	See respective DNEL summary table below
Sn	Sn ion is the toxic driver	Hazard assumed as if UVCB consists of 100% worst-case speciation	See respective DNEL summary table below
Other Minors: Au, Bi, C, Ce, Pd, Mg, Mn	Speciation with worst-case DNEL	Hazard assumed as if UVCB consists of 100% worst-case speciation	See respective DNEL summary in table below
Other Oxides	SiO2, CaO, etc	Hazard assumed as if UVCB consists of 100% worst-case speciation	See respective DNEL summary in table below

  

Different speciation is relevant to consider. In some cases, human health toxicity is driven by free metal ion. In other cases, human health toxicity is different per species and since the speciation of the exposure is not always known, the species with the worst-case DNEL was further considered for the assessment. Toxicological information on the individual UVCB constituents is reported in each constituent summary for which a quantitative exposure and risk assessment was conducted (the information is taken from the respective constituent IUCLID dossiers).

 

The relevant copper speciations for occupational exposure are Cu²⁺ion, CuSO₄, Cu₂O and CuO. There is no difference between the DNEL values of these speciations (apart from the molecular weight conversion). The DNEL values are therefore based on the soluble form. There is no separate DNEL derived for powder form. The common DNEL values are taken forward to risk characterisation.

 

The relevant lead speciations for occupational exposure are lead metal, lead oxide and lead sulfate. All DNELs are based upon systemic biomarkers of exposure and not on external exposure. The DNEL values used for occupational exposure assessment are therefore based on internal concentration of soluble lead concentrations.

 

Workers can be exposed to arsenic under different speciations i.e. arsenic metal, arsenic sulfide, arsenic sulphate and diarsenic trioxide. Only DNEL values are available for diarsenic trioxide. It is assumed that the arsenic ion is the driver for toxicity. The DNEL for arsenic can therefore be calculated based on the DNEL of arsenic oxide using the molecular weight conversion. These recalculated DNEL values are used for the risk assessment of arsenic. The same rationale holds for antimony.

 

The relevant nickel speciations are Ni metal, Ni sulphates, Ni sulfide and Ni oxide. There are differences in DNEL values between these speciations for a few type of effects. The DNEL values of the worst-case speciation form are therefore taken forward to risk characterisation. Ni sulphate has the lowest systemic acute inhalation DNEL of 16 mg Ni/m³(16-680 mg Ni/m³). Ni sulfide has a DNEL of 0.47 mg/m³for the local acute inhalation effects (range 0.47-4 mg Ni/m³). The local long-term dermal DNEL of 0.00044 mg Ni/cm²/day (range 0.00044 -0.07 mg Ni/cm²/day) is taken forward to risk characterisation.

 

Zn substances are divided in 2 solubility groups: “soluble” substances or “slightly soluble”/“insoluble” substances. The “soluble” DNEL values are selected since these have the lowest (worst-case) DNEL values.

 

During pyrometallurgical processs, Metal sulphides are oxidised and transformed into SO₂. The SO₂DNEL values are therefore taken forward for the occupational effect assessment and risk characterisation.

 

SnSO₄has the lowest DNEL values compared to SnS and Sn metal and are taken forward to risk characterisation. For the other elements such as Co and Ba, the same approach has been taken for the relevant metallic, sulfide, sulfate, and oxide speciations.

 

Carbon is speciated as charcoal. There are no other relevant speciations to consider. For silicate and aluminates, non-crystaline metal and oxide speciations are considered. Toxicological effects can be attributed to Al ion. Chromium is in the trivalent form.

 

For Ca, Mg, K and Na, these elements are considered to be non-hazardous at the levels of potential exposure. Any potential toxicological effects from these alkali and alkali-earth metals elements are due to the speciation as counter-ion. These effects are already covered by the existing (transition) metal elements.

Table: Human health hazard conclusions taken forward to CSA

Please see respective DNEL summaries

General Population - Hazard via inhalation route

Systemic effects

Long term exposure

Hazard assessment conclusion:

high hazard (no threshold derived)

Acute/short term exposure

Hazard assessment conclusion:

low hazard (no threshold derived)

DNEL related information

Local effects

Long term exposure

Hazard assessment conclusion:

no hazard identified

Acute/short term exposure

Hazard assessment conclusion:

low hazard (no threshold derived)

DNEL related information

General Population - Hazard via dermal route

Systemic effects

Long term exposure

Hazard assessment conclusion:

high hazard (no threshold derived)

Acute/short term exposure

Hazard assessment conclusion:

no hazard identified

DNEL related information

Local effects

Long term exposure

Hazard assessment conclusion:

high hazard (no threshold derived)

Acute/short term exposure

Hazard assessment conclusion:

no hazard identified

General Population - Hazard via oral route

Systemic effects

Long term exposure

Hazard assessment conclusion:

high hazard (no threshold derived)

Acute/short term exposure

Hazard assessment conclusion:

low hazard (no threshold derived)

DNEL related information

General Population - Hazard for the eyes

Local effects

Hazard assessment conclusion:

no hazard identified

Additional information - General Population

DNELs for the general population are currently not included because an assessment of exposure of man via the environment is not reported but instead considered to be already included in the dossiers of the constituents. However, DNELs for the general population and the assessment of exposure of man via the environment might be amended by further analysis (please refer to Chapter 9.0.2.3. for further details).