Fumes of germanium dioxide, calcium carbonate, iron oxides, sodium chloride and amorphous silica from smelting of Ge containing residues during germanium refining

GHS

General Information

Name:

Fumes of germanium dioxide, calcium carbonate, iron oxides, sodium chloride and amorphous silica from smelting of Ge containing residues during germanium refining

Implementation:

EU

Remarks:

Classification is calculated with MeClas tool (http://www.meclas.eu) based on classification of the individual constituents and using available data from elemental composition and available information on mineralogy (see attachment).

General approach

An iUVCB substance is a complex substance. Its main characteristics are a known but variable elemental composition and the -in some cases- partly unknown speciation of the constituents.

 

The classification of the iUVCB is based on the hazard of its constituents and the classification rules for the hazard assessment of mixtures under the UN Globally Harmonised System (GHS) and its EU implementation (CLP). To derive the iUVCB classification, one therefore needs to have information on 

• iUVCB variability (elemental concentration),the physical form (e.g. massive, powder),
• the physical form (e.g. massive, powder), the hazard profile for all the elemental constituents, and
• the hazard profile for all the elemental constituents,
• and the speciation of the constituents (and the uncertainty associated if partly unknown the speciation of the constituents (and the uncertainty associated if partly unknown)

The official ECHA guidance (e.g. from the European Chemicals Agency, ECHA for the CLP^[1]) is used as basis for the assessment and includes metal-specific guidance.

 

The unknown constituents speciation and elemental variability are addressed following a precautionary and conservative approach. In practice:

The starting point is the iUVCB composition (as defined in IUCLID 1.2): the composition is provided listing variability (i.e. concentration range) including the available information on the chemical speciation of each constituent (i.e. specifying whether analytical tests could identify if the element is present as oxide, sulfide,…).

• When the speciation of the elemental constituent is known, it is used as such for the classification assessment of the iUVCB; when the speciation of the elemental constituent is unknown, the speciation with the worst-case classification is selected and assigned to the constituent for the iUVCB classification calculation.
• The typical iUVCB variability in elemental constituents (i.e. wide range concentration of the iUVCB constituents) is assessed by selecting a worst-case concentration, which is defined as the maximum of all company typical concentrations for each constituent.

Within one iUVCB substance, the variability in elemental composition can potentially lead to different hazard profiles. Therefore, there can be a practical need (for the purpose of SDS and labelling) to differentiate more hazardous from less hazardous individual streams within the iUVCB. Generic groups/grades/clusters within one iUVCB - each group with a common worst-case classification profile – can be developed and reported in IUCLID to increase general understanding of the variability of the hazard of the iUVCB and to allow registrants to easily derive a worst-case classification for possible new streams.

The MeClas tool (www.meclas.eu) has been developed to facilitate the classification of complex inorganic materials, considering the aspects raised above) is used. The tool allows the use of constituent specific information to derive iUVCB classification based on mixture rules (CLP).

 

MeClas

The classification of iUVCBs is assessed using the MeClas tool (Metal Classification tool,www.meclas.eu).

MeClas was developed to:

• deal with the complexity of the hazard classification of complex iUVCBs

• ensure consistent classification of complex iUVCBs throughout the industry

• provide full recognition to metal specific aspects

• provide a platform for relevant data centralisation between metal consortia (self-classifications and (eco)toxicity reference values) and between metal consortia and companies (read-across of speciation and bio-availability tests)

The tool allows the use of constituent specific information to derive iUVCB classification based on mixture rules (CLP).

 

MeClas is therefore facilitating the hazard identification for complex metal materials under CLP/ DSD/GHS throughout the metal industry.

MeClas is built on a limited number of simple and basic principles:

• A tiered and inorganic specific approach, allowing refinement in accordance with the following (not necessarily sequential) steps/and available information:

• Tier 0: elemental concentrations only (and worst-case speciation and worst-case 100% solubility)

• Tier 1: speciation data and mineralogical evidence

• Tier 2: correction based on release/solubility test data on the complex material

• An up-to-date database including the official EU harmonised (Annex VI of the CLP and subsequent ATPs) and self-classifications, specific concentration limits, M-factors, (eco)toxicity reference values (ERVs) values,…

• An open building block structure, enabling the inclusion of specific side modules if relevant (e.g. for ores and concentrates, for transport classification, additional reference lists (e.g. Japan), alloys, etc.). The core engine contains the UN-GHS, CLP (and DSD/DPD) hazard ID rulings, forming the base of the MeClas tool.

• Confidentiality assurance for proprietary information: confidentiality of proprietary data is assured by having the ERVs for such substances hidden from normal users of the tool in a dedicated layer of MeClas.

Self-classification of the iUVCB substance was performed using the MeClas tool based on the following outline:

i. Characterisation

The material is accurately described from its elemental composition (typical concentrations and concentration ranges across production sites –IUCLID Section 1.2), and the specific speciation data (mineralogical information, hazard) obtained from representative samples. This information is estimated sufficient to initiate the classification process.

ii. Classification by the Mixture Approach

The iUVCB is treated as a complex metal containing substance with a number of discrete constituents (i.e. chemical element with discrete speciation). The hazard classifications of each compound are then factored into a combined classification of the iUVCB as a whole. For health endpoints, iUVCB classifications are based on the combined hazards of the compounds (i.e. chemical element with discrete speciation) 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. These concepts and rules are incorporated in the MeClas tool.

iii. Bridging

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

iv. Optional correction for bioavailability (Tier 2 in MeClas)

MeClas fulfills the OECD principles for validation of (Q)SARs model 

1. Well defined end points
2. Unambiguous algorithm from EU CLP Guidance: summation/additivity formula, to determine classification and, back-calculation (via Acute Toxicity Estimate formula, etc) to derive the corresponding toxicity of the substance
3.  Clear applicability domain: applicable to classify complex metal containing materials in a Tiered approach (see EU CLP Guidance pg 499 Annex IV.5.5, and for conceptual outline ICMM Fact Sheet “Ores & Concentrates –An industry approach to EU hazard classification”, November 2009). Input information at tier 1: elemental composition and representative mineralogical information
4. Mechanistic interpretation

• Mechanistic interpretation - metal speciation:

The tool translates the elemental composition into a mineralogical composition relevant for classification (i.e. mineralogical distribution pattern for each element/constituent of the iUVCB substance).

In the Tier 1, the classification is derived (by means of the summation formula) without taking into account any bioavailability correction. In the Tier 2, the classification is derived (e.g. for environment by means of the additivity formula) taking into account bioavailability correction.

• Mechanistic interpretation - metal-ion additivity for environment:

(1) The additivity assumption for the toxicity of mixtures of metals was evaluated by C. Nys, TVan Regenmortel, CR Janssen, K Oorts, E Smolders & KAC De Schamphelaere, (2018). A framework for ecological risk assessment of metal mixtures in aquatic systems. (Environ. Toxicol. Chem. 37, 623–642).The additivity mode was judged conservative for the prediction of the toxicity of metal mixture at low effect concentrations in a meta-analysis of chronic metal mixture toxicity to freshwater organisms.

(2) A. Stockdale, E Tipping, S Lofts & SJ Ormod, combined metal speciation to the additive toxicity approach and predicted the combined metal toxicity in a range of UK river systems impacted by metals: in "Modeling multiple metal toxic effects in the field - evaluation of the Toxicity Binding Model (TBM) ", ICA Report November 2009. 

 

[1]ECHA, July 2017. Guidance on the Application of the CLP Criteria. Guidance to Regulation (EC) No 1272/2008 on classification, labelling and packaging (CLP) of substances and mixtures.

Related composition

Related composition:

Fumes of germanium dioxide, calcium carbonate, iron oxides, sodium chloride and amorphous silica from smelting of Ge containing residues during germanium refining

Fumes of germanium dioxide, calcium carbonate, iron oxides, sodium chloride and amorphous silica from smelting of Ge containing residues during germanium refining

Classification

Physical hazards

Explosives

Reason for no classification:

data conclusive but not sufficient for classification

Flammable gases and chemically unstable gases

Reason for no classification:

data lacking

Aerosols

Reason for no classification:

data lacking

Reason for no classification:

hazard class not assessed

Oxidising gases

Reason for no classification:

data lacking

Gases under pressure

Reason for no classification:

data lacking

Flammable liquids

Reason for no classification:

data lacking

Flammable solids

Reason for no classification:

data conclusive but not sufficient for classification

Self-reactive substances and mixtures

Reason for no classification:

data lacking

Pyrophoric liquids

Reason for no classification:

data lacking

Pyrophoric solids

Reason for no classification:

data lacking

Self-heating substances and mixtures

Reason for no classification:

data lacking

Substances and mixtures which in contact with water emit flammable gases

Reason for no classification:

data lacking

Oxidising liquids

Reason for no classification:

data lacking

Oxidising solids

Reason for no classification:

data conclusive but not sufficient for classification

Organic peroxides

Reason for no classification:

data lacking

Corrosive to metals

Reason for no classification:

data lacking

Desensitized explosives

Reason for no classification:

data lacking

Health hazards

Acute toxicity - oral

Hazard category:

Acute Tox. 4

Hazard statement:

H302: Harmful if swallowed.

Acute toxicity - dermal

Reason for no classification:

data conclusive but not sufficient for classification

Acute toxicity - inhalation

Reason for no classification:

data conclusive but not sufficient for classification

Skin corrosion / irritation

Reason for no classification:

data conclusive but not sufficient for classification

Serious eye damage / eye irritation

Reason for no classification:

data conclusive but not sufficient for classification

Respiratory sensitisation

Reason for no classification:

data lacking

Skin sensitisation

Reason for no classification:

data conclusive but not sufficient for classification

Aspiration hazard

Reason for no classification:

data lacking

Reproductive toxicity

Hazard category:

Repr. 2

Hazard statement:

H361: Suspected of damaging fertility or the unborn child <state specific effect if known> <state route of exposure if it is conclusively proven that no other routes of exposure cause the hazard>.

Route of exposure:

oral

Effects on or via lactation

Reason for no classification:

data lacking

Germ cell mutagenicity

Reason for no classification:

data conclusive but not sufficient for classification

Carcinogenicity

Hazard category:

Carc. 1A

Hazard statement:

H350: May cause cancer <state route of exposure if it is conclusively proven that no other routes of exposure cause the hazard>.

1. Specific target organ toxicity - single (STOT-SE)

Reason for no classification:

data conclusive but not sufficient for classification

1. Specific target organ toxicity - repeated (STOT-RE)

Hazard category:

STOT Rep. Exp. 2

Hazard statement:

H373: May cause damage to organs <or state all organs affected, if known> through prolonged or repeated exposure <state route of exposure if it is conclusively proven that no other routes of exposure cause the hazard>.

Affected organs:

other: kidneys

Route of exposure:

inhalation

oral

Environmental hazards

Hazardous to the aquatic environment (acute / short-term)

Hazard category:

Aquatic Acute 1

Hazard statement:

H400: Very toxic to aquatic life.

Hazardous to the aquatic environment (long-term)

Hazard category:

Aquatic Chronic 3

Hazard statement:

H412: Harmful to aquatic life with long lasting effects.

Hazardous to the ozone layer

Reason for no classification:

data lacking

Labelling

Signal word:

Danger

Hazard pictogram

GHS07: exclamation mark

GHS08: health hazard

GHS09: environment

Hazard statements

H302: Harmful if swallowed.

H350: May cause cancer <state route of exposure if it is conclusively proven that no other routes of exposure cause the hazard>.

H361: Suspected of damaging fertility or the unborn child <state specific effect if known> <state route of exposure if it is conclusively proven that no other routes of exposure cause the hazard>.

H373: May cause damage to organs <or state all organs affected, if known> through prolonged or repeated exposure <state route of exposure if it is conclusively proven that no other routes of exposure cause the hazard>.

H412: Harmful to aquatic life with long lasting effects.

H400: Very toxic to aquatic life.

Precautionary statements

P202: Do not handle until all safety precautions have been read and understood.

P280: Wear protective gloves/protective clothing/eye protection/face protection/hearing protection/...

P273: Avoid release to the environment.

P260: Do not breathe dust/fume/gas/mist/vapours/spray.

P270: Do not eat, drink or smoke when using this product.

P314: Get medical advice/attention if you feel unwell.