NITE - Chemical Management Field

GHS Classification Result

GENERAL INFORMATION

Item	Information
CAS RN	1313-13-9
Chemical Name	Manganese(IV)dioxide
Substance ID	H26-B-098, R-044
Classification year (FY)	FY2014
Ministry who conducted the classification	Ministry of Health, Labour and Welfare (MHLW)/Ministry of the Environment (MOE)
New/Revised	Revised
Classification result in other fiscal year	FY2006
Download of Excel format	Excel file

REFERENCE INFORMATION

Item	Information
Guidance used for the classification (External link)	GHS Classification Guidance for the Japanese Government (FY2013 revised edition)
UN GHS document (External link)	UN GHS document
Definitions/Abbreviations (Excel file)	Definitions/Abbreviations
Model Label by MHLW (External link)	MHLW Website (in Japanese Only)
Model SDS by MHLW (External link)	MHLW Website (in Japanese Only)
OECD/eChemPortal (External link)	eChemPortal

PHYSICAL HAZARDS

Hazard class		Classification	Pictogram Signal word	Hazard statement (code)	Precautionary statement (code)	Rationale for the classification
1	Explosives	Not applicable	- -	-	-	There are no chemical groups present in the molecule associated with explosive properties.
2	Flammable gases (including chemically unstable gases)	Not applicable	- -	-	-	Solid (GHS definition).
3	Aerosols	Not applicable	- -	-	-	Not aerosol products.
4	Oxidizing gases	Not applicable	- -	-	-	Solid (GHS definition).
5	Gases under pressure	Not applicable	- -	-	-	Solid (GHS definition).
6	Flammable liquids	Not applicable	- -	-	-	Solid (GHS definition).
7	Flammable solids	Not classified	- -	-	-	It is not combustible (ICSC (2003)).
8	Self-reactive substances and mixtures	Not applicable	- -	-	-	There are no chemical groups present in the molecule associated with explosive or self-reactive properties.
9	Pyrophoric liquids	Not applicable	- -	-	-	Solid (GHS definition).
10	Pyrophoric solids	Not classified	- -	-	-	It is not combustible (ICSC (2003)).
11	Self-heating substances and mixtures	Not classified	- -	-	-	It is not combustible (ICSC (2003)).
12	Substances and mixtures which, in contact with water, emit flammable gases	Not classified	- -	-	-	From the observation result that it is insoluble in water (ICSC (2003)), it is estimated that it does not react vigorously with water.
13	Oxidizing liquids	Not applicable	- -	-	-	Solid (GHS definition).
14	Oxidizing solids	Classification not possible	- -	-	-	It is an inorganic compound containing oxygen (but not halogen), but the classification is not possible due to no data.
15	Organic peroxides	Not applicable	- -	-	-	It is an inorganic compound.
16	Corrosive to metals	Classification not possible	- -	-	-	Test methods applicable to solid substances are not available.

HEALTH HAZARDS

Hazard class		Classification	Pictogram Signal word	Hazard statement (code)	Precautionary statement (code)	Rationale for the classification
1	Acute toxicity (Oral)	Not classified	- -	-	-	Based on a report of an LD50 value of > 2,197 mg/kg for rats (SIDS (2012), Initial Risk Assessment Report (NITE, CERI, NEDO, 2008)), it was classified as "Not classified."
1	Acute toxicity (Dermal)	Not classified	- -	-	-	Based on an LD50 value of > 2,000 mg/kg for rats (SIDS (2012)), it was classified as "Not classified."
1	Acute toxicity (Inhalation: Gases)	Not applicable	- -	-	-	Solid (GHS definition)
1	Acute toxicity (Inhalation: Vapours)	Not applicable	- -	-	-	Solid (GHS definition)
1	Acute toxicity (Inhalation: Dusts and mists)	Classification not possible	- -	-	-	Classification not possible due to lack of data. There is a report that an LC50 value for rats is > 1.5 mg/L (SIDS (2012)), but the category cannot be specified only with this data. Besides, since this substance is a solid and is not sublimable, a reference value in the units of mg/L was applied.
2	Skin corrosion/irritation	Classification not possible	- -	-	-	Classification not possible due to lack of data. Besides, although there are descriptions that this substance showed slight irritation to humans (SIDS (2012)) and no irritation (species unknown) (SIDS (2012)), details are unknown. Since they were not used for evaluation as data with low reliability in SIDS (2012), they were judged insufficient data for classification.
3	Serious eye damage/eye irritation	Classification not possible	- -	-	-	Classification not possible due to lack of data. Besides, there are descriptions that it showed slight irritation to human eyes (SIDS (2012)), that it is not irritating (species unknown) (SIDS (2012)) and that it is irritating (species unknown) (SIDS (2012)). However, the details are unknown, and they were not used for evaluation as they were data with low reliability in SIDS (2012), therefore, they were judged insufficient data for classification.
4	Respiratory sensitization	Classification not possible	- -	-	-	Classification not possible due to lack of data.
4	Skin sensitization	Classification not possible	- -	-	-	Classification not possible due to lack of data. Besides, it is reported that after applying 10% of this substance to 190 humans, 2 persons showed sensitization (SIDS (2012)) and that 2 out of 48 workers showed sensitization to this substance (CICAD 12 (1999)). However, no conclusions were drawn in SIDS (2012) and CICAD 12 (1999).Therefore, they were judged as insufficient data for this classification.
5	Germ cell mutagenicity	Category 2	Warning	H341	P308+P313 P201 P202 P280 P405 P501	As for in vivo, it was positive in a mouse bone marrow micronucleus test (SIDS (2012)). As for in vitro, it was negative in a bacterial reverse mutation test and positive in a chromosomal aberration test with cultured mammalian cells (SIDS (2012)). From the above, this substance is considered to induce chromosomal aberrations and it was classified in Category 2.
6	Carcinogenicity	Classification not possible	- -	-	-	There is no classification by other international organizations for this substance. Classification not possible due to lack of data. Besides, EPA classified manganese as D (IRIS (1995)).
7	Reproductive toxicity	Classification not possible	- -	-	-	Classification not possible due to lack of data. There are reports of effects on the nervous system in dams and decreased locomotor activity in pups in a reproductive toxicity test by the inhalation route with female mice (SIDS (2012), Initial Risk Assessment Report (NITE, CERI, NEDO, 2008)). However, since it is a test with only one dose and is not a normal reproductive and developmental toxicity study, it was not adopted for the classification. In addition, as an epidemiological report, it is reported by Lauwerys et al. (1985) that a decrease in the number of offspring was observed in 85 workers exposed to not only manganese dioxide but also other manganese oxides or salts (SIDS (2012), Initial Risk Assessment Report (NITE, CERI, NEDO, 2008), ACGIH (7th, 2001), IRIS (1995)). ACGIH (7th, 2001) described that a concentration of 1 mg manganese/m3 may interfere with male fertility based on an epidemiological report by Lauwerys et al. However, a newer report by Gennart et al. (1992) stated that there was no difference among the fertility of 70 workers (SIDS (2012), Initial Risk Assessment Report (NITE, CERI, NEDO, 2008), IRIS (1995)). It is described in SIDS (2012) that in humans, clear conclusions on reproductive toxicity cannot be made due to equivocal data on male fertility and lack of reproductive data on women. Besides, in the Recommendation of Occupational Exposure Limits (2014) by the Japan Society for Occupational Health (JSOH), manganese and manganese compounds are classified as reproductive toxicants Group 2 (provisional) (corresponding to 1B), but this is not applicable to this substance since it is insoluble in water.
8	Specific target organ toxicity - Single exposure	Category 1 (respiratory organs)	Danger	H370	P308+P311 P260 P264 P270 P321 P405 P501	There is little information on single exposure to this substance. In humans, single inhalation exposure to manganese dioxide dusts caused inflammatory responses in the lung. The symptoms were cough, bronchitis, pneumonia, and decreased lung function. In addition, the occurrence of fume fever was observed by inhalation exposure to manganese fume (CICAD 12 (1999), Initial Risk Assessment Report (NITE, CERI, NEDO, 2008)). In experimental animals, lung inflammation by inhalation exposure of rodents (animal species unknown) to 2.8–43 mg/m3 (0.0028-0.043 mg/L) and histological changes in the lung by inhalation exposure (intratracheal injection, unknown dose) of rats were observed (CICAD 12 (1999), ACGIH (7th, 2001), EHC 17 (1981)). However, data from these experimental animals were not adopted for the classification. Based on the above, this substance is considered to have effects on the respiratory organs, and it was classified in Category 1 (respiratory organs).
9	Specific target organ toxicity - Repeated exposure	Category 1 (nervous system, respiratory organs)	Danger	H372	P260 P264 P270 P314 P501	As for humans, there are descriptions that due to chronic inhalation exposure to the particles of this substance, increased incidences of respiratory disorders (cough, bronchitis, pneumonia) and pneumonia, which is characterized by macrophages that have phagocytosed manganese particles were observed, and pulmonary edema accompanied this in some of the instances (SIDS (2012), Initial Risk Assessment Report (NITE, CERI, NEDO, 2008), ATSDR (2012)), and that due to occupational exposure to this substance at alkaline battery factories (inhalable dust concentration: 0.021-1.32 mg Mn/m3; exposure period: 0.2-17.7 years), hand stiffness, in addition to delayed simple response time of vision and decreased eye-hand coordination, was observed (SIDS (2012), Initial Risk Assessment Report (NITE, CERI, NEDO, 2008), ATSDR (2012)). ATSDR (2012) examined the epidemiological research report in detail, and concluded it was certain that as in the occupational exposure report in the alkaline battery factories mentioned above, the neurological effects of long-term exposure to low concentrations of manganese compounds are subtle changes such as functional decline in neuromotor tests and cognitive function tests and mood changes and are milder at first than in repeated high-concentration inhalation exposure to manganese compounds which are mainly composed of this substance, but they gradually progress to clear neurological disorders such as dull affect, altered gait, fine tremor, and psychiatric disturbances (ATSDR (2012)). As for experimental animals, there are descriptions that in a study in which rhesus monkeys were exposed by inhalation (22 hours/day) to the dust of this substance for 10 months, within the range of Category 1 (0.7 mg Mn/m3 (1.108 mg MnO2/m3): converted guidance value (0.0041 mg/L/6 hours)), catarrhal pneumonia and proliferation of pulmonary interstitial tissue were observed (SIDS (2012), Initial Risk Assessment Report (NITE, CERI, NEDO, 2008), ATSDR (2012)), and that interstitial pneumonia was caused even in rats by inhalation exposure for 10 days (Initial Risk Assessment Report (NITE, CERI, NEDO, 2008)). From the above, it was classified in Category 1 (nervous system, respiratory organs). Besides, in the previous classification, the cardiovascular system was added as the target organ based on the description in ATSDR (2000) that an increased incidence of lower diastolic blood pressure was seen in exposed humans. However, according to the corresponding data, it is described that the incidence is highest in the group of young workers with a short exposure period to this substance, the incidence is low in middle-aged workers with a long exposure period, and the incidence of abnormal cases on the electrocardiogram agreed with that of the age-matched control group (ATSDR (2012)), and since this report (1995) was published, no similar cardiovascular disorders have been reported. Therefore, "cardiovascular system" was deleted in this classification.
10	Aspiration hazard	Classification not possible	- -	-	-	Classification not possible due to lack of data.

ENVIRONMENTAL HAZARDS

Hazard class		Classification	Pictogram Signal word	Hazard statement (code)	Precautionary statement (code)	Rationale for the classification
11	Hazardous to the aquatic environment (Acute)	Not classified	- -	-	-	It was classified as "Not classified" from 72-hour ErC50 > 100 mg/L for algae (Pseudokirchneriella subcapitata), 48-hour EC50 > 100 mg/L for crustacea (Daphnia magna), and 96-hour LC50 > 100 mg/L for fish (Oryzias latipes) (all SIDS, 2012).
11	Hazardous to the aquatic environment (Long-term)	Category 4	- -	H413	P273 P501	Reliable chronic toxicity data were not obtained. Although acute toxicity effects were not found at up to water solubility, it was classified in Category 4 because it is water-insoluble (insoluble in water, SIDS, 2012), and information on environmental dynamics of the metal compound is lacking.
12	Hazardous to the ozone layer	Classification not possible	- -	-	-	This substance is not listed in the Annexes to the Montreal Protocol.

NOTE:

GHS Classification Result by the Japanese Government is intended to provide a reference for preparing a GHS label or SDS for users. To include the same classification result in a label or SDS for Japan is NOT mandatory.
Users can cite or copy this classification result when preparing a GHS label or SDS. Please be aware, however, that the responsibility for a label or SDS prepared by citing or copying this classification result lies with users.
This GHS classification was conducted based on the information sources and the guidance for classification and judgement which are described in the GHS Classification Guidance for the Japanese Government etc. Using other literature, test results etc. as evidence and including different content from this classification result in a label or SDS are allowed.
Hazard statement and precautionary statement will show by hovering the mouse cursor over a code in the column of "Hazard statement" and "Precautionary statement," respectively. In the excel file, both the codes and statements are provided.
A blank or "-" in the column of "Classification" denotes that a classification for the hazard class was not conducted in the year.

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