MANGANESE DIOXIDE

Chemwatch Material Safety Data Sheet

Issue Date: 23-Jun-2005                                                                      CHEMWATCH 10492

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           Section 1 - CHEMICAL PRODUCT AND COMPANY IDENTIFICATION





PRODUCT NAME

        MANGANESE DIOXIDE



SYNONYMS

       Mn-O2, "black manganese oxide", "Bog manganese", Braustein, Bruinsteen, "cement

       black", "C.I. 77728", "C.I. Pigment Black 14", "C.I. Pigment Brown 8",

       "manganese black", "manganese peroxide", "manganese dioxide black", "manganese

       superoxide", "manganese(IV) oxide", "pigment black 14", pyrolusite,

       "electrolytic manganese dioxide"



PRODUCT USE

        The mineral is the source of manganese and all its compounds; largely used in

        the manufacture of manganese steel; in alkaline batteries (dry cell); for making

        amethyst glass, decolourising glass. Also used for painting on porcelain,

        faience and majolica. The solid is used in electrotechnics, pigments, browning

        gun barrels. Manganese salts are driers for paints and varnishes, printing and

        dyeing textiles.



SUPPLIER

Quantum Chemicals Pty Ltd

70 Quantum Close

Quantum Industrial Park

Dandenong South VIC 3175

Australia

Telephone: 1300 782 688

Emergency Tel: 1300 131 001

Fax: 1300 782 699





HAZARD RATINGS





      Flammability

          Toxicity

     Body Contact

         Reactivity

          Chronic



           SCALE:      Min/Nil=0       Low=1       Moderate=2       High=3      Extreme=4

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Chemwatch Material Safety Data Sheet

Issue Date: 23-Jun-2005                                                                         CHEMWATCH 10492

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           Section 2 - HAZARDS IDENTIFICATION





STATEMENT OF HAZARDOUS NATURE

        HAZARDOUS SUBSTANCE. NON-DANGEROUS GOODS. According to the

        Criteria of NOHSC, and the ADG Code.









POISONS SCHEDULE

         None



RISK

           Harmful by inhalation and if swallowed.

           Cumulative effects may result following exposure*.

           May produce discomfort of the eyes, respiratory tract and skin*.

           * (limited evidence).



SAFETY

           Do not breathe dust.

           Wear eye/face protection.

           Use only in well ventilated areas.

           Keep container in a well ventilated place.

           Take off immediately all contaminated clothing.

           In case of contact with eyes, rinse with plenty of water and contact Doctor or

             Poisons Information Centre.





           Section 3 - COMPOSITION / INFORMATION ON INGREDIENTS



NAME                                                                                        CAS RN         %

manganese dioxide                                                                           1313-13-9      >95

commercial product may be mixture of

pyrolugite

(75-80%)

cryitome (KMn8O16)                   }

pgilomelane BaMn8O16                   }

rhodonite MnSiO3                   }

lithiophorite (A1,Li)MnO2(OH)2          }

goethite FeO.OH                   }

(total of 20-25%)





           Section 4 - FIRST AID MEASURES





SWALLOWED

       � IF SWALLOWED, REFER FOR MEDICAL ATTENTION, WHERE POSSIBLE, WITHOUT DELAY.

       � For advice, contact a Poisons Information Centre or a doctor.

       � Urgent hospital treatment is likely to be needed.

       � In the mean time, qualified first-aid personnel should treat the patient

       following observation and employing supportive measures as indicated by the

       patient's condition.

       � If the services of a medical officer or medical doctor are readily available,

       the patient should be placed in his/her care and a copy of the MSDS should be

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Chemwatch Material Safety Data Sheet

Issue Date: 23-Jun-2005                                                                               CHEMWATCH 10492

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                                                                                        Section 4 - FIRST AID MEASURES



              provided. Further action will be the responsibility of the medical specialist.

              � If medical attention is not available on the worksite or surroundings send the

              patient to a hospital together with a copy of the MSDS.

              � Where Medical attention is not immediately available or where the patient is

              more than 15 minutes from a hospital or unless instructed otherwise:

              � INDUCE vomiting with fingers down the back of the throat, ONLY IF CONSCIOUS.

              Lean patient forward or place on left side (head-down position, if possible) to

              maintain open airway and prevent aspiration.

              NOTE: Wear a protective glove when inducing vomiting by mechanical means.



EYE

              If this product comes in contact with the eyes:

              � Wash out immediately with fresh running water.

              � Ensure complete irrigation of the eye by keeping eyelids apart and away from

              eye and moving the eyelids by occasionally lifting the upper and lower lids.

              � If pain persists or recurs seek medical attention.

              � Removal of contact lenses after an eye injury should only be undertaken by

              skilled personnel.



SKIN

              If skin contact occurs:

              � Immediately remove all contaminated clothing, including footwear

              � Flush skin and hair with running water (and soap if available).

              � Seek medical attention in event of irritation.



INHALED

              � If fumes or combustion products are inhaled remove from contaminated area.

              � Lay patient down. Keep warm and rested.

              � Prostheses such as false teeth, which may block airway, should be removed,

              where possible, prior to initiating first aid procedures.

              � Apply artificial respiration if not breathing, preferably with a demand valve

              resuscitator, bag-valve mask device, or pocket mask as trained. Perform CPR if

              necessary.

              � Transport to hospital, or doctor.



NOTES TO PHYSICIAN

         Treat symptomatically.





              Section 5 - FIRE FIGHTING MEASURES





EXTINGUISHING MEDIA

� There is no restriction on the type of extinguisher which may be used.

Use extinguishing media suitable for surrounding area.



FIRE FIGHTING

� Alert Fire Brigade and tell them location and nature of hazard.

� Wear breathing apparatus plus protective gloves for fire only.

� Prevent, by any means available, spillage from entering drains or water

courses.

� Use fire fighting procedures suitable for surrounding area.

� DO NOT approach containers suspected to be hot.

� Cool fire exposed containers with water spray from a protected location.

� If safe to do so, remove containers from path of fire.

� Equipment should be thoroughly decontaminated after use.



FIRE/EXPLOSION HAZARD

� Will not burn but increases intensity of fire.

� Heating may cause expansion or decomposition leading to violent rupture of

containers.

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                                                                             Section 5 - FIRE FIGHTING MEASURES



� Heat affected containers remain hazardous.

� Contact with combustibles such as wood, paper, oil or finely divided metal may

produce spontaneous combustion or violent decomposition.

� May emit irritating, poisonous or corrosive fumes.



FIRE INCOMPATIBILITY

None known.



HAZCHEM

            None



Personal Protective Equipment

          Gloves, boots (chemical resistant).

          Breathing apparatus.





            Section 6 - ACCIDENTAL RELEASE MEASURES





EMERGENCY PROCEDURES



      MINOR SPILLS

          � Clean up all spills immediately.

          � No smoking, naked lights, ignition sources.

          � Avoid all contact with any organic matter including fuel, solvents, sawdust,

          paper or cloth and other incompatible materials, as ignition may result.

          � Avoid breathing dust or vapours and all contact with skin and eyes.

          � Control personal contact by using protective equipment.

          � Contain and absorb spill with dry sand, earth, inert material or vermiculite.

          � DO NOT use sawdust as fire may result.

          � Scoop up solid residues and seal in labelled drums for disposal.

          � Neutralise/decontaminate area.



      MAJOR SPILLS

          � Clear area of personnel and move upwind.

          � Alert Fire Brigade and tell them location and nature of hazard.

          � May be violently or explosively reactive.

          � Wear full body protective clothing with breathing apparatus.

          � Prevent, by any means available, spillage from entering drains or water

          course.

          � Consider evacuation (or protect in place).

          � No smoking, flames or ignition sources.

          � Increase ventilation.

          � Contain spill with sand, earth or other clean, inert materials.

          � NEVER use organic absorbents such as sawdust, paper, cloth; as fire may

          result.

          � Avoid any contamination by organic matter.

          � Use spark-free and explosion-proof equipment.

          � Collect any recoverable product into labelled containers for possible

          recycling.

          � DO NOT mix fresh with recovered material.

          � Collect residues and seal in labelled drums for disposal.

          � Wash area and prevent runoff into drains.

          � Decontaminate equipment and launder all protective clothing before storage and

          re-use.

          � If contamination of drains or waterways occurs advise emergency services.

          Moderate hazard.

          � CAUTION: Advise personnel in area.

          � Alert Emergency Services and tell them location and nature of hazard.

          � Control personal contact by wearing protective clothing.

          � Prevent, by any means available, spillage from entering drains or water

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                                                                  Section 6 - ACCIDENTAL RELEASE MEASURES



           courses.

           � Recover product wherever possible.

           � IF DRY: Use dry clean up procedures and avoid generating dust. Collect

           residues and place in sealed plastic bags or other containers for disposal. IF

           WET: Vacuum/shovel up and place in labelled containers for disposal.

           � ALWAYS: Wash area down with large amounts of water and prevent runoff into

           drains.

           � If contamination of drains or waterways occurs, advise Emergency Services.



EMERGENCY RESPONSE PLANNING GUIDELINES (ERPG)

The maximum airborne concentration below which it is believed that nearly all

individuals could be exposed for up to one hour WITHOUT experiencing or developing



  life-threatening health effects is:

      manganese dioxide       500 mg/m³



  irreversible or other serious effects or symptoms which could

  impair an individual's ability to take protective action is:

     manganese dioxide         75 mg/m³



  other than mild, transient adverse effects

  without perceiving a clearly defined odour is:

     manganese dioxide        4 mg/m³



  The threshold concentration below which most people.

  will experience no appreciable risk of health effects:

     manganese dioxide      0.3 mg/m³



American Industrial Hygiene Association (AIHA)



Ingredients considered according to the following cutoffs

   Very Toxic (T+)     >= 0.1%                Toxic (T)          >= 3.0%

   R50                 >= 0.25%               Corrosive (C)      >= 5.0%

   R51                 >= 2.5%

else                   >= 10%

where percentage is percentage of ingredient found in the mixture



SAFE STORAGE WITH OTHER CLASSIFIED CHEMICALS

___________________________________________







  +     X      +       X      0       +

___________________________________________

+: May be stored together

O: May be stored together with specific preventions

X: Must not be stored together





           Personal Protective Equipment advice is contained in Section 8 of the MSDS.





           Section 7 - HANDLING AND STORAGE





PROCEDURE FOR HANDLING

       � Avoid personal contact and inhalation of dust, mist or vapours.

       � Provide adequate ventilation.

       � Always wear protective equipment and wash off any spillage from clothing.

       � Keep material away from light, heat, flammables or combustibles.

       � Keep cool, dry and away from incompatible materials.

                                      MANGANESE DIOXIDE

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                                                                            Section 7 - HANDLING AND STORAGE



           � Avoid physical damage to containers.

           � DO NOT repack or return unused portions to original containers. Withdraw only

           sufficient amounts for immediate use.

           � Contamination can lead to decomposition leading to possible intense heat and

           fire.

           � When handling NEVER smoke, eat or drink.

           � Always wash hands with soap and water after handling.

           � Use only good occupational work practice.

           � Observe manufacturer's storing and handling directions.



SUITABLE CONTAINER

         � Polyethylene or polypropylene container.

         � Check all containers are clearly labelled and free from leaks.



STORAGE INCOMPATIBILITY

        Contact with readily oxidisable organic material may cause ignition /fire.



STORAGE REQUIREMENTS

        Observe manufacturer's storing and handling recommendations.

        DO NOT stack on wooden pallets.

        DO NOT store on wooden floors.





           Section 8 - EXPOSURE CONTROLS / PERSONAL PROTECTION





EXPOSURE CONTROLS

Source                            Material              TWA        TWA      STEL      STEL       Peak     Peak

                                                        ppm        mg/m³    ppm       m5/m³      ppm      mg/m³

_________________________         ________________      _____      _____    _____     _____      _____    _____

Australia Exposure                manganese                        1                  3

Standards                         dioxide

Australia Exposure                manganese                        1

Standards                         dioxide



The following materials had no OELs on our record under the following CAS or Chemwatch (CW) numbers

manganese dioxide: No data available for CAS:1313-13-9





     EMERGENCY EXPOSURE LIMITS

Material          Original IDLH              Original IDLH       Revised IDLH Value          Revised IDLH Value

                  Value (ppm)                Value (mg/m3)       (mg/m3)                     (ppm)

manganese dioxide N.E.                       N.E.                500



Ceiling values were recommended for manganese and compounds in earlier

publications. As manganese is a chronic toxin a TWA is considered more

appropriate. Because workers exposed to fume exhibited manganism at air-borne

concentrations below those that affect workers exposed to dust a lower value has

been proposed to provide an extra margin of safety. This value is still above

that experienced by two workers exposed to manganese fume in the course of one

study.

A number of studies have shown that susceptibility to the effects of manganese

at or about 1 - 5 mg/m³ (TWA) can lead to clinical manifestations of manganism

or more commonly to the development of indicators of sub-clinical manganism

(e.g. hand tremor, exaggerated reflexes, short-term memory deficits, poor

psychomotor performance). Controlling long-term exposure to the recommended ES

TWA level or below should provide protection for those individuals susceptible

to neurological effects of prolonged exposure.



      EXPOSURE STANDARDS FOR MIXTURE

     "Worst Case" computer-aided prediction of spray/ mist or fume/ dust components

                                      MANGANESE DIOXIDE

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                                                    Section 8 - EXPOSURE CONTROLS / PERSONAL PROTECTION



    and concentration:



    Composite Exposure Standard for Mixture (TWA) :0.2 mg/m³.

    Operations which produce a spray/mist or fume/dust, introduce particulates to

    the breathing zone.

    If the breathing zone concentration of ANY of the components listed below is

    exceeded, "Worst Case" considerations deem the individual to be overexposed.

    Component Breathing Zone ppm Breathing Zone mg/m³ Mixture Conc (%).



    Component               Breathing Zone      Mixture Conc

                            (mg/m³)             (%)

    manganese dioxide       0.2000              100.0



PERSONAL PROTECTION









     EYE

           � Safety glasses with side shields.

           � Chemical goggles.

           � Contact lenses may pose a special hazard; soft contact lenses may absorb and

           concentrate irritants. A written policy document, describing the wearing of lens

           or restrictions on use, should be created for each workplace or task. This

           should include a review of lens absorption and adsorption for the class of

           chemicals in use and an account of injury experience. Medical and first-aid

           personnel should be trained in their removal and suitable equipment should be

           readily available. In the event of chemical exposure, begin eye irrigation

           immediately and remove contact lens as soon as practicable. Lens should be

           removed at the first signs of eye redness or irritation - lens should be removed

           in a clean environment only after workers have washed hands thoroughly. [CDC

           NIOSH Current Intelligence Bulletin 59].



     HANDS/FEET

         Wear chemical protective gloves, eg. PVC.

         Wear safety footwear or safety gumboots, eg. Rubber.



     OTHER

         � Overalls.

         � P.V.C. apron.

         � Barrier cream.

         � Skin cleansing cream.

         � Eye wash unit.



     RESPIRATOR

         Protection Factor           Half-Face            Full-Face        Powered Air

                                     Respirator           Respirator       Respirator

           10 x ES                   P1 Air-line*         --               PAPR-P1 -

           50 x ES                   Air-line**           P2               PAPR-P2

           100 x ES                  -                    P3               -

                                                          Air-line*        -

           100+ x ES                 -                    Air-line**       PAPR-P3



           * - Negative pressure demand ** - Continuous flow.



           The local concentration of material, quantity and

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                                                   Section 8 - EXPOSURE CONTROLS / PERSONAL PROTECTION



           conditions of use determine the type of personal

           protective equipment required.

           For further information consult site specific

           CHEMWATCH data (if available), or your

           Occupational Health and Safety Advisor.



ENGINEERING CONTROLS

        General exhaust is adequate under normal operating conditions. Local exhaust

        ventilation may be required in specific circumstances. If risk of overexposure

        exists, wear approved respirator. Correct fit is essential to obtain adequate

        protection. Provide adequate ventilation in warehouse or closed storage areas.

        Air contaminants generated in the workplace possess varying "escape" velocities

        which, in turn, determine the "capture velocities" of fresh circulating air

        required to effectively remove the contaminant.



           Type of Contaminant:                                Air Speed:

           solvent " "vapours " degreasing "etc.               0.25-0.5 m/s (50-100 f/min)

           " evaporating from tank (in still

           air).

           aerosols " fumes from pouring                       0.5-1 m/s (100-200 f/min.)

           "operations " intermittent container

           "filling " low speed conveyer

           "transfers " "welding " spray "drift "

           plating acid "fumes " pickling

           (released at low velocity into zone of

           active generation)

           direct "spray " spray painting in                   1-2.5 m/s (200-500 f/min.)

           shallow "booths " drum "filling "

           conveyer "loading " crusher "dusts "

           gas discharge (active generation into

           zone of rapid air motion)

           grinding " abrasive "blasting "                     2.5-10 m/s (500-2000 f/min.)

           "tumbling " high speed wheel generated

           dusts (released at high initial

           velocity into zone of very high rapid

           air motion).



           Within each range the appropriate value depends on:



           Lower end of the range                             Upper end of the range

           1: Room air currents minimal or                    1: Disturbing room air currents

           favourable to capture

           2: Contaminants of low toxicity or of              2: Contaminants of high toxicity

           nuisance value only.

           3: Intermittent, low production.                   3: High production, heavy use

           4: Large hood or large air mass in                 4: Small hood-local control only

           motion



           Simple theory shows that air velocity falls rapidly with distance away from the

           opening of a simple extraction pipe. Velocity generally decreases with the

           square of distance from the extraction point (in simple cases). Therefore the

           air speed at the extraction point should be adjusted, accordingly, after

           reference to distance from the contaminating source. The air velocity at the

           extraction fan, for example, should be a minimum of 1-2 m/s (200-400 f/min) for

           extraction of solvents generated in a tank 2 meters distant from the extraction

           point. Other mechanical considerations, producing performance deficits within

           the extraction apparatus, make it essential that theoretical air velocities are

           multiplied by factors of 10 or more when extraction systems are installed or

           used.

                                       MANGANESE DIOXIDE

Chemwatch Material Safety Data Sheet

Issue Date: 23-Jun-2005                                                                      CHEMWATCH 10492

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             Section 9 - PHYSICAL AND CHEMICAL PROPERTIES





APPEARANCE

        Black to brownish-black fine powder with no odour.

        Oxidizing agent. Insoluble in water, nitric or cold sulphuric acid;

        slowly dissolves in cold hydrochloric acid with evolution of heat.



PHYSICAL PROPERTIES

Solid.

Does not mix with water.

Sinks in water.



Molecular Weight: 86.94                                           Boiling Range (°C): Not applicable.

Melting Range (°C): 535 (decomposes)                              Specific Gravity (water=1): 4.45

Solubility in water (g/L): Immiscible                             pH (as supplied): Not applicable

pH (1% solution): Not applicable.                                 Vapour Pressure (kPa): Not applicable.

Volatile Component (%vol): Not applicable.                        Evaporation Rate: Not applicable

Relative Vapour Density (air=1): Not applicable.                  Flash Point (°C): Not applicable

Lower Explosive Limit (%): Not applicable                         Upper Explosive Limit (%): Not applicable

Autoignition Temp (°C): Not applicable                            Decomposition Temp (°C): 535

State: Divided solid                                              Viscosity: Not available





             Section 10 - CHEMICAL STABILITY AND REACTIVITY INFORMATION





CONDITIONS CONTRIBUTING TO INSTABILITY

         � Presence of incompatible materials.

         � Product is considered stable.

         � Hazardous polymerisation will not occur.





             Section 11 - TOXICOLOGICAL INFORMATION





POTENTIAL HEALTH EFFECTS



ACUTE HEALTH EFFECTS



      SWALLOWED

          Accidental ingestion of the material may be harmful; animal experiments indicate

          that ingestion of less than 150 gram may be fatal or may produce serious damage

          to the health of the individual.

          Poisonings rarely occur after oral administration of manganese salts because

          they are poorly absorbed from the gut.



      EYE

             This material can cause eye irritation and damage in some persons.



      SKIN

             There is some evidence to suggest that this material can cause inflammation of

             the skin on contact in some persons.

             Skin contact is not thought to produce harmful health effects (as classified

             under EC Directives using animal models). Systemic harm, however, has been

             identified following exposure of animals by at least one other route and the

             material may still produce health damage following entry through wounds, lesions

             or abrasions. Good hygiene practice requires that exposure be kept to a minimum

             and that suitable gloves be used in an occupational setting.

             Entry into the blood-stream, through, for example, cuts, abrasions or lesions,

             may produce systemic injury with harmful effects. Examine the skin prior to the

                                       MANGANESE DIOXIDE

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                                                                       Section 11 - TOXICOLOGICAL INFORMATION



            use of the material and ensure that any external damage is suitably protected.



      INHALED

          Inhalation of dusts, generated by the material, during the course of normal

          handling, may be harmful.

          There is some evidence to suggest that the material can cause respiratory

          irritation in some persons. The body's response to such irritation can cause

          further lung damage.



      CHRONIC HEALTH EFFECTS

          Long term exposure to high dust concentrations may cause changes in lung

          function i.e. pneumoconiosis; caused by particles less than 0.5 micron

          penetrating and remaining in the lung. Prime symptom is breathlessness; lung

          shadows show on X-ray. Substance accumulation, in the human body, may occur and

          may cause some concern following repeated or long-term occupational exposure.

          Manganese is an essential trace element. Chronic exposure to low levels of

          manganese can include a mask-like facial expression, spastic gait, tremors,

          slurred speech, disordered muscle tone, fatigue, anorexia, loss of strength and

          energy, apathy and poor concentration.



TOXICITY AND IRRITATION

TOXICITY                                                               IRRITATION

Oral (Rat) LD50: >3478 mg/kg

No data of toxicological significance identified in literature search.





            Section 12 - ECOLOGICAL INFORMATION



            DO NOT discharge into sewer or waterways.





            Section 13 - DISPOSAL CONSIDERATIONS



            If container can not be cleaned sufficiently well to ensure none of the original

            product remains or if the container cannot be used to store the same product,

            then puncture containers, to prevent re-use, and bury at an authorised landfill.

            � Recycle wherever possible.

            � Consult manufacturer for recycling options or consult local or regional waste

            management authority for disposal if no suitable treatment or disposal facility

            can be identified.

            � Dispose of by: Burial in a licenced land-fill or Incineration in a licenced

            apparatus (after admixture with suitable combustible material)

            � Decontaminate empty containers. Observe all label safeguards until containers

            are cleaned and destroyed.





            Section 14 - TRANSPORTATION INFORMATION





HAZCHEM

            None





            NOT REGULATED FOR TRANSPORT OF DANGEROUS GOODS:UN,IATA,IMDG





            Section 15 - REGULATORY INFORMATION





POISONS SCHEDULE

         None

                                    MANGANESE DIOXIDE

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                                                                     Section 15 - REGULATORY INFORMATION



REGULATIONS



          manganese dioxide (CAS: 1313-13-9) is found on the following regulatory lists;

          Australia Inventory of Chemical Substances (AICS)

          OECD Representative List of High Production Volume (HPV) Chemicals





          Section 16 - OTHER INFORMATION





          This document is copyright. Apart from any fair dealing for the purposes of

          private study, research, review or criticism, as permitted under the Copyright

          Act, no part may be reproduced by any process without written permission from

          CHEMWATCH. TEL (+61 3) 9572 4700.



          Issue Date: 23-Jun-2005

          Print Date: 3-Jul-2006