Ferro Silicon

FERRO SILICONChemwatch Safety Data Sheet (Conforms to Regulation (EC) No 1907/2006)Issue Date: 15-Mar-2006 CHEMWATCH 7022-54NA160TCP Version No:3

CD 2010/1 Page 1 of 16

Section 1 - CHEMICAL PRODUCT AND COMPANY IDENTIFICATION

PRODUCT NAMEFERRO SILICON

SUPPLIERChemwatch Pty Ltd+61 3 9573 3112 or (where available) Toll Free +800 2436 2255Email [email protected]: [email protected]

PRODUCT USE■ Operators should be trained in procedures for safe use of this material.Used to add alloying silicon to molten steel and iron.

SYNONYMS"Manufacturer's Code FO1", "ferro silicon stabilised", ferrosilicon, "iron silicon alloy", F01

Section 2 - HAZARDS IDENTIFICATION

STATEMENT OF HAZARDOUS NATURECONSIDERED A DANGEROUS SUBSTANCE ACCORDING TO DIRECTIVE 1999/45/EC AND ITS AMENDMENTS.

HAZARD RATINGS

Flammability Toxicity

Body Contact Reactivity

Chronic

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

RISKRisk Codes Risk PhrasesR15 ■ Contact with water liberates extremely flammable gases.R53 ■ May cause long- term adverse effects in the aquatic environment.

Section 3 - COMPOSITION / INFORMATION ON INGREDIENTS

NAME CAS RN INT HAZ %ferrosilicon 8049-17-0 Xn 100 R CODES: R10, R15, R53with 30- 90% silicon10- 70% iron< 10% aluminiumdecomposition products includephosphine 7803-51-2 F+,T+,N EC NO: 232-260-8 R CODES: R12, R17, R26, R34, R50arsine 7784-42-1 F+,T+,N EC NO: 232-066-3 R CODES: R12, R26, R48/20, R50/53

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CD 2010/1 Page 2 of 16Section 3 - COMPOSITION / INFORMATION ON INGREDIENTS

and hydrogen gas

Section 4 - FIRST AID MEASURES

SWALLOWED• For advice, contact a Poisons Information Centre or a doctor at once.• Urgent hospital treatment is likely to be needed.• If swallowed do NOT induce vomiting.• If vomiting occurs, lean patient forward or place on left side (head-down position, if possible) to maintain open airway and prevent aspiration.• Observe the patient carefully.• Never give liquid to a person showing signs of being sleepy or with reduced awareness; i.e. becoming unconscious.• Give water to rinse out mouth, then provide liquid slowly and as much as casualty can comfortably drink.• Transport to hospital or doctor without delay.

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.• Seek medical attention without delay; if pain persists or recurs seek medical attention.• Removal of contact lenses after an eye injury should only be undertaken by skilled personnel.

SKIN■ Brush off dust.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.For severe acute or short term repeated exposures to phosphine:• There is no antidote. Clinical manifestations include headache, fatigue, nausea, vomiting, cough, dyspnoea,

paresthaesias, jaundice, ataxia, intention tremor, weakness and diplopia.• i Care is supportive and all obviously symptomatic patients should be monitored in an intensive care

setting. Watch for dysrhythmias. ii Replace fluids/electrolytes iii Follow blood chemistries (calcium,phosphorus, glucose, prothrombin time, CBC) at least daily iv Follow renal and hepatic function at leastdaily. Avoid any alcohol intake.

• The risk of pulmonary oedema after severe exposure requires observation for 24-48 hours but can appearseveral days later. Initial X-ray may be useful in assessing development of oedema. If oedema develops,nurse with trunk upright and administer oxygen at atmospheric pressure. Diuretics, morphine, theophyllinederivatives are of little benefit since oedema is exudate rather than transudate. Bronchodilators bynebulizer or metered aerosol may reduce bronchospasm and dyspnoea. Where immediate respiratory symptomssuggest lower airway exposure, steroids may be beneficial, with intravenous injection of methylprednisoloneup to 30 mg/kg body weight initially with subsequent smaller doses. Prophylactic antibiotics are indicatedin all but mild cases. Intermittent positive pressure ventilation with bronchial toilet and suction may be

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CD 2010/1 Page 3 of 16Section 4 - FIRST AID MEASURES

important elements of treatment. [I.L.O. Health and Safety Guide No. 28].

Section 5 - FIRE FIGHTING MEASURES

EXTINGUISHING MEDIA■ Dry agent or • Dry chemical powder.• Dry sand.

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

FIRE INCOMPATIBILITY• If any material becomes wet, immediately increase ventilation then, if safe or using personal protective

gear, move to under cover open air storage.Avoid contact with water, strong alkalis, strong acids.• Reacts slowly with water.• CAUTION contamination with moisture will liberate explosive hydrogen gas, causing pressure build up in

sealed containers.• Reacts with acids producing flammable / explosive hydrogen (H2) gas.• Reacts violently with caustic soda, other alkalies - generating heat, highly flammable hydrogen gas.• If alkali is dry, heat generated may ignite hydrogen - if alkali is in solution may cause violent foaming.

PERSONAL PROTECTIONGlasses: Gloves: Respirator:Chemical goggles. PVC chemical resistant type. Type B- P Filter of sufficient capacity

Section 6 - ACCIDENTAL RELEASE MEASURES

MINOR SPILLS• Remove all ignition sources.• Clean up all spills immediately.• Avoid contact with skin and eyes.• Control personal contact by using protective equipment.• Use dry clean up procedures and avoid generating dust.• Place in a suitable, labelled container for waste disposal.

MAJOR SPILLS■ Clear area of personnel and move upwind.Alert Fire Brigade and tell them location and nature of hazard.Wear protective clothing, gloves, safety glasses and dust respirator.Prevent, by any means available, spillage from entering drains or water courses.No smoking, naked lights or ignition sources. Increase ventilation.Stop leak if safe to do so.Use dry clean up procedures and avoid generating dust.Use only spark-free shovels and explosion proof equipment.Collect recoverable product into labelled containers for recycling.Collect residues and seal in labelled drums for disposal.Wash area down with large quantity of water and prevent runoff into drains.• After clean up operations, decontaminate and launder all protective clothing and equipment before storing

and re-using, If contamination of drains or waterwaysoccurs, advise emergency services.continued...


CD 2010/1 Page 4 of 16Section 6 - ACCIDENTAL RELEASE MEASURES

PROTECTIVE ACTIONS FOR SPILL

down wind distanceisolationdistance

PROTECTIVE ACTION ZONE

evacuationdirection

evacuationdirection

halfdownwinddistance

halfdownwinddistance

INITIALISOLATIONZONE

winddirection

From IERG (Canada/Australia)Isolation Distance 50 metresDownwindProtection Distance 500 metres

FOOTNOTES1 PROTECTIVE ACTION ZONE is defined as the area in which people are at risk of harmful exposure. This zoneassumes that random changes in wind direction confines the vapour plume to an area within 30 degrees oneither side of the predominant wind direction, resulting in a crosswind protective action distance equal tothe downwindprotective action distance.2 PROTECTIVE ACTIONS should be initiated to the extent possible, beginning with those closest to the spilland working away from the site in the downwinddirection. Within the protective action zone a level of vapourconcentration may exist resulting in nearly all unprotected persons becoming incapacitated and unable to takeprotective action and/or incurring serious or irreversible health effects.3 INITIAL ISOLATION ZONE is determined as an area, including upwind of the incident, within which a highprobability of localised wind reversal may expose nearly all persons without appropriate protection to life-threatening concentrations of the material.4 SMALL SPILLS involve a leaking package of 200 litres (55 US gallons) or less, such as a drum (jerrican orbox with inner containers). Larger packages leaking less than 200 litres and compressed gas leaking from asmall cylinder are also considered "small spills".

LARGE SPILLS involve many small leaking packages or a leaking package of greater than 200 litres, such asa cargo tank, portable tank or a "one-tonne" compressed gas cylinder.5 Guide 139 is taken from the US DOT emergency response guide book.6 IERG information is derived from CANUTEC - Transport Canada.

Section 7 - HANDLING AND STORAGE

PROCEDURE FOR HANDLING■ Avoid generating and breathing dust Use spark-free tools when handling.Handle and open container with care.Before opening sealed drums, spike through the sides near the bottom flange and then near the top flange on several points around the circumference with a non-sparking pick (e.g. beryllium-copper) to release gas pressure.Avoid all personal contact, including inhalation.Wear protective clothing when risk of exposure occurs.• Avoid smoking, naked lights, heat or ignition sources.Avoid contact with incompatible materials.When handling, DO NOT eat, drink or smoke.Avoid contact with moisture Keep containers securely sealed when not in use.Avoid physical damage to containers.Always wash hands with soap and water after handling. Work clothes should be laundered separately.

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CD 2010/1 Page 5 of 16Section 7 - HANDLING AND STORAGE

Use good occupational work practice. Observe manufacturer's storing and handling recommendations.• Atmosphere should be regularly checked against established exposure standards to ensure safe working conditions are maintained.

SUITABLE CONTAINER■ Steel drum Container must be air-tight.• Check that containers are clearly labelled.• Packaging as recommended by manufacturer.

STORAGE INCOMPATIBILITY■ Segregate from strong acids, strong alkalis.

STORAGE REQUIREMENTS■ Reject any shipments giving off odour. DO NOT unload in unventilated store. Any material giving off odour should only be stored in open air but under cover until tests indicate that it is safe.• Keep dry Avoid physical damage to containers.• Store in original containers.• Keep containers securely sealed.• No smoking, naked lights or ignition sources.• Store in a cool, dry, well-ventilated area.• Store away from incompatible materials and foodstuff containers.• Protect containers against physical damage and check regularly for leaks.• Observe manufacturer's storing and handling recommendations.

_____________________________________________________

SAFE STORAGE WITH OTHER CLASSIFIED CHEMICALS

+ X + X X +_____________________________________________________+: May be stored togetherO: May be stored togetherwith specificpreventionsX: Must not be stored together

Section 8 - EXPOSURE CONTROLS / PERSONAL PROTECTION

EXPOSURE CONTROLSSource Material TWA ppm TWA mg/m³ STEL ppm STEL mg/m³ Notes___________ ___________ _______ _______ _______ _______ _______EU Consolidated List phosphine (Phosphine) 0.1 0.14 0.2 0.28of IndicativeOccupational ExposureLimit Values (IOELVs)European Union (EU) phosphine (Phosphine) 0, 1 0, 14 0, 2 0, 28Commission Directive2006/15/ECestablishing a secondlist of indicativeoccupational exposurelimit values (IOELVs)UK Workplace Exposure phosphine (Phosphine) 0.1 0.14 0.2 0.28 R12, 17,Limits (WELs) 26, 34, 50

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CD 2010/1 Page 6 of 16Section 8 - EXPOSURE CONTROLS / PERSONAL PROTECTION

Source Material TWA ppm TWA mg/m³ STEL ppm STEL mg/m³ Notes___________ ___________ _______ _______ _______ _______ _______

UK Workplace Exposure arsine (Arsine) 0.05 0.16 R12, 26,Limits (WELs) 48/20,

50/53

The following materials had no OELs on our records• ferrosilicon: CAS:8049- 17- 0

EMERGENCY EXPOSURE LIMITSMaterial Revised IDLH Value (mg/m3) Revised IDLH Value (ppm)phosphine 50arsine 3

ODOUR SAFETY FACTOR (OSF)OSF=0.1 (ferrosilicon)■ Exposed individuals are NOT reasonably expected to be warned, by smell, that the Exposure Standard is beingexceeded.Odour Safety Factor (OSF) is determined to fall into either Class C, D or E.The Odour Safety Factor (OSF) is defined as:OSF= Exposure Standard (TWA) ppm/ Odour Threshold Value (OTV) ppmClassification into classes follows:

Class OSF DescriptionA 550 Over 90% of exposed individuals are aware by smell that

the Exposure Standard (TLV- TWA for example) is beingreached, even when distracted by working activities

B 26- 550 As " A" for 50- 90% of persons being distractedC 1- 26 As " A" for less than 50% of persons being distractedD 0.18- 1 10- 50% of persons aware of being tested perceive by

smell that the Exposure Standard is being reachedE <0.18 As " D" for less than 10% of persons aware of being

tested

.

MATERIAL DATAFERRO SILICON:

Not available

FERROSILICON:■ Sensory irritants are chemicals that produce temporary and undesirable side-effects on the eyes, nose or

throat. Historically occupational exposure standards for these irritants have been based on observation ofworkers' responses to various airborne concentrations. Present day expectations require that nearly everyindividual should be protected against even minor sensory irritation and exposure standards are establishedusing uncertainty factors or safety factors of 5 to 10 or more. On occasion animal no-observable-effect-levels (NOEL) are used to determine these limits where human results are unavailable. An additional approach,typically used by the TLV committee (USA) in determining respiratory standards for this group of chemicals,has been to assign ceiling values (TLV C) to rapidly acting irritants and to assign short-term exposurelimits (TLV STELs) when the weight of evidence from irritation, bioaccumulation and other endpoints combineto warrant such a limit. In contrast the MAK Commission (Germany) uses a five-category system based onintensive odour, local irritation, and elimination half-life. However this system is being replaced to beconsistent with the European Union (EU) Scientific Committee for Occupational Exposure Limits (SCOEL); thisis more closely allied to that of the USA.

OSHA (USA) concluded that exposure to sensory irritants can:• cause inflammation

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• cause increased susceptibility to other irritants and infectious agents• lead to permanent injury or dysfunction• permit greater absorption of hazardous substances and• acclimate the worker to the irritant warning properties of these substances thus increasing the risk of

overexposure.Odour Threshold Value: 0.5 ppmNOTE: Detector tubes for arsine, measuring in excess of 0.05 ppm, are commercially available.The TLV-TWA for arsine is thought to be protective against both the acute and chronic effects (cumulative

damage) of arsine on red-blood cells and kidneys and also provides protection against the oxidation of arsineto other inorganic arsenic compounds following the inhalation of arsine.

Odour Safety Factor(OSF)OSF=0.1 (ARSINE).Odour Threshold Value: 0.010-0.014 ppm (recognition)NOTE: Detector tubes for phosphine, measuring in excess of 0.1 ppm, are commercially available.The TLV-TWA is protective against respiratory irritation, lung injury and gastrointestinal symptoms

(nausea, vomiting) and central nervous system symptoms noted in workers exposed at mean concentrations below10 ppm.

This limit does not take into account possible chronic phosphorus poisoning said to result from prolongedexposure to phosphine.

Odour Safety Factor(OSF)OSF=0.1 (PHOSPHINE).Data for decomposition products only.

PHOSPHINE:■ Odour Threshold Value: 0.010-0.014 ppm (recognition)NOTE: Detector tubes for phosphine, measuring in excess of 0.1 ppm, are commercially available.The TLV-TWA is protective against respiratory irritation, lung injury and gastrointestinal symptoms

(nausea, vomiting) and central nervous system symptoms noted in workers exposed at mean concentrations below10 ppm.

This limit does not take into account possible chronic phosphorus poisoning said to result from prolongedexposure to phosphine.

Odour Safety Factor(OSF)OSF=0.1 (PHOSPHINE).

ARSINE:■ Odour Threshold Value: 0.5 ppmNOTE: Detector tubes for arsine, measuring in excess of 0.05 ppm, are commercially available.The TLV-TWA for arsine is thought to be protective against both the acute and chronic effects (cumulative

damage) of arsine on red-blood cells and kidneys and also provides protection against the oxidation of arsineto other inorganic arsenic compounds following the inhalation of arsine.

Odour Safety Factor(OSF)OSF=0.1 (ARSINE).

PERSONAL PROTECTION

EYE• Safety glasses with side shields; or as required,• 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 eachcontinued...



workplace or task. This should include a review of lens absorption and adsorption for the class ofchemicals in use and an account of injury experience. Medical and first-aid personnel should be trained intheir removal and suitable equipment should be readily available. In the event of chemical exposure, begineye irrigation immediately and remove contact lens as soon as practicable. Lens should be removed at thefirst signs of eye redness or irritation - lens should be removed in a clean environment only after workershave washed hands thoroughly. [CDC NIOSH Current Intelligence Bulletin 59].

HANDS/FEET■ Wear chemical protective gloves, eg. PVC.Wear safety footwear.

OTHER• Overalls.• Eyewash unit.Operators should be trained in correct use.

RESPIRATOR■ Selection of the Class and Type of respirator will depend upon the level of breathing zone contaminant andthe chemical nature of the contaminant. Protection Factors (defined as the ratio of contaminant outside andinside the mask) may also be important.

Breathing Zone Level Maximum Protection Half- face Respirator Full- Face Respiratorppm (volume) Factor1000 10 B- AUS P -1000 50 - B- AUS P5000 50 Airline * -5000 100 - B- 2 P10000 100 - B- 3 P

100+ Airline**

* - Continuous Flow ** - Continuous-flow or positive pressure demand.

The local concentration of material, quantity and conditions of use determine the type of personal protectiveequipment required. For further information consult site specific CHEMWATCH data (if available), or yourOccupational Health and Safety Advisor.

ENGINEERING CONTROLS■ Use in a well-ventilated area.General exhaust is adequate under normal operating conditions. Local exhaust ventilation may be required inspecific circumstances. If risk of overexposure exists, wear approved respirator. Correct fit is essential toobtain adequate protection. Provide adequate ventilation in warehouse or closed storage areas. Aircontaminants 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., evaporating 0.25- 0.5 m/s (50- 100 f/min)from tank (in still air).aerosols, fumes from pouring operations, 0.5- 1 m/s (100- 200 f/min.)intermittent container filling, low speedconveyer transfers, welding, spray drift,plating acid fumes, pickling (released at lowvelocity into zone of active generation)

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direct spray, spray painting in shallow booths, 1- 2.5 m/s (200- 500 f/min.)drum filling, conveyer loading, crusher dusts,gas discharge (active generation into zone ofrapid air motion)grinding, abrasive blasting, tumbling, high 2.5- 10 m/s (500- 2000 f/min.)speed wheel generated dusts (released at highinitial velocity into zone of very high rapidair motion).

Within each range the appropriate value depends on:

Lower end of the range Upper end of the range1: Room air currents minimal or favourable to 1: Disturbing room air currentscapture2: Contaminants of low toxicity or of nuisance 2: Contaminants of high toxicityvalue only.3: Intermittent, low production. 3: High production, heavy use4: Large hood or large air mass in motion 4: Small hood- local control only

Simple theory shows that air velocity falls rapidly with distance away from the opening of a simpleextraction pipe. Velocity generally decreases with the square of distance from the extraction point (insimple cases). Therefore the air speed at the extraction point should be adjusted, accordingly, afterreference 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 metersdistant from the extraction point. Other mechanical considerations, producing performance deficits within theextraction apparatus, make it essential that theoretical air velocities are multiplied by factors of 10 ormore when extraction systems are installed or used.

Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

PHYSICAL PROPERTIESSolid.Does not mix with water.Sinks in water.

State Divided solid Molecular Weight Not applicable.Melting Range (°C) 1382 Viscosity Not availableBoiling Range (°C) 2250 Solubility in water (g/L) ImmiscibleFlash Point (°C) Not applicable pH (1% solution) Not applicable.Decomposition Temp (°C) Not available pH (as supplied) Not applicableAutoignition Temp (°C) Not applicable Vapour Pressure (kPa) Not applicableUpper Explosive Limit (%) Not applicable Specific Gravity (water=1) 6.1Lower Explosive Limit (%) Not applicable Relative Vapour Density Not applicable.

(air=1)Volatile Component (%vol) Not applicable. Evaporation Rate Not applicable

APPEARANCEMetallic silver, dense brittle lumps of iron and silicon alloy.No odour when dry but garlic smell when wet. Insoluble in water / alcohol.May contain phosphorus and arsenic impurities with the result the materialwhen wet with water may release highly toxic phosphine and arsine gases;plus highly flammable and explosive hydrogen gas.

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CD 2010/1 Page 10 of 16Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Finer particle sizes react more rapidly with water with rapid generationof toxic, flammable gases.

Section 10 - CHEMICAL STABILITY AND REACTIVITY INFORMATION

CONDITIONS CONTRIBUTING TO INSTABILITY■ Storage in unsealed containers.• Presence of incompatible materials.• Product is considered stable.• Hazardous polymerisation will not occur.For incompatible materials - refer to Section 7 - Handling and Storage.

Section 11 - TOXICOLOGICAL INFORMATION

POTENTIAL HEALTH EFFECTS

ACUTE HEALTH EFFECTS

SWALLOWED■ Although ingestion is not thought to produce harmful effects (as classified under EC Directives), thematerial may still be damaging to the health of the individual, following ingestion, especially where pre-existing organ (e.g liver, kidney) damage is evident. Present definitions of harmful or toxic substances aregenerally based on doses producing mortality rather than those producing morbidity (disease, ill-health).Gastrointestinal tract discomfort may produce nausea and vomiting. In an occupational setting however,ingestion of insignificant quantities is not thought to be cause for concern.■ Considered an unlikely route of entry in commercial/industrial environments.■ Ingestion may result in nausea, abdominal irritation, pain and vomiting.

EYE■ Although the material is not thought to be an irritant (as classified by EC Directives), direct contactwith the eye may produce transient discomfort characterised by tearing or conjunctival redness (as withwindburn).

SKIN■ Skin contact with the material may damage the health of the individual; systemic effects may resultfollowing absorption.■ The material is not thought to be a skin irritant (i.e. is unlikely to produce irritant dermatitis asdescribed in EC Directives using animal models). Temporary discomfort, however, may result from prolongeddermal exposures. Good hygiene practice requires that exposure be kept to a minimum and that suitable glovesbe used in an occupational setting.■ Toxic effects may result from skin absorption.

INHALED■ The material is not thought to produce respiratory irritation (as classified by EC Directives using animalmodels). Nevertheless inhalation, of the material, especially for prolonged periods, may produce respiratorydiscomfort and occasionally, distress.■ Persons with impaired respiratory function, airway diseases and conditions such as emphysema or chronicbronchitis, may incur further disability if excessive concentrations of particulate are inhaled.If prior damage to the circulatory or nervous systems has occurred or if kidney damage has been sustained,proper screenings should be conducted on individuals who may be exposed to further risk if handling and useof the material resultin excessive exposures.

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CD 2010/1 Page 11 of 16Section 11 - TOXICOLOGICAL INFORMATION

CHRONIC HEALTH EFFECTS■ Principal routes of exposure are usually by inhalation of generated dust and inhalation of vapour given offby material that has become wet or damp.Chronic Phosphine / arsine exposures with severe anaemia are documented.Ferrosilicon dust can produce thickening of the alveolar walls with theoccasional disappearance of the alveolar structure. Chronic pulmonarydisease can result from excessive exposure to the dust or aerosolsencountered in ferrosilicon plants. [ILO Encyclopaedia]Very highly toxic phosphine (with characteristic rotting fish smell) whichmay be formed by wet ferrosilicon causes dizziness, tremors, gastro-intestinal distress and cough with green sputum. Convulsions and deathmay follow.Very highly toxic arsine (with characteristic garlic-like odour) which maybe formed by wet ferrosilicon causes rapid intravascular haemolysis,haemoglobinuria with accompanying dark urine, malaise, dizziness, headache,nausea, vomiting, abdominal pain, diarrhoea and collapse.

Ferro Silicon

TOXICITY AND IRRITATION■ Not available. Refer to individual constituents.

FERROSILICON:■ unless otherwise specified data extracted from RTECS - Register of Toxic Effects of Chemical Substances.

TOXICITY IRRITATIONDermal (rabbit) LD50: >20000 mg/kg Nil ReportedInhalation (rat) TCLo: 194 mg/m³/6H/26W- I

data for decomposition products only

CARCINOGENNon- arsenical International Agency Group 2Ainsecticides for Research on Cancer(occupational exposures (IARC) - Agentsin spraying and Reviewed by the IARCapplication of) MonographsArsenic and arsenic International Agency Group 1compounds (NB: This for Research on Cancerevaluation applies to (IARC) - Agentsthe group of compounds Reviewed by the IARCas a whole and not Monographsnecessarily to allindividual compoundswithin the group)

Section 12 - ECOLOGICAL INFORMATION

Refer to data for ingredients, which follows:

ARSINE:PHOSPHINE:■ Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment.

PHOSPHINE:ARSINE:

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CD 2010/1 Page 12 of 16Section 12 - ECOLOGICAL INFORMATION

FERROSILICON:■ DO NOT discharge into sewer or waterways.■ Do NOT allow product to come in contact with surface waters or to intertidal areas below the mean highwater mark. Do not contaminate water when cleaning equipment or disposing of equipment wash-waters.Wastes resulting from use of the product must be disposed of on site or at approved waste sites.

ARSINE:FERROSILICON:■ Speciation of arsenic is an important consideration in the fate, movement, and action of this substance.Chemical and biochemical transformations of arsenic include oxidation, reduction and methylation whichaffects its volatilisation, adsorption, dissolution and biological disposition. The transport of arsenic inthe environment is largely controlled by absorption/desorption processes in soils and sediments. Sedimentmovement is responsible for transport of arsenic soil residues to their ultimate sinks in deep oceansediments. The clay fraction, plus ferrous and aluminium oxides which coat clay particles, adsorb arsenicalswhich then undergo transformation as discussed earlier. Conversions of arsenic to volatile alkylarsines leadsto air transport losses from soil. Inorganic arsenic occurs in water in different oxidation states dependingon the pH and Eh of the water. Arsenate is apparently reduced by bacteria to arsenite in marine environmentsbecause the ratio of total arsenate to total arsenic is much lower than that predicted thermodynamically.Methylation of arsenic occurs in both freshwater and marine systems where arsenate occurs as arsenate,arsenite, methanearsonic acid and dimethylarsinic acid. Arsenate predominates because this is the most stableform.Bioaccumulation occurs in some aquatic species such as seaweeds, freshwater algae and crustaceans. Somearsenic in water flea (Daphnia Magna) and algae occurs as arseno-analogues of phospholipids leading to themistaken impression that accumulation and utilisation of arsenic takes place at the expense of phosphate.Crabs, lobsters and other marine organisms accumulate organo-arsenicals in the food chain. Although humanactivity may alter the local picture of environmental arsenic there is little evidence that this affects theglobal scale arsenic cycle.Airborne concentrations of arsenic in urban areas may range from a few nanograms to a few tenths of amicrogram per cubic meter; airborne arsenic is generally inorganic. In oxygenated soils inorganic arsenic ispresent in pentavalent form; under reducing conditions it occurs as the trivalent form.Drinking Water Standards:arsenic: 50 ug/1 (UK max.) 0.01mg/L (WHO provisional guideline)chloride:400 mg/l (UK max.)250 mg/l (WHO guideline)Soil Guideline:Dutch Criteria: 29 mg/kg (target)55 mg/kg (intervention)Air Quality Standard:No safe levels recommended due to carcinogenic properties (WHO guideline).

PHOSPHINE:FERROSILICON:■ The principal problems of phosphate contamination of the environment relates to eutrophication processes inlakes and ponds. Phosphorus is an essential plant nutrient and is usually the limiting nutrient for blue-green algae. A lake undergoing eutrophication shows a rapid growth of algae in surface waters. Planktonicalgae cause turbidity and flotation films. Shore algae cause ugly muddying, films and damage to reeds. Decayof these algae causes oxygen depletion in the deep water and shallow water near the shore. The process isself-perpetuating because anoxic conditions at the sediment/water interface causes the release of moreadsorbed phosphates from the sediment. The growth of algae produces undesirable effects on the treatment ofwater for drinking purposes, on fisheries, and on the use of lakes for recreational purposes.■ Phosphine will oxidise rapidly under influence of radiation and UV light. Phosphine is highly toxic toaquatic life.Phosphine is a gas with a low water solubility; it either oxidises or volatises rapidly from water. Becauseof its lower water solubility, physical state (gas), and slow reactivity, phosphine persists in theatmosphere for relatively long times. In most natural water, phosphine is very unstable and oxidises evenunder anoxic conditions. Depending upon the redox potential of water, the oxidation products are diphosphine(P2H4), phosphorus, hypophosphorus acid, phosphorus acid, and phosphoric acid. Diphosphane is a potentialalkylating agent, which finally forms H2PO4 (phosphoric acid), salts, and water. In the presence of oxygen,these breakdown products are formed rapidly from phosphine . Only a small fraction of phosphine

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CD 2010/1 Page 13 of 16Section 12 - ECOLOGICAL INFORMATION

oxidation with the formation of phosphates. Based on soil studies, small amounts of phosphine may also beadsorbed (reversible sorption) or chemisorbed (irreversible sorption) to suspended solid and sediments inwater. However, based on the estimated Henry's law constant (H) of 0.09 atm•m3/mol and the expectedvolatility associated with various ranges of H, volatilisation is expected to be the most important lossprocess for phosphine in water.In sealed tubes, phosphine completely disappeared in less than 40 days from three different types of soilwith varying amounts of moisture. The disappearance was attributed to initial sorption, and the subsequentbiotic and abiotic oxidation of part of the sorbed compound. The rate of adsorption increased with decreasingmoisture content and increasing organic soil content . The study showed that phosphine sorption in soil canoccur by both physical and chemical sorption processes, and that the chemisorption process is higher in soilswith a low organic matter and high mineral content Chemisorption irreversibly binds phosphine in soil sothat it is not available for volatilisation. However, since phosphine is gaseous and is only slightly solublein water, volatilisation from soil may be the most important process by which phosphine is lost from soilwhen chemisorption is not occurring.The important process for the loss of phosphine in the atmosphere is most likely its reaction with hydroxylradicals. Based on measured rates under simulated conditions, the estimated lifetime of phosphine in thetroposphere due to reaction with hydroxyl radicals is <1 day. The hydrogen abstraction reaction may producethe free radical [PH2], which may react with ozone to produce H2PO. [ PH2] another free radical, which ishighly reactive, with or without ozone. Ultraviolet (U]V) light can also induce phosphine to form [PH2]. H2POmay produce hypophosphorus acid (H2PO2) as a result of a reaction with nitrogen dioxide in air andsubsequent hydrolysis. The hypophosphorus acid is ultimately oxidized to phosphorus and phosphoric acid.Oxidation to phosphate is likely in biological systems with no suggestion of bioaccumulation orbiomagnification.Toxicity of phosphine to one or two day old pupae of Triboleum castaneum was increased by atmospheric CO2concentration up to 40% in air. A maximum pupal mortality of 11% was observed for CO2 levels at 10-70% for 24hours.Frog LC50 (30 min) : 0.56 mg/lBacterial EC50: Baccillus subtilis 2.7 mg/l (growth inhibition).

FERROSILICON:■ May cause long-term adverse effects in the aquatic environment.

PHOSPHINE:■ Hazardous Air Pollutant: Yes

ARSINE:■ Hazardous Air Pollutant: Yes

Toxicity Fish: LC50(96)31mg/LToxicity invertebrate: LC50(48)24.5mg/LIn water, arsine undergoes rapid hydrolysis to arsenic acid and hydrides.

EcotoxicityIngredient Persistence: Persistence: Air Bioaccumulation Mobility

Water/Soilphosphine LOW LOW HIGHarsine LOW

Section 13 - DISPOSAL CONSIDERATIONS

• Recycle wherever possible or consult manufacturer for recycling options.• Consult State Land Waste Management Authority for disposal.• Bury residue in an authorised landfill.• Recycle containers if possible, or dispose of in an authorised landfill.

■ According to the European Waste Catalogue, Waste Codes are not product specific but application specific.

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CD 2010/1 Page 14 of 16Section 13 - DISPOSAL CONSIDERATIONS

Waste Codes should be assigned by the User based on the application in which the product is used.

Section 14 - TRANSPORTATION INFORMATION

Labels Required: DANGEROUS WHEN WET,TOXIC

HAZCHEM: 4Y

Land transport ADR/RID (cross-border):ADR/RID Class: 4.3 Hazard identification 462

(Kemler):UN Number: 1408 Packing Group: IIIClassification Code: WT2 Hazard Label: 4.3+6.1Special provisions: 39Shipping Name: FERROSILICONwith 30% or more but less than

90% silicon

Air Transport IATA:ICAO/IATA Class: 4.3 (6.1) ICAO/IATA Subrisk: NoneUN/ID Number: 1408 Packing Group: IIISpecial provisions: A3Shipping Name: FERROSILICON

Maritime Transport IMDG:IMDG Class: 4.3 IMDG Subrisk: 6.1UN Number: 1408 Packing Group: IIIEMS Number: F- G, S- N Special provisions: 39 223 932Limited Quantities: 1 kgShipping Name: FERROSILICONwith 30% or more but less than90% silicon

Section 15 - REGULATORY INFORMATION

RISKRisk Codes Risk PhrasesR15 ■ Contact with water liberates extremely flammable gases.R53 ■ May cause long- term adverse effects in the aquatic

environment.continued...


CD 2010/1 Page 15 of 16Section 15 - REGULATORY INFORMATION

SAFETYSafety Codes Safety PhrasesS30 ■ Never add water to this product.S22 ■ Do not breathe dust.S25 ■ Avoid contact with eyes.S36 ■ Wear suitable protective clothing.S08 ■ Keep container dry.S51 ■ Use only in well ventilated areas.S09 ■ Keep container in a well ventilated place.S13 ■ Keep away from food, drink and animal feeding stuffs.S26 ■ In case of contact with eyes, rinse with plenty of water

and contact Doctor or Poisons Information Centre.S46 ■ If swallowed, IMMEDIATELYcontact Doctor or Poisons

Information Centre. (show this container or label).S60 ■ This material and its container must be disposed of as

hazardous waste.

ANNEX 2: Indications of DangerXn Harmful

REGULATIONSRegulations for ingredients

ferrosilicon (CAS: 8049-17-0) is found on the following regulatory lists;"International Air Transport Association (IATA) Dangerous Goods Regulations"

phosphine (CAS: 7803-51-2) is found on the following regulatory lists;"EU Consolidated List of Indicative Occupational Exposure Limit Values (IOELVs)","European Customs Inventory of Chemical Substances (English)","European Union -European Inventory of Existing Commercial Chemical Substances (EINECS) (English)","European Union (EU) Annex I to Directive 67/548/EEC on Classification and Labelling of Dangerous Substances - updated by ATP: 31","European Union (EU) Commission Directive 2006/15/EC establishing a second list of indicative occupational exposure limit values (IOELVs)","European Union (EU) Control of Major Accident Hazards Involving Dangerous Substances - Seveso Category","European Union (EU) Regulation (EC) No 1272/2008 on Classification, Labelling and Packaging of Substances and Mixtures - Annex VI","UK The Control of Major Accident Hazards (Amendment) Regulations 2005 (COMAH)","UK Workplace Exposure Limits (WELs)"

arsine (CAS: 7784-42-1) is found on the following regulatory lists;"European Customs Inventory of Chemical Substances (English)","European Union - European Inventory of Existing Commercial Chemical Substances (EINECS) (English)","European Union (EU) Annex I to Directive 67/548/EEC on Classification and Labelling of Dangerous Substances - updated by ATP: 31","European Union (EU) Control of Major Accident Hazards Involving Dangerous Substances - Seveso Category","European Union (EU) Regulation (EC) No 1272/2008 on Classification, Labelling and Packaging of Substances and Mixtures - Annex VI","UK The Control of Major Accident Hazards (Amendment) Regulations 2005 (COMAH)","UK Workplace Exposure Limits (WELs)"

No data for Ferro Silicon (CW: 7022-54)

This safety data sheet is in compliance with the following EU legislation and its adaptations – as far as applicable - : 67/548/EEC, 1999/45/EC, 76/769/EEC, 98/24/EC, 92/85/EEC, 94/33/EC, 91/689/EEC, 1999/13/EC, as well as the following British legislation: - The Control of Substances Hazardous to Health Regulations (COSHH) 2002 - COSHH Essentials - The Management of Health and Safety at Work Regulations 1999

Section 16 - OTHER INFORMATION

LIMITED EVIDENCE■ Inhalation skin contact and/or ingestion may produce health damage*.■ Cumulative effects may result following exposure*.■ May produce discomfort of the eyes*.■ Vapours potentially cause drowsiness and dizziness*.

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CD 2010/1 Page 16 of 16Section 16 - OTHER INFORMATION

* (limited evidence).

RISK

Explanation of risk codes used on this MSDSRisk Codes Risk PhrasesR10 ■ Flammable.R12 ■ Extremely flammable.R15 ■ Contact with water liberates extremely flammable gases.R17 ■ Spontaneously flammable in air.R26 ■ Very toxic by inhalation.R34 ■ Causes burns.R48/20 ■ Harmful: danger of serious damage to health by prolonged

exposure through inhalation.R50/53 ■ Very toxic to aquatic organisms, may cause long- term

adverse effects in the aquatic environment.R50 ■ Very toxic to aquatic organisms.R53 ■ May cause long- term adverse effects in the aquatic

environment.

ANNEX 2: Indications of DangerF+ Extremely flammableN Dangerous for the environmentT+ Very toxicXn Harmful■ Classification of the preparation and its individual components has drawn on official and authoritative sources as well as independent review by the Chemwatch Classification committee using available literature references.A list of reference resources used to assist the committee may be found at: www.chemwatch.net/references.

■ The (M)SDS is a Hazard Communication tool and should be used to assist in the Risk Assessment. Many factors determine whether the reported Hazards are Risks in the workplace or other settings. Risks may be determined by reference to Exposures Scenarios. Scale of use, frequency of use and current or available engineering controls must be considered.

■ For detailed advice on Personal Protective Equipment, refer to the following EU CEN Standards:EN 16 Personal eye-protectionEN 340 Protective clothingEN 374 Protective gloves against chemicals and micro-organismsEN 13832 Footwear protecting against chemicalsEN 133 Respiratory protective devices.

This document is copyright. Apart from any fair dealing for the purposes of private study, research, review orcriticism, as permitted under the Copyright Act, no part may be reproduced by any process without writtenpermission from CHEMWATCH. TEL (+61 3) 9572 4700.

Issue Date: 15-Mar-2006Print Date: 22-Nov-2010

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Ferro Silicon