Section 2: Guidance at the scene of an Incident

This section is intended to assist first responders (for example, police, fire or ambulatory services) or trained chemical responders arriving at the scene of an incident where bromine is involved.  It is recognized that first responders may not have experience dealing with chemical emergencies or bromine related emergencies.  When in doubt, first responders should err on the side of personal safety and await the assistance of trained chemical responders.  Trained chemical responders typically have the equipment and experience necessary to effectively address a bromine spill or leak. 

What to do if you are the first on the scene at a chemical spill.

Though Bromaid focuses on bromine, the following advice applies to situations involving any chemical.  Bromaid recognizes that accidents involving bromine might also include other chemicals of a hazardous nature.

GENERAL SAFETY PRECAUTIONS

APPROACH CAUTIOUSLY FROM UPWIND.  If wind direction allows, consider approaching the incident from uphill.  Resist the urge to rush in; others cannot be helped until the situation has been fully assessed.

SECURE THE SCENE.  Without entering the immediate hazard area, isolate the area and assure the safety of people and the environment, keep people away from the scene and outside the safety perimeter.  Allow enough room to move and remove your own equipment.

IDENTIFY THE HAZARDS.  Placards, container labels, shipping documents, material safety data sheets and/or knowledgeable persons on the scene are valuable information sources.  Evaluate all available information to reduce immediate risks.  As more information becomes available, the response should be further tailored to the situation.

ASSESS THE SITUATION. Consider the following:

  • Is there a fire, a spill or a leak?
  • What are the weather conditions?
  • What is the terrain like?
  • Who/what is at risk: people, property or the environment?
  • What actions should be taken:  Is an evacuation necessary?
  • Is diking necessary?  What resources (human and equipment) are required and are readily available?
  • What can be done immediately?

OBTAIN HELP.  Advise your headquarters to notify responsible agencies and call for assistance from qualified personnel.

DECIDE ON SITE ENTRY.  Any efforts made to rescue persons, protect property or the environment must be weighed against the possibility that you could become part of the problem.  Enter the area only when wearing appropriate protective gear.

RESPOND.  Respond in an appropriate manner.  Establish a command post and lines of communication.  Rescue casualties where possible and evacuate if necessary.  Maintain control of the site.  Continually reassess the situation and modify the response accordingly.  The first duty is to consider the safety of people in the immediate area, including your own.

ABOVE ALL.  Do not walk into or touch spilled material. Avoid inhalation of fumes, smoke and vapours, even if no dangerous goods are known to be involved.  Do not assume that gases or vapours are harmless because of lack of a smell—odourless gases or vapours may be harmful.  Use CAUTION when handling empty containers because they may still present hazards until they are cleaned and purged of all residues.

WHO TO CALL FOR ASSISTANCE

Upon arrival at the scene, a first responder is expected to recognize the presence of dangerous goods, protect oneself and the public, secure the area, and call for the assistance of trained personnel as soon as conditions permit. Follow the steps outlined in your organization’s standard operating procedures and/or local emergency response plan for obtaining qualified assistance. Generally, the notification sequence and requests for technical information beyond what is available in this guidebook should occur in the following order:

1. ORGANIZATION/AGENCY

Notify your organization/agency.  This will set in motion a series of events based upon the information provided.  Actions may range from dispatching additional trained personnel to the scene to activating the local emergency response plan.  Ensure that local fire and police departments have been notified.

2. EMERGENCY RESPONSE TELEPHONE NUMBER

Locate and call the telephone number listed on the shipping document. The person answering the phone at the listed emergency response number should be knowledgeable of the materials and mitigation actions to be taken, or should have immediate access to a person who has the required knowledge.

3. NATIONAL ASSISTANCE

In all EU countries, National or International emergency response agency’s are in place. Local authorities can ask for assistance / expertise concerning dangerous goods in general and bromine more specific. Bromaid established close contacts with the following centres.  

NCEC / CarechemUK and Ireland        
Landelijk Informatiepunt Ongevallen Gevaarlijke StoffenNetherlands
Belintra /BASFBelgium
TUISGermany
MSEFrance / Spain

 

Upon receipt of a call describing the nature of the incident, the agency will provide immediate advice on handling the early stages of the incident.  The agency will also contact the shipper or manufacturer of the material for more detailed information and request on-scene assistance when necessary.

Collect and provide as much of the following information as can safely be obtained to your chain of command and specialists contacted for technical guidance:

  • Your name, call back telephone number, FAX number
  • Location and nature of problem (spill, fire, etc.)
  • Name and identification number of material(s) involved
  • Shipper/consignee/point of origin
  • Carrier name, rail car or truck number
  • Container type and size
  • Quantity of material transported/released
    • Local conditions (weather, terrain, proximity to schools, hospitals, waterways, etc.)
  • Injuries and exposures

Local emergency services that have been notified

2.2.1   Container Assessment

  • From a distance, perform a visual inspection of the container looking for evidence of damage, leaks or staining
  • Be sure to put on the correct personal protective equipment for closer inspections or before taking steps to repair suspected damage or leaks.
  • Inspect the gasketed fittings under the container dome which are more susceptible to leaks.  
  • If possible, utilize the guidance provided in this document to repair any active leaks associated with the fittings (See Section 2.3).
  • If wet stains or residues are noted, clean the container using neutralizing solutions (see Section 2.2.4) followed by a water rinse. 

2.12.2   Small Spills – General Advice

Small spills from a small package or small leak from a large package

  • Call the emergency response number on the shipping papers first.  If there is no answer, dial the appropriate phone number provided in section 2.1.
  • As an immediate precautionary measure, isolate a bromine spill and leak area in all directions for at least 60 metres.
  • Consider taking steps to protect people downwind of the bromine spill through evacuation.  For daylight hours the protection can extend up to 0.6 km downwind from the spill.  During night-time the protection zone can extend up to 1.8 km.
  • Keep unauthorized personnel away.  If possible, isolate the container with barriers.
  • Stay upwind and keep out of low lying areas.
  • Only trained chemical emergency responders should be allowed to clean up the spill.
  • Professional responders should always wear correct personal protective equipment when dealing with a bromine spill.
  • Responders should always work in pairs.
  • Neutralising chemicals should be in small quantities incrementally as needed (i.e – do NOT dump large amounts of neutralising chemicals onto spilled bromine all at once).
  • Wash the container afterwards using a brush and neutralizing solution followed by a water rinse.

2.2.3  Large Spills – General Advice

Large spill from a large package or many small packages

  • Call the emergency response number on the shipping papers first.  If there is no answer, dial the appropriate phone number provided in section 2.1.
  • As an immediate precautionary measure, isolate a bromine spill and leak area in all directions for at least 300 metres.
  • Consider taking steps to protect people downwind of the bromine spill through evacuation.  For daylight hours the protection can extend up to 3.1 km downwind from the spill.  During night-time the protection zone can extend up to 6.6 km.
  • Keep unauthorized personnel away.  If possible, isolate the container with barriers.
  • Stay upwind and keep out of low lying areas.
  • Only trained chemical emergency responders should be allowed to clean up the spill.
  • Professional responders should always wear correct personal protective equipment when dealing with a bromine spill.
  • Responders should always work in pairs.
  • Neutralising chemicals should be in small quantities incrementally as needed (i.e – do NOT dump large amounts of neutralising chemicals onto spilled bromine all at once).
  • Wash the container afterwards using a brush and neutralizing solution followed by a water rinse.

2.2.4  Personal Protective Equipment

Standard clothing during a bromine accident without liquid spill or vapour leak

  • Safety shoes
  • Safety helmet
  • Work gloves
  • Overalls
  • Safety glasses

Standard protective equipment when container assessment indicates only a small bromine vapour leak (only a small amount of vapours; no liquid present; for example, a leak from an open vapour valve)

  • Full face mask with ABEK/P canister or positive pressure self contained breathing apparatus (SCBA)
  • PVC/Neoprene suit
  • Pair of PVC/rubber boots
  • Neoprene, nitrile or other bromine resistant gloves

Standard protective equipment when container assessment provides strong indication of a liquid bromine spill or large amounts of bromine vapours present (large visible vapour clouds or other indications of large vapour leak; evidence of standing liquid bromine; evidence of bromine egress into soil or water ways)

  • Bromine resistant gas tight suit (level A responder suit)
  • Positive pressure SCBA, fully encapsulated

Notes:

  • Wear chemical protective clothing that is specifically recommended by the manufacturer for bromine service.  Note that chemical protective clothing will generally provide little or no thermal protection.
  • Structural firefighters’ protective clothing provides limited protection in fire situations ONLY; it is not effective in spill situations where direct contact with a chemical substance, including bromine, is possible. 
  • Chemical responders and personal protective equipment that have been exposed to bromine and its vapors should be fully decontaminated prior to equipment removal. 
  • When in doubt about the level of bromine vapours present, the highest level of PPE protection should be utilized  

2.2.5 Neutralisers for Bromine

There are a wide variety of chemicals that can be used to neutralize bromine.  A summary of commonly available neutralising materials appear in the table below.  In an emergency situation, where time is of the essence, an available neutralizing chemical, even if less preferred, may be the best option for use.  For instance, though sodium thiosulfate is less preferred than other options for a variety of reasons, it may still be the best option if it is already at the scene and slake lime or soda ash will not be available for another hour.

 

Bromine Neutralizing Agents - Summary Table 

  

Slaked Lime [Ca(OH)2]

Slaked lime (solid) is recommended because it:

  • is usually readily available (it can be found in home and garden shops as garden lime
  • can be used to form a dike around a bromine spill
  • will adsorb the bromine. 

Slaked lime will only begin to react with bromine when water is added.

The balanced equation for the neutralisation reaction is as follows:

6Ca(OH)2 + 6Br2 –> Ca(BrO3)2 + 5CaBr2 + 6H20

A 20% – 40% slaked lime water slurry can be used.

Procedure for use
  • Form a dam of solid slaked lime around the bromine spill
  • Adsorb the bromine in the slaked lime and mix with a shovel or other suitable device
  • Slowly add water to a small amount of the mixed solids to activate neutralisation
  • mix water/bromine/slaked lime mixture thoroughly using a shovel or other mixing aid
  • Proceed incrementally in a step-wise manner by repeating steps 2 – 4 until all the bromine is neutralized
  • Collect the neutralised materials for further remediation at an approved site.
Sodium carbonate (soda ash) slurry

Sodium carbonate can be used as a 35% suspended solution, as a solid or as a dissolved solid .

In order of preference:

35% solution >> solid > dissolved.

3Na2CO3 + 3 Br2   —>  NaBrO3 + 5NaBr + 3CO2

  • 1,3 kg sodium carbonate destroys 1 kg of bromine.
  • Heat of Reaction: 14.2 Kcal/mole Br2 (endothermic).
  • 10 – 30% potassium carbonate solution can also be used if more readily available.

Suspensions at concentration of more than 35% should not be used. The desired weight ratio between suspension and bromine is 1:1 to 1:2.

The neutralisation of bromine with sodium carbonate suspension yields products containing about 40% reacted bromine.

It is important to note that the reaction between soda ash and bromine will release large volumes of CO2 gas.  CO2 gas may increase bromine fumes if it percolates through the liquid bromine

Caustic (Sodium hydroxide 5 – 10%)

In an area where the spillage has been contained, a 5% to 10% solution of caustic soda is sometimes used but is not recommended. Sodium bromate can form, which is an oxidising agent and can be explosive under some conditions.

6NaOH + 3 Br2 —> NaBrO3 + 5NaBr + 3H2O

Heat of Reaction: – 10.8 Kcal/mole Br2 (exothermic)

Sodium thiosulfate (sodium hyposulfite)

A solution of 40% sodium thiosulphate (hyposulphite) in water containing 1% soda ash [Na2(CO3)2] can also be used. The solution has limited shelf life.

Sodium thiosulphate has a very high heat of reaction and should only should be used for neutralising small quantities

2Na2S2O3 + Br2 —> Na2S406 + 2NaBr

Roughly 1 kg sodium thiosulfate will destroy 1 kg bromine.
The solution is made of the following components:

  • 90 kg sodium thiosulphate.
  • 2,5 kg sodium carbonate (Na2CO3).
  • 200 L water.
CAUTION! – Bromates (Br03)

Bromates can form during some neutralisation reactions and may need to be removed.  Bromates are strong oxidising agent.  Dried bromates can be shock sensitive and consequently may explode under some conditions.

Neutralisation streams containing bromates will generate bromine and bromine vapours if acidified.  A 10 – 30% sodium thiosulfate (aqueous) solution or an aqueous sodium bisulphite solution can be used to reduce bromates to their corresponding bromide salt.  Reactions to reduce bromates to bromide are highly exothermic. 

Anhydrous Ammonia gas (Vapours only)

Anhydrous ammonia gas can be used to assist chemical responders in significantly reducing bromine vapours in a spill situation.  This technique is for trained responders only.  Anhydrous hydrogen bromide is itself flammable and hazardous and careful consideration must be given prior to use in a given situation.

The salt forming reaction is exothermic.  Too much heat development will cause the formation of explosive intermediates.  Do not pour liquid ammonia on a bromine leak as a violent reaction may occur.

8NH3 + 3Br2 —> 6NH4Br + N2

One kilogram of NH3 will react with about 4 kg Br2.

Ammonia Solution

A 10-25% ammonia solution in water reacts with bromine in an alkaline environment.  Anhydrous ammonia is a strong irritant for the skin, eyes and respiratory tract. It has a characteristic sharp, penetrating odour and is flammable.
25% ammonia reacts with bromine per the following equation:

3Br2 + 8NH4OH —> 6NH4Br + 8H20 + N2

Stock

It is recommended that a bulk bromine user keep about two tons of bagged slaked lime [Ca(OH)2] or bagged soda ash [Na2CO3] on site. If the potential for a major emergency exist, provisions that would allow supply of as much as about 20 tons of bagged slaked lime or bagged soda ash should be considered.

Stored neutralizing materials should be protected against weather damage and replaced periodically after caking.

An additional source of neutralizing materials within a reasonable distance from the site should be available on short notice.

2.3.1  Bromine Leaks from Fittings

 Introduction: Typical Valve Arrangement

ISO containers are typically fitted with either two or three valves.  Where three valves are used, the centre valve (the valve centred on the manlid) is used for discharge, one off-centre valve is used for pressuring the container and one off-centre valve is used for venting the container.  When fitted with two valves, the centre valve is used for discharge and the second, off-centre valve is used to both pressurize and vent the container.  Colour coding for the valves can vary by geographic region.  For instance, the valve colours in Europe often differ from the valve colours used in North America.  In Europe, the valve colours typically used are yellow for discharge, green for pressurization and red for the connection of a vent line.

 A diagram of a typical valve arrangement appears below:

2.3.1   Bromine Leaks from Fittings

Notes:

  • for simplification purposes, pressure relief devices are not shown in the above diagram.  See section XX for advice on pressure relief devices.
  • All valves turn clockwise to close and turn counter-clockwise to open
  • Do not over-tighten diaphragm valves.  Over-tightening a valve could perforate the diaphragm.
  • Bromine leaks are often not often obvious.  Aqueous ammonia can be used to help identify the leaks and their location.  When vapours from aqueous ammonia contact bromine vapours a white cloud of ammonium bromide will form.  DO NOT allow liquid ammonia to come in contact with bromine.

 

 1. LEAKING FROM ABOVE A VALVE

1. LEAKING FROM ABOVE A VALVE

Make sure the leaking valve is properly closed by turning the hand wheel clockwise.

  1. Check the condition of the gasket under the valve blind flange.  Replace if torn, scratched or otherwise damaged.
  2. Reassemble and tighten the valve’s blind flange bolts.

 

2. LEAKING VALVE BONNET OR BODY GASKET

2. LEAKING VALVE BONNET OR BODY GASKET

  • Remove the blind flange from the vent valve (the valve used for pressure relief).  Relieve any pressure in the vessel by opening the vent valve, slowly and cautiously.  Close the vent valve.
  • Open the leaking valve by turning the hand wheel counter-clockwise then tighten the four nuts connecting the bonnet to the valve body.
  • Close the leaking valve and the vent valve.  Check for leaks.
  • If the leak has not stopped, repeat step a.  Then replace the faulty valve with the gasket and blind flange that had been above the faulty valve.  Ensure a tight connection.

 

3. LEAKING FROM BELOW A VALVE

3. LEAKING FROM BELOW A VALVE

Tighten the nuts on the studs used to connect the valve to the vessel flange.

  • If the leak continues, dismantle the blind flange from the vent valve (for pressure relief).  Relieve any pressure in the vessel by opening the vent valve, slowly and cautiously.
  • Remove the leaking valve and check the flanges.  They should be smooth and without deep scratches.  If necessary, carefully smooth out any scratches.
    Check the gaskets and replace if torn or damaged.
  • Reinstall and then close the valve and then close the vent valve.  Check for leaks.  If there are no leaks, replace the blind flange on the valve.  Ensure a tight connection.
  • If the leak has not stopped, repeat step b.  Then remove the valve again but replace it upside down.  Check for leakage.
    If there is no leakage, replace the blind flange over the valve.
    Ensure a tight connection
  • If the leak has not stopped, repeat step b.  Then replace the faulty valve with the gasket and blind flange that had been above the faulty valve.  Ensure a tight connection.

 

4. LEAKING DIP PIPE

4. LEAKING DIP PIPE

Tighten the nuts on the studs that connect the dip pipe flange and valve.

  • If a leak continues, remove the blind flange from the vent valve (for pressure relief).  Relieve any pressure in the vessel by opening the vent valve slowly and cautiously.
  • Caution:   
    – Wear full body personal protective clothes and equipment including respiratory and face protection and rubber boots.
    – Remove valve and dip pipe
    – Remember that the dip pipe may be wet with liquid bromine.
  • Check the flange faces.  They should be smooth and without deep scratches.  If necessary, smooth out any scratches.
    Check the gaskets and replace if torn or damaged.
  • Reinstall the dip pipe and valve, close the vent valve.  Check for leakage.  If there is no leakage, replace the blind flange over the valve.  Ensure a tight connection.
  • If the first attempt to reseat the dip pipe and valve does not work and the leak has not stopped, repeat steps 3-5.   Again, remember that the dip pipe may be wet with liquid bromine.
  • If the dip pipe continues to leak then install a gasket and a blind flange directly onto the container outlet.  Ensure a tight connection.

 

5. LEAKING BETWEEN DIP PIPE FLANGE AND VALVE.

5. LEAKING BETWEEN DIP PIPE FLANGE AND VALVE.

Tighten the nuts of the studs concerning the dip pipe flange and valve.

  • If a leak continues, remove the blind flange from the vent valve.
    Relieve any pressure in the vessel by opening the vent valve slowly and cautiously.
  • Remove the valve and check the flanges.  They should be smooth and without deep scratches.  If necessary, carefully smooth out any scratches.
    Check the gaskets and replace if torn or damaged.
  • Reinstall the valve, close it, then close the red vent valve.  Check for leakage.  If there is no leakage, replace the blind flange over the valve.  Ensure tight connection.
  • If the leak has not stopped, repeat step b.  Then remove the faulty valve and install the gasket and blind flange in place of the faulty valve.  Ensure tight connection.

 

 6. LEAKING FROM UNDER THE MANHOLE COVER FLANGE

 6. LEAKING FROM UNDER THE MANHOLE COVER FLANGE

Tighten the nuts of the manhole cover.  If possible, use a spanner with a long arm to maximize tightening capability.

 

Leaks from Pressure Relief Devices

ISO containers are fitted with pressure relief devices to prevent over-pressurisation of the vessel, for instance, when exposed to heat from a fire.  ISO containers can be fitted with two types of pressure relief devices.  The more common device is a pressure relief valve (PRV) which actuates to release when container pressure set points are exceeded.  The second type is a fusible element.  The fusible element is typically not used on its own but rather in conjunction with a PRV.  Fusible elements contain a low melting alloy that will melt in a fire situation to increase the container vapour venting capacity.

The drawing below shows an example of the possible placement of pressure relief devices.  Note that placement may vary by container design.  In many cases, a fusible element will not be fitted.

Leaks from Pressure Relief Devices

1. LEAKING FROM UNDER SAFETY VALVE

1. LEAKING FROM UNDER SAFETY VALVE

  1. Tighten the nuts on the studs that connect the vessel flange and the pressure relief device.
  2. If a leak continues, remove the blind flange from the vent valve (for pressure relief).
  3. Relieve any pressure in the vessel by opening the vent valve slowly and cautiously.
  4. Remove the valve and check the flanges.  They should be smooth and without deep scratches.  If necessary, carefully smooth out any scratches.
  5. Check the gaskets and replace if torn or damaged.
  6. Reinstall the valve and then close the vent valve. Ensure a tight connection and check for leakage.
  7. If the leak has not stopped, repeat steps 3-6. 
  8. If the safety valve is still leaking after several attempts at reseating as described above then a piece of lead sheeting can be used as a temporary means of stopping the leak until the container can be fitted with a replacement safety valve.


2. VAPOURS LEAKING FROM UNDER THE FUSIBLE ELEMENT (WHEN INSTALLED).

2. VAPOURS LEAKING FROM UNDER THE FUSIBLE ELEMENT (WHEN INSTALLED).

Tighten the bolts connecting the fusible element to the tank outlet.

  • If a leak continues, remove the blind flange from the red vent valve (for pressure relief).
    Relieve any pressure in the vessel by opening the red vent valve, slowly and cautiously.
  • Remove the leaking fusible element.
    Install in place of the fusible element, the blind flange from above the red vent valve.

 

2.3.2   Bromine Spill Response Techniques

A bromine spill or leak is very quickly indicated by reddish-brown vapours and harsh irritating odours.

After the vehicle driver becomes aware of a bromine leak, he should attempt, if possible, to move the vehicle to a less populated area, stop the vehicle, escape the irritating fumes while putting on the escape mask and walk quickly towards a spot higher than the roads, above the bromine fumes. From this safe spot, the driver should stop the oncoming traffic, alert the police, the nearest fire department and the nearest bromine user, if possible. People not properly equipped must be kept out of the area, and depending on the size of the leak, evacuated from the spill danger zone.

Only properly protected and trained responders should attempt to stop a bromine leak, using emergency repair materials (i.e. wooden cones, leadwool, etc) or by freezing the bromine as its escape an opening.

If the bromine is leaking out from between fittings or flanges, the responders should follow the troubleshooting recommendations in 2.3.1. To contain a bromine spill on the ground, earth and sandbag dams should be built around the spill and the contained bromine neutralised.

2.3.3   Sealing  a major leak from a container

Properly trained emergency response personnel have typically been trained to deal with liquid leaks.  Common techniques used for liquid leaks of other chemicals can be utilized for sealing leaking bromine containers.  Note that every leak scenario is different.  A leak sealing technique that is useful under one set of circumstances may not be useful under another set of circumstances.  First responders and chemical emergency responders must responsibly assess a given spill or leak situation prior to taking any actions.

Vapour leaks are generally less pose less severe consequences than liquid leaks.  Consequently, if it is judged safe to do so, a container leaking liquid bromine should be reoriented so that the leak point is confined to the vapour space (i.e. – the hole is above the liquid level in the container).   For instance, if a container has a hole in the very bottom of the container, it should be turned 180° so that the hole is instead at the very top of the container, in the vapour space.  This will minimize the amount of bromine released and make access and repairs to the leak area easier.  Prior to reorienting the container, the integrity of the valves and fittings should be evaluated and confirmed as closed and sound to ensure that the action will just result in a different liquid leak.  This technique will require special lifting.

 2.3.3   Sealing  a major leak from a container

There are different techniques that can be used based on the type of leak and the resources available.   Attempts to seal a container leak, whether vapour or liquid, should only be performed by trained responders outfitted with appropriate PPE.

For leaks from fittings, please see section 2.3.1.  Leaks from the body of the container can be sealed in a few ways.

  • A wooden cone can be used to stop the leak.  In this common leak sealing technique, a wooden cone is hammered into the leak opening to plug the container.  This can only be done in situation where the size of the leak opening makes this possible.
  • Use a leak sealing cushion or pillow to cover the leak. Special cushions for this purpose are available by most of the fire departments. The cushions strap around the outside of the container.  The cushion is either inflated to apply pressure across the leak opening or clamps are tightened to apply pressure.  Other variations of this device include those which adhere to the container using heavy magnets or suction cups.
  • Chemically resistant leak sealing putties have been found to be effective in some situations. 
  • If equipment or expertise is available and the leak has been isolated to vapour only, a steel patch can be welded over the leak opening.
  • Another possibility for consideration, though never practiced, is chill the leak area in order to freeze the bromine to stop the leak. Because bromine freezes at -7 °C this should be considered as a possibility if other means of sealing the leak are not available.

The above leak sealing techniques offer only a temporary solution to immediately contain the bromine.  After the leak is sealed, the remaining bromine should be transferred to another tank as soon as possible.

2.3.4  Tank to tank transfer techniques

After sealing a major leak from an ISO container, the tank should be emptied on the spot if possible.  However, with proper authorization, the container might be carefully moved to a preferred transfer location.  For instance, a location may be more preferred because it is more isolated, is better equipped or will minimize disruption to transportation or the community.

A pressure transfer is the simplest means of transferring bromine from one container to another.  The pressure transfer method can only be used if the temporary repair can withstand the pressure needed to empty the container. If a pressure transfer is not possible then a transfer pump may be used to empty the patched container.  The pump used must be resistant to the corrosive effects of bromine (for example, Teflon, PVDF, viton or ceramic wetted parts)  Regardless of the transfer techniques used a scrubber system is required.

RECOMMENDED PROCEDURE (Two Valve System)
(See figure below for typical set-up and iso-container valve arrangement.)

  • Wear recommended personal protective equipment.
  • Assemble an absorber scrubber unit. This can simply be a vessel with caustic soda and sodium bisulphite (if available).  Even better is the scrubber system can be a circulated solution of caustic and sodium bisulphite (if available).  Be sure the absorber unit is working and capable of handling vented bromine fumes.
  • Use dry air air or dry nitrogen (-40 °C dew point) to transfer the damaged container.  Keep the pressure as low as possible.  During the course of this procedure only apply just enough pressure to maintain the flow from the patched container to the receiving container . Be sure that dry air or dry nitrogen is used to pressure the transfer.

Patched Container Preparation

  • Check that all the patched ISO container valves are closed and blind flanges are in place.
  • Remove the blind flange above the red valve of the patched container.
  • Connect the pressure release line to the red valve outlet. If standard bromine container gaskets are not available then use a new rubber gasket (maximum use time is 24 hours) to ensure a tight connection.
  • Open the red valve and then the depressurising valve, slowly, to release any pressure that might have developed in the ISO container.
  • The depressurising line should vent to the absorber scrubber unit.
  • Remove the blind flange above the yellow valve.
  • Connect your transfer line to the yellow valve outlet.  If standard bromine container gaskets are not available then use a new rubber gasket (maximum use time is 24 hours) to ensure tight connection. A sight glass in the connection is needed.

Empty Receiving Container Preparation

  • Check that all the receiving ISO container valves are closed and blind flanges are in place.
  • Remove the blind flange from the red valve of the receiving container.
  • Connect this line to the absorber scrubber unit.
  • Open the red valve on the receiver unit and then the depressurising valve, slowly, to release any pressure that might have developed in the ISO container.
  • Remove the blind flange above the yellow valve of the receiving container.
  • Connect the transfer line from the patched container to the yellow valve outlet.  If standard bromine container gaskets are not available then use a new rubber gasket (maximum use time is 24 hours) to ensure a tight connection.
  • Open the yellow valve on both containeres and all the valves in your liquid transfer line.
  • Close the depressurising valve connected to the patched ISO container.
  • Open the pressurising valve very slowly at first to check for bromine leaks.  If b leaks are observed then close the valve and tighted connections as necessary.  If no leaks are observed, then more pressure can be applied to begin the bromine transfer. Use only enough pressure to lift the bromine to the high point in the unloading system (1 atm. pressure will lift bromine about 3.3 meters).
  • When air/nitrogen blows through the unloading line into your storage tank, the ISO container is empty.  You will recognize this when the transfer line begins to shake.
  • Close the pressurising valve
  • Close the yellow valves and then all the other valves in your liquid transfer line.
  • Close the red valve and then the depressurising valve.
  • Slowly open the depressurising valve to release the air/nitrogen pressure on the iso-container to your absorber unit.  Wait 5 minutes.
  • Cautiously disconnect your liquid unloading line from the yellow valve of the receiving ISO container. Replace its blind flange, tightening all the bolts. Do not forget to reinstall the proper gasket.
  • Disconnect your pressure release line from the red valve of the iso-container. Replace its blind flange, tightening all the bolts. Do not forget to reinstall the proper gasket.
  • If there has been a bromine spillage, wash it off the iso-container with plenty of water to prevent corrosion. Small bromine spills on the ground may be neutralised with a clear soda ash or a sodium thiosulphate solution. Then dispose of in a manner approved by the local authorities.

Close the cover dome and pin it securely

A bromine spill or leak is very quickly indicated by the reddish – brown vapours and the harsh irritating odours. After someone becomes aware of a bromine leak, he should escape the irritating fumes while putting on the escape gas mask (if available), and walk quickly to towards a safe spot. From this safe spot, the person should warn other people not to go in the area and alert the police and the nearest fire department. Properly protected and trained responders should attempt to stop the leak, using emergency repair materials (i.e. wooden cones, lead wool, etc.), or by freezing the bromine at it’s escape opening.

Attention is needed for the following environmental issues:

Bromine vapour

To avoid evaporation of bromine, several techniques are available:

  • Cover bromine by foam. Be aware that certain fire fighting foams have varying effectiveness in reducing the evaporation of bromine. The foams do not neutralise the bromine and are not instead of neutralisation materials.
  • Water spray can be used to knock down bromine vapours. When spraying water and when a bromine puddle is drenched with the water, there may be a temporary increase in bromine vapour emission. Once a water layer is formed the vapours will decrease. Also in this situation bromine is not neutralised.
  • Bromine vapours can be neutralised with ammonia vapours. Ammonia vapours should be released in the direction of the bromine vapour until a white cloud is formed (ammonium bromide). Using ammonia should be done by well-trained people. Ammonia itself is a dangerous substance.

Emission to water (sewer systems)

If bromine containers are stored within a bunded area then bromine leaks that  occur can be covered by a layer of water to minimize bromine vapours.  A minimum water layer of 15 cm is recommended.  Fire fighting foam (AFFF)  can also be used if more readily available though it could possible complicate remediation efforts.  Bromine spills contained in a bunded areas, ditches or sewers can be pumped out to a waste treatment facility for neutralisation or recovery.  Be aware that bromine and its vapours may persist in pits, hollows, depressions, sewers and confined spaces.

Bromine can be ‘neutralised’ in several ways as described in section 2.2. From and environmental point of view three situations might result from remediation efforts.

  • Bromine is absorbed in or on a material, but no chemical reaction has taken place.   Such materials should not be washed into waterways.  Post treatment is recommended.
  • Bromine has been converted, in part, to a bromate.  Bromates are substances with a high toxicity level for the aqueous environment.  Consequently, bromate emissions should be avoided at all time.  Bromates should be to reacted further to form bromides using neuralization chemicals described in section 2.2 (thiosulphate, bisulphite).
  • Conversion to bromides. This is the best solution to reduce the possibility of emissions that could harm the environment. It’s not always possible to do this in one step. Sometimes one of the two above-mentioned steps is needed.

Soil pollution

To contain a bromine spill on the ground, earth and sand-bag dams should be built around the spill and the contained bromine neutralised with dry soda ash or a slaked lime-water slurry. 

Soils suspected of containing bromine residues should be collected as soon as access is available.  Slaked lime can be added to the soil to neutralise the bromine. The remediated soil should be put in emergency drums and disposed of according to local regulatory requirements.

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Handbook

The purpose of this document is to provide information and guidance to both bromine users and trained response personnel. The manual contains technical facts, engineering detail, health information and media response data.