THE AZF PLANT CHEMICAL EXPLOSION

Kankana Dutta 205, Saumya Goel 208

THE AZF PLANT CHEMICAL EXPLOSION

This report describes a runaway reaction and subsequent explosion, massive shock waves and fire which resulted in 29 deaths and about 10,000 injuries, also destroying the companys facilities and several residential structures while disrupting businesses all around the city of Toulouse. It also resulted in the formation of highly toxic chemical clouds which posed a high danger to drinking water and healthy living of citizens even for months to come. The accident occurred at the Grande Paroisse (AZF) factory in Toulouse, France on the 21st of September, 2001. This report is made in a bid to highlight the importance of safety and emergency management practices in control reactive hazards. (Information for this report was based on the officially released report on the accident by the French government via investigation conducted by INERIS).

INTRODUCTION
It was just 10 days after the devastating 9/11 terrorist attack on the United States. At exactly 10:18am, the city of Toulouse was rocked by a shocking chemical explosion originating from production halls of the Grande Paroisse, AZF fertilizer factory, involving ammonia nitrate (AN). The blast claimed 30 lives making it the most lethal modern industrial explosion in the history of the country. This report will be considering in concise details the accident as a whole, while focusing the flashlight on the dangers of ammonium nitrate, domino effects, aftermath, emergency response, public perception and lastly providing carefully, recommendations upon critical analysis of the shortcomings of the company and factory workers and events that preceded the explosion.

COMPANY OVERVIEW
Grande Paroisse (AZF), the company, was formed in 1924 (ONIA) and has since then metamorphosed to what it was before the explosion, being a very significant part of ATOCHEM- the chemical segment of TOTAL FINA ELF group, who till date is a major player in the oil and Gas industry, garnering sales of up to a billion dollars worldwide. The Grande Paroisse factory concerned was situated on a 70 hectare site which is to the south of the urban French city Toulouse, being strategically located on the left bank of the famous River Garonne and just about 3km to the centre of the urban city. The factory was well renowned for the production of fertilizers and other related nitrogenous chemicals, producing well up to 1,150 tonnes of ammonia per day, 1250 tonnes of ammonia nitrate granules per day of which, up to 850 tonnes is used for fertilizers and the remainder for industrial uses (mainly explosive foul nitrate). The companys factory, with about 470 people on its payroll also produces in addition over, 3,000 tonnes of other nitrogen based chemicals ranging from urea to nitric acid, formalin to melamine (used in manufacture of resins).

INCIDENT OVERVIEW
The explosion which occurred in the morning of September 21, according to reports released by INERIS, originated from a downgraded ammonium nitrate store, building 221 (2,400m2) located in the plants nitrate sector, where less than 400 tonnes of Ammonium nitrate went off, resulting in a enormous explosion accompanied by a colossal shockwave which had an effect around 40km circumference of the incident. The blast attained a 3.5 reading on the Richter scale, creating a crater of about 65 m 54 m in diameter and 7 m in depth, at the site. The explosion resulted in large cloud of dust and red smoke which was assumed to be due to the emergency shut-down of the nitric acid producing plant. This cloud was reportedly toxic, containing high concentrations of ammonia and nitric acid, which upon further dissipation resulted in other pollutants (haute-Garonne, 2007). The Haute-Garonne Prefecture requested that the population keep themselves safe indoors, a measure which of little help to people whose house had already being shattered by the shockwave, but nevertheless reduced traffic issues especially after the accident (haute-Garonne, 2007).

EFFECTS OF THE EXPLOSION

Effects by the French ministry of environment was classified under 3 sections, Human and social consequences, environmental consequences and economic consequences. Under human and social aspect, the accident led to 29 deaths (21 at AZF site, 1 at SNPE, 6 offsite and 2 in nearby hospitals) and according to official records by the Haute-Garonne prefecture, a total of 2,442 people were hospitalized and about 29 seriously injured. Injuries ranged from mutilations, compound fractures to pierced eardrums which were due to noise, flying glasses and shockwave. Although no long term effects for the pollutants released, yet they were responsible for a fair share of the injuries recorded, mostly relating to transitory ocular and respiratory irritations. The INVS and the Midi- Pyrenees DRASS in 2003, reported post-traumatic stress in more than 8,000 people while health services considering toxicological and epidemiological knowledge on the exposure-hazard relationship, showed a near-zero health risk associated with asbestos released via the blast (cancer). Of most concern for environmental consequences was the pollution of the river Garonne, a claim reported by ORAMIP detecting very high levels of certain pollutants in the river. For economic consequences, extensive and substantial damage were recorded on the AZF site and colossal sums of 1,100 employees were restricted according to a prefectoral injunction. Several establishments, up to 51,300 (up to 20,000 employees) lamented losses to various degrees

Emergency response was spontaneous with effective crisis management

operations also, immediate fire fighting actions and rescue measures were deployed, and reinforcements were requested to assist departmental fire service, while the civil protection mobilized a chemical hazard. Hospitals were able to accept a large number of injured people. The site was also secured at the request of the registered installations inspectorate. Compensations have also being paid (mostly out of court) to over 80,000 people as at 2009 costing the company over 2 billion Euros (Total el Fina, 2010). The site has also been remediated and presently the location for a cancer research project also funded by the Grande Paroisse.

DOMINO EFFECTS
Surprisingly there were no serious domino effects both on the facility and surrounding installations. A pressurized ammonia storage tank, and a liquid ammonia storage tank, chlorine storage facility, standing at 300M, 600m and 500m (in that order) from the explosion didnt suffer any direct damage as they were shielded by buildings that were ripped apart by the shockwaves themselves. Domino effect wasnt recorded on the neighbouring facilities either, also by great chance for the former Braqueville national explosive factory, on which remains thousands of tonnes of gun powder (INERIS, 2001), Although, not by chance at the SNPE (national society of powders and explosives) site, but for the technical know-how of 6 pyrotechnicians, an incredible automatic safety systems employed by SNPE, and quake resistant phosgene storage system. This resulted in a reduction damage which an explosion of this magnitude might have caused. Reports garnered by investigating bodies showed, an estimated 120% increase in victims would have been recorded if not for the SNPE safety systems. Absence of domino effects on other facilities can be attributed to distance.

REACTION OVERVIEW- AMMONIA NITRATE

It took a while to ascertain, but the cause of the accident, according to official reports produced by the INERIS, to the ministry of Environment, bore down to a chemical explosion which was linked to the mixture of a chlorine derivative (SDIC) with wet ammonium nitrate resulting in the production of the highly unstable trichloroamine (NCL3), which according to report is very sensitive and likely to explode. Ammonia Nitrate (NH4NO3) is synthesized industrially from anhydrous ammonia (NH3) and concentrated nitric acid (HNO3) via a partly violent and very exothermic reaction. After which excess water in product is evaporated to give specific grade of Ammonium nitrate depending on the intended specific use. Factory in question mainly specifically produces fertilizer grade (95% nitrate) and technical grade (as oxidizing agent in explosive preparations) (99% nitrate) (Grandeparoisse, 2009). Pure, compact and crystallized AN requires temperature well above 200oC to decompose although the resulting, runaway reaction evokes so much heat, that it is normally unstoppable. The energy required for detonation is believed to reduce with increasing impurities, but under normal handling conditions this chemical is stable and doesnt necessarily pose a threat of explosion. Ammonia nitrate, although, tagged as an explosive chemical under the EU legislation, and several laws have been enacted as regards its storage, handling, and usage by industries and effectively monitored by the SEVESCO directive, despite the fact that Scientific reports have ascertained that it doesnt directly pose any direct risk of explosion except there is a high energy interference which acts as detonator, forcing the chemical to decompose aggressively resulting in an explosion. But its role in industrial explosions in history has forced the laws. In 1947, the GrandCamp, an American liberty ship, on Texas shoreline, containing about 961 tonnes of 38% ammonium nitrate (highly impure) meant for rebuilding of Europes agriculture just after the world war, went off, resulting in the deadliest industrial accident in America, till date. Although the explosion was believed to be triggered by a fire source, (a phenomenon expert refer to as deflagration-to-detonation transition), although a shock-to-detonation transition was responsible for the explosion on an adjacent ship with about the same quantity of Ammonium nitrate.

INCIDENT ANALYSIS
INERIS investigators highlighted issues resulting in this incident, even though several sects still argue the original cause, (with terrorism claims surrounding the blast), the INERIS findings is presently been accepted as the official cause of the accident. Two days after the incident, INERIS investigators, discovered an empty, turned-inside-out bag of SDIC in shed 335 (storage site for empty bags that had contained ammonia nitrate and industrial nitrate). In theory, no bags that had contained chlorine derivatives should have been stored in that shed. Judicial investigation also revealed that a warehouse worker in Shed 335 might have mistakenly tipped a few kilos of a chlorinated derivative (SDIC), which he assumed was ammonium nitrate, into a tipper containing real ammonium nitrate, whos content were apparently transferred onto a pile of nitrate awaiting disposal inside the entrance zone of Shed 221. Some 15 minutes later this mixture exploded and the blast spread to the ammonium nitrate stockpile in the main part of Shed 221, which all exploded. Based on the reports provided by INERIS, we would suppose the factors below are key in the occurrence and impact of this accidentInadequate corporate oversight of process safety Lack of automatic safeguards Inadequate emergency plan drills Poor operator training/negligence Urban setting Pyrotechnical ignorance

PYROTECHNICAL IGNORANCE
TMG showed a very low level of pyrotechnical know how, principally ignoring the three basic principles in storage of powders and explosive: dividing them up into small amounts, erection of partitions and the overabundance of safety systems. This singular feat counted on the SNPE site making all the difference unlike AZF storing 400tonnes of dirty AN in a singular heap, this shows a level of negligence for which the judicial sessions are putting the blame on the management for(AZF, trial, 2003).

LACK OF AUTOMATIC SAFEGUARDS

According to official reports, courtesy of the INERIS, Building 221, was located adjacent to the sack filling building 123, 124, 125 where combustible products were stored. None of which was fitted with a fire detection system, reports showed building of this facilities to the accepted level have been going for years, the building 221 itself lacks any nitrogen oxide detectors, which have been proven to the a year before to reduce alarm time and consequently putting out the fire. This devices were present on other larger facilities on-site, the operator was quoted by Barthelemy et al as saying the risk of explosion was very negligible, he was of course wrong.

URBAN SETTLEMENT
The urban arrangement actually contributed also to the extent of damages caused by the explosion. On proper historical analysis of urban settlement in this area it was observed that chemical industries in the area, as at the 17TH century (ile de Tounis- explosives factory) were actually moved away from the growing city because of frequent accidental explosion (1781, 1816, 1840), and due to advantage of energy promised by the river Garonne, they were moved to this region. The city grew rapidly in the 19th century and as shown in Figure 3 below, it is quite unbelievable how the city had so much encompass the industries with little regards to the risks and dangers they pose. And as reported by Marianne Arens and Francois Thull, four days after the incident, where they purportedly admitted the explosion is a punishment for the complacency of the department for regional and urban development over the years, a claim I support as even high-risk government buildings such as the Toulouse-blagnac airport stations, 90 schools (in one of which the youngest victim, age 15, died) and even railway stations were situated.

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REGULATORY ANALYSIS
AZF facility was just one of the thousands of factories labelled high risk by regulatory bodies months before the explosion, AZF factory had a SEVESCO II directive of 9th December, 1996, which transposed into French law, in the millennium. The decree, although is often issued requires operators to set up a safety management system and to carry out a periodic examination of the hazard studies every 5 years, helping to and o control urban development. The company must also enlighten the public on what to do in case of emergency. Although the factory passed this stage, according to reports the with the company managing to put issues such as air-crash on site into consideration, when lodging a request to extend the production capacity of ammonia in 1999 but ignored crucial bits such as major risks of accidents linked to ammonia leaks or chlorine escape. The non-technical summary of the hazard study, in particular was succinct, but in no way gave any idea to the risk posed by the factory, not even the most probable- Flooding. The extension was granted by an order of 4th October, 2000 after examination by the SPPPIs and information committee and public verdicts, but it didnt take long before the weakness of the regulatory body were punished.

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RECOMMENDATION
In order to prevent further occurrence of such accidents, we would recommend a standard program to ensure that reactive hazards are managed in accordance with careful and good industrial practices based under strict scrutiny by both the public and the government. At a minimum the program should highlight and characterize the probabilities of reactive hazards while strictly implementing, documenting and maintaining appropriate safeguards with extreme training for personnel on how to prevent accidents and a good and suitable emergency plan alarm procedure to be complemented by a fairly efficient evacuation scheme. A strict assessment through periodic audits and sharing of information amongst European states on accident and near-misses might also help prevent such in the future we would also suggest new laws as regards sub-contracting, a effective plan for controlling of subcontractors such as labelling in the petroleum industry is highly recommended.

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CONCLUSION
This incident provides basic lessons for manufacturers with reactive operations or storages. It is highly essential, as this accident have revealed, for factories to point to the slightest details what could possibly go wrong and strive as hard as possible to prevent the reactive chemistry that can precede a similar disaster, while still implementing and maintaining adequate safeguards to help reduce the effect in a worst-case scenario. It is also very important for factories not to wholly disengage in the management of their process and stressing the importance of safety even to the most aware subcontractor. Periodic internal audit should also be encouraged while training individual personnel for response in an emergency situation.

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REFERENCES
The AZF Trial, Toulouse magistrate court, Grand paroisse, accessed 24/04/2011, available (online ) at en.azf.fr/fichiers/mediaLibrary/AZF/the-azf-trial-publication-va.pdf.