For long, a lot of accidents related to goods transportation proved the need of hazards identification. International regulations are in existence for air, ground (road, rail), sea and waterways transportation. For about 25 years, a committee of experts has been dealing at United Nations level on Transportation of Dangerous Goods (TDG) and recently (beginning 2001) extended its work to Globally Harmonized System of Classification and Labelling for Chemicals. In this lecture, will be presented first some typical accidents occurred with different types of goods : explosives, flammable substances (sinking of Ievoli Sun transporting chemicals and Erika transporting oil), toxic and corrosive, unclassified goods (Channel Tunnel in 1995, Mont-Blanc and Tauern tunnels in 1999). Then, a brief description of international regulations and of dangerous goods will be presented. Comments will be given on classification methods and procedures

Kordek, Marie-Astrid

Michot, Christian

Pineau, Jean-Philippe

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Hazard identification of dangerous goodsJean-Philippe Pineau, Christian Michot, Marie-Astrid KordekTo cite this version:Jean-Philippe Pineau, Christian Michot, Marie-Astrid Kordek. Hazard identification of dan-gerous goods. International Conference on Safety and Reliability (ESREL 2001), Sep 2001,Turin, Italy. <ineris-00972225>HAL Id: ineris-00972225https://hal-ineris.ccsd.cnrs.fr/ineris-00972225Submitted on 3 Apr 2014HAL is a multi-disciplinary open accessarchive for the deposit and dissemination of sci-entific research documents, whether they are pub-lished or not. The documents may come fromteaching and research institutions in France orabroad, or from public or private research centers.L’archive ouverte pluridisciplinaire HAL, estdestine´e au de´poˆt et a` la diffusion de documentsscientifiques de niveau recherche, publie´s ou non,e´manant des e´tablissements d’enseignement et derecherche franc¸ais ou e´trangers, des laboratoirespublics ou prive´s.1 Accidents related to goods transportationThe transportation of goods is linked with a lot of accidents with possible consequences onman, environment and equipment.All types of transportation systems are involved and data are worldwide collected with thepurpose of learning from experience. In ARIA databases (France), every year, about140 accidents (on a total of 1.100 reported) are mentioned concerning the transportation ofdangerous goods.On a total of 805 transportation accidents included in this database, 67 % are road accidents,2 % involved inland waterways and coastal transportation and 23 % rail transportation.Road transportation is a field in which a large number of accidents occurred, the consequencesbeing worst with explosive, flammable and toxic materials. In many instances, the toxicproducts were the consequences of a fire (toxic fumes).1.1 Road transportation of flammable liquidsSome typical examples are related to the transportation of flammable liquids (fuel andgasoline). A brakeless lorry containing soap and liquid alcohol involved in an accident at thebottom of a steep hill induced 10 fatalities (Les Eparres, France, January 7th, 1993).1.2 Road transportation of explosivesIn rare occasions, explosive substances and articles are involved : a typical example is anaccident on a highway on May 13th, 1993 at Etoile-sur-Rhône, France, in which 3 tons ofpyrotechnic substances were involved. A fire and an explosion were triggered by a collisionand the lorry driver was killed. Fortunately, this accident occurred during the night with a verysparse traffic.Another example is the Walden Truck accident, occurred on August 5th, 1998 in Canada, inwhich a transport containing about 18 tons of explosives fired after a collision on the roadsideand detonated. Fortunately, an area approximately 600 meters in both directions of this four-lane highway was vacated. Nobody was hurt by flyrocks and truck fragments (maximumthrown distance : about 2.5 km). The highway has been closed for a period of 11 days.1.3 Accidents in road tunnelsThe consequences of such types of accidents are worst when they arise in a tunnel. As regardsstrictly dangerous goods, only very few accidents are worldwide known. But it should beemphasized that the impact of tunnel transportation is low by relationship with the other partsof road systems.Reported accidents involved carbon disulfide (Holland, USA, 1927), gasoline (Caldecott,USA, 1964), aerosol dispensers and paints, (Tauern, A, 1999). In the Mont-Blanc tunnel,in 2000, ordinary goods were involved such as margarine. In other accidents (Mont-Blanc inFrance, date unknown, Fréjus in France in 1980, Gothard in Switzerland in 1980, BillwerderMoorfleet in Germany in 1963, the plastic materials were involved in three cases and cottonballs in one case (Mont-Blanc).1.4 Rail accident in tunnelThe only opportunity where dangerous goods were involved in rail tunnel is the accident inSummit tunnel in UK in 1984, after the derailment of a white spirit wagon. The initiated firelasted 3 days. In the Channel tunnel, in 1984, only ordinary goods were involved at thebeginning of a fire in a lorry embarked in the train (fats).1.5 Rail accidents on plant premises and marshalling yardsOn plant tracks and in marshalling yards, a lot of accidents are known. Only the followingexamples can be briefly explained.At Aix-les-Bains station (France, 1992), a derailment of a train with three wagons containingdangerous goods (dimethylamine and ammonia) was at the origin of a release of the liquiddimethylamine. Buildings were evacuated within 400 m from the accident. The emergencysituation lasted 4 days.At La Voulte (France 1993) 20 wagons containing gasoline derailed. 3 tanks were rupturedand exploded. The fire propagated to houses and to a sewer system. A soil pollution on 26 hawas also induced.1.5 Wreck of shipsThe wreck of chemical or oil tankers is also frequently at the origin of sea and shore pollution.In 1999, the oil tanker Erika sank close to the South Brittany shores and, in 2000, thechemical tanker Ievoli Sun 30 kms ashore of Cotentin, France, with partial release of styreneand some local pollution of shellfish.2. General background of regulationsIn order to avoid or minimize the consequences «f these accidents, regulations were developed(and are still under further development), respectively on :• road transportation ADR, last version, restructured applicable as from July 1st, 2001 :• rail transportation RID, last version restructured applicable as from July 1st, 2001• sea transportation IMDG, Code, edition 2000, IMO, London, 2001• air transportation I AT A, 42nd edition, 2001• inland waterways ADNR, edition 1999.In these regulations, requirements are given for the training of persons involved in the carriageand safety obligations of the participants. As regards safety obligations, appropriate measuresshall be taken according to the nature and the extent of foreseeable hazards, so as to avoiddamage or injury and, if necessary, to minimize their effects. When there is an immediate riskthat public safety may be jeopardized, the participants shall immediately notify the emergencyservices and shall make available to them the information they require to take action.2.1. Classes of dangerous goodsClass 1 : explosive substances and articlesClass 2 : gasesClass 3 : flammable liquidsClass 4.1 : flammable solids, self reactive substances and solid desensitized explosivesClass 4.2 : substances liable to spontaneous combustionClass 4.3 : substances which, in contact with water, emit flammable gasesClass 5.1 : oxidizing substancesClass 5.2 : organic peroxidesClass 6.1 : toxic substancesClass 6.2 : infectious substancesClass 7 : radioactive materialsClass 8 : corrosive substancesClass 9 : miscellaneous dangerous substances and articles.2.2. Principles of classificationFor the majority of classes, the assignment is made in accordance with defined tests,procedures and criteria (see "UN Manual of tests and criteria").Limitative classes :« classes 1, 7 and partially 4.1 (self reactive substances) and 5.2 (organic peroxides)Non limitative classes include remaining classes, and generally include tests, procedures andcriteria.More explanations about the criteria for classification can be found in table 1.Table 1 : classes of dangerous goodsClass1234.14.24.35.15.26.16.2789Substanceexplosive substances and articlesgasesflammable liquidsflammable solids, self reactivesubstances and solid desensitizedexplosivessubstances liable to spontaneouscombustionsubstances which, in contact withwater, emit flammable gasesoxidizing substancesorganic peroxidestoxic substancesinfectious substancesradioactive materialscorrosive substancesmiscellaneous dangeroussubstances and articlesLimitative classyesnonopartiallynononopartiallynonoyesnonoMain criteria forclassificationexplosive propertiescritical temperature< 50°C or vapor pres-sure at 50°C < 3 barboiling pointflash pointexothermal reaction,bulk combustionself ignitionwater actionburning velocitydecompositiontemperatureinhalation, ingestion,action on skin ormucous membranesnoaction on skin ormucous membranesee belowThe heading of Class 9 covers substances and articles which, during carriage, present a dangernot covered by the heading of other classes.The substances and articles of Class 9 are subdivided as follows :Ml : substances which, on inhalation as fine dust, may endanger healthM2 : substances and apparatus which, in the event of fire, may form dioxinsM3 : substances evolving flammable vaporM4 : lithium batteriesM5 : life-saving appliancesM6-M8 : environmentally hazardous substances :» M6 : pollutant to the aquatic environment, liquid« M7 : pollutant to the aquatic environment, solid» M8 : genetically modified micro-organisms and organismsM9-M1 : elevated temperature substances :• M9 : liquid• M10 : solidMi l : other substances presenting a danger during carriage, but not meeting the definitions ofanother class.2.3. Packing groupsThe requirements are different according to the various classes.The packing is a maximum volume of 4501 or can contain a maximum amount of 400 kg.There is a testing and approval procedure dealing with drop test, tightness, internal pressure,storage and specific tests.As regards the packaging, the compatibility between material and goods shall be examined.3. Issues to be dealt withFor about ten years, strong efforts were devoted to harmonization of classification andlabelling of chemicals. Considerations were also paid to more relevant methods forcharacterization of energetic materials and still unclassified substances. Another importantinternational work (OECD, UE DG Environment) concerned the DG transportation in roadtunnel considering a QRA approach.3.1. The Globally Harmonized System of Classification and Labelling for ChemicalsSince 1992, the work on the Globally Harmonized System of Classification and Labelling forChemicals (GHS) has been carried out by the International Labour Office, the Organisationfor Economic Co-operation and Development and the UN Committee of Experts on theTransport of Dangerous Goods and on the Globally Harmonized System of Classification andLabelling for Chemicals. Two sub-committees are involved :• the sub-committee of experts on TDF• the sub-committee of GHS.The sub-committee of GHS had been created to keep the GHS up-to-date and to promote itseffective implementation.A first GHS guiding document should be finalized by July 2002 : the draft document will beready for discussion in December 2001.The GHS will be taking into account the classification criteria for :• physical hazards : about the physical hazards, the work is completed except for criteria forthe flammability of aerosols. The criteria proposed are :definition of gases, liquids and solidstest conditionsflammability (solids, liquids and gases)reactivity (pyrophoric substances, self-heating substances, substances which, incontact with water, emit flammable gases, oxidizing substances, organic peroxides,self reactive substances, explosives and substances that are corrosive to metals)compressed gases• health hazards• hazards to the environment : the Globally Harmonized System of Classification andLabelling for Chemicals covers the nine hazard endpoints considered in existingclassification systems : hazards to the aquatic environment, acute toxicity, skinirritation/corrosion, sensitisation, germ cell mutagenicity, carcinogenicity, reproductivetoxicity and target organ toxicity. In addition, this system will also include the followinghazards not yet covered by existing systems : neurotoxic effects, immunotoxic and effectshazardous to the terrestrial environment.3.2. Classification of energetic materialsEnergetic materials are those materials with a high or medium energy content typically greaterthan 800 J/g. They comprise explosives in Class 1, desensitized explosives in Classes 3 and4.1, selfreactives in Class 4.1, organic peroxides in Class 5.2 and a lot of substances allocatedto different Classes for various reasons, e.g. :• nitromethane as a flammable liquid - Class 3• ammonium nitrate as an oxidizer - Class 5.1« nitrocompounds as toxic substances - Class 6.1.So there is no unified scheme for classifying energetic materials even for transport. Moreoverthe GHS exercise for physical hazards demonstrated recently how important are thedifficulties for merging systems dedicated to different purposes : UN for transport, EC forlabelling chemicals, OSHA in US, etc.Finally the best approach is to concentrate on properties, like detonability, deflagrability,behaviour in heating under confinement, thermal stability, sensitiveness to mechanicalstimuli, for identifying properly the hazards and to adapt as far as possible the conditions oftransport, storage, handling accordingly.As an example, the transport of nitromethane authorized in tanks in the past has beenforbidden after a severe rail accident in USA resulting in a mass explosion due to a cavitationprocess after impact.Because of the actual situation which is not really satisfactory, the trend is to push to refoundthe UN classification system for energetic materials, creating a new Class for these materialsbeside the Class 1 for explosives. It will provide the opportunity to have unified classificationprocedures and methods and will allow industry to reduce the explosion hazard by dilution orby other means. Nevertheless attention is to be paid to such a process as addition of diluantsmay emphasize thermal effects in a case of extended fire.3.3. Unclassified (but dangerous) substances in tunnelFurther to a recommendation following the enquiry on the Mont-Blanc tunnel accident, someliquid substances or substances to be easily liquefied, solid substances with heat ofcombustion similar to hydrocarbons should be studied for a possible classification in the roadtransportation legislation.About one hundred products (oil, fats, polymers, animal or natural fats) having a high heat ofcombustion can be taken into consideration for such transportation and can burn. When a fireis induced in the vicinity, these material melt and can flow with a possibility of developing apool fire.It means that the following characteristics shall be determined :• heat of combustion and burning rate• formation of thick and opaque fumes with soot and toxic substances production• interaction with the packing.For these substances, possible regulations (in France and abroad) are still under discussion,considering either classification in class 9 or prohibition of transportation in runnel or possibletransportation without classification when tunnels are adequately designed as regards thedevelopment of such fires, or grouping as proposed by OECD/AICPR.3.4. QRA and decision making for DG road transportationOECD developed a research program for defining a quantitative risk assessment for thetransportation of dangerous goods in road tunnel. This program gave input data for a decisionmaking system and helped for defining practical measures for minimizing the risks. All thiswork was funded both by OECD and European Union (DG VII). INERIS (France),W.S.Atkins (UK) and University of Waterloo (Canada) were involved in the QRA research.The final objective of this QRA model is the production of quantitative data on DGtransportation risk levels on various routes, some of which being tunnels.The risk is characterized by the probability of occurrence and the severity (as a number offatalities or injuries, damages to buildings and structures or environment). F/N curvesqualifying the societal risk (annual frequency F to get an accident in which more thanN people are killed) were defined ; individual risks are also determined considering thefrequency for permanent populations. Damages to structures are semi-quantitatively definedand damage to environment are only qualitative.A lot of simplifications were introduced in the model in which a limited number of relevantscenarios (ten) are included.Two lorry fires scenarios (not considering DG) are also included because of the very severerisk (Mont-Blanc and Tauern accidents in 1999) in tunnel. Such scenarios are really morefrequent than those implying dangerous goods.Some ventilation configurations and the safety measures adopted (traffic control, flammableliquid drainage, monitoring system) have been studied to examine their influence on the F/Ncurves.At the end of the work programme, the QRA model was produced as a software tool,available in a CD-ROM and includes a user guide and specialized guidance documents.

Hazard identification of dangerous goods

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Hazard identification of dangerous goods

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