of the subs-

SECTION 2: Hazards identification

Need to refer to similar past of consequences incidents (similar conditions or hazards) Humans

Physical hazards

of HNS Probability for of population - Number of proven PREPAREDNESS danger class(es), sub to be being exposed to HNS or potentially injured class(es) of danger, people, - Toxicological levels - Health impact on - Hazards related to the vessel population, responders - Environmental conditions not otherwise classified (refer to Safety Data Sheet) BEHAVIOURS HNS AND Examples of related case studies: PREPAREDNESS ammonium nitrate (3,160 tonnes) sodium, hydrides of calcium), with phosphorus, Reactivity Main Risks & Hazards - Related case studies Examples of substances Ignition, explosion. Some alkali metals (e.g. potassium, sodium, Ocean Liberty, 1947, port of Brest, France; calcium), some metal hydrides (e.g. hydrides of With oxygen (air) + oil (300 tonnes). Cause of spill: fire and some oxidants (e.g. acetaldehyde; diethyl ether, subsequent explosion. isopropyl ether), pyrophoric liquids (tributyl- phosphine, trimethyl aluminum) Explosion or formation of hazardous pro-

Environmental hazards

Consider hazards of HNS Probability of the pollutant Proven or potential on for the environment reaching environmentally impacts on the environ- - Ecotoxicological effects sensitive areas identified in ment (value, structure, STUDIES - Leakage of gas from a - Direct injuries due to fire - No major expected - Window-shattering sealine (subsea pipeline) or explosion chronic impact expec- explosion, CASE - Mixing of reactive chemi- cially in confined space - Leakage of liquefied gas - Possible indirect - Anoxia, asphyxia, espe- ted - Building destruction cals forming gas - Depending on chemi- impact (e.g. fire resi- - Evaporation from slicks cals: toxicity or corrosi- dues) - Gas cloud formed after vity reaction of chemicals SHEETS Table 18 Flammable and Explosive substances applicability and main risks 132 - Marine HNS response manual 1 Events leading to a flammable/explosive situation SHEET 5.6 Response considerations: Flammable and explosive - Leakage of toxic chemicals - Chronic impact - Mixing of reactive chemicals for- - Carcinogenetic issues - Possible indirect impact (e.g. ming gas extinguishing water, dissol- - Evaporation from slicks ver in water curtain) STUDIES - Gas cloud formed after reaction of chemicals 1 Events that may lead to a toxic atmosphere CASE Table 19 Toxic substances applicability and main risks SHEETS 135 - Marine HNS response manual SHEET 5.7 Response considerations: Toxic substances AND - Leakage of corrosive - Injuries due to - Direct impact on animals - Chemical corroding liquid or gas from drum direct contact with and the environment drums or tanks, leading necrosis, inhalation, IMO - Mixing of reactive che- impact - Corrosion of metals ingestion) PROTOCOLS micals forming corro- (ship’s deck, crane, etc.) sive gas or compound - Possible indirect impact (e.g. extinguishing water, (limitation/interference to - Evaporation from slicks dissolver in water cur- with the legitimate uses BEHAVIOURS tain) of the sea/amenities) 1 Events that may lead to a toxic atmosphere Table 20 Corrosives substances applicability and main risks HNS AND Risk assessment For the general consideration of corrosive substances, responders should focus on: • Assessing the risks of atmospheric and marine toxicity by gathering data on the substances; PREPAREDNESS • Assessing the risks of exposure to corrosive substances on the basis of its physical state and behaviour, monitoring pH if applicable; • Assessing associated hazards if present and evaluate the priority for response; cor- rosive substances are often associated with other hazards such as flammability and/ or explosivity and/or toxicity; 5.6 Response considerations: Flammable and explosive substances AND Leakage of - Direct injuries due to fire - No major expected chronic - Direct and indirect PROTOCOLS reactive explosion or explosion or highly exo- ignite combustible material impact expected damages (or destruc- scenarios, even at a that cause explosion) dings, other maritime IMO ignition/ - Oxidising substances could (e.g. fire residues) infrastructures (in some or destroy material (e.g. considerable distance responder equipment) from the accidentinci- BEHAVIOURS - Anoxia, asphyxia, especially reactive contact with substance and the environment dent). drums or tanks, leading in confined spaces Leakage of - Injuries due to direct - Direct impact on animals - Chemical corroding HNS AND that form cor- tion, ingestion) substances - Possible indirect impact (dermal necrosis, inhala- - Corrosion of metals - Chronic impact to a pollution spill rosive (e.g. extinguishing water, (ship’s deck, crane, etc.) products dissolver in water curtain) (limitation/interference to with the legitimate PREPAREDNESS that form toxic ingestion, inhalation) - Possible indirect impact may lead to a closure/ uses of the sea/ameni- ties) Leakage of - Injuries due to direct - Direct impact on animals Contamination of the reactive contact with substance and the environment marine environment by substances (skin/mucosa contact, - Acute and chronic impact toxic-persistent product products - Carcinogenetic issues (e.g. extinguishing water, limitation/interference to dissolver in water curtain) with the legitimate uses of the sea 1 Events that may lead to a corrosive spill or atmosphere (e.g. protein solution (low Biochemical IMO renew the water when quantity of drums, Oxygen Demand) substance is too high compared to flexitank) flora and fauna Incident pipeline, 2013; Hawaii harbour, US. Cargo molasses BEHAVIOURS goods Seed cake (soya es and potentially 5.39 HNS response Solid bulk Grain (wheat, Fermentation and Removal of the substances Packaged rapeseed…), Rice production of gas- (by ROV, dredging or divers) (e.g. bags) meal/pellet, oil harmful by-products HNS AND on the seabed by-products….). Sinker: reduction of 5.24 Remotely Operated oxygen rate due to Vehicles increase in bacteria; smothering PREPAREDNESS Coarse chopped Incident Fénès, 1996; Lavezzi islands off Corsica, France. Cargo wheat and fish; Removal of the substances (by ROV, Plastic Solid bulk Chopped rub- Depending on the Recovery at the surface/on the sea- pellets Packaged ber and plastic size of pellet: bed/shoreline goods insulation, Granu- - Floater: risk of 5.43 Recovery techniques: (e.g. bags) lated tyre rubber, ingestion for birds Pumps and skimmers tyres, Recycled - Suspended matter: dredging or divers) plastic increase of turbid- 5.39 HNS response on the seabed resin/pellets, ity, impact on spe- 5.24 Remotely Operated Vehicles Nurdles cies on respiratory/ Manual recovery of pellets on the (e.g. bags) on respiratory/diges- 5.38 HNS response CASE Sedimentation or solidification on the Removal of sunken solidified part if necessary seabed 5.39 HNS response on the seabed Table 27: Main categories of products frequently transported in large quantities by sea which may present issues when spilled at sea SHEETS 156 - Marine HNS response manual SHEET 5.13 space-limited impact (generally low) on pelagic ecosystem; risks could be For hazards and risks see also 3.2 Hazards Table 29: Processes and Factors affecting behaviour and fate of gases and evaporators STUDIES Considerations CASE • Main risks for safety and/or human health (crew; population if source and cloud near to the coast) 5.6 Response considerations: Flammable and explosive substances 5.7 Response considerations: Toxic substances • Minor risks for the marine environment (non-persistent substances) SHEETS • Response actions are conducted on board the ship 157 - Marine HNS response manual SHEET 5.13 Response considerations: Gases and evaporators spills. FE and FED substances can generate potentially dangerous vapours; the main social effects are related to navigational safety and strong limitations for legitimate uses of the sea. For hazards and risks see also 3.2 Hazards SHEETS Table 32: Processes and factors affecting behaviour and fate of floaters in a marine accident incident 162 - Marine HNS response manual SHEET 5.14 Response considerations: Floaters Sea sate, air/water temperature, water-column turbulence/humidity (if on board) tal factors Sea-bottom influencing currents, bottom intensity of morphology, processes bathymetry Production of plumes in water column; dispersion, diffusion, dilution FATE Dissolving sub- Floating on POST-SPILL MANAGEMENT spread of dispersion superficial layer. tely dissol- column. Sea bot- Floating slick until Solids and their and merged floating sea surface completely dissol- dissolving plume plume. Residuals until comple- Drift and Atmospheric ved. Involves sea can accumulate on sink in water sea bottom. ved. Involves HNS tom is potentially Atmospheric sea surface BEHAVIOUR involved. dispersion layer Evaluate risk of violent reactions with smoke/gas/aerosol production, possibly toxic (e.g. exo- STUDIES thermic reaction from strong acids and bases). Evaluate risks of flammability/explosivity. Other Toxicity; reactivity; flammability; explosivity; pH relevant HNS viscosity CASE properties ∆d (dsw – dliquid): affects speed of sinking and buoyancy Impact Main risks are primarily for pelagic ecosystem. In the case of dissolver and sinker substances, on marine the benthic ecosystem could be also affected. Possible severe interference with and restrictions on coastal amenities. For hazards and risks see also 3.2 Hazards SHEETS Table 35: Processes and factors affecting behaviour and fate of dissolver in a marine accident incident 168 - Marine HNS response manual SHEET 5.15 Response considerations: Dissolvers decomposition of grain to form hydrogen sulphide). Some insoluble sinkers are per- sistent in marine environment. Table 38: Processes and factors affecting behaviour and fate of dissolver in a marine accident incident Considerations STUDIES CASE • High cost for research and recovery activities; • In case of emergency on board a ship it should be considered to avoid dangerous situation related to hazard of the substances involved. SHEETS 173 - Marine HNS response manual SHEET 5.16 Response considerations: Sinkers

Response

Environmental conditions the contingency plan function or ecosystem) Socio-econo- On Hazards for areas Probability for of the pollu- Losses: proven or poten- mic activities or entities, for instance: tant to reaching socio-econo- tial costs, loss of activity, and amenities aquaculture, - water intakes, mically etc. tourism, etc. sensitive areas identified in the contingency plan POST-SPILL MANAGEMENT Table 17: Description of the three main steps of situation assessment As far as possible, relevant data to assess hazards, risk/vulnerability, as well as conse- quences, should be quantitative. All these data can subsequently be gathered in a table, dated and recorded for further archiving. STUDIES To anticipate possible changes in the situation, some input data should be considered as they worsen or become increasingly favourable. These can be for instance: CASE • Environmental conditions (change of weather, tide, etc.); • Sensitive period (forthcoming peak period, for instance during holidays, political elections, etc.) or location (remote area, difficult access, etc.). SHEETS 130 - Marine HNS response manual SHEET 5.5 Situation assessment Situation assessment and action plan CODES when faced with several hundreds or even thousands of containers. This Special care for incidents involving containers AND Searching for information in cargo manifest is drastically time-consuming PROTOCOLS with (or at least with sufficient knowledge of) the use of the IMDG Ccode and IMO task should be performed through a collaborative effort and by people familiar information resources related to containers. BEHAVIOURS blematic containers. If the situation were to evolve, this would allow the response Tips: use a spread sheet obtained from an expert organisation to identify contai- ners, danger classes, UN number, etc. It is useful to rank and highlight more pro- HNS AND team to modify the ranking (for instance initial ranking for a vessel on fire will be modified in case of shipwreck). PREPAREDNESS Required personnel/equipment Personnel involved in the Incident Team should include: • Experts in different fields involved: naval officer, chemical engineer, environmental engineer (biologist, ecologist, etc.); • Local experts on potentially impacted sensitive areas. Considerations • A situation assessment may be time-consuming due to a lack of available data (on HNS, vessel, contingency plan). • In case of a mixture of chemicals: possible hazards due to the mixing MANAGEMENT of chemicals should be considered and a medical expert should be consulted to assess the possible effects of combined exposure to multiple POST-SPILL chemicals. • The reliability level of the situation assessment is directly correlated to the quantity and reliability of information gathered from the incident. STUDIES 5.2 Incident data gathering CASE SHEETS 131 - Marine HNS response manual SHEET 5.6 Situation assessment and action plan AND PROTOCOLS IMO Examples of related case studies: BEHAVIOURS forms; 1100 tonnes transported and spilled). Cause of spill: fire on board (reaction • Cason, 1987, Cape Finisterre, Galicia, Spain; Sodium (1,400 barrels) and other hazar- dous chemicals (flammable/toxic/corrosive products in 5,000 different package HNS AND of sodium with seawater) and subsequent grounding. Val Rosandra, 1990, Port of Brindisi, Italy; Propylene (1,800 tonnes in bulk, controlled burning, quantity spilled 0). Cause fire. • Alessandro Primo, 1991, 30 km off Molfetta, Adriatic Sea, Italy. Acrylonitrile (549 PREPAREDNESS tonnes in 594 barrels) and of Dichloroethane (3, 013 tonnes); recovery from sunken wreck. Cause: structural damage subsequent due to a storm. Igloo Moon, 1996, outside Key Biscayne in South, Florida; Butadiene (6,589 tonnes, recovery of the cargo, quantity spilled 0). Cause grounding. • MF Ytterøyningen, 2019, Norwegian; Ethylene Glycol leak (coolant components). Cause: fire and subsequent explosion (failure communication failure between the Alert and notification in case of a potential leak: EMX –Energy management system– and the battery packs). Depending on the location of the incident, the MRCC, site emergency services and public emergency services must be alerted. Ships (crew) and the population downwind (vapour cloud) and downstream (spill) must also be warned in order to prevent compli- MANAGEMENT For more information and a description of the flammability and explosivity of subs- cations arising. POST-SPILL Applicability and main risks: tances, refer to Chapter 3 on hazardous substances. Applicability1 Risks for humans/ Risks for the Risks for amenities responders Situation assessment and action plan CODES Risk assessment 5.25 Portable gas detectors for first responders AND • Risks of flammability or explosion must be assessed by monitoring the LEL/LFL and UEL/UFL values and the evolution of concentrations over time. PROTOCOLS IMO 5.26 Sampling techniques and protocols • Forecast of the gas cloud drift must be requested from experts. • If applicable (regarding the characteristics of the chemical and the situation), the BEHAVIOURS 5.8 Response considerations: Corrosive substances toxicity risk should be assessed, as well as corrosivity. 5.7 Response considerations: Toxic substances HNS AND WIND Overpressure limit Flammability/ PREPAREDNESS explosivity area Cloud Source/leak Ignition point Spreading of (ship or facility) (ship’s engine, spark...) Cedre the flame • Areas to consider for intervention: in the cloud © Figure 52: Risk assessment • Consider (and control) aggravating factors: - in the event of fire, prevent the risk of BLEVE by cooling tanks in direct contact with heat radiation; risk of toxic gas production. MANAGEMENT - The distressed vessel’s crew: the helicopter/rescue ship must approach from Protective measures (human health, environment and amenities) POST-SPILL • Evacuation: downwind. - The population: modelling should be carried out to determine the specific area STUDIES to evacuate or the containment measures to be implemented. • Protection: - Ventilation of the explosive atmosphere in order to lower the LEL/LFL; CASE - Activation of the existing firefighting systems; - Gas or vapour cloud should be prevented from entering confined or closed areas and obstacles must be removed (if possible) to reduce turbulence; - Protection of responders against inhalation of vapours or mist. SHEETS 5.20 Personal Protective Equipment 133 - Marine HNS response manual SHEET 5.6 Response considerations: Flammable and explosive Situation assessment and action plan CODES Reminder: a flammable cloud may become explosive when the speed of AND the front flame exceeds several meters per second (due to HNS nature, PROTOCOLS atmosphere turbulence and obstacles) or in a confined space. Continue to IMO monitor the LEL/LFL throughout the response. Response measures BEHAVIOURS • Elimination of sources of ignition. • Stopping the leakage; 5.32 Sealing and plugging HNS AND - Behaviour: 5.13 Response considerations: Gases and evaporators 5.14 Response considerations: Floaters PREPAREDNESS - Techniques: 5.19 Safety zones 5.34 Using water curtain 5.35 Using foam 5.36 Maintain in the environment and monitoring POST-SPILL MANAGEMENT STUDIES CASE SHEETS 134 - Marine HNS response manual SHEET 5.7 Situation assessment and action plan AND PROTOCOLS IMO BEHAVIOURS • Burgenstein,1977, port of Bremerhaven, Germany, Sodium Cyanide, Examples of related case studies: • Cavtat, 1974, southern Italy, Tetraethyl lead and tetramethyl lead; HNS AND Potassium Cyanide; • Sindbad, 1979, North Sea, Chlorine; • Testbank, 1980, Louisiana, USA, Hydrogen Bromide • Rio Neuquen, 1984, Port of Houston, USA, Aluminium Phosphide; PREPAREDNESS • Santa Claira, 1991, New Jersey, USA, Arsenic Trioxide Alert and notification in case of a potential leak: Depending on the location of the accident, the Munster Regional Communications Centre (MRCC), site emergency services and public emergency services must be alerted. Ships (crew) and the population downwind (vapour cloud) and downstream (spill) must also be warned in order to prevent complications arising. Applicability and main risks: For more information and description of toxic substances, refer to Chapter 3 on hazar- dous substances. POST-SPILL MANAGEMENT contact, ingestion, inhalation) Applicability1 Risks for humans/responders Risks for the environment - Leakage of toxic gas from drum - Injuries due to direct contact - Direct impact on animals and or tank with substance (skin/mucosa Situation assessment and action plan CODES Risk assessment • Model the behaviour and movements of the toxic cloud. AND • Assess the risks of atmospheric and marine toxicity by gathering data on the substances. • Consider toxic exposure limits (Chapter 3) to assess the risk for the population. PROTOCOLS IMO • Evaluate the environmental compartment(s) (atmosphere, water column…) liable to be impacted by the toxic substance or any by-products that may be formed in the scena- rios. BEHAVIOURS - Weather conditions: wind, current, temperature, rain and fog, atmospheric stabi- • Assess route of entry of the toxic substances (dermal contact, ingestion, inhalation…). • Consider (and control) aggravating factors: HNS AND lity, etc. - Reactions between chemicals, reactions due to the increase in temperature, time of exposure… PREPAREDNESS Protective measures (human health, environment and amenities) Protective measures must be tailored to the penetration process of the substance invol- ved and its characteristics. Toxicity is not only related to airborne substances; the popu- lation and responders can also be affected through contact, ingestion, etc. 5.20 Personal Protective Equipment (e.g. Self-Contained Breathing Apparatus -SBCA for toxic gas, specific protective clothing for dermal risks…) 5.25 Portable gas detectors for first responders • Evacuation: - The distressed vessel’s crew: the heli- Mucosa: eyes, nose, MANAGEMENT - The population: modelling should be mouth, ears copter/rescue ship must approach from downwind in case of a toxic POST-SPILL cloud; Respiratory system used to determine specific areas to evacuate or shelter-in-place measures STUDIES to implement (in case of a toxic cloud). Digestive system • Protection: - In the case of marine toxic subs- CASE tances, resources (e.g. fisheries, water intakes…) liable to be impac- ted should be assessed along with Skin contact Cedre measures to protect them if required; © SHEETS 5.40 HNS response on the shore Figure 53: Toxicity on human health 136 - Marine HNS response manual SHEET 5.7 Response considerations: Toxic substances Situation assessment and action plan CODES - Additional contamination due to by-products resulting from the response to AND the incident must be avoided by containing and recovering these substances (residual water from water curtain techniques, extinguishing water…) PROTOCOLS IMO Response measures • The source of the leakage must be isolated if possible (tank or drum storage) to facilitate the response. BEHAVIOURS • Depending on the substances: • Protective Action Criteria (PACs, see dedicated part in Chapter 3) should be used for intervention and to select proper PPE. HNS AND - Behaviour: 5.13 Response considerations: Gases and evaporators 5.14 Response considerations: Floaters PREPAREDNESS 5.15 Response considerations: Dissolvers 5.16 Response considerations: Sinkers - Techniques: 5.34 Using water curtain 5.35 Using foam 5.36 Maintain in the environment and monitoring POST-SPILL MANAGEMENT STUDIES CASE SHEETS 137 - Marine HNS response manual SHEET 5.8 Situation assessment and action plan AND PROTOCOLS IMO Examples of related case studies: BEHAVIOURS lost deck cargo. • Unknown lost packages, 1975, Swedish West Coast about 100 km north of Gothen- burg, Sweden. Propionic Acid (approximately 30 drums lost at sea). Cause: probably HNS AND • Puerto Rican, 1984, 8 miles west of Golden Gate Bridge, San Francisco Bay, Califor- nia, USA. Caustic soda solution, 50% (quantity spilled 400-500 m3). Cause of spill: explosion (reaction of caustic soda with the epoxy coating). • Julie A, 1989, Port of Aarhus, Denmark. Hydrochloric Acid (quantity spilled: 1 to PREPAREDNESS tonnes of HCl 31%; quantity transported 300 tonnes). Cause of spill structural damage to internal tank coating (reaction of hydrochloric acid with sheet iron, with formation of hydrogen gas). • Kenos Athena, 2012, in water adjacent to Zheland Island, southern Guangdong Pro- vince, China. Sulphuric Acid (ship loaded with 7,000 tonnes and 140 tonnes of resi- dual fuel oil; chemical and bunker-oil removal from sunken ship). Cause: shipwreck, Alert and notification in case of a potential leak: sunk after about a month. Depending on the location of the accident, the Munster Regional Communications Centre (MRCC), site emergency services and public emergency services must be alerted. Ships (crew) and the population downwind (corrosive gases) and downstream MANAGEMENT For more information and a description of corrosive substances, refer to Chapter 3 on (spill) must also be warned in order to prevent complications arising. POST-SPILL Applicability and main risks: hazardous substances. STUDIES CASE SHEETS 138 - Marine HNS response manual or tank substance (dermal CODES - Acute and chronic Applicability1 to a pollutionspill Risks for humans/ Risks for the Risks for amenities responders • Analysing weather data and detector measurements; 5.7 Response considerations: Toxic substances 5.8 Response considerations: Reactive substances • Modelling the behaviour and movements of the corrosive gas/vapours/fume clouds, if applicable. Consider modelling corrosive floater/dissolver/sinker if spilled in water column, if applicable; MANAGEMENT sing the associated hazard levels (smoke from fire, reaction with the environment, • Assessing measures to protect sensitive areas (environmental, ecological, social, industrial sites) and facilities, including through preventive shutdown, determining POST-SPILL the hazards posed by any products that may be formed in the scenarios and asses- etc.); 5.2 Incident data gathering STUDIES • Avaluating the location of facilities and equipment for quick response. Areas to consider for intervention: CASE • Evaluate/model the extent of the area affected by dangerous concentrations of cor- rosive substances in the water column and/or in the atmosphere to limit legitimate uses of the sea and amenities. 5.19 Safety zones SHEETS 139 - Marine HNS response manual SHEET 5.8 Response considerations: Corrosive substances Situation assessment and action plan CODES Consider (and control) aggravating factors: • Possible highly exothermic reaction when certain acids or bases are spilled in water; AND • Reactions between acids and bases, reactions due to the increase in temperature, time of exposure; PROTOCOLS IMO • Maximum precautionary measures must be taken especially in the case of in situ response on the vessel (confined space); • High viscosity values slow down dilution and dispersion processes at sea. BEHAVIOURS As corrosive substances gather a large group of chemicals, protective measure must Protective measures (human health, environment & amenities) HNS AND comply with the conclusions of the risk assessment: • Corrosive liquids (mineral acids, alkali solutions and some oxidisers): eyes and skin are particularly vulnerable due to splashes of the substance and effects on tissues are generally very fast. PREPAREDNESS • Corrosive gases and vapours: effect is generally related to the solubility of the subs- tances in the body fluids. Highly soluble gases like ammonia or hydrogen chloride cause severe nose and throat irritation, whereas lower solubility vapours (phosgene, sulphur dioxide, etc.) penetrate deep into the lungs. • Corrosive solids: direct contact can cause burns to the skin (phenol, sodium hydroxide…) and dust affects the respiratory system. Many corrosive solids may produce highly exothermic reactions when dissolved in water. the water surface and the spill must be contained (construct berms, sand dikes…). • In case of a water-reactive product, the substance must be prevented from reaching 5.20 Personal Protective Equipment 5.25 Portable gas detectors for first responders MANAGEMENT space; do not operate without self-contained breathing apparatus; On board: • Attention should be paid to avoiding direct contact with the skin and protecting POST-SPILL against inhalation of vapours or mists. Check atmosphere before entering a confined 5.20 Personal Protective Equipment 5.25 Portable gas detectors for first responders STUDIES • Evacuation must be implemented immediately downwind (gas/evaporator/fumes); • Attention should be paid to decontaminating protective clothing: wash down with water and then remove. CASE SHEETS 140 - Marine HNS response manual SHEET 5.8 Response considerations: Corrosive substances Situation assessment and action plan CODES Population and amenities: cloud or marine environment contamination); AND • Modelling will need to be conducted to determine the specific area to decide on the implementation of evacuation or shelter-in-place measures (in case of a corrosive PROTOCOLS IMO • Evacuation must be implemented in downwind impacted areas (in case of hazar- dous vapours, gas clouds, fumes); • Zoning: downstream area of the spill (targets of polluted runoff, liquid and solid BEHAVIOURS Response measures spills) and evaluate any limitations on the use of the sea and amenities. HNS AND On board: • If possible, other chemicals or organic products must be isolated from the leaking substances until its reactive potential has been assessed; • If the substance is not water-reactive, acids and bases may be neutralised by a dilu- PREPAREDNESS tion process in order to reduce the concentration (overboard washing with indirect water jets if possible). pH should be measured before discharging the diluted mix- ture in the environment; 5.34 Using water curtain 5.36 Maintain in the environment and monitoring • Water-reactive substances may be treated by compatible sorbent or inert materials; and techniques according to the substances involved and scenarios should be used 5.37 Using sorbents • In the case of an on board leak, appropriate containment and recovery methods (Emergency Schedules (EmS), IMO, 2018). In the environment: Refer to the characteristics, behaviour and fate and of the spilled (or leaked) substances, POST-SPILL MANAGEMENT using specific precautions for the risk of corrosivity. Behaviour: 5.13 Response considerations: Gases and evaporators 5.14 Response considerations: Floaters STUDIES 5.15 Response considerations: Dissolvers 5.16 Response considerations: Sinkers 5.41 Response to packaged goods CASE Techniques: See Chapter 5.6.3 SHEETS 141 - Marine HNS response manual SHEET 5.9 Situation assessment and action plan AND Flammable / explosive: Oxidising / peroxidising: GHS PROTOCOLS GHS UN Regulation IMO possible reaction with and diesel (470 tonnes). Risk of production chloride, calcium carbide, cyanide salts With water ducts (corrosive, toxic or flammable). (hydrolysis, hydration, Adamandas, 2003, Réunion Island; deoxi- Some alkaline metals, sodium or potassium oxidation; consider also diseds iron of ore balls (21,000 tonnes) phosphide, alkali metal cyanide salts, aluminum moisture in the air) of hydrogen gas.Cause of spill: structural damage Highly exothermic reaction (with violent explosion in some cases) due to self-reaction MANAGEMENT tion and ignition of styrene. of a monomer; Acrylonitrile; cyclopentadiene, hydrocyanic acid; Polymerisation Stolt Groenland, 2019, Ulsan, South Korea; methacrylic acid; methyl acrylate; vinyl acetate Styrene monomer (5,200 tonnes). Cause of POST-SPILL spill: explosion, fire due to over-pressurisa- Fire, explosion or release of toxic vapours depending on amounts, and surrounding Some incompatible groups: flammables and conditions); toxics products; flammables products and oxi- STUDIES With other dous products including Cyanide. Cause of Burgenstein, 1977, port of Bremerhaven, NOAA dizers; acids and bases; oxidizers and reducers substances Germany; Sodium peroxide and other hazar- See The Chemical Reactivity Worksheet (CRW) - spill: structural damage to a drum of sodium CASE peroxide. SHEETS 142 - Marine HNS response manual Table 21: Related case studies of reactive substances accident SHEET 5.9 Response considerations: Reactive substances Situation assessment and action plan CODES Self- Explosive reactions A self-reactive substance means a thermally unstable liquid or solid substance liable to undergo strongly exothermic decomposition even without the participation of oxygen (air). This definition excludes subs- AND tances or mixtures classified under the GHS as explosive, organic peroxides or as oxidising agents (GHS, 2019). PROTOCOLS Mechani- terdam; Chlorine (51 steel cylinders/51 Acetylides, oxides, organic nitrates and many IMO reactive Light- M/V Sinbad, 1979, 20 nautical miles west Hydrogen and chlorine substances induced of Ijmuiden, Netherlands, offshore of Ams- cal shock tonnes). Losst of deck cargo at depth of 30 peroxides Inherently m. Cause of spill: structural damage (adverse Acetylene BEHAVIOURS unstable weather) Can detonate under certain pres- Table 21: Related case studies of reactive substances accident sure and temperature conditions. HNS AND Alert and notification in case of a potential leak: Depending on the location of the incident, the Munster Regional Communications Centre (MRCC), site emergency services and public emergency services must be alerted. PREPAREDNESS Ships (crew) and the population downwind (vapour cloud) and downstream (spill) must also be warned in order to prevent complications arising. Applicability and main risks: Reactive substances include a wide range of potential consequences which depend heavily upon their chemical nature (see above table). For more information and a des- cription of reactive substances, see 3.2.5 Hazard: reactivity. Also note: • In the case of a fire/spillage involving self-reactive substances, non-water-reactive but flammable substances, polymerising substances: 5.6 Response considerations: Flammable and explosive substances MANAGEMENT 5.8 Response considerations: Corrosive substances • In the case of fire/spillage of chemicals which form toxic or corrosive products by reaction with other materials or other spills: POST-SPILL 5.7 Response considerations: Toxic substances STUDIES CASE SHEETS 143 - Marine HNS response manual substances thermic reactions (violent - Possible indirect impact CODES Applicability1 tions) to vessels, buil- Risks for humans/ Risks for the Risks for amenities responders Table 22 Reactive substances applicability and main risks Risk assessment For the general consideration of corrosive substances, responders should focus on: MANAGEMENT state and behaviour, monitoring pH if applicable; • Assessing the risks of atmospheric and marine toxicity by gathering data on the substances; POST-SPILL • Assessing the risks of exposure to corrosive substances on the basis of its physical • Assessing associated hazards if present and evaluate the priority for response; cor- rosive substances are often associated with other hazards such as flammability and/ STUDIES or explosivity and/or toxicity; 5.6 Response considerations: Flammable and explosive substances 5.7 Response considerations: Toxic substances CASE 5.9 Response considerations: Reactive substances • Analysing weather data and detector measurements; • Modelling the behaviour and movements of the corrosive gas/vapours/fume clouds, if applicable. Consider modelling corrosive floater/dissolver/sinker if spilled in water SHEETS column, if applicable; 144 - Marine HNS response manual SHEET 5.9 Response considerations: Reactive substances Situation assessment and action plan CODES • Assessing measures to protect sensitive areas (environmental, ecological, social, sing the associated hazard levels (smoke from fire, reaction with the environment, AND industrial sites) and facilities, including through preventive shutdown, determining the hazards posed by any products that may be formed in the scenarios and asses- PROTOCOLS IMO etc.); 5.2 Incident data gathering • Evaluating the location of facilities and equipment for quick response. BEHAVIOURS • Evaluate/model the extent of the area affected by dangerous concentrations of cor- Areas to consider for intervention: HNS AND rosive substances in the water column and/or in the atmosphere to limit legitimate uses of the sea and amenities. 5.19 Safety zones PREPAREDNESS Consider (and control) aggravating factors: • Reactions between acids and bases, reactions due to the increase in temperature, time of exposure; • Possible highly exothermic reaction when certain acids or bases are spilled in water; • Maximum precautionary measures must be taken especially in the case of in situ response on the vessel (confined space); • High viscosity values slow down dilution and dispersion processes at sea. Protective measures (human health, environment & amenities) As corrosive substances gather a large group of chemicals, protective measure must comply with the conclusions of the risk assessment: • Corrosive liquids (mineral acids, alkali solutions and some oxidisers): eyes and skin MANAGEMENT tances in the body fluids. Highly soluble gases like ammonia or hydrogen chloride are particularly vulnerable due to splashes of the substance and effects on tissues are generally very fast; POST-SPILL • Corrosive gases and vapours: effect is generally related to the solubility of the subs- cause severe nose and throat irritation, whereas lower solubility vapours (phosgene, sulphur dioxide, etc.) penetrate deep into the lungs; STUDIES • Corrosive solids: direct contact can cause burns to the skin (phenol, sodium hydroxide…) and dust affects the respiratory system. Many corrosive solids may produce highly exothermic reactions when dissolved in water; CASE • In case of a water-reactive product, the substance must be prevented from reaching the water surface and the spill must be contained (construct berms, sand dikes…). 5.20 Personal protective equipment 5.25 Portable gas detectors for first responders SHEETS 145 - Marine HNS response manual SHEET 5.9 Response considerations: Reactive substances Situation assessment and action plan CODES On board: space; do not operate without self-contained breathing apparatus; AND • Attention should be paid to avoiding direct contact with the skin and protecting against inhalation of vapours or mists. Check atmosphere before entering a confined PROTOCOLS IMO 5.20 Personal protective equipment 5.25 Portable gas detectors for first responders • Evacuation must be implemented immediately downwind (gas/evaporator/fumes); BEHAVIOURS • Attention should be paid to decontaminating protective clothing: wash down with water and then remove. HNS AND Population and amenities: • Modelling will need to be conducted to determine the specific area to decide on the implementation of evacuation or shelter-in-place measures (in case of a corrosive cloud or marine environment contamination). PREPAREDNESS • Evacuation must be implemented in downwind impacted areas (in case of hazar- dous vapours, gas clouds, fumes). • Zoning: downstream area of the spill (targets of polluted runoff, liquid and solid spills) and evaluate any limitations on the use of the sea and amenities. Response measures On board: substances until its reactive potential has been assessed. • If possible, other chemicals or organic products must be isolated from the leaking • If the substance is not water-reactive, acids and bases may be neutralised by a dilu- tion process in order to reduce the concentration (overboard washing with indirect water jets if possible). pH should be measured before discharging the diluted mix- MANAGEMENT • Water-reactive substances may be treated by compatible sorbent or inert materials. ture in the environment. 5.34 Using water curtain POST-SPILL 5.36 Maintain in the environment and monitoring 5.37 Using sorbents • In the case of an on board leak, appropriate containment and recovery methods STUDIES and techniques according to the substances involved and scenarios should be used (Emergency Schedules (EmS), IMO, 2018). CASE In the environment: Refer to the characteristics, behaviour and fate and of the spilled (or leaked) substances, using specific precautions for the risk of corrosivity. SHEETS 146 - Marine HNS response manual SHEET 5.9 Response considerations: Reactive substances Situation assessment and action plan CODES Behaviour: 5.15 Response considerations: Dissolvers AND 5.13 Response considerations: Gases and evaporators 5.14 Response considerations: Floaters PROTOCOLS IMO 5.16 Response considerations: Sinkers 5.41 Packaged goods response BEHAVIOURS Techniques: See Chapter 5.6.3 HNS AND PREPAREDNESS Navy Netherlands Royal © Hyundai Fortune marine accident, March 2006, Gulf of Aden, at about 100 km south of Yemen; following an explosion and fire on board, 60 to 90 containers were lost at sea. POST-SPILL MANAGEMENT STUDIES CASE SHEETS 147 - Marine HNS response manual SHEET 5.10 Situation assessment and action plan SEBC: G AND Type-C tank, pressure lower than 4 bars lower than 10 bars Bunker 500 – 10,000 m3 Temperature range: 162°C up to -121°C 40 m3 ISO tank (IMDG compliance), pressure Table 23: Type of LNG POST-SPILL MANAGEMENT Cedre © Cargo Xxx STUDIES CASE Cedre Xxx © SHEETS Jiyeh power plant after the Israeli ISO tank (IMDG compliance) bombing, 2006 148 - Marine HNS response manual SHEET 5.10 LNG Situation assessment and action plan CODES Physical and chemical properties Boiling point -162°C LFL-UFL 5-15% AND The main physical and chemical properties of LNG are summed up in the following table. PROTOCOLS IMO Flash point -188°C Density of LNG 0.4 Auto ignition temperature 595°C Density of methane (20°C) 0.6 Table 24: Physical and chemical properties of LNG BEHAVIOURS Hazards and behaviour 90%, and a few other alkanes (such as ethane, propane and butane) with a total concen- LNG is mostly composed of methane CAS Number 74-82-8), representing about (CH4, HNS AND tration of less than 10%. LNG is odourless, both in cargo or bunkers. No additive is present to detect a release by a characteristic odour. LNG is a colourless liquid when liquefied at -162°C. At this temperature cryogenic effects can be expected. Water in contact with LNG can form ice and block safety devices. PREPAREDNESS A 1 m3 release of LNG will represent 600 m3 after evaporation into the atmosphere. The anoxia or asphyxia hazard may also be high, especially in a confined area. When released into surface waters it can form a pool that will evaporate rapidly and create a flammable cloud when mixed with air with the subsequent formation of a white cloud due to the condensation of water humidity in the air. If the vapour ignites it can create a jet (pressurised gas release) or pool fire, a flash fire or even a vapour cloud explosion surised tanks, BLEVE may also occur in case of fire. when the surrounding environment creates overpressure and blast damage. For pres- See Chapter 3 Methane does not exhibit violent reactivity with products that are frequently used or POST-SPILL MANAGEMENT transported on ships. However it reacts violently with liquid oxygen. Possible impacts on people, environment and amenities are summarised in the fol- lowing table. Effects on: STUDIES Cryogenic liquid Serious injuries due Can form ice in water.In Origin of risk People Amenities to cold burn or due absence of fire, no damage Brittle fracture CASE is not soluble in water and it projections in case to aquatic life because LNG damage to steel of Rapid Phase will evaporate rapidly into the structures Transition atmosphere. Evaporation of methane Anoxia/asphyxia Extremely low solubility - into the atmosphere in water SHEETS Ignition of LNG slick Injuries or death No major damage expected Fire, temperature 149 - Marine HNS response manual SHEET 5.10 LNG Situation assessment and action plan CODES Injuries or death No major damage expected Fire, temperature Inflammation of vapour cloud AND Explosion of gas in - Glass explosion confined space (for ins- Injuries or death Extremely low solubility - Building PROTOCOLS tank containing LNG Injuries or death to explosion - Building tance engine room) in water destruction IMO BLEVE following fire of Possible physical damage due - Glass explosion under pressure destruction Table 25: Possible impacts on people, environment and amenities BEHAVIOURS As with gaseous products, LNG has fast-moving kinetics. It is important to properly Situation assessment HNS AND assess the situation using all the tools available to effectively protect the population and stakeholders but also to initiate a response on the ground: 5.5 Situation assessment 5.6 Response considerations: Flammable and explosive substances PREPAREDNESS 5.11 HNS spill modelling 5.22 Remote sensing technologies 5.25 Portable gas detectors for first responders Depending on the situation, especially the type of release and whether LNG is pressu- rised or only refrigerated, the following decision tree can support risk assessment. Release of LNG Risks for LNG at Risks for pressurised atmospheric pressure LNG (< 4 bars) Yes Instantaneous ? Direct ignition ? Pool fi re BLEVE, Fire ball POST-SPILL MANAGEMENT No Yes Vapour cloud, BLEVE, vapour Delayed ignition ? Confi ned vapour cloud explosion, cloud explosion, pool fi re pool fi re No BLEVE, fl ash fi re, Flash fi re, pool fi re pool fi re Cryogenic effects BLEVE, cryogenic effects Yes STUDIES Direct ignition ? Pool fi re Jet/pool fi re No Yes Confi ned vapour Yes Vapour cloud, CASE No Delayed ignition ? cloud explosion, pool fi re Jet/pool fi re No Flash fi re, pool fi re Vapour cloud explosion, jet/pool fi re Cedre Cryogenic effects SHEETS © Figure 54: Decision tree regarding release of LNG 150 - Marine HNS response manual SHEET 5.10 LNG Situation assessment and action plan CODES Operational features relating to LNG Protective measures (human health, environment and amenities): AND PROTOCOLS IMO • Zoning should be established ( 5.19 Safety zones) and monitoring performed over time to assess the risk of flammability. In case of evacuation of the crew from a distressed vessel, the helicopter/rescue ship must approach from downwind; BEHAVIOURS • Flammable ignition sources should be removed. Before responders plan to enter in 5.20 Personal Protective Equipment 5.11 HNS detection and analysis methods HNS AND confined space, ventilation can be carried out to lower the concentration below the LEL. Response following a leak of LNG: PREPAREDNESS • All sources of ignition should be eliminated; • Nobody should walk on or touch the spilled LNG; • If the LNG is likely to leak, water can be sprayed on the vessel’s hull to prevent brittle fracture on the steel structure due to cryogenic effect; • Water should not be sprayed directly onto LNG to avoid Rapid Phase Transition or RPT (no spray or run-off); • Water curtains should be used, especially to reduce the concentration below the 5.34 Using water curtain LEL; • If leakage cannot be stopped, the substance should preferentially be released in gaseous state rather than as cryogenic liquid; • Water can form ice when in contact with LNG, which can represent an advantage to MANAGEMENT • A leak of burning gas should never be extinguished, unless the source of the leak temporarily block a leak. POST-SPILL Response in case of fire: can be stopped; • Water curtains should be used, especially to reduce radiation effects; • Fire should be fought from a maximum distance or with use of water cannons; STUDIES • Minor fire (bunker for instance): dry chemical powder or CO2; • Major fire: water spray or fog; CASE • If possible, combustible products should be moved away from LNG on fire. SHEETS 151 - Marine HNS response manual SHEET 5.11 Modelling to simulate almost any scenario, however, to make a model from scratch will require AND ly, these models are computer programmes that are designed to simulate what might (forecast) or what did happen (hindcast/backcast) in a situation. They can be created PROTOCOLS IMO expertise and a lot of testing to ensure the model is working. Many organisations and research institutes have developed models to simulate different aspects of HNS spills. Specific model capabilities include: BEHAVIOURS Fate models predict how a pollutant changes Predicting the fate of pollutants HNS AND both physically and chemically when released into the environment. Such models are used as a tool to help understand the expected cha- racteristics and behaviour of a pollutant and PREPAREDNESS prepare for an efficient response (Figure 55). Cedre Although fate models can be stand-alone, they © are usually built within a trajectory model, as physical and chemical changes can alter a pol- Figure 55: Fate model output lutant’s behaviour and subsequently, its trajec- tory. Fate models require detailed specifications of the pollutant, such as physical and che- mical properties, along with environmental data, such as temperature and wind speed. Predicting a pollutant trajectory in water MANAGEMENT tion as well as the substance’s physical charac- Trajectory models can simulate the movement of a pollutant in water, using environmental POST-SPILL data such as wind, currents, and wave informa- teristics. The simulation can be either forward- looking or backtracking. Forward modelling can STUDIES help with predicting where the pollutant may Cedre strand along a shoreline or provide warning if it is heading towards a particularly sensitive CASE area. Likewise, by using the model to backtrack © a situation, it can be used to work out where the Figure 56: Pollutant trajectory on sea surface pollutant may have come from. These models can be either 2D (movement at the water surface only) or 3D (movement within the entire water column) (Figure 56). SHEETS 152 - Marine HNS response manual SHEET 5.11 HNS spill modelling Modelling CODES Predicting a pollutant trajectory in the air using an atmospheric dispersion model. Gene- AND Trajectories of hazardous gas clouds that are a result of an HNS incident can be modelled PROTOCOLS IMO rally, these models can estimate how quickly the chemical will be released into the atmosphere and how it will travel downwind (Figure 57). BEHAVIOURS cal properties, the models require environmen- Along with the pollutants’ physical and chemi- AND tal data, relating to wind and temperature. Cedre HNS © The model results can then be used as an indi- Figure 57: Air pollutant trajectory cation of where there may be significant threat PREPAREDNESS to human life. Analysing response methods Models can also be used to analyse different res- ponse methods. They are used only as a guide Skimmed to help manage resources, which is particularly 20% At-Sea useful in the case of a large incident with limited 35% resources (Figure 58). Fate models are usually used in conjunction with Burned 45% response models as the pollutant may change physically and chemically over time, resulting in Cedre MANAGEMENT dent will evolve and be managed. different possible recovery totals. However, they © Figure 58: Response model output can also be combined with trajectory models, POST-SPILL allowing for an overall prediction of how the inci- Model limitations STUDIES To work, a model needs information regarding the incident, pollutant, and environmen- tal conditions, for instance the incident time and location, pollutant properties, atmos- pheric and water temperatures, and wind speed and direction. However, for a model to CASE produce reliable results, the input data needs to be as accurate as possible. Accurate data is not always feasibly obtainable for several reasons. Firstly, there may not be any environmental data available in the required area or timeframe, information may be missing regarding the incident, or the pollutant properties may be unknown. SHEETS 153 - Marine HNS response manual SHEET 5.11 HNS spill modelling Modelling CODES Secondly, the spatial and temporal resolution in environmental datasets may be too data. In addition to input data inaccuracies, during the construction of a model, approxi- AND large to represent certain physical processes. For example, turbulent eddies in water, prevalent around coastlines and in rivers, may be too small to be represented in current PROTOCOLS IMO mations and assumptions are unavoidable, therefore no model will, unfortunately, ever be entirely exact. Also, models cannot take into consideration multiple substances and reactivity. With these points in mind, it is important that models should not be relied BEHAVIOURS upon entirely but rather used simply as a guide, validating results through in situ obser- vations where feasibly possible. HNS AND Models available Specialist training to learn to use models for an HNS incident and understand their limi- tations is advised. Alternatively, many modelling providers or developers can carry out the modelling themselves and provide an explanation of the results, through contract- PREPAREDNESS based work. Usually, modelling providers will also have access to the environmental data needed for the model, such as wind speed and direction, sea temperatures, wave heights, in addition to chemical and SDS databases. The table below lists some, but by no means all, models that have been created for use in an HNS incident. Oil spill models have been added since they might be suitable to predict the fate and behaviour of subs- tances such as vegetable oils. Model Developer/provider Capability ADIOS (open source) NOAA Oil fate AIRMAP RPS ASA Chemical air trajectory and fate ALOHA (open source) NOAA Chemical air trajectory and fate CALPUFF TetraTech Chemical fate CHEMMAP RPS ASA Chemical air and sea trajectory and fate POST-SPILL MANAGEMENT MOTHY Meteo-France 2D at-sea oil and floating objects GNOME (open source) NOAA 2D at-sea oil trajectory and fate MOHID Water MOHID 3D at-sea and air chemical trajectory (such as containers) trajectory OILMAP RPS ASA 3D at-sea oil trajectory, fate, and response analysis OpenDrift/OpenOil MET Norway Chemical/objects at sea and air trajectory and fate (open source) STUDIES SPILLCALC TetraTech 3D at-sea oil trajectory OSCAR SINTEF 3D at-sea oil trajectory and fate CASE ROC (open source) NOAA Oil response method analysis Table 26: Models available SHEETS 154 - Marine HNS response manual or could be harmful for the environment. Some advice on approach or first elements of AND To draw the attention of decision-makers and operators to products not strictly classified as dangerous, as per international classification, but could present risks for responders PROTOCOLS IMO response are provided for some categories of products. Applicability BEHAVIOURS Convention and corresponding codes (IGC, IBC, IMSBC, IMDG). Many non-dangerous All the sheets and the structure of this Manual are based on identified and classified hazards according to international regulations and consistent with the 2010 HNS HNS AND products are also shipped and past incidents have shown that some non-dangerous products may be harmful and have considerable impacts on humans or the environ- ment. The location of the incident is of high importance as it may amplify the risks for humans, or the environmental sensitivity may cause severe damages and alter or com- PREPAREDNESS promise the natural restoration of the environment. Method description Issues posed by non-dangerous goods may be related in some cases to the quantity released in the environment. A product introduced in relatively large quantities com- pared to the size of the area may cause issues, and possible impacts can differ depen- ding on physical, chemical or biological effects. Physical damage can first occur through in the chemical composition of the water compartment may alter biological processes. shading/smothering of the seabed and dust may impact turbidity. Additionally a change For instance an unusual and important provision of organic products can lead to oxy- gen depletion, creating an anoxic medium with fish mortality. Decomposition of orga- nic matter will result in an exothermic reaction, creating favourable conditions for the MANAGEMENT development of sulphate-reducing microflora. This microflora will degrade the organic matter on the site, with significant production of hydrogen sulphide (H2S), a highly toxic POST-SPILL gas for humans. For these reasons, an effective post-incident monitoring programme should be set up to assess impacts, in particular on species/habitats of nature conservation importance STUDIES (e.g. in relation to the EU Birds and Habitats Directives, OSPAR), commercial stocks of fish and shellfish, the wider ecosystem and its functionality, and the human food chain, as well as to support subsequent compensation claims. CASE The following table presents an overview of the main categories of products frequently transported in large quantities by sea and that may present issues when spilled at sea. Each category can be transported by different presents SHEETS 155 - Marine HNS response manual SHEET 5.12 Non dangerous goods cargo Modelling CODES goods juice, vegetable oxygen depletion stirring, or creation of a current to Type of Transport Examples Potential impact product mode AND Organic Liquid bulk Glucose solution, In low renewal shal- Depending on exact conditions: PROTOCOLS Packaged tank, Lecithin, orange low waters, risk of leading to death of oxygenation, thanks to mechanical seabed. digestive system; shoreline - Sinker: smothering 5.38 HNS response of life on the in the water column Incident MSC Susanna, 2018; South Africa. Cargo plastic nurdles packaged in 25 kgs bags Minerals Solid bulk Chamotte, Depending on the When possible and if quantity of Packaged Chlorite, grain size: spilled product is too high com- goods Limestone, - Suspended matter: pared to the environment, the water (e.g. bags) Magnesite, Clay POST-SPILL increase of turbid- MANAGEMENT should be renewed or polluted water - Smothering of life Removal of the substances ity, impact on spe- pumped and filtered cies on respiratory/ 5.38 HNS response digestivesystem; in the water column on the seabed (divers, dredging) (sinkers) 5.39 HNS response on the seabed Cement Solid bulk Cement, Cement Suspended matter: Dilution or filtration if quantity of sub- Packaged clinkers increase of turbidity, STUDIES stance is too high compared to the tivesystem; in the water column goods impact on species Modelling Response considerations: Gases and evaporators CODES (applicable to all groups with “G” and “E” as SEBC behaviour) AND STATE GASEOUS LIQUID SEBC CODE G GD E PROTOCOLS E/G ED Density at 20°C Solubility (%) - < seawater density < 10 > 10 < 1 1-5 IMO Vapour pressure (kPa) at 20°C > 101.3 > 10 Table 28: Gases and Evaporators behaviour BEHAVIOURS Note for SEBC subgroups “GD” and “ED” see also Response considerations Dissolvers term processes when spilled at sea, due to their physic state (for G) or hight volatility (for E). Response strategies need to consider the factors affecting the behaviour and fate of the released substances, taking into account that gases and evaporators mainly undergo short- HNS AND PROCESSES AND FACTORS AFFECTING BEHAVIOUR AND FATE OF GASES AND EVAPORATORS STATE GASEOUS LIQUID PREPAREDNESS SEBC CODE G GD E ED Immediate evaporation/ Rapid evaporation Processes when atmospheric partitioning spilled at sea Dissolution Environmental Sea state /wind intensity/air and water temperature/humidity (when on board)/ factors influencing solar irradiance / coastline morphology intensity of process FATE Atmospheric dispersion with potential production of dangerous air mixture. diffusion, dilution Potential violent reactions with smoke/gas/aerosol production, possibly toxic. and Non-persistent. Drift and spread of HNS BEHAVIOUR Other relevant Dispersion, Flash point, explosive range, reactivity, toxicity, corrosivity, Dispersion, diffusion, in sea surface dilution in sea surface waters HNS properties gas/ vapour density MANAGEMENT more significant for avifauna and more sensitive pleuston organisms. and hazards Gas/evaporator substances tend to readily leave the water column by par- Impact on marine titioning first in the sea surface layer and then in the atmosphere: time- and POST-SPILL Modelling CODES Situation assessment and first actions • Immediately refer to Safety Data Sheet or chemical databases. In the case of an AND Information gathering: PROTOCOLS IMO unknown substance, act as in the case of maximum risk 3.1 Safety Data Sheet content • Immediately refer to data related to the location of the incident and other relevant BEHAVIOURS 5.1 Incident notification information • Consider sea and weather forecast HNS AND 5.2 Incident data gathering 5.3 Information resources Situation assessment: PREPAREDNESS • On the basis of the information gathered on the incident and the risks identified during contingency planning, consider conducting: 5.6 Response considerations: Flammable and explosive substances 5.7 Response considerations: Toxic substances 5.8 Response considerations: Corrosive substances • Evaluation of consequences 5.9 Response considerations: Reactive substances • Estimation of risk and vulnerability 5.5 Situation assessment First actions: MANAGEMENT 5.17 First actions (casualty) • Take into account the first actions to guarantee safe conditions for the responders by identifying and reducing the hazards of explosion, fire, exposure to toxic clouds, POST-SPILL etc. and then stop or reduce the source of the HNS spill; 5.18 First actions (responders) • Consider public safety STUDIES 5.19 Safety zones • Equipment/logistics 5.20 Personal Protective Equipment CASE 5.25 Portable gas detectors for first responders SHEETS 158 - Marine HNS response manual SHEET 5.13 Response considerations: Gases and evaporators Modelling CODES Monitoring ters of the substance, weather condition and forecast, type of spill source. AND Modelling: • Modelling of gas cloud in air; Input to be considered: chemical and physical parame- PROTOCOLS IMO 5.11 HNS spill modelling Monitoring using remote measuring instruments and search techniques: BEHAVIOURS 5.22 Remote sensing technologies • Aerial surveillance: planes and helicopters (not in case of explosive or unknown gas); drones; HNS AND • Use of markers (not in case of explosive or unknown gas) for safety and operational reasons. 5.23 Substance marking PREPAREDNESS Monitoring using in situ measuring instruments and search techniques: Air sampling • Trace gas sensors: explosimeter and gas detection to detect explosion or fire risks; detectors for toxic substances (on board and in environment); • Oxygen deficiency: electrochemical oxygen sensor. 5.25 Portable gas detectors for first responders • Water sampling by “niskin” bottles and storage of samples for laboratory analysis Water sampling (for not surface spill)/bottle sampling for surface water (for substances “DE” and “ED”). For GD substances (in particular with regard for VOC and semi-VOC). 5.26 Sampling techniques and protocols MANAGEMENT Action on vessel: 5.28 Emergency boarding 5.27 HNS detection and analysis methods POST-SPILL Response options • Mark out the risk area on board; • Stop the release of substance from its source ; STUDIES 5.32 Sealing and plugging • Ventilate when possible (e.g. with ventilators) to reduce concentration but be careful if there is a very rich atmosphere (> UEL). In this case, ventilation could reduce the CASE concentration below the UEL; 5.6 Response considerations: Flammable and explosive substances • For small spills, consider using techniques to prevent/control ignition or evaporation of the chemicals; SHEETS 5.35 Using foam 159 - Marine HNS response manual SHEET 5.13 Response considerations: Gases and evaporators Modelling CODES • Recovery operation of the residual load 5.29 Emergency towing AND 5.31 Cargo transfer • Towing & boarding PROTOCOLS IMO 5.30 Place of refuge Action on pollutant: BEHAVIOURS • Re-condensation of spilled gas in liquid state: for small spillage • High pressure water spray jet 5.34 Using water curtain HNS AND • Controlled release technique 5.36 Maintain in the environment and monitoring • Wildlife response focuses on toxic effects on avifauna or marine mammals (inhala- tion hazards) PREPAREDNESS 5.44 Wildlife response (SeaAlarm) Containment and recovery: None. Monitoring only. Option zero: • Evaluate the non-intervention strategy in the case of: high risks for human health; no risks of cloud advection towards the coast. Set up exclusion/ban areas, until natural 5.36 Maintain in the environment and monitoring processes have reduced pollutant concentrations Post-Spill Environmental investigation: MANAGEMENT • For soluble substances (GD): detection of concentrations in water and evaluation of • Generally UNNECESSARY in the case of gaseous and highly volatile substances. To be considered in the case of damages following a release of gas/evaporator (e.g. POST-SPILL fire and/or explosion); the effects on sensitive organisms; • Chemical and ecotoxicological analysis of samples of contaminated water; STUDIES • Chemical analysis and studies on biomarkers of sedentary species; • The same investigations must always be carried out in areas chosen as a reference. Not for explosive HNS. CASE 5.27 HNS detection and analysis methods 6.2 Post-spill monitoring 6.2 Environmental restoration and recovery SHEETS 160 - Marine HNS response manual SHEET 5.13 Response considerations: Gases and evaporators Modelling CODES EXAMPLES OF GASEOUS/EVAPORATOR CHEMICALS OF MARINE ENVIRONMENTAL CONCERN AND SEBC group Main characteristics and impact on the marine environment Table 30: Examples of gaseous/evaporator chemicals of marine environmental concern Incident: Carla Maersk, 2015; Houston Ship Channelgo, US. Car: bulk 5,600 tonnes of MTBE. POST-SPILL MANAGEMENT STUDIES CASE SHEETS 161 - Marine HNS response manual SHEET 5.14 Modelling SEBC Code F FD FED FE F FD AND Physical state Liquids PROTOCOLS Solids Vapour pressure (kPa) at 20°C <0,3 0,3 - 3 - F Density at 20°C < seawater density IMO Solubility at 20°C (%) ≤ 0.1 0.1-5 < 0.1 ≤ 10 10-100 BEHAVIOURS Table 31: Floaters behaviours Note for SEBC subgroups “FD” and “FED“ see also 5.16 Response considerations Dissolvers for SEBC subgroup “FED” 5.13 Response considerations: Gases and evaporators HNS AND Response strategies need to consider the factors affecting the behaviour and fate of the released substances as well as the short- and long-term processes when spilled at sea. PREPAREDNESS Processes Spreading PROCESSES AND FACTORS AFFECTING BEHAVIOUR AND FATE OF FLOATERS IN A MARINE ACCIDENT INCIDENT Physical state LIQUIDS SOLIDS SEBC Code F FD FED FE F FD when spilled Evaporation at sea Dissolution Environmental Drifting of the slick at sea surface (temporal continuity factors influen- Sea state, wind intensity, air and water temperature cing intensity of processes and persistence are variable). Drifting at sea surface Possible impact on shoreline. FATE Possible emul- Dispersion, dilution sification, and Drift and production of Potential BEHAVIOUR spread of HNS aggregates that substances) Atmospheric dispersion micals shoreline Dispersion, could sink or with potential production involve- dilution POST-SPILL affect shoreline of dangerous air mixture ment MANAGEMENT (high viscosity in case of hazardous che- Evaluate potential violent reactions and aerosol production. Other relevant Viscosity Buoyancy STUDIES Floaters mainly affect surface, pelagic and pleuston ecosystems, and their slicks (F- HNS properties Vapour density Viscosity and behaviour Persistence CASE Impact on marine liquids) can alter atmospheric/sea-surface gas exchange, especially if the substance is persistent (F(p)). Shoreline ecosystems can also be affected by floating chemical Modelling CODES Considerations AND PROTOCOLS • Oil spill response techniques could be used for floater spills. • In the case of floater-dissolver substances, containment and recovery IMO operations could be very limited. Usually, the only response option is to leave natural processes (e.g. dispersion, dilution) to deal with the spill, and, where possible, accelerate these processes. BEHAVIOURS • The selection of response techniques is strongly related to weather conditions HNS AND Situation assessment and first actions Information gathering: • Immediately refer to SDS or chemical databases. In the case of an unknown subs- tance, act as in the case of maximum risk; PREPAREDNESS 3.1 Safety Data Sheet content • Immediately refer to data related to the location of the incident and other relevant information; • Consider sea and weather conditions; 5.1 Incident notification 5.2 Incident data gathering Situation assessment: 5.3 Information resources On the basis of the information gathered on the incident and the contingency planning risk, conduct: MANAGEMENT 5.9 Response considerations: Reactive substances 5.6 Response considerations: Flammable and explosive substances 5.7 Response considerations: Toxic substances POST-SPILL 5.8 Response considerations: Corrosive substances • Estimation of risk and vulnerability; • Evaluation of consequences STUDIES 5.5 Situation assessment First actions: CASE • Take into account the first actions to guarantee safe conditions for the responders by identifying and reducing possible exposure to toxic vapours and/or hazards of explosion, fire, etc. and then stop or reduce the source of the HNS spill. 5.17 First actions (casualty) SHEETS 5.18 First actions (responders) 163 - Marine HNS response manual SHEET 5.14 Response considerations: Floaters Modelling CODES • Consider public safety 5.20 Personal Protective Equipment AND 5.19 Safety zones • Equipment/logistics PROTOCOLS IMO 5.25 Portable gas detectors for first responders Monitoring BEHAVIOURS be considered: chemical and physical parameters of the substance (e.g. viscosity), Modelling: • Modelling of drifting floaters (solids and liquid slicks) at the sea surface. Input to HNS AND current sea and weather conditions and weather forecast, type of spill source 5.11 HNS spill modelling • Modelling of gas cloud in air (for FE substances) PREPAREDNESS 5.13 Response considerations: Gases and evaporators Monitoring using remote measuring instruments and search techniques: • Aerial surveillance: planes and helicopters (not in case of dangerous situations); drones; • Use of markers to make the substance visually detectable at the sea surface: NOT applicable in the case of an explosion hazard or unknown substances. 5.23 Substance marking 5.26 Sampling techniques and protocols 5.24 Remote sensing technologies In situ monitoring using measuring instruments and research techniques: • Trace gas sensors/explosimeter and gas detection (in case of explosion or fire risks MANAGEMENT required. or toxic vapours/aerosol formation or unknown substances); • Acquisition of physicochemical parameters of surface waters by multi-parametric POST-SPILL probe (T, fluorescence, pH, conductibility, etc.); Specialised personnel could be 5.25 Portable gas detectors for first responders 5.26 Sampling techniques and protocols STUDIES Water sampling • Sampling of sea surface (surface waters and/or sea surface microlayer) using spe- CASE cific methods to obtain samples of spilled floating substance as free as possible of marine environmental matrices (e.g., polyethylene cornet, PFTE pad, BSH Helicopter sampling apparatus); in the field and/or laboratory: determination and/or analysis of physicochemical properties (e.g. GC-MS, GC-FID, GC-PD, IR, etc.). Specialised SHEETS personnel could be required, especially for high viscosity fluids; 164 - Marine HNS response manual SHEET 5.14 Response considerations: Floaters Modelling CODES • Water sampling by “niskin” bottles (or other methods) and storage of samples for column (specialised personnel could be required); AND laboratory analysis or field measurements. In the case of a deep or subsurface spill, consider the use of a multi-parametric probe to locate the substances in the water PROTOCOLS IMO • Sampling of solid floaters in the surface and sub-surface layer of the water column (e.g. with specific nets, ROV, divers). 5.24 Remotely Operated Vehicles BEHAVIOURS 5.26 Sampling techniques and protocols 5.27 HNS detection and analysis methods HNS AND Air sampling • Trace gas sensors: detectors for toxic substances (on board and in the environment); explosimeter and gas detection to detect explosion or fire risks; • Oxygen deficiency: electrochemical oxygen sensor PREPAREDNESS 5.25 Portable gas detectors for first responders Response options Action on vessel: 5.28 Emergency boarding • Stop the release of substance from its source; 5.32 Sealing and plugging • Recovery operation of the residual load; • On board: collect spillage, where practicable, using sorbent material for safe dispo- 5.31 Cargo transfer sal if applicable; 5.37 Using sorbents • Towing & boarding; MANAGEMENT exploitation of marine resources (for FE, FED); 5.29 Emergency towing 5.30 Place of refuge POST-SPILL • Evacuate the downwind area and evaluate the need for a ban on navigation or other • Prevent the formation of dangerous vapours (inject inert gas, ventilate and/or dehu- midify the atmosphere). STUDIES 5.6 Response considerations: Flammable and explosive substances 5.7 Response considerations: Toxic substances 5.8 Response considerations: Corrosive substances CASE 5.9 Response considerations: Reactive substances Action on pollutant: • Containment techniques with a physical barrier (in particular for insoluble/low solu- SHEETS bility liquids): 165 - Marine HNS response manual SHEET 5.14 Response considerations: Floaters Modelling CODES - Using special barriers developed for solids and liquids, in shallow waters; 5.43 Recovery techniques: Pumps and skimmers AND - Oil spill booms; often in association with sorbents (slicks or floating solids); 5.42 Containment techniques: Booms PROTOCOLS IMO - Contain by water barriers, in the presence of vapour or smoke; for FE/FED; 5.34 Using water curtain BEHAVIOURS - By pumping operations with various types of skimming; • Recovery techniques: - Sorbents (booms, sheets, pillows…); HNS AND - Trawl nets or net bags towed by boats; for high viscosity chemicals or small floating solids. 5.42 Containment techniques: Booms PREPAREDNESS 5.43 Recovery techniques: Pumps and skimmers • Cleaning techniques: - Chemical dispersant; only for “dispersible” F substances (evaluation based on the value of kinematic viscosity) and only in very limited scenarios. 5.38 HNS response in the water column • Standard intervention techniques on wildlife (avifauna, marine mammals, marine reptiles) affected by oil spills could be applied in the case of some floater spills, on the basis of physico-chemical characteristics and behaviour. 5.44 Wildlife response (SeaAlarm) Controlled release technique: • Controlled release of substances still stored on board (not advisable – evaluate for offshore, only implement after a rigorous evaluation). MANAGEMENT implement after a rigorous evaluation). Option zero: POST-SPILL • Evaluate the non-intervention strategy (not advisable – evaluate for offshore, only 5.36 Maintain in the environment and monitoring Post-Spill STUDIES • Chemical and ecotoxicological analysis of the sea surface layer and/or undiluted substance; CASE • Chemical analysis (e.g. bioaccumulation) and biological analysis (e.g. biomarkers) of involved fauna to evaluate toxic effects (even on the coast, if involved). 6.2 Environmental restoration and recovery SHEETS 166 - Marine HNS response manual SHEET 5.14 Response considerations: Floaters Modelling CODES EXAMPLES OF FLOATERS THAT POSE HEALTH AND/OR MARINE ENVIRONMENTAL HAZARDS AND SEBC group Main characteristics high risk of affecting the coast, also with effect on wildlife. Par- affins undergo weathering processes; in the case of sunken No classification: Paraffin wax emulsified products benthonic habitats could also be affected data conclusive but (F(p) - solid) (suffocation, inhibition of feeding and other non-specific toxic not sufficient for effects). Poses limitations on uses of the sea. Modelling solubility > 5% (applicable to all group with “D” as SEBC behaviour) D SEBC Code GD D DE D AND Liquids Gas Solids Physical state floaters sinkers floaters sinkers IMO Density at 20°C - < seawater > seawater < seawater > seawater PROTOCOLS density Vapour pressure at 20°C (kPa) > 101.3 < 10 10 < 10 - BEHAVIOURS Solubility at 20°C (%) Gases and evaporators. For floaters and sinkers see also respectively 5.14 Response > 10 > 5 100 Table 34: Dissolvers behaviour Note: for SEBC subgroup “GD”, “DE”, “ED” see also 5.13 Response considerations: HNS AND considerations Floaters 5.16 Response considerations Sinkers Response strategies need to consider the factors affecting the behaviour and fate of the released substances as well as the short- and long-term processes when spilled at sea. PREPAREDNESS SEBC Code PROCESSES AND FACTORS AFFECTING BEHAVIOUR AND FATE OF DISSOLVER IN A MARINE ACCIDENT INCIDENT Physical state LIQUIDS SOLIDS GAS floaters sinkers floaters sinkers GD D DE D Processes Dissolution, dispersion, diffusion dilution, potential violent reactions. when Immediately Partial evaporation spilled at sea evaporation Modelling CODES Considerations AND PROTOCOLS • Very narrow time window for response at sea • In case of dissolving substances, containment and recovery operations IMO are very limited. Usually, the only response option is to leave natural pro- cesses like dispersion and dilution to deal with the spill, and, wherever possible, to accelerate these processes. BEHAVIOURS Situation assessment and first actions HNS AND Information gathering: • Immediately refer to Safety Data Sheet or chemical databases. In the case of an unknown substance, act as in the case of maximum risk; PREPAREDNESS 3.1 Safety Data Sheet content • Immediately refer to data related to the location of the incident and other relevant information; • Consider sea and weather conditions. 5.1 Incident notification 5.2 Incident data gathering 5.3 Information resources On the basis of the information gathered on the incident and the contingency planning Situation assessment: risk, conduct: 5.6 Response considerations: Flammable and explosive substances MANAGEMENT • Estimation of risk and vulnerability; 5.7 Response considerations: Toxic substances 5.8 Response considerations: Corrosive substances POST-SPILL 5.9 Response considerations: Reactive substances • Evaluation of consequences. 5.5 Situation assessment STUDIES First actions: • Take into account the first actions to guarantee safe conditions for the responders CASE by identifying and reducing the hazards of explosion, fire, exposure to toxic vapours, etc. and then stop or reduce the source of the HNS spill. 5.17 First actions (casualty) 5.18 First actions (responders) SHEETS 169 - Marine HNS response manual SHEET 5.15 Response considerations: Dissolvers Modelling CODES • Identification of the main hazards 5.8 Response considerations: Corrosive substances AND 5.6 Response considerations: Flammable and explosive substances 5.7 Response considerations: Toxic substances PROTOCOLS IMO 5.9 Response considerations: Reactive substances • Consider public safety 5.19 Safety zones BEHAVIOURS 5.25 Portable gas detectors for first responders • Equipment/logistics 5.20 Personal Protective Equipment HNS AND Monitoring Modelling: • Modelling dissolved plume in water column. Input to be considered: chemical and PREPAREDNESS physical parameters of the substance, weather condition and forecast, type of spill source 5.11 HNS spill modelling Monitoring using remote measuring instruments and search techniques: • Aerial surveillance: planes and helicopters (not in case of dangerous situations); • Use of markers to make the substance visually detectable in water column with ROV drones 5.22 Remote sensing technologies or specific sensor (e.g. fluorimeter): NOT applicable in the case of an explosive or unknown dissolver. 5.23 Substance marking 5.24 Remotely Operated Vehicles POST-SPILL MANAGEMENT 5.26 Sampling techniques and protocols Monitoring using in situ measuring instruments and search techniques: • Acquisition of chemical and physical parameters of the water column by multi-pa- rametric probe and analytical determinations using field instruments (e.g. GC-MS, STUDIES GC-FID, GC-PD, IR, etc.); • Trace gas sensors/explosimeter and gas detection (in case of explosion or fire risks or flammable/toxic vapours/aerosol formation or unknown substances. CASE Portable gas detectors for first responders Sampling techniques and protocols SHEETS 170 - Marine HNS response manual SHEET 5.15 Response considerations: Dissolvers Modelling CODES Water sampling laboratory analysis. Use of multi-parametric probe to locate the plume. Very narrow AND • Water sampling by “niskin” bottles (for deep or sub-surface sampling) or by manual sampling (e.g. with a glass bottle for floating substances) and storage of samples for PROTOCOLS IMO time window. Specialised personnel could be required; • Sampling solid substances (if not completely dissolved) in surface and sub-surface seawaters with specific nets, etc. Very narrow time window. BEHAVIOURS 5.26 Sampling techniques and protocols 5.27 HNS detection and analysis methods HNS AND Air sampling • Trace gas sensors: detectors for toxic substances (on board and in the environment); explosimeter and gas detection to detect explosion or fire risks; • Oxygen deficiency: electrochemical oxygen sensors. PREPAREDNESS 5.25 Portable gas detectors for first responders Response options Action on the vessel: 5.28 Emergency boarding • Stop the release of substance from its source; 5.32 Sealing and plugging • Recovery operation of the residual load; • On board: collect spillage, where practicable, using sorbent material for safe dispo- 5.31 Cargo transfer sal; 5.37 Using Sorbents • Towing & boarding. 5.29 Emergency towing POST-SPILL MANAGEMENT 5.30 Place of refuge Action on pollutant: 5.38 HNS response in the water column • Neutralising agent: in the case of accidents involving substances that induce strong pH variations. Applicable only for small spills, restricted areas and no current, consi- STUDIES der dissolution kinetics; • Suction of contaminated water and suitable purification treatment (e.g. adsorption on activated carbon; flocculating agents). Applicable only for shallow waters and CASE calm waters; • Physical barrier to stop or slow down the spread of the pollutant. In the presence of vapour or smoke, contain using bubble barriers. Applicable for small spills and calm weather conditions; SHEETS • Filtering flow to protect intakes; 171 - Marine HNS response manual SHEET 5.15 Response considerations: Dissolvers Modelling CODES • Recovery of solids suspended in the water column; corrosive substances. AND 5.38 HNS response in the water column • Wildlife response will focus on avifauna and marine mammals exposed to toxic or PROTOCOLS IMO 5.44 Wildlife response (SeaAlarm) Controlled release technique: BEHAVIOURS • Controlled release of substance still stored on board (not advisable – evaluate for offshore, only implement after a rigorous evaluation). HNS AND Option zero: • Evaluate the non-intervention strategy (not advisable – evaluate for offshore only). 5.36 Maintain in the environment and monitoring PREPAREDNESS Post-Spill Environmental investigation: • Chemical and ecotoxicological analysis of contaminated seawater and/or undiluted substance. • Chemical and biological analysis of marine organisms (e.g. biomarkers) and invol- ved wildlife 5.27 HNS detection and analysis methods 6.2 Environmental restoration and recovery EXAMPLES OF DISSOLVERS THAT POSE HEALTH AND/OR MARINE ENVIRONMENTAL HAZARDS SEBC group Main characteristics Modelling S AND Physical state Liquids Solids PROTOCOLS SEBC Code S SD S SD Density at 20°C IMO > seawater density Vapour pressure at 20°C (kPa) - Solubility at 20°C (%) ≤ 0.1 ≤ 10 0.1-5 >10 Table 37: Sinkers behaviours BEHAVIOURS Response strategies need to consider the factors affecting the behaviour and fate of the Note for SEBC subgroup “SD” see also 5.15 Response considerations Dissolvers HNS AND released substances as well as the short- and long-term processes when spilled at sea. PROCESSES AND FACTORS AFFECTING BEHAVIOUR AND FATE OF DISSOLVER IN A MARINE ACCIDENT INCIDENT Physical state PREPAREDNESS LIQUIDS SOLIDS LIQUIDS SOLIDS SEBC Code S SD Environmental Water column/sea bottom currents, water temperature; bottom morphology, factors influencing bathymetry intensity of processes Drift, dispersion, floating in water column before deposit; drift on sea bottom Drift and spread of While sinking: dissolution, dilution and disper- FATE potential penetration into sediment floating plume). Residuals accumulate on sea HNS Accumulation on sea bottom/ sion in water column (potential submerged Other relevant logKow / log and bottom BEHAVIOUR Reactivity, toxicity, persistency ∆d (density) (dsw - dsolid): affect sinking speed viscosity of the liquid or dissolved fraction HNS properties Koc Impact on marine environment mainly related to benthic ecosystems; water column Impact on marine could be also affected. Microbial degradation of some sinkers may occur (e.g. POST-SPILL MANAGEMENT For hazards and risks see also 3.2 Hazards Modelling CODES Situation assessment and first actions tance, act as in the case of maximum risk AND Information gathering: • Immediately refer to SDS or chemical databases. In the case of an unknown subs- PROTOCOLS IMO 3.1 Safety Data Sheet content • Immediately refer to bathymetric and geomorphological data related to sea-bottom and to incident information. BEHAVIOURS 5.2 Incident data gathering • Consider sea and weather conditions 5.1 Incident notification HNS AND 5.3 Information resources Situation assessment: On the basis of the information gathered on the incident and the contingency planning PREPAREDNESS risk, consider conducting: 5.6 Response considerations: Flammable and explosive substances 5.7 Response considerations: Toxic substances 5.8 Response considerations: Corrosive substances 5.9 Response considerations: Reactive substances • Estimation of risk and vulnerability; 5.5 Situation assessment • Evaluation of consequences. First actions: • Take into account the first actions to guarantee safe conditions for the responders MANAGEMENT 5.18 First actions (responders) by identifying and reducing the hazards of explosion, fire, exposure to toxic clouds, etc. and then stop or reduce the source of the HS spill POST-SPILL 5.17 First actions (casualty) • Consider public safety 5.19 Safety zones STUDIES • Equipment/logistics 5.20 Personal Protective Equipment 5.25 Portable gas detectors for first responders CASE SHEETS 174 - Marine HNS response manual SHEET 5.16 Response considerations: Sinkers Modelling CODES Monitoring • For sinkers, to be considered: type of release, environmental conditions during the AND Modelling: • Spill modelling: trajectories, drifting on seabed; PROTOCOLS IMO incident; evaluate prevailing weather and sea conditions to determine way and dis- tribution of chemical on sea bottom. 5.11 HNS spill modelling BEHAVIOURS • Towing dredge (for solid substances) or absorbent material (for some liquid subs- Monitoring using in situ measuring instruments and search techniques: HNS AND tances) along sea bottom; • Sonar systems: side scan sonar (solids) and multibeam echosounder (seafloor depression or accumulation, bottom pool of sinking liquids), ROV investigations. PREPAREDNESS 5.22 Remote sensing technologies 5.24 Remotely Operated Vehicles Sediment sampling: • Sampling: box corer, grabs/videos using ROV and/or professional divers Water sampling: • Acquisition of chemical-physical parameters in (deep) water column by multi-pa- GC-FID, GC-PD, IR, etc.). Only for SD or dissolved reaction products. rametric probe and analytical determinations using field instruments (e.g. GC-MS, Reactivity Air sampling on board: MANAGEMENT • Trace gas sensors for explosion or fire risks: explosimeter and gas detection; • Some sinkers, such as calcium carbide, can react violently with water and can be ignited under almost all ambient temperature conditions, while others, such as POST-SPILL naphthalene, are reactive to air and flammable; • Oxygen deficiency: electrochemical oxygen sensor. 5.25 Portable gas detectors for first responders STUDIES 5.26 Sampling techniques and protocols 5.27 HNS detection and analysis methods CASE Response options Action on vessel: 5.28 Emergency boarding • Stop the release of substance from its source; 5.32 Sealing and plugging SHEETS 175 - Marine HNS response manual SHEET 5.16 Response considerations: Sinkers Modelling CODES • Transfer cargo or tow the ship to a place of refuge; 5.31 Cargo transfer AND 5.29 Emergency towing 5.30 Place of refuge PROTOCOLS IMO • Retain all or part of the flow of the pollutant on board before it can reach marine environment. BEHAVIOURS solid sinkers; pumping systems for liquid sinkers (also operated with ROV or with Action on pollutant: 5.27 HNS response on the seabed • Containment and recovery: dredging (mechanical, pneumatic or hydraulic) for HNS AND underwater operators, depending on how dangerous the substance is and the depth of the seabed); • Wildlife response focuses on the seafloor to minimise the impact on benthic ecosys- tems. PREPAREDNESS 5.44 Wildlife response (SeaAlarm) Controlled release technique: • Controlled release of a substance still stored on board (e.g. in the case of loss of ship stability due to heavy weather; not advisable – evaluate for offshore, only implement after a rigorous evaluation). • Evaluate the non-intervention strategy: recovery of sunken substance is often not Option zero: possible. 5.36 Maintain in the environment and monitoring MANAGEMENT • Chemical analysis on sea bottom and in water column (for persistent substances). Post-Spill • Chemical and biological analysis (e.g. biomarkers) on pelagic and benthic orga- POST-SPILL nisms; 5.27 HNS detection and analysis methods 6.2 Post-spill monitoring STUDIES 6.2 Environmental restoration and recovery CASE SHEETS 176 - Marine HNS response manual SHEET 5.16 Response considerations: Sinkers Modelling CODES EXAMPLE OF SINKER CHEMICALS THAT POSE HEALTH AND/OR MARINE ENVIRONMENTAL HAZARDS SEBC group AND Main characteristics Naphthalene highly acutely toxicity, long-lasting effects, moderate Harmful for human health. Presents hazards and risks for the marine environment: (S - solid) bioaccumulation and bioconcentration. Persistent in the marine environment. for molten Molten naphthalene is also flammable. naphalene also: POST-SPILL MANAGEMENT Table 39: Example of sinker chemicals that pose health and/or marine environmental hazards STUDIES CASE SHEETS 177 - Marine HNS response manual SHEET 5.17 First actions the owner on board. On merchant vessels, the Chief Mate or First Officer is the “second AND A ship’s crew can be grouped into four main departments: deck, engine, hospitality and others. The Captain or Master is the highest-ranking officer and the representative of PROTOCOLS IMO in command” and responsible for all cargo operations, the vessel’s safety and security and he/she leads the deck department. The Chief Engineer is the head of the engine department and responsible for all machinery (including engines, propulsion, electrical BEHAVIOURS The key contact person linking the vessel’s crew on board and the owner/charterer on power supply, etc.). HNS AND land is the Designated Person Ashore (DPA). The office-based DPA should have direct access to the highest management level. Shipboard contingency plans PREPAREDNESS As per MARPOL Annex I, oil tankers ≥ 150 GT and all ships ≥ 400 GT need to carry an approved Shipboard Oil Pollution Emergency Plan (SOPEP) and, as per MARPOL Annex II, vessels ≥ 150 GT carrying noxious liquid substances in bulk need to carry a Shipboard Marine Pollution Emergency Plan (SMPEP). Should a vessel be required to carry both plans, they are merged into a single SMPEP. Shipboard contingency plans are drawn up in accordance with specific MEPC guidelines (Resolutions MEPC. 54 (32) and MEPC. 85(44)). These plans stipulate the actions to be taken by the captain and the vessel’s crew during a marine pollution incident; they include reporting requirements, response protocols/ procedures and national and local contact points. MANAGEMENT Code) are of particular importance to guide the crew’s actions. In case of an incident involving dangerous goods, the Emergency Response Procedures for Ships Carrying Dangerous Goods (EmS) Guide and Medical First Aid Guide for Use POST-SPILL in Accidents Involving Dangerous Goods (MFAG) (both of which are part of the IMDG Equipment STUDIES Depending on their type, size and area of trading/operations, ships are equipped with various forms of lifesaving appliances and firefighting equipment corresponding to the provisions stated in the applicable IMO code and specific flag state requirements. CASE All equipment on board is indicated (type and location) in the Fire Control and Safety Plan. Copies of this plan are permanently located in conspicuous locations throughout the vessel. It should also be permanently kept in a weathertight container outside the SHEETS superstructure for easy access for shore-side support when the vessel is in port. 178 - Marine HNS response manual SHEET 5.17 First actions (casualty) First actions CODES Communication equipment and ship-to-shore communication. Depending on a vessel’s operational trading area, AND A vast mix of communication equipment is carried on board ships. Almost all vessels carry fixed and/or portable VHF radios for internal ship communication, ship-to-ship PROTOCOLS IMO special emergency communication systems may need to be installed in line with the Global Maritime Distress and Safety System (GMDSS). The GMDSS components are satellite telephony, high and medium frequency radiotelephony, digital selective calling, BEHAVIOURS Transponders). NAVTEX (automated system for the distribution of maritime safety information), EPIRB (Emergency Position Indicating Radio Beacon) and SART (Search and Rescue Radar HNS AND Lifesaving appliances To protect human life at sea, vessels are required to carry lifesaving appliances (as per SOLAS), which might include lifeboats, rescue boats, life rafts, various types of life buoys, PREPAREDNESS immersion suits, life jackets, signalling equipment (flares and smoke signals), and line throwing apparatus. Technical specifications are listed in the International Life-Saving Appliance (LSA) Code. Firefighting Firefighting equipment requirements vary according to ship types/sizes. Specifications are laid out in the Fire Safety Systems (FSS) Code. In addition to structural fire preven- (heat/smoke detectors) most vessels will be equipped with portable and fixed firefigh- tive measures (fire retardant bulkheads, fire doors, dampers) and detection systems ting systems such as: • A series of hydrants (coupled with hoses and nozzles) placed throughout the ship (within the superstructure and on deck), which are loaded with sea water by desi- MANAGEMENT • Sprinkler/water mist extinguishing system; gnated fire pumps. If a fire breaks out on board a vessel whilst in port and the ship’s fire pump system is not operational, the International Shore Connection can be used POST-SPILL to connect shore water to the vessel’s system; • Fixed CO2 systems might be used to flood specific enclosed spaces of a vessel (engine room, cargo hold); STUDIES • Various types of portable fire extinguishers (powder, CO2, foam). The ship’s crew is equipped with at least two firefighters’ outfits including self-contained CASE breathing apparatus. SHEETS 179 - Marine HNS response manual SHEET 5.17 First actions (casualty) First actions CODES Unlike firefighting on land, an excess of water can be very dangerous inside a ship since vessel’s cargo might react with extinguishing water and release hazardous gasses or AND it might cause the vessel to develop a severe list or trim, a reduction of freeboard or ultimately cause the vessel to sink. An additional consideration is reactivity, whereby the PROTOCOLS IMO cause further fires and/or explosions. 5.9 Response considerations: Reactive substances BEHAVIOURS Oil spill response equipment kit, which is likely to include oil absorbent pads/socks/cushions/booms, Personal Protec- As per the specifications identified in the SOPEP, a vessel is likely to carry a SOPEP spill HNS AND tive Equipments (coveralls, masks, goggles, gloves), a hand pump, buckets, non-spark shovels and disposable bags. These kits are designed to respond to minor spills of oil on deck only, but some of this equipment might be useful to limit the spread of an HNS spill. PREPAREDNESS POST-SPILL MANAGEMENT STUDIES CASE SHEETS 180 - Marine HNS response manual SHEET 5.18 First actions environment and finally amenities. These actions are carried out in complement or AND To implement immediate actions in safe conditions for the responders, in order to miti- gate potential spill impacts. The priority has to focus first on protecting people, the PROTOCOLS IMO subsequent to those already initiated by the crew members or the master of the vessel. 5.17 First actions (casualty) BEHAVIOURS Who may implement first actions? emergency response plan, and who are familiar with the HNS involved, its behaviour These actions must be carried out by trained and qualified responders identified in the HNS AND and associated hazards. 5.6 Response considerations: Flammable and explosive substances 5.7 Response considerations: Toxic substances 5.8 Response considerations: Corrosive substances PREPAREDNESS 5.9 Response considerations: Reactive substances These personnel might be from the maritime or port authority and may be firefighters, coast guards, or port facility security officers. Principle First actions are taken to prevent the situation from worsening, especially to reduce the toxic cloud, etc., and to stop or reduce the source of the HNS spill. hazards of explosion, fire, reaction with other substances (e.g. water, air), release of a All the initial actions described below must be performed in safe conditions for the res- ponders, who must select proper Personal Protective Equipment and portable sensors MANAGEMENT Monitoring should be performed immediately at different levels in order to implement according to the identified hazards. POST-SPILL Monitoring zoning, assess the situation and provide input to the information gathering process. External assistance must be requested at early stage to perform remote detection STUDIES 5.6.2 Monitoring Lifesaving CASE Consider Search and Rescue* (SAR) actions and the protection of the population 5.19 Safety zones. SHEETS *See Handbook for Maritime SAR in HNS Incidents 181 - Marine HNS response manual SHEET 5.18 First actions (responders) First actions CODES Immediate actions to respond to the substance Isolate the source of the spill AND Action Description PROTOCOLS 5.29 Emergency towing IMO At the source Assess interest/possibility of towing 5.30 Place of refuge Mobilise and activate collective protective equipment. BEHAVIOURS Offshore or on the shoreline: On the flow Mark the hazardous material in order to make its fumes and/or floating slicks visible, see sheets on behaviour and substance marking. HNS AND - Warning to seafarers and possibly prohibit shipping in incident area as well as any legitimate uses of the sea; 5.19 Safety zones - Monitor wildlife; In the area 5.44 Wildlife response (SeaAlarm) PREPAREDNESS rapy, recreational fishing, etc.) and possibly stop these activities; surrounding incident location On the shoreline or in a port: - Close water intakes; - Notify industries (nuclear power station, desalination plant), aquaculture acti- vities (fish ponds, fish tanks, etc.) and socio-economic activities (thalassothe- - Warn local authorities and population. Table 40: Immediate actions to respond to the substance POST-SPILL MANAGEMENT Guard STUDIES Coast CASE Swedish © Isolation of the source of the spill SHEETS 182 - Marine HNS response manual SHEET 5.19 First actions been released to give the response team time to assess the situation and respond in an AND Safety zones are established immediately after an incident involving dangerous goods to prevent any further damage. This approach is used even if no hazardous product has PROTOCOLS IMO organised and safe way. Each zone is defined with limits related to the hazard levels and type of operations that could be conducted, with access restricted to authorised and protected personnel. The end of the enforcement of safety zones should be announced BEHAVIOURS only after a thorough situation assessment, including evaluation of residual risks based on advice from experts and thoroughly verified field measurements. HNS AND Three types of zones may be established, for which safe distances are defined conside- ring the levels of hazards due to the presence of the chemical but also considering other potential hazards, especially the status of the distressed vessel. PREPAREDNESS Any entry point to one of the safety zones should be defined in order to: • Stay upwind of the hazardous area; • Consider the weather forecast; • Ensure the response vessel or response team that has entered a high or medium risk zone can escape safely prior to immediate decontamination 5.21 Decontami- nation. Only vessels with the capacity to perform rescue operations in a hazardous atmosphere should enter the safety zone 4.5 Response vessels. The following table presents the different types of zones, with the corresponding hazard level, potential effects and limits to consider for each type of hazard. Potential effects and limits to consider based on hazards POST-SPILL MANAGEMENT Exclusion/ Area with highest Type of zone due to overpressure. Definition sure for flammable for toxic vapours. Explosivity Flammability Toxicity Highest potential expo- Highest injuring effect Highest potential exposure high* risk zone risk vapours or fumes. No access except for SAR No access except for SAR No access except for SAR Contamination Transition area reduction/ between high Entrance only by authorised responders equipped with appropriate PPE for the STUDIES medium* risk and low risk risk. Any entrance should be recorded. zone zones. Used for workers CASE Support/low* risk zone supporting the response opera- Hazards related to normal working area. Entry point and perimeter under surveillance to prevent unauthorised access tions Table 41: Different types of zones and the potential effects and limits to consider based on hazards SHEETS *Other terminology can be found in some documents: hot/warm/cold zones, with equivalent correspondence respec- tively to high/medium/low risk zone. 183 - Marine HNS response manual SHEET 5.19 Safety zones First actions CODES Defining safety zones case of an explosion risk. of around 30° angle (high risk zone) and AND Safety zones may be hemispheres cente- Safety zones may be cones in case of red around the distressed vessel (DV) in PROTOCOLS possible atmospheric plumes: triangle IMO around 60° (medium risk zone) from the release or in case of fire or toxic cloud. BEHAVIOURS DV Wind direction HNS AND DV PREPAREDNESS Low risk High risk Cedre High risk Medium risk © Figure 59: Safety zones Procedure Possible sources of information Steps 5.3 Information resources See Chapter 5.3 1) Establishment of immediate danger zone, inclu- - Immediate safe distance included in guides or Safety ding for navigation (maritime and air) and possibly Data Sheet MANAGEMENT - Databases the population (evacuation or shelter–in-place) - No information: at least 2 NM radius from the DV - Experts - Monitoring POST-SPILL 2) Definition of safety zones - Forecast models - National and local warnings (contingency plan) - High, medium, low risk zones 3) Implementation of safety zones - Entry points STUDIES 4) Implementation of navigational warnings related - to safety zones 5) Monitoring and surveillance - CASE Table 42: Procedure to establish safety zones SHEETS 184 - Marine HNS response manual SHEET 5.20 On scene response - Protection AND To determine how to choose the protection level as well as how to wear PPE. PROTOCOLS IMO PPE refers to the clothing and respiratory equipment that is necessary to protect a per- son from the hazardous properties of chemicals. Its selection should be appropriate to the particular hazards associated with the chemical(s) spilt. The following should be BEHAVIOURS • PPE material (durability, heat resistance); considered: • Chemical spilt (concentration, exposure time); HNS AND • Level of respiratory protection required; • Responder’s ability to undertake specific work tasks. General considerations to add: all PPE needs to be certified and may have an expiration PREPAREDNESS date. Always follow the manufacturer’s instructions, store appropriately, train personnel in donning and doffing. In all cases, communication systems should be considered. EU categories In Europe, Regulation (EU) 2016/425 of 9 March 2016 on personal protective equipment tive equipment. It specifies three categories I, II and III, with category III addressing all (the PPE Regulation) covers the design, manufacture and marketing of personal protec- risks that “may cause very serious consequences such as death or irreversible damage to health”: • Category I: products of simple structure, used in a low-risk environment. The user is MANAGEMENT • Category III: products of complex structure, protecting in the situations of serious or able to independently assess the PPE protection effectiveness; • Category II: products protecting against hazards which can cause injuries. The POST-SPILL hazard for injury is determined as “not very low and not very high”; permanent hazard which can affect the user’s life and health. STUDIES Chemical protection suits are classified into six types (Table 43). If the spilled chemical has not been identified, responders should assume a worst-case CASE scenario and wear the highest level of protection. It is important that responders are thoroughly trained in the use of PPE to minimise the risk of harm. SHEETS 185 - Marine HNS response manual SHEET 5.20 Personal Protective Equipment (PPE) On scene response - Protection CODES US certification system tection required (Levels A, B, C and D). Generally, the number of chemicals and condi- AND A number of government agencies, including the US Occupational Safety and Health Administration (OSHA) have devised four categories of PPE based on the level of pro- PROTOCOLS IMO tions for testing are higher compared to EU levels. These four levels are recognised by most response organisations: • Level A offers the highest level of respiratory, skin, eye and mucous membrane pro- BEHAVIOURS tection is needed, but a lesser level of skin and eye protection is needed. Level B tection; • Level B protection should be selected when the highest level of respiratory pro- HNS AND is considered the minimum level of protection when the nature of the product and the relative danger has not yet been defined and therefore before any monitoring, sampling and all the related analysis methods; • Level C protection should be worn when the type of airborne substance is known, PREPAREDNESS concentration measured, criteria for using air-purifying respirators met, and skin and eye exposure is unlikely. A full-face mask may be considered sufficient, with suitable filters; • Level D is similar to a work uniform and should only be worn when it is certain that personnel will not be exposed to harmful levels of HNS. Table 43 compares the two classification systems: level Category III Category II Category I European Type 1 Type 2 Type 3 Type 4 Type 5 Type 6 Level of Protects protection against parts of liquid and liquid aeroso aerosol body against gaseous chemicals MANAGEMENT chemicals equipment liquid chemi- Contained respirator chemicals for a limited (spray tight) for a limited cals (gas tight) (non-gas period tight) (liquid tight) POST-SPILL Respiratory Self- Air-purifying Breathing Apparatus Apparatus or air-purifying respirator Approx. STUDIES equivalent level A level B level C American level D CASE level Table 43: EU and US PPE classification systems SHEETS 186 - Marine HNS response manual SHEET 5.20 Personal Protective Equipment (PPE) On scene response - Protection CODES The flowchart below is designed to help in the selection of the most appropriate PPE in AND case of an HNS incident. PROTOCOLS concentration ? NO Wear EU Is there a risk of YES Cat. III, Is there a risk of exposure to Type 3 or 4 POST-SPILL MANAGEMENT splashing or contact particolates ? (US, Level B) with skin ? equipment YES NO Wear EU Cat. II, Cat. I, STUDIES Type 5 Type 6 (US, Level C) (US, Level D) (US, Level C) CASE © equipment Cedre Figure 60: List of PPE with respect to protection level SHEETS 187 - Marine HNS response manual SHEET 5.20 Personal Protective Equipment (PPE) On scene response - Protection CODES Below is a list of PPE according to the level of protection required (European catego- • SCBA (Self-Contained Breathing Apparatus); • SCBA (Self-Contained Breathing Apparatus); AND ries). Type 1 Category III Type 2 Category III IMO • Full coverage hazmat suit (gas-tight); • Full coverage hazmat suit (non-gas-tight); PROTOCOLS • Inner chemical resistant gloves; • Inner chemical resistant gloves; • Outer chemical resistant gloves; • Outer chemical resistant gloves; • Chemical resistant boots with steel toe; • Chemical resistant boots with steel toe; • Long-sleeved cotton shirt (under suit); • Disposable boot covers: BEHAVIOURS • Helmet (under suit); • Radio communication system; • Work overalls (under hazmat suit); • Helmet (optional); • Radio communication system (under suit). • External protective visor (optional). Type 3 Category III HNS AND Type 4 Category III • SCBA (Self-Contained Breathing Apparatus) or • Full coverage mask with filters; air-purifying respirator; • Disposable chemical protective coveralls (spray- • Full coverage temporarily hazmat suit (liquid- tight); • Inner chemical resistant gloves; • Inner chemical resistant gloves; PREPAREDNESS • Helmet (optional); • Outer chemical resistant gloves; • External protective visor (optional); • Outer chemical resistant gloves; • Chemical resistant boots with steel toe and leg; • Chemical resistant boots with steel toe; • Disposable boot covers; • Disposable boot covers; • Work overalls (under disposable coveralls); • Work overalls (under disposable coveralls); • Radio communication systems; • Radio communication system; • Helmet (optional); • External protective visor. • Escape mask (optional). Type 5 Category II Type 6 Category I • Air-purifying respirator; • Uniform for non-dangerous chemicals • Chemical resistant boots with steel toe and leg; • Disposable chemical protective coveralls (spray- Other protective devices should be considered accor- • Work overalls; tight); • Safety shoes or boots. • Chemical resistant gloves; • Disposable boot covers; ding to specific needs (e.g. air-purifying respirator). It • Radio communication system; is essential to have a certified absence of risks to the • Helmet (optional). respiratory tract and of other possible potential risks. Table 44: List of PPE according to the level of protection required (European categories) POST-SPILL MANAGEMENT STUDIES HD HD MANQUANT MANQUANT HD HD MANQUANT MANQUANT HD HD MANQUANT MANQUANT CASE HD HD MANQUANT MANQUANT HELCOM ISPRA © SHEETS Category III Type 1 Category III Type 2 Category III Type 4 PPE for Category I Type 6 188 - Marine HNS response manual SHEET 5.20 Personal Protective Equipment (PPE) On scene response - Protection CODES Increasing or decreasing the level of protection • Potential or highly probable emission of gases or vapours; AND Consideration criteria for increasing the level of protection: • Confirmed or suspected presence of risk through skin contact; PROTOCOLS IMO • Change of tasks that increases level of (potential) contact with dangerous subs- tances; • Reporting from responders that describes a scenario worse than expected; BEHAVIOURS Consideration criteria for decreasing the level of protection: • Risk of encountering unknown substances. HNS AND • Information indicating the presence of risk lower than originally expected; • Decreased hazard due to effectiveness of intervention; • Change of tasks that decreases the level of contact or potential contact with dange- rous substances. PREPAREDNESS Donning of PPE Donning: Donning protective suits can be difficult. It is therefore advisable to be assisted by ano- ther person. Supervisors should oversee this task. The order may differ depending on the PPE. For a Category III suit: • Remove jewellery and any potentially dangerous personal belongings: pen, cell phone, belt, etc.; • Place suit on ground in a clean, flat location; MANAGEMENT • Put suit on; • Open the cylinder, check the volume of air available (regulator pressure) and put the equipment on your back. POST-SPILL • Open zipper completely; • Carefully close the locking system of the suit; • Put on gloves and boots and fasten closures; STUDIES • Check that the pressure relief valve is functional. Doffing: CASE • Decontaminate before removing PPE suit; 5.21 Decontamination • When removing the PPE suit, take care to avoid contact with any potential traces of the substance. SHEETS 189 - Marine HNS response manual SHEET 5.20 Personal Protective Equipment (PPE) On scene response - Protection CODES Personal protective equipment for divers Therefore, equipping operators with a suitable diving support system (including both AND The main objectives of safety measures are to minimise the possibility of skin contact and the inhalation of pollutant that can penetrate both suit materials and the diver’s skin. PROTOCOLS IMO respiratory and physical protection) must be the primary concern (IMO, 2017). The standby divers must be equipped with at least an equal level of protection. BEHAVIOURS HAZARDS A full-face mask may reasonably protect mucous membranes of the eyes, nose, and Mask: HNS AND mouth. Full-face masks can be configured to operate with compressed gas SCUBA tanks, a configuration that affords the diver freedom of movement and provides mode- rate protection. Most full-face masks can also be configured to operate with surface-sup- plied compressed gas which affords greater endurance but restricts mobility compared PREPAREDNESS to SCUBA. Moreover, a full-face mask which incorporates a positive-pressure regulator will help eliminate water entering the mouth. Additionally, full-face masks offer no pro- tection for the diver’s head, neck, or ears, all potential sites exposed to waterborne hazards. As regards the first stage of the breathing apparatus, the so-called “environmental kit” RESPONSE is often optional; it prevents water entrance and even if it is ideated for diving into icy water it seals the mechanism from polluted water. A rigid helmet is coupled to a vulcanized dry suit; it isolates the diver in contaminated water. In this case the level of protection for divers is highest. Main problems with using helmets are linked to the amount of air consumed, which requires a supply boat with MANAGEMENT an air compressor on board and leads to limited mobility of operators. Moreover, in heavily contaminated water, some latex components of helmets are highly susceptible POST-SPILL to degradation, requiring frequent replacement (US Navy, 2008). STUDIES CASE ISPRA © SHEETS Diver equipped with a rigid helmet and a vulcanised dry suit 190 - Marine HNS response manual SHEET 5.20

UN Number

1972 PROTOCOLS IMO Objective To deliver generalities on LNG, its properties and transport, and to provide information BEHAVIOURS General features relating to LNG on potential risks in the event of a spill. HNS AND LNG, or Liquefied Natural Gas, is increasingly used as a source of energy as its main advantages are to release significantly less carbon and lower pollutant emissions, inclu- ding NOx, SOx and particulate matter. In the maritime shipping world, LNG can either be transported as cargo or used as bunkering fuel. For the latter, LNG can be used alone PREPAREDNESS 10,000 - 45,000 m3 per tank or with a dual fuel engine. Type of LNG Tank volume Type of tank type Cargo Maximum cargo 266,000 m3 for Q-max vessel Thermally insulated tank, pressure lower 20,000 m3 than 0.7 bar

Hazard pictograms

Highly flammable, shows long-term toxicity (carcinogen), ther- PROTOCOLS (G) Cargo: bulk (1,300 tonnes of vinyl chloride monomer) mal degradation with the formation of toxic/corrosive fumes. IMO Vinyl chloride Incident: Brigitta Montanari, 1984; off Croatian coast. Incident: tanker-barge Pampero, 2020; at the locks in Sablons, Rhône France. Cargo: bulk (2,200 tonnes) BEHAVIOURS (GD) Anhydrous Corrosive, highly toxic to aquatic organisms due to formation of ammonia a highly corrosive solution with water. HNS AND shipped in liquid state Incident: René 16, 1976; Port of Landskrona, Sweden. Cargo: bulk (533 tonnes of anhydrous ammonia) Toxic liquid for humans and the environment. Not persistent in the water column, tends to partition in the atmosphere. De- pending on the release conditions, it could be toxic for marine Benzene (E) organisms, in particular for pleuston due to the tendency of benzene to float. Dangerous for marine mammals and avifauna if inhaled. Vapours of benzene are heavier than air. Incident: Barge, 1997; Mississippi River, US. PREPAREDNESS Cargo: bulk (pyrolysis gasoline contains 41.0% benzene) It has low acute and chronic toxicity for marine species but acute effects were found at high concentrations for the grass Methyl-t-butyl shrimp and marine mussel. It poses limitations on uses of the ether (ED) sea. Vapours heavier than air. Formation of persistent biodegradable surface films, dissolved PROTOCOLS derived oils Incident: Kimya, 1987; off coast of Anglesey, Wales. not sufficient for oxygen consumption and alteration of gas exchange. Some oils may polymerise. They undergo weathering processes (emulsifi- Vegetable IMO and animal cation). Poses limitations on uses of the sea. No classification: data conclusive but (F(p) - liquid) Cargo: bulk liquid Methyl amine solution in Irritating and toxic for humans. Slight acute toxicity for marine or- POST-SPILL MANAGEMENT water <42% ganisms. Poses limitations on the use of the sea. (DE) (L - liquid) Highly reactive metal. May ignite spontaneously in air. Reacts vio- lently with water to give sodium hydroxide and hydrogen, which ig- Sodium metal nites spontaneously. Highly soluble salt production when in water. (D - solid) Time -and space- limited impact on the marine environment. Its STUDIES high viscosity slows down dilution and dispersion. Incident Cason, 1987; off North Spain; Cargo package CASE Corrosive and irritating substance. Main risks for intervention team, on-board personnel; social and economic impact. Generally low NaOH acute toxicity for marine organisms but high risks due corrosive and Caustic soda irritating power. High viscosity slows down dilution and dispersion. (D - solid) For pH values > 8.5-9 or < 3-5 very high danger for aquatic life. Incident: Puerto Rican, 1984; San Francisco Bay, US; SHEETS Cargo: bulk Table 36: Examples of dissolvers that pose health and/or marine environmental hazards 172 - Marine HNS response manual SHEET 5.16 Flammable and moderately explosive when exposed to PROTOCOLS chloride in water. heat or flame. When heated to decomposition, it emits toxic and cor- IMO Benzyl rosive fumes. Harmful for human health. Rapid reaction (S - liquid) Moderately acute aquatic toxicity. Interference with and restriction of legitimate uses of the sea and coastal structures (warning issued leading to the closure of BEHAVIOURS bustion, forms toxic and corrosive fumes. Reacts with amenities). Highly flammable liquid and vapour (poison). On com- oxidisers. Slight acute toxicity for marine organisms. AND Ethylene Effects on wildlife and bottom habitats (smothering of HNS dichloride the seabed). Not readily biodegradable. (SD - liquid) Incident: Alessandro I, 1991; 30 km from Molfetta, Adriatic Sea, Italy; Cargo: bulk (ethylene dichloride and PREPAREDNESS carbide acrylonitrile) Incident: Stanislaw Dubois, 1981; Off Texel Island, Reacts violently with water forming highly flammable and explosive gas (acetylene) and can be ignited under almost all ambient temperature conditions. Harmful for Calcium humans. Low impact on marine environment. (SD - solid) Netherlands. Cargo: packages (857 tonnes of calcium carbide, 955 tonnes of caustic soda (solid sodium hydroxide), 5.4 tonnes of a flammable organic peroxide and 5.6 tonnes of explosives.

2.1 Classification of the substance or mixture

Incident: Allegra, 1997; off the coast of Guernsey, English BEHAVIOURS Channel. Cargo: 15,000 tonnes of palm oil (solid) Very toxic liquid; when heated, vapours may form explosive mixtures with air; risk of hazardous polymerisation. Very harmful Aniline oil HNS AND for aquatic life (high acute toxicity and long-lasting effects). (FD - liquid) Incident: Herald of Free Enterprise, 1987; Zeebrugge, Belgium. Cargo: package PREPAREDNESS Cargo: package Highly flammable and polymerisable; vapours (heavier than air) form explosive mixture with air. Slight acute toxic for aquatic Butyl acrylate organisms. It undergoes weathering processes (emulsification). (FED - liquid) Risks of impact on the coast. Incident: Sam Houston, 1982; off New Orleans, US. Highly flammable liquid, explosive, not biodegradable. Xylene Toxic to aquatic organisms with moderate potential to bioaccu- (FE - liquid) mulate. Incident Ariadne, 1985; Mogadishu, Somalia. Cargo package Appears as yellow-white aggregation on the sea surface. Very Incident: unknown source, Tirrenian Sea, 2018. POST-SPILL MANAGEMENT Table 33: Examples of floaters that pose health and/or marine environmental hazards STUDIES CASE SHEETS 167 - Marine HNS response manual SHEET 5.15

Hazardous Ingredients

Type 1 (US Level A) Are the nature and Do not enter, or IMO exposure routes of the NO use EU Cat. III known ? equipement BEHAVIOURS YES HNS AND Is there a risk of YES Wear EU Cat. III, exposure to gas Type 1 or 2 or vapours ? (US, Level A) equipment PREPAREDNESS NO YES Can the liquid Is there a risk of YES produce vapours exposure to liquids ? in toxic