Turun yliopisto MERENKULKUALAN KOULUTUS- JA TUTKIMUSKESKUS 0 Overview of Maritime Accidents Involving Chemicals Worldwide and in the Baltic Sea Jani Häkkinen

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MERENKULKUALAN KOULUTUS- JA TUTKIMUSKESKUS

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Overview of Maritime Accidents Involving Chemicals Worldwide and in the Baltic Sea

Jani Häkkinen & Antti Posti, Chembaltic project

TransNav 2013, Gdynia, 19−21.6.2013

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Themes of the Chembaltic project

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The topic of our paper

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Aim of the paper

• Provide an overview of the past tanker accidents in the Baltic Sea, and chemical-related accidents in seas worldwide A statistical review Literature review on maritime accidents involving hazardous substances and

especially chemicals.

• To find out what can be learned from these past accidents, including e.g. occurrence, causes, general rules and particular patterns for the accidents.

• The project focuses mainly on chemicals transported in liquefied bulk form, but in this paper also other HNS accidents and chemical accidents involving substances in packaged form are also studied.

• Conventional oil and oil products are observed only on a general level. The special scope in the study is put on environmental impact assessment.

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Transport volumes of liquid bulk chemicals in the Baltic Sea and in Finland (Posti & Häkkinen 2012)

• Over 11 million tonnes of liquid bulk chemicals are handled in the Baltic Sea ports (half of those are handled in Finnish and Swedish ports).

• The most handled chemicals in the whole Baltic Sea area are methanol, sodium hydroxide solution, phenol, ammonia, sulphuric and phosphoric acid, pentanes, xylenes, methyl tert-butyl ether (MTBE), ethanol and ethanol solutions. All of these > 100 000 or even ≥ 1 milj. tonnes Chemical-specific data from all countries are not complete or not available

• Besides these chemicals, there are also other high volume chemicals (e.g. ethylene, propane, butane), and large amounts of liquid fertilisers and vegetable oils which are handled in the Baltic Sea ports, but exact volumes of these substances are unknown as well.

• Chemicals transported the most in the Baltic Sea are mainly similar when compared to chemicals transported the most in other sea areas.

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The most commonly handled chemicals in Finnish ports in 2008 and 2010 (Posti & Häkkinen 2012)

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2008 2010 Methanol 866,323 Methanol 746,141 Sodium hydroxide solution 359,424 Sodium hydroxide solution 380,331 Xylenes 206,558 Pentanes 315,978 Ethanol and ethanol solutions 149,535 Xylenes 161,894 Phosphoric acid 133,147 Methyl tert-butyl ether (MTBE) 159,660

Pentanes 124,548 Aromatic free solvents (e.g. white

spirit and NESSOL) 155,363

Methyl tert-butyl ether (MTBE) 119,539 Ethanol and ethanol solutions 122,018 Phenol + acetone 119,065 Parafines 111,079 Aromatic free solvents (e.g. white spirit and NESSOL)

111,479

Phosphoric acid 91,797

Propane 107,260 Phenol 87,359 Ethyl tert-butyl ether (ETBE) 73,646 Propane 84,027 Phenol 73,040 Acetone 73,815 Ammonia 72,088 NExBTL 73,298 Propylene 66,818 Phenol + acetone 72,427 Sulphuric acid 62,822 Styrene 71,934 Butadiene 60,340 Benzene 69,240 Styrene 59,423 Formic acid 68,427 Hexafluorosilicic acid 57,896 Butanoles 67,890 Benzene 56,841 Hexafluorosilicic acid 56,006 Tert-amyl ethyl ether (TAEE) 54,239 Ammonia 51,632 Butane 53,491 Ethylene 45,166 Acetone 53,074 Pyrolysis gasoline 39,426 Parafines 51,450 Butadiene 38,852 Crude palm oil 48,413 Coal tar 36,114 Nitric acid 40,666 Propylene 29,919 Nonylphenol ethoxylates 29,160 Sulphuric acid 25,172 Ethylene 27,795 Tert-amyl ethyl ether (TAEE) 23,186 Monoethylene glycol 27,725 Nexbase 20,401 Butyl acrylate 27,641 Hydrogen peroxide 20,059 CO2 27,253 Ethyl tert-butyl ether (ETBE) 19,273 Butanoles 24,399 Nitric acid 16,838 Hydrogen peroxide 23,379 CO2 13,592 Butane + propane 19,702 VERSENEX 80/100 12,968 Raffinate 17,269 ETBE + TAEE 12,309 VERSENEX 80/100 15,463 Nonylphenol ethoxylates 11,082 NExBTL 12,806 Alcohol fuel mixture 10,372 Butyl acetate 12,026 Palm stearine 10,009 Tert-amyl methyl ether (TAME) 10,148 Butyl acrylate 9,273 Vinyl acetate 9,414 Linear alkyl benzene 6,779 Epichlorohydrin 9,328 Butyl acetate 4,558 Other chemical products (NOS) 7,762 Piperylene 4,476 Alpha-olefines 7,058 Alpha-olefines 3,737 Linear alkyl benzene 6,740 Rapeseed oil 3,152 Formic acid 6,614 Diisononyl phthalate 2,999 Tall pitch oil 5,734 Cumene 2,611 Nexbase 5,029 Butane 2,257 Hydrocarbon, l iquid (NOS) 4,807 Dioctyl phthlate 1,994 Methylmetacrylate 4,763 Hexane 1,950

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Past vessel accidents in the Baltic Sea

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/

Collisions and grounding main types of accident/incidents. Human factor main cause, followed by technical reasons No major chemical spills nor oil accident like Erika, Prestige have happened etc. The latest severe oil spill in the Baltic Sea was in 2001: The Bulk Carrier Tern and the tanker Baltic Carrier

collided. Appr. 20,000 seabirds were contaminated Antonio Gramsci 1987, grounding, spill 650 tonnes

Figure 1. Vessel accidents in the Baltic Sea in 1989–2010 by accident types. (Häkkinen and Posti 2013 based on HELCOM 2012)

Figure 2. Vessel accidents in the Baltic Sea in 1989–2010 by vessel types. (Häkkinen and Posti 2013 based on HELCOM 2012)

n=1520

n=1400 n=1520

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Tanker accidents and the share of pollution cases in the Baltic Sea in 1989–2010. (Häkkinen and Posti 2013 based on HELCOM 2012)

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Tanker accidents with no

pollution 86,7 %

Oil/oil product

pollution cases 12,8 %

Chemical pollution

cases 0,5 %

Total number of tanker accidents: 211Amount of pollution in total: appr. 3,100 m3

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Tanker accidents involved a pollution in the Baltic Sea in 1989–2010 (n=29). (Häkkinen and Posti 2013 based on HELCOM 2012)

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Place Time Vessel name Type of accidentType of pollution

Pollution cubm

Gothenburg (SE) 29.12.1989 Forsvik (SE) Loading Oil 0,3

Karlskrona (SE) 14.5.1990 Volganeft 263 (RU) Collision Oil 125South Kvarken (SE) 1.12.1992 Konstantin Tsiolkovski (RU) Collision Oil 12,5Tallinn (EE) 16.1.1993 Kihnu (EE) Grounding Oil 102,5Karlskrona (SE) 10.8.1993 Valaam (LV) Collision Oil 6,25Gothenburg (SE) 13.12.1995 Tritoa Av Goteborg (SE) Leakage Oil 0,2Gothenburg (SE) 13.2.1996 Tom Lis (PT) Leakage Orthoxylen 0,5Sea of Åland 8.1.1998 Anne Sif (DE) Oil spill Oil 0,4Between Sweden and Estonia 3.5.1998 United Tony Oil spill Oil 0,05Sea of Åland 8.7.1998 Victoire (LR) Oil spill Oil 0,99Near to Gdynia (PL) 5.8.1998 Oresund Oil spill Oil 2Klaipeda (LT) 26.4.1999 Nemunas (LT) N/A Oil 0,6Nörrköping (SE) 26.8.1999 Zanis Griva (LR) Technical failure Oil 6,25Saint Petersburg (RU) 9/1999 Nefterudovoz-7 (RU) Grounding Oil 75Near to Klaipeda (LT) 6.12.1999 Almanama (BH) Broken hose Oil 4South side of Gotland (SE) 19.6.2000 Falcon Chemist (LR) Oil spill Oil 0,02Near to Tallinn (EE) 16.9.2000 Alambra (MT) Hull damage Oil 250Near to south side of Gotland (SE) 3.12.2000 Spirit E (PA) Oil spill N/A N/AFlensburg Fjord 29.3.2001 Tern (CY) Collision Oil 2500

Near to Klaipeda (LT) 3.6.2001 North Pacific (NO) Technical failure Oil 3,89

Riga (LV) 12.5.2004 Fure star (SE) PollutionIntermediate fuel oil 0,1

Riga (LV) 17.1.2005 Silene (LV) Contact with bollard Marine diesel oil 0,5Riga (LV) 4.3.2005 Vikland (MT) Pollution Gasoline 0,1Near to Klaipeda (LT) 31.1.2008 Stena Antarctica (KY) Pollution Crude oil 2,2437

Saint Petersburg (RU) 9.7.2008 Narva (RU) Pollution Mazut 0,5Stockholm (SE) 8.6.2009 Zebron (SE) Machinery damage Hydraulic oil N/A

Świnoujście (DK) 11.12.2009 Happy Eagle (IM) CollisionOil mixed with water 0,010 tonnes

Kemi (FI) 21.1.2010 Jurmo (FI) Pollution Oil 0,5 tonnesHalmstad (SE) 14.6.2010 Fox Luna (SE) Grounding Hydraulic oil N/A

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FINLAND: Accidents involving a liquid bulk vessel investigated by the Finnish Safety Investigation Authority in the years 1997–2011

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Place Time Vessel name Accident type Cargo Pollution Amount of pollution

Kotka 1 Dec 1997 Crystal Amethyst Grounding Nonyl phenol ethoxylate

No 0

Emäsalo 13 Oct 1998 Natura Grounding Crude oil No 0

Hamina 20 July 2000 Crystal Rubino Spill Nonyl phenol ethoxylate

Yes 2 tonnes

Lövskär 19 Feb 2002 Douro Chemist Grounding Ballast No 0

Sköldvik 27 Feb 2002 Tebo Olympia Spill Bensin Yes 2 m3

Porvoo 10 Dec 2005 Omega af Donsö Grounding Diesel oil No 0

The Kiel Canal

2 Feb 2006 Wolgastern Collision with other vessel

Gas oil No 0

The Sea of Åland

14 Oct 2006 Arctica Collision with sea mark

Ballast No 0

N/A

4 Nov 2008 N/A Personal injury Diesel and gas oil

No 0

Orrengrund channel

26 Jan 2009 Crystal Pearl Collision with sea mark

Nonyl phenol ethoxylate, n-parafine and paraxylen

No 0

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M/T C. RUBINO, environmental accident during loading, Port of Hamina, July 20, 2000

• At least two tonnes of nonylphenol ethoxylate spilled to the sea and started to foam. Nonylphenol ethoxylate behaves as a sinker and dissolver. Thus it was impossible to gather it from the sea.

• Nonylphenol ethoxylates degraded readily to more harmful substance, nonylphenol. The substance is very toxic to fish and other marine organisms, and it is also a hormone disrupting substance that mimics estrogen.

• Consequently, fishes started to die soon after the spill. The seagulls that ate the dead fish probably suffered from reproduction problems in the following spring. Bioconcentration, bioaccumulation, and persistence of nonylphenol is high. Thus it is possible that the substances could be transported significant distances.

http://www.turvallisuustutkinta.fi

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Lessons learnt from accidents worldwide

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Key findings of the literature review

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• Chemical tanker accidents are very rare, even though there is always the possibility that such incident may happen

• Over 60 well-documented accidents including bulk chemicals or HNS (period of ca. 7 decades). In addition over 40 accidents with cargo including packaged chemicals. Accident probability increases in areas where the density of the maritime traffic is at

its highest point, where bad weather conditions exists, as well as the ship-shore interface in ports where unloading/loading take place.

Many studies have shown that the most commonly transported chemicals are the ones most likely to be involved in an accident i.e. liquid fuels and acids.

The maritime accidents frequently involved chemicals or chemical groups like acids, gases, vegetable oils, phenol, ammonia, caustic soda and acrylonitrile.

• The volume of spill will be less than in case of oil accident.

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• Compared to oil, the liquid chemicals in bulk can be more dangerous to human beings and property because cargoes can be more: Explosive, combustible, poisonous, irritating and reactive

• Past maritime accident cases demonstrated that the risks affecting human health come from reactive substances (reactivity with air or water or between products themselves) and toxic substances. Certain substances such as chlorine, ammonia, acrylonitrile and vinyl acetate are transported in

large quantities and may pose very serious threat to human health. Even though smaller volumes are transported, packaged chemicals can also be extremely

dangerous to humans e.g. epichlorohydrine

• The important difference between chemical and oil spill is related to response actions. The air quality or explosion risk are not usually of any concern for response personnel in case

of oil spills, however, it should be carefully evaluated if some response actions are made in case of chemical spills.

In case of chemical spills, the response may be limited, in most cases, to initial evaluation, establishing exclusions zones, modeling and monitoring, followed by planning of controlled release, recovery or leaving in-situ. This process will take many weeks of even months.

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• From environmental point of view, the previous studies highlighted accident were pesticides released to water but also substances considered as non-pollutants (vegetable oils) seem to affect negatively to biota in water environment.

• The evaluation of the chemical risks is very difficult when ship is carrying diverse chemicals (especially container ships) and some of those are unknown during the first hours after the accident.

• When compared hazardous chemicals and oil, it can be said that the danger of coastline pollution is far greater concern for oil spills than in chemical spills. On the other hand, the toxic clouds are much higher concern in the case of chemical accidents.

• Little is known about the actual marine pollution effect of most of these heavily transported substances.

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Environmental risk assessment studies

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GE

F

D

S

Wind

Current

Dispersion

Photolysis, emulsification, fragmentation

Adsorption, bioaccumulation etc

Biodegradation, burial

Fate of chemical

E.g. if nonylphenol is released to water: 49-59 % stay at water, 41-50 % end up to sediment and 1 % to air.

Main Category Gas (G)(methane)

Evaporator (E)(benzene)

Floater (F)(palm oil)

Sinker (S)(coal tar)

Dissolver (D)(phosphoric acid)

Sub-categories GDGas/Dissolves(ammonia)

EDEvaporates/Dissolves(MTBE)

FDFloats/Dissolves(butanol)

SDSinks/Dissolves(dichloroethane)

DEDissolves/Evaporates(acetone)FE

Floats/Evaporates(xylenes)FEDFloats/Evaporates/Dissolves(ethyl acrylate)

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Birds

Pelagic fish Plankton

Mammals

Benthic communitiesSediment

Water column

Surface

Air GE

D

F

S

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Scoring method

• The most hazardous chemicals are those which sinks, have a high solubility, stay maybe at the water column, persistent, bioavailable and are very toxic and maybe have long-term effects

• Altogether 15 chemicals that are transported in the Baltic Sea were assessed using the scoring method developed originally by Häkkinen et al. (2010), though slightly modified for the purpose of this paper (Häkkinen et al. 2013).

• The chemicals were assessed based on 9 parameters which were considered the main factors affecting their environmental fate or mobility, ecotoxicology and probability of being involved in an accident. For each parameter, the chemicals were assessed on a scale of 1 to 3, the most hazardous chemicals receiving 3 points.

• In addition, some chemicals scored 0.5–1 additional points if they had significant hazardous environmental impacts, for instance based on their carcinogenic potential or endocrine effects

• The total number of points was added up, and a priority list for hazardous chemicals was formed.

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Table 1. Parameters and threshold levels for the scoring used in risk assessment. Addtional points (0,5-1) were given to chemicals having other significant hazardous environmental impacts

Parameter 1 point 2 points 3 points

Volatility

(Vapour pressure)b

> 0.1 kPa

highly volatile

10-5–0.1 kPa

semi-volatile

<10-5 kPa

non-volatile

Density b

< 1.025 g/cm3

floater

> 1.025 g/cm3

sinker

Water solubilityac 0.1–10 mg/l

poorly soluble

10–1 000 mg/l

soluble

> 1 000 mg/l

highly soluble

Persistence* (BIOWIN3 half

life)

Days to weeks Weeks Weeks to months

Bioaccumulation (logKOW)a <3

not bioaccumulative

3–5

slightly/moderately

bioaccumulative

>5

very bioaccumulative

Acute toxicity (LC/EC50)a > 100 mg/l

slightly toxic

1–100 mg/l

toxic/hazardous

< 1mg/l

very toxic

Chronic toxicity (NOEC)a > 1mg/l

slightly toxic

0.1–1.0 mg/l

toxic/hazardous

< 0.1 mg/l

very toxic

Transportation volume <10,000

tonnes

10,000–100,000

tonnes

>100,000

tonnes

aThreshold values from Nikunen and Leinonen (2002) were used for guidance in the classification of most parameters.

bVolatility threshold values and density were determined according to French McKay et al. (2006).

c TDI (toluene diisocyanate) only scored 1 point for solubility due to degradation by hydrolysis.

*NExBTL does not have a BIOWIN value but 1 point was given to it based on experimental half-lives from literature.

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Ranking list based on scorings

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Chemical

Vol

atili

ty

Bio

degr

adab

ility

Acc

umul

atio

n

Acu

te t

oxic

ity

Chr

onic

tox

icity

Tra

nspo

rt v

olum

e

Oth

er h

azar

dous

im

pact

s

Wat

er s

olub

ility

Den

sity

Tot

al s

um

Pla

cem

ent

Nonylphenol 1 2 2 3 3 3 3 2 1 20 1 Sulphuric acid 3 2 3 2 1 2 2.5 2 0 17.5 2 Phenol 3 2 2 2 1 2 2 3 0 17 3 Ammonia 3 1 1 2 1 3 2.5 2 1 16.5 4 Benzene 3 1 1 3 1 2 1.5 2 0.5 15 5 Styrene 2 1 1 2 2 2.3 2.5 2 0 14.8 6 Xylenes 2 1 1 2 2 2 1.3 3 0 14.3 7 Epichlorohydrin 3 2 1 2 1 2 1.5 1 0.5 14 8 MTBE 3 1 1 2 1 1 1 3 0 13 9 n-Pentane 2 1 1 1 2 2 1 3 0 13 9 Methanol 3 1 1 1 1 1.3 1 3 0 12.3 11 TDI 1 2 2 1 2 1.7 1 1 0.5 12.2 12 Ethanol 3 1 1 1 1 1 1 3 0 12 13 1-Decene 1 1 1 2 3 1.3 1 1 0 11.3 14 NExBTL 1 1 1 1 3 1 1 2 0 11 15

Scores of different parameters, the total sum and placement in the priority list. The

chemicals with the highest points pose the greatest environmental risk.

Published in: Häkkinen J, Malk V, Posti A, Penttinen OP, Mäkelä R, Kiiski A (2013). Environmental risk assessment of the most commonly transported chemicals - Case Finnish coastal areas. WMU Journal of Maritime Affairs. DOI 10.1007/s13437-013-0046-5

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Other risk assessment studies

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• The HASREP (2005) project identified 100 chemicals most transported between major European ports and involved in trade through the English Channel to the rest of the World. The assessment was based on both transport volumes and the GESAMP hazard profile.

• They highlighted chemicals like benzene, styrene, vegetable oil, xylene, methanol, sulphuric acid, phenol, vinyl acetate, and acrylonitrile. They concluded that these chemicals were the ones that have high spillage probability but may not result in significant environmental impact.

• Similarly, French McKay et al. (2006) applied a predictive modelling approach for a selected range of chemicals transported by sea in bulk and concluded that phenol and formaldehyde present the greatest risk to aquatic biota.

• Harold et al. (2011) evaluated human health risks of transported chemicals based on the GESAMP ratings for toxicity and irritancy. This gives more weight to chemicals that are floaters, form gas clouds, irritate and are toxic, such as chlorine (Harold et al. 2011).

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Summary and conclusions

• Neither major chemical spills nor oil spills, such as Erika or Prestige, have happened in the Baltic Sea.

• The spilled substance has in most cases been oil or an oil product – only very few chemical spill cases have been reported in the Baltic Sea.

• The most commonly transported chemicals are the ones most likely to be involved in an accident.

• Very little is known about the actual marine pollution effect of most of highly transported substances.

• When comparing hazardous chemicals with oil, it can be said that the danger of coastline pollution is a far greater concern in oil spills than in chemical spills.

• The chemicals in turn might be more dangerous to human health

• The most important difference between chemical and oil spill may be related to response actions.

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The funding providers and partners of the Chembaltic project (www.merikotka.fi/chembaltic)

More information:www.merikotka.fi/chembalticJani Häkkinen, Project managerTel. +358 40 5633 276e-mail: [email protected] of Turku

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Turun yliopisto MERENKULKUALAN KOULUTUS- JA TUTKIMUSKESKUS 0 Overview of Maritime Accidents Involving Chemicals Worldwide and in the Baltic Sea Jani Häkkinen