Transportation volumes and risk assessment of liquid ... · Multi-Tank Ascania UK, 1999 Vinyl acetate Jessie Maersk Gibraltar, 1999 Ammonia Young Chemi South Korea, 1999 Chloroform

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MERENKULKUALAN KOULUTUS- JA TUTKIMUSKESKUS

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Transportation volumes and risk assessment of

liquid chemicals transported in the Baltic Sea

Jani HäkkinenUniversity of Turku, Centre for Maritime Studies, Kotka

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Presentation

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Environmental Risk Assessment

Past accidentsAssessment with Scoring

method

Accident Probability

Case Gulf of Finland Chemicals vs oil

Chemical transport volumes

Baltic Sea Especially Finnish Ports

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In Sweden, the volume of liquid bulk chemicals is most probably higher than 0.9 million tonnes. For example, Molitor

(2006) and Suominen (2007) have reported that the annual chemical handling volume in Swedish ports has been from

2.5 million tonnes. Inaddition, Holma et al. (2011) stated that no liquid chemicals are handled in German ports but

results of this study indicate that high amounts of chemicals are also handled in these ports (see more detailed in

Posti and Häkkinen 2012).

Cargo traffic in Baltic Sea ports

Dry bulk Other dry

cargo

Liquid bulk International

cargo total Oil and oil

products

Liquid

chemicals

Other liquid

bulk

Rus sian ports 26,656 35,335 112,842 85 317 175,235

Swedish ports 26,094 68,661 53,634 930 1,826 151,145

Finnish ports 27,351 38,846 20,240 6,266 301 93,004

Latvian ports 29,737 10,227 20,485 690 73 61,212

Pol i sh ports 24,015 17,055 16,242 811 447 58,570

Danish ports 17,617 23,148 15,967 218 857 57,807

German ports 17,351 25,170 4,153 0 42 46,716

Es tonian ports 10,145 5,354 28,575 1,157 53 45,284

Li thuanian ports 11,774 9,694 17,780 792 255 40,295

Baltic ports total 190,740 233,490 289,918 10,949 4,171 729,268

Table 3.1 International cargo traffic in the Baltic Sea ports in 2010, thousand tonnes.

(Holma et al. 2011)

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Transport volumes of chemicals in the Baltic Sea and in

Finland

• The study revealed that every year more than 11 million tonnes of liquid bulk chemicals are

handled in the Baltic Sea ports.

• Over half of all the liquid bulk chemicals in the Baltic Sea ports are handled in Finnish and

Swedish ports.

• The PortNet review showed that in 2010 Finnish ports handled approximately 3.5 million tonnes

of liquid bulk chemicals including about 60 different chemicals.

• The most handled chemicals in Finnish ports were methanol, sodium hydroxide solution and

pentanes.

• There were 8 chemicals that were handled more than 100,000 tonnes and 37 chemicals handled

more than 10,000 tonnes.

• Of all liquid bulk chemicals handled in Finnish ports in 2010, the export of liquid bulk

chemicals accounted for about 73 % and the import of liquid bulk chemicals about 27 %.

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Chemicals handled in Finnish Ports

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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

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0

200

400

600

800

1000

1200

1400

1994

2002

2007

2008

2010

References: Posti & Häkkinen 2012, Häkkinen 2004, 2009, Hänninen & Rytkönen 2006

Most handled chemicals in Finnish ports (thousand tonnes)

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Swedish statistics

Table 3.11 Chemicals handled in Swedish ports in 2004, tonnes. (Molitor 2006)

Chemical Volume Chemical Volume

Sulphuric acid 827,322 Ethyl acetate 22,620

Sodium hydroxide solution 369,736 Aluminium chloride 14,200

Ammonia 198,038 Acetic anhydride 10,991

Propane 188,549 Nitric acid 10,733

Ethanol 151,812 Benzene 7,000

Phosphoric acid 72,239 Ammonium nitrate 6,100

Fluorinated Sil ica 65,800 Acetic acid 5,500

Coal tar 56,244 Propionic acid 3,600

n-Butanol 42,200 Acetone 3,292

2-ethylhexanol 40,600 Ferric chloride 3,200

Xylene 39,700 Turpentine 2,127

Calcium chloride 39,600 Toluene 1,982

Methanol 35,871 Ammonia solution 1,964

2-ethylhexanoic acid 28,200 Butyl acetate 1,550

Styrene 23,920 Methyl ethyl ketone 150

Tall oil pitch 23,900 Total 2,322,540

Aluminium sulphate 23,800

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Findings

• The results indicated that the most transported chemicals in the whole Baltic Sea are methanol,

sodium hydroxide solution, 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

� The exact tonnes for whole Baltic Sea could not be calculated

• Besides these chemicals, there are also other high volume chemicals or gases (e.g. ethylene,

propane, butane), and large amounts of liquid fertilisers and vegetable oils which are handled in the

Baltic Sea ports, but exact tonnes of these substances are unknown as well.

• New substances includes e.g. ETBE, TAAE, NExBTL.

• Chemicals transported most in the Baltic Sea are mainly similar when compared to chemicals

transported most in other sea areas.

• According to AMRIE (2005), most transported chemicals in the largest Atlantic EU ports were

palm and other vegetable oils, methanol, benzene and its mixtures, sodium hydroxide solution,

xylenes, styrene, MTBE, molasses and ammonia.

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Accident probabilityAalto University

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Ship size

With permission of P.Kujala

With permission of P.Kujala

Modelling the scenario - tankers traffic in the GoF

x 10e-3

x 10e-4

Expected number of struck

tankers per year

Expected number of struck

chemical tankers per year

The risk of oil and chemical transportation in the Baltic Sea

Risk of the tankers traffic in the GoFMean expected cargo outflow,

chemical tanker as struck vessel in collision

Mean expected oil outflow,

oil tanker as struck vessel in collision

Tonnes of spilled cargo

Tonnes of spilled cargo

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PAST ACCIDENTS

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Past vessel accidents in the Baltic Sea

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Compiled from http://www.helcom.fi/shipping/accidents/en_GB/accidents/

� 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

2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 Total

Collisions 10 9 8 19 44 57 54 40 41 34 40 356

Groundings 36 37 43 30 58 54 46 54 60 38 36 492

Fires 3 1 3 1 10 8 7 8 9 10 14 74

Machinery damages 0 0 0 4 12 2 5 7 4 5 9 47

Technical failures 3 3 2 2 0 12 0 0 0 1 0 23

Pollutions 5 2 4 11 4 3 5 4 9 9 6 62

Other accidents 5 5 3 4 17 15 0 7 12 8 19 96

Total 62 57 63 71 145 151 117 120 135 105 124 1150

2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 Total

Cargo vessels 40 34 41 43 92 94 81 74 68 34 64 666

Tankers 12 13 12 11 18 24 22 18 15 23 15 182

Passenger vessels 1 0 0 9 25 19 25 27 27 32 35 200

Other type of vessels 9 9 10 9 17 20 17 15 41 33 28 208

No information 0 1 0 7 0 0 0 0 0 0 4 12

Total 62 57 63 79 152 157 145 134 152 122 146 1269

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Baltic Sea

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Compiled from HELCOM

reports

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Ship Place and year Chemical involved

Grandcamp Texas City, USA, 1947 ammonium nitrate

Ocean Liberty France, 1947 ammonium nitrate

Mundogas Oslo Finland/Sweden 1966 Ammonia (2000 t)

Poona Sweden, 1971 Sodium chlorate and rapeseed oil

Amalie Essberger Sweden, 1973 Phenol

Yoyo Maru N°10 Japan, 1974 Propane, butane and naphtha

Lindenbank Hawaii, 1975 Sugars, foodstuff and vegetable oils (palm and coconut oil)

René 16 Sweden, 1976 Anhydrous ammonia

Stanislaw Dubois Netherland, 1981 Calcium carbide + caustic soda

Brigitta Montanari Yugoslavia, 1984 Vinyl chloride monomer (VCM)

Castillo De Salas Spain, 1984 Coal (100000 t)

Puerto Rican USA, 1984 Caustic soda

Anna Broere Netherland, 1988 Acrylonitrile and Dodecylbenzene

Ocean Spirit Malta,1988 Lead concentrate

Val Rosanda Italy, 1990 Propylene

Alessandro Primo Italy, 1991 Acrylonitrile and Dichloroethane

Continental Lotus Eastern Mediterranean, 1991 Iron ore

Erato Algeria, 1991 Phosphate and bunker fuel

Kimya UK, 1991 Sunflower oil

Nordfrakt Germany, 1992 Lead sulphur (1600 t)

Weisshorn Spain, 1992 Rice

Grape One UK, 1993 Xylene

Cynthia M New Jersey, USA, 1994 Caustic soda

Infiniti Curacao, 1995 Rice

N°1 Chung Mu China, 1995 Styrene

Fenes France, 1996 Wheat

Formosa Eight Japan, 1996 Acrylonitrile

Igloo Moon USA, 1996 Butadiene

Kira Greece, 1996 Phosphoric acid

Kowloon Bridge USA, 1996 Iron ore

Albion II Bay of Biscay, France, 1997 10 dangerous chemicals (IMO code) and 1100 t of fuel (IFO 180).

Allegra France, 1997 Palm nut oil

Bow Panther Japan, 1997 Xylene

Panam Perla Atlantic, 1998 Sulphuric acid

Bahamas Brazil, 1998 Sulphuric acid

Champion Trader Mississippi River, USA, 1998 Palm oil

Multi-Tank Ascania UK, 1999 Vinyl acetate

Jessie Maersk Gibraltar, 1999 Ammonia

Young Chemi South Korea, 1999 Chloroform

Eurobulker IV Sardinia, 2000 Coal

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Past accident analysis

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• Chemical accidents are rare

• Accident probability increases substantially in dense traffic areas

• The greatest accident risks are posed by the substances that are transported the most i.e. liquid

fuels and acids. This was apparent from almost all of the data sources used

• Cedre/Transport Canada (2012) analysed 196 HNS accidents across the world´s seas: Structural

damage (18 %) was main cause followed by severe weather conditions (16 %) and collisions (13

%) and groundings (11 %). Loading/unloading was cause only in 7 % of the accidents

• Compared to oil the liquid cargoes in bulk can be more dangerous to human beings and property

because cargoes can be more: Explosive, combustible, poisonous, irritating and/or reactive.

• In most maritime accident cases involving chemicals the risks affecting human health comes

from reactive substances (reactivity with air or water or between products themselves) and toxic

substances.

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Past accident analysis

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

� The air quality or explosion risk 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.

• The previous studies highlighted accident were pesticides (packaged usually) 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 (Marchand 2002, Mamaca 2009).

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

substances.

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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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Environmental risk assessment

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GESAMP categorization

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• Based on the GESAMP evaluation IMO has formed 4 different hazard categories X

(major hazard), Y (hazard), Z (minor hazard) and OS i.e. other substances (no hazard)

(IMO 2007).

• Approximately 80 % of all chemicals transported in maritime are classified as belonging

to the Y category

• This GESAMP categorization is very comprehensive but different chemicals having very

different hazard potential and toxicity mechanisms either humans or biota, environmental

fate and other physico-chemical properties may end up to same MARPOL category.

• The GESAMP will not answer the question what chemicals are the most dangerous ones

from an environmental perspective if they belong to same Y category.

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Environmental risk assessment of the chemicals

• The objective of the study was to

assess the risks of the regionally most

transported chemicals (oil and

petroleum fuels excluded) with a

simple scoring system and to highlight

the chemicals that require special

attention from an environmental point

of view in potential marine accident

situations in the Baltic Sea area.

• In co-operation with RIMA

(www.rimaproject.eu) and Chembaltic

projects.

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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 GD

Gas/Dissolves

(ammonia)

ED

Evaporates/

Dissolves

(MTBE)

FD

Floats/Dissolves

(butanol)

SD

Sinks/Dissolves

(dichloroethane)

DE

Dissolves/

Evaporates

(acetone)FE

Floats/Evaporates

(xylenes)

FED

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Birds

Pelagic

fish Plankton

Mammals

Benthic communitiesSediment

Water column

Surface

Air GE

D

F

S

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Effect for water biota was weighted in the study

For water biota

• 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

Human health

• Most hazardous chemicals are

those that form gas clouds either

very toxic or irritating (or

explosive) and maybe have also

long-term effects like

carsinogenic effects.

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Scoring method

• 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.

• The chemicals were scored from 1 to 3 according to factors affecting their

environmental fate or mobility, ecotoxicology (both acute and chronic) and

probability for accident. Additional point 0.5-1 might given based on other

health or environment impact (e.g carsinogenic…)

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0,01

0,1

1

10

100

1000

10000

No

ny

yli

fen

oli

Am

mo

nia

kk

i

Bro

no

po

li

Na

triu

mh

yp

okl

ori

itti

Glu

tara

lde

hy

di

Sty

ree

ni

Div

iny

yli

be

nts

ee

ni

Kre

oso

ott

i

Ksy

lee

nit

Ep

iklo

ori

hy

dri

ini

n-P

en

taa

ni

TD

A

To

lue

en

i

Klo

rofo

rmi

Rik

kih

iili

1-D

ek

ee

ni

1-H

ek

see

ni

Ety

lee

nid

iklo

rid

i

Be

nts

ee

ni

HC

FC

Na

triu

mk

lora

att

i

Me

tyy

lim

eta

kry

laa

tti

MT

BE

Re

sors

ino

li

Fe

no

li

Me

tan

oli

Eta

no

li

TD

I

Ak

uu

tti t

ok

sisu

usa

rvo

(m

g/l

)

123

1-100 mg/l< 1 mg/l > 100 mg/l

Example about ecotoxicity

scoring method (The figure

presented originally in

ChemRisk project)

Acute toxicity of different

chemicals to algae. The most

toxic get highest scoring

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Parameter 1 point 2 points 3 points

Volatility

(Vapor 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

10–1000 mg/L

soluble

> 1000 mg/L

very soluble

Persistence* (BIOWIN3 half life)

Days to weeks Weeks Weeks to months

Bioaccumulation (logKOW)a <3

not accumulative

3–5

slightly/moderate

accumulative

>5

very accumulative

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

very slightly toxic

0,1–1,0 mg/L

slightly toxic

< 0,1 mg/L

very toxic

Transportation volume <10 000

tonnes

10,000–100,000

tonnes

>100 000

tonnesaThe threshold values from Nikunen and Leinonen (2002) were used as guidance in classification in most parameters. b bVolatility threshold values and density determined according to French McKay et al. (2006).

c For TDI only 1 point was given for solubility due to degradation by hydrolysis.

*NExBTL does not have a BIOWIN value, but 1 point was given for NexBTL according to experimental half-lifes from literature.

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

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Ranking list based on scorings

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Chemical

Vo

latili

ty

Bio

deg

radab

ilit

y

Acc

um

ula

tion

Acu

te t

ox

icity

Ch

ron

ic t

oxic

ity

Tra

nsp

ort

vo

lum

e

Oth

er h

azar

do

us

imp

acts

Wat

er s

olu

bility

Den

sity

Tota

l su

m

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.

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Source: ITOPF

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Other risk assessments

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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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Conclusions

• Risk for chemical transportation accident is considerably

smaller if compared to oil transportation

• Amount of spilled substance also smaller

• On the other hand possibility exists and Baltic Sea is unique…

• Risk for human health higher than in oil accident

• From environmental point of view, nonylphenol is the most

toxic and hazardous of the studied chemicals.

• Other very hazardous substances in the case of maritime spills

were sulphuric acid and ammonia.

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Further information about the projects

www.merikotka.fi/chembaltic

Jani Häkkinen, Project manager

Tel. +358 40 5633 276

e-mail: [email protected]

University of Turku

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The financiers and partners of the Chembaltic project

Documents

Transportation volumes and risk assessment of liquid ... · Multi-Tank Ascania UK, 1999 Vinyl acetate Jessie Maersk Gibraltar, 1999 Ammonia Young Chemi South Korea, 1999 Chloroform