INTERNATIONAL MARITIME ORGANIZATION
E
IMO
BLG WORKING GROUP ON THE
EVALUATION OF SAFETY AND
POLLUTION HAZARDS OF CHEMICALS
10th session
Agenda item 3
ESPH 10/3/8
29 July 2004
ENGLISH ONLY
EVALUATION OF NEW PRODUCTS
Lard
Submitted by the United Kingdom
SUMMARY
1
Executive summary:
Lard is proposed for inclusion in Chapter 17 of the IBC Code
Action to be taken:
Paragraph 3
Related documents:
MEPC 51/11, Circular letter No.2538, Circular letter No.2539
Background
1.1
The ESPH Working Group noted that, on the request of BLG 8, the GESAMP/EHS
Working Group had provisionally evaluated the outstanding aspects of the revised hazard profiles
for those vegetable oils identified by the industry as being transported in bulk by sea. It was
recognized that the provisional evaluations made by GESAMP/EHS Working Group, allowed the
Pollution Category and the Ship Type to be determined for those vegetable oils.
1.2
At ESPH 9 the Working Group noted that, currently, the IBC Code includes the following
entries for animal/vegetable oils:
.1
Animal and fish oils n.o.s;
.2
Cashew nut shell oil (untreated); and
.3
Vegetable oils.
1.3
The Working Group agreed that that these three entries would be deleted from the next
edition of the IBC Code as the GESAMP/EHS Working Group had provisionally evaluated the
animal/vegetables oils on an individual basis. In addition it was agreed that, in future any
vegetable oil considered for carriage must be evaluated on the basis of data provided.
For reasons of economy, this document is printed in a limited number. Delegates are
kindly asked to bring their copies to meetings and not to request additional copies.
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Details of the proposal
2.1
Based on data provided by the industry, it is proposed that Castor Oil be included in
Chapter 17 of the new revised IBC with the following carriage requirements:
Column
Entry
a. Product Name:
LARD
c. Pollution Category:
Y
d. Hazards:
P
e. Ship type:
2
f. Tank type:
2G
g. Tank vents:
Open
h. Tank environmental control:
No.
i. Electrical equipment
i′ Class:
i′′ Group:
i′′′Flash point greater than 600 C:
T3
IIB
Yes
j. Gauging:
Open
k. Vapour detection:
No
l. Fire protection:
A, B
m. Materials of construction:
--
n. Respiratory and eye protection:
No.
o. Special requirements:
15.19.6 and 16.2.6.
2.2
In addition the Index of Dangerous Chemicals in Bulk should be updated to include the
following Associated Synonyms for Lard – Crude Lard, Lard, Steam Lard, Leaf Lard,
Edible Lard, Inedible Lard, Choice Kettle Lard.
2.3
The data related to this product is attached to this document for information.
3
Action requested of the Working Group
3.1
The Working Group is invited to consider the data associated with this product and assign
carriage requirements as shown in 2.1 and 2.2 above.
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ESPH 10/3/8
BLG Product Data Reporting Form
(Characteristics of Liquid Chemicals Proposed for Bulk Marine Transport)
SECTION 1 : PRODUCT IDENTITY
Shipping Name
:
LARD
This is the only name that should appear on the shipping documents and will be reflected in the IBC Code
______________________________________________________________________
1.1 : Other Names and Identification Numbers
Main Trade Name
:
Lard
_________________________________________________________________________________________________________
:
Triglycerides of fatty acids of chain length C-12 to C-24,
predominantly C-16 and C-18
_________________________________________________________________________________________________________
Main Chemical Name
:
See Structure
Chemical Formula
_________________________________________________________________________
Structure
Chemical Class
:
_________________________________________________________________________
:
61789-99-9
CAS Number
_________________________________________________________________________
CH2.OOCR1
EHS Number
:
I
_________________________________________________________________________
CH.OOCR2
BMR Number
:
I
_________________________________________________________________________
CH2.OOCR3
:
RTECS Number
_________________________________________________________________________
:
______________________________________________________________________
UN Number
1.2 : Associated Synonyms
Crude Lard, Lard, Steam Lard, Leaf Lard, Edible Lard, Inedible Lard, Choice Kettle Lard.
______________________________________________________________________
1.3 : Composition (Typical)
C
Triglycerides
> 90%
I
I
I
I
Free Fatty Acids
Unsaponifiable Matter
Moisture
Insoluble Impurities
< 10.0%
< 1.0%
< 1.0%
< 0.5%
Triglycerides of fatty acids of chain length C-12 to C-24,
predominantly C-16 to C-18
______________________________________________________________________
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SECTION 2 : PHYSICAL PROPERTIES
Property
Units
Qual
Lower
Value
Upper
Value
References and Comments
______________________________________________________________________
833
863
Molecular Weight
_________________________________________________________________________________________________________
Relative Density
(kg/m3)
Bailey P188
925
932
at 20ºC
_________________________________________________________________________________________________________
Flash Point
(ºC)
Bailey P212
> 240
(Closed Cup)
Ullmans P185
_________________________________________________________________________________________________________
Boiling Point
(ºC)
> 250
Melting Point (Slip)
(ºC)
35
Triglycerides decompose
before ebullition
_________________________________________________________________________________________________________
48
Bailey P193
_________________________________________________________________________________________________________
Solubility in Water
(mg/l)
Insoluble
at 20ºC
_________________________________________________________________________________________________________
Solid
Viscosity
(mPa.s)
25 at 50°C
at 20ºC
Ullmans P186
_________________________________________________________________________________________________________
Vapour Pressure
(Pa)
Bailey P205
< 0.001
at 20ºC
_________________________________________________________________________________________________________
Autoignition Temp
(ºC)
IMO Guidelines BLG/3/12/1,
Annex 1, Para 3.3.2
_________________________________________________________________________________________________________
E
> 280
Not explosive
IMO Guidelines BLG/3/12/1,
Annex 1, Para 3.3.2
_________________________________________________________________________________________________________
Explosion Limits
(% v/v)
Normal Carriage
(ºC)
Unloading Temp
NF
38
51
(ºC)
41
54
ISO 5555 (1991)
IASC Handbook (1993),
Section 4 (1995 Amdt)
_________________________________________________________________________________________________________
Max Experimental
Safe Gap (MESG)
(mm)
NF
_________________________________________________________________________________________________________
References -
Bailey's Industrial Oil and Fat Products, 4th Edition (1979), ISBN 0-471-83957-4.
Ullmans Encyclopaedia of Industrial Chemistry, 5th Edition (1987).
______________________________________________________________________
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ESPH 10/3/8
SECTION 3 : RELEVANT CHEMICAL PROPERTIES
Water Reactivity Index
(0-2)
0
0 = No Reactivity
1 = Reactive
2 = Highly Reactive Details
_________________________________________________________________________________________________________
Does the product react with air to cause a potentially hazardous situation?
N
(Y/N)
_________________________________________________________________________________________________________
Is an Inhibitor or Stabilizer needed to prevent a hazardous reaction?
(Y/N)
N
_________________________________________________________________________________________________________
Is refrigeration needed to prevent a hazardous reaction?
N
(Y/N)
______________________________________________________________________
SECTION 4 : MAMMALIAN TOXICITY
Qual
Lower
Value
Upper
Value
Species
References and Comments
______________________________________________________________________
4.1 : Acute Toxicity
Oral (LD50)
(mg/kg)
> 10000
Rats
Biotech Index (1)
_________________________________________________________________________________________________________
Dermal (LD50)
(mg/kg)
Non toxic
_________________________________________________________________________________________________________
Inhalation (LC50)
(mg/I/4h)
______________________________________________________________________
4.2 : Corrosivity and Irritation
4
Skin Corrosion Time (hours)
Non corrosive (2)
_________________________________________________________________________________________________________
Resultant Observation
Skin Irritation (4h Exposure)
Species
Prolonged contact with skin
may cause dermatitis (1)
Not irritating
Not Irritating, Mildly Irritating, Moderately Irritating, Markedly Irritating or Corrosive
_________________________________________________________________________________________________________
Resultant Observation
Eye Irritation
Species
Mildly irritating
Mild conjunctive erythema
(after 24h of application of a
45% solution) but completely
subsided at 72h (2)
Not Irritating, Mildly Irritating, Moderately Irritating, Markedly Irritating or Corrosive
______________________________________________________________________
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4.4 : Sensitization
Respiratory Sensitizer
(In Humans)
(Y/N)
Skin Sensitizer
(Y/N)
E
N
E
N
______________________________________________________________________
4.5 : Other Specific Long-Term Effects
Carcinogen
(Yes/No)
No
_________________________________________________________________________________________________________
Mutagen
(Yes/No)
No
_________________________________________________________________________________________________________
Toxic to Reproduction
(Yes/No)
No
_________________________________________________________________________________________________________
Other Long-Term Effects
(Yes/No)
No
______________________________________________________________________
Calculated Saturated Vapour Concentration (ppm)
Calculated Saturated Vapour Concentration (mg/I)
Calculated Inhalation Toxicity (from Oral Toxicity)
______________________________________________________________________
4.6 : Other Relevant Mammalian Toxicity Remarks
Lard is a foodstuff; fit for human consumption.
Lard derivatives are known to play a role in high cholesterol levels and atherosclerotic disease (1).
Lard derivatives have GRAS approval from the FDA.
_________________________________________________________________________________________________________
References -
(1)
Biotech Index NG02888.
(2)
G B Briggs, et al, "Studies on a Series of Fatty Acids", Am Ind Hyg Ass J, April 1976, P235.
______________________________________________________________________
SECTION 5 : MARINE POLLUTION
Given a rating of 0 for Acute Aquatic Toxicity by GESAMP.
______________________________________________________________________
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ESPH 10/3/8
5.2: Biodegradation and Bioaccumulation
Biodegradation
The generic structure of animal and vegetable triglycerides implies that the whole range will have a similar inherent potential to
biodegrade. The triglycerides consist of various alkyl chain length distributions and ranges in the degree of unsaturation of these
alkyl chains. All of these structures can be completely biodegraded by a wide range of micro-organisms. Differences in the rate of
biodegradation are due to differences in water solubility and, therefore, bioavailability rather than an inherent resistance to degrade.
Technical measures are used in ready biodegradation tests to overcome the problems of low bioavailability. These usually involve
emulsification of the poorly soluble oil with a non-degradable surfactant.
The triglycerides, triolein (1,2,3-tri[(cis)-9-octadecenoyl]glycerol) and tripalmitin (1,2,3-trihexadecanoylglycerol) were both found to be
readily biodegradable in the Sturm test [1]. Both substances are highly representative of the chain lengths typically found in natural
triglycerides. Refined canola/rapeseed oil underwent 70% biodegradation in a shake flask test [2]. Cornish et al [3] state that the
high biodegradability of vegetable oils is to be expected since there are a wide range of micro-organisms that produce effective
lipases and the pathways for the degradation are ubiquitous. Vegetable oil biodegradation begins with de-esterification of the
triglyceride by extracellular lipases, with substrate specificity, to form glycerol and fatty carboxylic acids. The carboxylic acids are
then further degraded by beta-oxidation and glycol is absorbed by facilitated diffusion followed by conversion to a central metabolite
[4].
Biodegradation of olive oil, sunflower oil and linseed oil in sea water by natural populations of bacteria has been reported by Mudge
et al [5]. Rates between 3 and 8% per day were observed for unpolymerised oils and <1% per day for polymerised oils.
Bioconcentration
No studies reporting the bioconcentration of natural triglycerides in fish have been found. The use of Kow (see below) as a surrogate
for estimating the potential to bioconcentrate is not useful for triglycerides which form part of the normal diet and proprietary fish
foods.
As for the determination of aquatic toxicity, it would be difficult to obtain a representative measure of accumulation because truly
soluble concentrations of triglycerides in water are extremely low. However, this is an academic consideration because the
metabolism of triglycerides is well understood. Due to their low solubility, the major uptake of fats and oils by fish is via the diet.
Digestion occurs in the gut followed by accumulation of the breakdown intermediates (fatty acids and glycerol). These are utilised in
the normal metabolic pathways of the fish. Therefore, bioaccumulation is not considered to represent a hazard to fish.
Octanol/Water Partition Coefficient
Measured values of Kow have not been found. However, it is possible to calculate Kow from fragment values according to the
method of Hansch and Leo [12]. Since there is a strong structural similarity between all natural triglycerides, the Kow of a
representative structure has been calculated, tripalmitin (1,2,3-propanetriol tris(hexadecanoate). The calculated Kow value is
estimated to be 21 [13]. A Kow of this magnitude is immeasurable but indicates that practically no triglyceride would be expected to
occur in a water body that contains a lipid sink for them to partition into. Triglycerides with similar alkyl chain lengths will have similar
Kow values.
References
[1]
Battersby NS, Pack SE and Watkinson RJ. A correlation between the biodegradability of oil products in the CEC L-33-T-82
and modified Sturm tests. Chemosphere 24 No 12 1989-2000 1992.
[2]
EPA 560/6-82-003 Shake Flask Test.
[3]
Cornish A, Battersby NS and Watkinson RJ. Environmental fate of mineral, vegetable and transesterified vegetable oils.
Pesticide Science 37 pg 173-178 1993.
[4]
Lehninger AL Biochemistry, 2nd Edition. Worth Publishers Inc, NY 1975 pg 543-558.
[5]
Mudge SM, Saunders H and Latchford J (1994) Degradation of Vegetable Oils in the Marine Environment. Countryside
Commission for Wales, Report pp 67.
[6]
Marshall SJ and van Egmond RA. Bioavailability. UK DoE Research Contract, Final Report (1995).
[7]
Mudge SM, Salgado MA and East J (1993) Marine Pollution Bulletin 26: 40-44.
[8]
Draft Guidance Document on Aquatic Toxicity Testing of Difficult Substances. OECD Series on Testing and Assessment,
March 1999.
[9]
Guidance on the Aquatic Toxicity Testing of Difficult Substances. DoE (1996). Published by the UK DoE, London.
[10]
Aquatic Toxicity Testing of Sparingly Soluble, Volatile and Unstable Substances. ECETOC Monograph No 26, ECETOC,
Brussels.
[11]
Bowmer CT, Schoonmade JA Henzen L and van der Veen. (1999) The Environmental Properties of Poorly Soluble
(Lipophilic) Substances: the Aquatic Toxicity of Selected Vegetable Oils and n-alkanes, each in Combination with a model
Surfactant. TNO Report V99.069 TNO Department of Environmental Toxicology, Delft, NL.
[12]
Hansch C and Leo AJ. Substituent constants for correlation analysis in chemistry and biology. Wiley New York. 1979.
[13]
US EPA EPIWIN QSAR program v3.01.
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SECTION 6 : GESAMP HAZARD PROFILES AND CARRIAGE REQUIREMENTS
6.1 : GESAMP Hazard Profiles
New Hazards Profile
sssssssss
Column Number : Property
Old Hazard Profile
Existing
Proposed
A1a:
Low Kow
0
A1b:
BioConcentration Factor
0
A2:
Biodegradation
R
B1:
Acute Aquatic Toxicity
0
B2:
Chronic Aquatic Toxicity
NI
C1:
Acute Oral Toxicity
0
C2:
Acute Dermal Toxicity
0
C3:
Acute Inhalation Toxicity
(0)
D1:
Skin Irritation/Corrosivity
0
D2:
Eye Irritation/Corrosivity
1
D3:
Specific Health Concerns
E1:
Tainting and Odour
E2:
Beaches and Amenities
F
E3:
Wildlife and Seabed
2
F:
Remarks
Column Number
Existing Proposed
A
B
C
D
E
6.2 : Carriage Requirements
Does the product meet the Minimum Safety Criteria to be included in Chapter 17 of the IBC Code?
(Y/N)
Does the product meet the Minimum Pollution Criteria to be included in Chapter 17 of the IBC Code?
(Y/N)
Carriage Conditions
C:
Pollution Category
D:
Safety/Pollution Properties
E:
Ship Type
F:
Tank Type
G:
Tank Vents
H:
Tank Environmental Control
Ii:
Elec Equip - Class
ii
I:
Elec Equip - Group
Iiii:
Elec Equip - Fpt>60 C
J:
Gauging
K:
Vapour Detection
L:
Fire Protection
M:
Materials of Construction
N:
Resp Eye Protection
O:
Special requirements
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Existing
Calculated