WO1999064547A1 - Contaminant reduced marine oil - Google Patents

Contaminant reduced marine oil Download PDF

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Publication number
WO1999064547A1
WO1999064547A1 PCT/EP1999/003657 EP9903657W WO9964547A1 WO 1999064547 A1 WO1999064547 A1 WO 1999064547A1 EP 9903657 W EP9903657 W EP 9903657W WO 9964547 A1 WO9964547 A1 WO 9964547A1
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Prior art keywords
oil
polychlorinated
range
marine origin
teq
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PCT/EP1999/003657
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French (fr)
Inventor
Charles Wyatt Craven
Tommy Morrison
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Merck Patent GmbH
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Merck Patent GmbH
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Filing date
Publication date
Priority to EP99926436A priority Critical patent/EP1084214B1/en
Priority to CA002334022A priority patent/CA2334022C/en
Priority to US09/701,841 priority patent/US6469187B1/en
Priority to DE69933027T priority patent/DE69933027T2/en
Priority to AU43696/99A priority patent/AU758397B2/en
Priority to NZ507936A priority patent/NZ507936A/en
Priority to JP2000553537A priority patent/JP4727039B2/en
Priority to IL13984799A priority patent/IL139847A/en
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of WO1999064547A1 publication Critical patent/WO1999064547A1/en
Priority to IS5689A priority patent/IS2398B/en
Priority to NO20006160A priority patent/NO322025B1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS OR COOKING OILS
    • A23D9/00—Other edible oils or fats, e.g. shortenings or cooking oils
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/115—Fatty acids or derivatives thereof; Fats or oils
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/21—Esters, e.g. nitroglycerine, selenocyanates
    • A61K31/215—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids
    • A61K31/22—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids of acyclic acids, e.g. pravastatin
    • A61K31/23—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids of acyclic acids, e.g. pravastatin of acids having a carboxyl group bound to a chain of seven or more carbon atoms
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/44—Oils, fats or waxes according to two or more groups of A61K47/02-A61K47/42; Natural or modified natural oils, fats or waxes, e.g. castor oil, polyethoxylated castor oil, montan wax, lignite, shellac, rosin, beeswax or lanolin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/02—Refining fats or fatty oils by chemical reaction
    • C11B3/04—Refining fats or fatty oils by chemical reaction with acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/02—Refining fats or fatty oils by chemical reaction
    • C11B3/06—Refining fats or fatty oils by chemical reaction with bases
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/10—Refining fats or fatty oils by adsorption
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/12—Refining fats or fatty oils by distillation
    • C11B3/14—Refining fats or fatty oils by distillation with the use of indifferent gases or vapours, e.g. steam

Definitions

  • the present invention relates to a process for the preparation of oil of marine origin with reduced content of polychlorinated dioxins, furans, biphenyls, and polycyclic aromatic hydrocarbons.
  • This invention also relates to a composition of matter obtained by the process and the use thereof.
  • a method for reducing the content of PCBs in fish oil by means of silica gel or silicic acid is known from EP 0 340 635.
  • PCDD PCDD in crude and processed fish oils
  • E.M. Brevik et al. Organohalogen Compounds (1990), 1, 467-70. It is pointed out that neither deodorisation by steam stripping nor filtration through adsorbents is able to reduce the levels of any of the PCDD/PCDF isomers.
  • the invention was based on the object of finding contaminant reduced marine oils having useful properties, in particular those which can be used in foodstuffs or pharmaceutical formulations.
  • the fish body oils obtainable by the inventive process, have very useful properties. In particular, they exhibit extremely reduced contents of polychlorinated contaminants.
  • Dioxins is the generic term given to polychlorinated dibenzo-p-dioxins and dibenzofurans. Dioxins are unwanted by-products in the manufacture of certain chemicals. Small amounts are also produced during most combustion and incineration processes.
  • PCBs polychlorinated biphenyls
  • PCBs polychlorinated biphenyls
  • Polychlorinated dioxins and polychlorinated furans means polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans.
  • Dioxins and furans have for some time been calculated in terms of a toxic equivalency (TEQ) related to the reportedly most toxic congener (2,3,7,8- TCDD).
  • TEQ toxic equivalency
  • the change referred to above is that a range of PCB congeners have now also been assigned toxic equivalency factors.
  • the results for all three classes of compounds are now converted to TEQs and are added together to give a total TEQ.
  • the addition of the PCBs to the calculation has significantly raised the TEQ values found in marine oils and in particular cod liver oil, whilst the tolerable daily intake for these compounds, also set by the WHO, has not been altered.
  • the process reduces the total TEQ in the product by 90 % in ⁇ n comparison to the natural fish oil.
  • the present invention relates to a process for the preparation of oil of marine origin with reduced content of polychlorinated dioxins, furans, biphenyls, and polycyclic aromatic hydrocarbons, characterized in that the 15 marine oil a) is refined with acid and/or alkali, b) is cold cleared, c) is stirred under reduced pressure in the temperature range of 40 to 100° C with activated carbon, d) is cooled to 20 to 40° C, e) is separated off the activated carbon, f) is deodorised with hot steam under reduced pressure for a period of 0.5 hour to 20 hours,
  • the present invention preferably relates to a process for the preparation of fish body oil and most preferably of cod liver oil with reduced content of 30 polychlorinated dioxins, furans and biphenyls.
  • the invention relates to the oils obtainable by the inventive processes which exhibit combined concentrations of polychlorinated dioxins, furans and biphenyls in the range 0.05 - 6 (ng TEQ/kg oil), 3 preferably in the range 0.5 - 5 (ng TEQ/kg oil), most preferably in the range 1 - 4 (ng TEQ/kg oil).
  • the present invention relates to the oil of marine origin obtainable by the inventive process, with a concentration of polychlorinated dioxins in the range 0.01 - 0.3 (ng TEQ/kg oil), preferably in the range 0.03
  • the present invention is not related to the analytical limits of determination, but relates to specific dioxin, furan and PCB congeners (those assigned a toxic equivalency factor) and their removal from and the residual levels in commercial quantities of marine oils.
  • Table 1 lists the chlorine-containing contaminants names.
  • the fish oil with reduced content of contaminants can be obtained preferably by the following process: a) The fish oil is first refined. Oil is heated via a heat exchanger and phosphoric acid is added followed by sodium hydroxide in a short mix refining plant. The oil is then water washed twice and vacuum tried.
  • the oil and the carbon are stirred and held at this temperature for 5 to 240 minutes, preferably for 10 to 100 minutes, most preferably for 20 to 50 minutes.
  • filter aid of a commercially available grade
  • a filter e.g. a vertical leaf "Niagara” type
  • the product is then deodorised.
  • the oil is charged into a deodorisation vessel equipment with heating and cooling coils, steam spray coils and a steam ejection vacuum system.
  • Steam is then purged through the oil using the steam spray coils and these conditions are maintained for 0.5 to 20 hours, preferably 1 to 10 hours, most preferably 2 to 6 hours.
  • the concentrations of PAHs are determined by capillary gas chromatography-mass spectrometry and quantified by reference to 13 C internal standards. Results are given in ⁇ g/kg (Table 3) for individual compounds and also as benzo-(a)-pyrene (BAP) equivalents (Table 4).
  • TEZFs Toxic Equivalency Factors
  • PAHs Polycyclic Aromatic Hydrocarbons

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microbiology (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Epidemiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Food Science & Technology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Nutrition Science (AREA)
  • Mycology (AREA)
  • Emergency Medicine (AREA)
  • Fats And Perfumes (AREA)
  • Edible Oils And Fats (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Medicinal Preparation (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Lubricants (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Abstract

Process for the preparation of oil of marine origin with reduced content of polychlorinated dioxins, furans, biphenyls and polycyclic aromatic hydrocarbons. The oil obtainable by the process has combined concentrations of polychloranited dioxins, furans and biphenyls in a range from 0.05 - 6 (ng TEQ/kg oil) and is used in foodstuffs or pharmaceutical formulations.

Description

Contaminant Reduced Marine Oil
The present invention relates to a process for the preparation of oil of marine origin with reduced content of polychlorinated dioxins, furans, biphenyls, and polycyclic aromatic hydrocarbons.
This invention also relates to a composition of matter obtained by the process and the use thereof.
A method for reducing the content of PCBs in fish oil by means of silica gel or silicic acid is known from EP 0 340 635.
R.F. Addison et al. describes the removal of Organochlohne Pesticides and Polychlorinated Biphenyls from Marine Oils by means of clay in J. Amer. Oil Chem. Soc. 51, 192-194 (1974). Products show 0.5 ppm polychlorinated biphenyls as a result of such processing. V.J.Krukonis describes the extraction of polychlorinated biphenyls by means of supercritical fluid processing of fish oils in J. Amer. Oil Chem. Soc. 66, 818-821 (1989). Obtained products have PCB concentrations of about 10 ppm. Levels of polychlorinated dibenzofurans (PCDF) and dibenzo-p-dioxins
(PCDD) in crude and processed fish oils are described by E.M. Brevik et al., Organohalogen Compounds (1990), 1, 467-70. It is pointed out that neither deodorisation by steam stripping nor filtration through adsorbents is able to reduce the levels of any of the PCDD/PCDF isomers.
The paper by Els G. van der Velde et al. relates to methodology for the analysis of PCBs in oils and describes supercritical fluid extraction as clean-up technique of PCBs in fatty samples in Organohalogen Compounds (1996), 27, 247-52. The process uses up to 2 g of fish oil and not the processing of bulk oils for the removal of these compounds.
Combined concentrations of dioxins and PCBs in cod liver oil were published in Food Surveillance Information Sheet, Vol. 106, June 1997, MAFF, London. Where full data were obtained, the combined concentrations of dioxins and PCBs in cod liver ranged from 18 - 41 (ng TEQ/kg oil) in 1996.
Due to a change in the international approach to the assessment of toxicity of a specific group of organochlorine environmental contaminants by the
WHO, it has proved necessary to develop a method of eliminating these contaminants from marine oil products.
The invention was based on the object of finding contaminant reduced marine oils having useful properties, in particular those which can be used in foodstuffs or pharmaceutical formulations.
It has been found that the fish body oils, obtainable by the inventive process, have very useful properties. In particular, they exhibit extremely reduced contents of polychlorinated contaminants.
"Dioxins" is the generic term given to polychlorinated dibenzo-p-dioxins and dibenzofurans. Dioxins are unwanted by-products in the manufacture of certain chemicals. Small amounts are also produced during most combustion and incineration processes. PCBs (polychlorinated biphenyls) are a group of 209 related compounds known as congeners. Advances in analytical methodolgy have allowed to separate and to quantify individual congeners. Appropriate methods now exist to quantify the separation of said contaminants. However, such analysis would be prohibitively costly and therefore specific congeners are usually selected for analysis.
Polychlorinated dioxins and polychlorinated furans means polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans.
Dioxins and furans have for some time been calculated in terms of a toxic equivalency (TEQ) related to the reportedly most toxic congener (2,3,7,8- TCDD). The change referred to above is that a range of PCB congeners have now also been assigned toxic equivalency factors. The results for all three classes of compounds are now converted to TEQs and are added together to give a total TEQ. The addition of the PCBs to the calculation has significantly raised the TEQ values found in marine oils and in particular cod liver oil, whilst the tolerable daily intake for these compounds, also set by the WHO, has not been altered.
Surprisingly, the process reduces the total TEQ in the product by 90 % in ι n comparison to the natural fish oil.
The present invention relates to a process for the preparation of oil of marine origin with reduced content of polychlorinated dioxins, furans, biphenyls, and polycyclic aromatic hydrocarbons, characterized in that the 15 marine oil a) is refined with acid and/or alkali, b) is cold cleared, c) is stirred under reduced pressure in the temperature range of 40 to 100° C with activated carbon, d) is cooled to 20 to 40° C, e) is separated off the activated carbon, f) is deodorised with hot steam under reduced pressure for a period of 0.5 hour to 20 hours,
25 g) and is cooled to 20 to 70° C.
The present invention preferably relates to a process for the preparation of fish body oil and most preferably of cod liver oil with reduced content of 30 polychlorinated dioxins, furans and biphenyls.
Furthermore, the invention relates to the oils obtainable by the inventive processes which exhibit combined concentrations of polychlorinated dioxins, furans and biphenyls in the range 0.05 - 6 (ng TEQ/kg oil), 3 preferably in the range 0.5 - 5 (ng TEQ/kg oil), most preferably in the range 1 - 4 (ng TEQ/kg oil). Moreover, the present invention relates to the oil of marine origin obtainable by the inventive process, with a concentration of polychlorinated dioxins in the range 0.01 - 0.3 (ng TEQ/kg oil), preferably in the range 0.03
- 0.22 (ng TEQ/kg oil), to an oil with a concentration of polychlorinated furans in the range 0.01 - 0.1 (ng TEQ/kg oil), preferably in the range 0.03
- 0.08 (ng TEQ/kg oil), to an oil with a concentration of polychlorinated biphenyls in the range 0.01 - 5 (ng TEQ/kg oil), preferably in the range 0.1
- 4 (ng TEQ/kg oil), and to an oil with a concentration of polycyclic aromatic hydrocarbons (PAH) in the range 0.005 - 0.4 (BAP-equivalents [μg/kg]), preferably in the range 0.01 - 0.35 (BAP-equivalents [μg/kg]).
The present invention is not related to the analytical limits of determination, but relates to specific dioxin, furan and PCB congeners (those assigned a toxic equivalency factor) and their removal from and the residual levels in commercial quantities of marine oils.
Table 1 lists the chlorine-containing contaminants names.
Table 1
Contaminant
Polychlorinated dibenzo-p-dioxins
2,3,7,8-tetrachlorodibenzo-p-dioxin (-TCDD)
1 ,2,3,7,8-pentachlorodibenzo-p-dioxin (-PeCDD)
1 ,2,3,4,7,8-hexachlorodibenzo-p-dioxin (-HxCDD)
1 ,2,3,6,7,8- hexachlorodibenzo-p-dioxin (-HxCDD)
1 ,2,3,7,8,9- hexachlorodibenzo-p-dioxin (-HxCDD)
1 ,2,3,4,6,7,8- heptachlorodibenzo-p-dioxin (-HpCDD)
Octachlorodibenzo-p-dioxin
Polychlorinated dibenzofurans
2,3,7, 8-tetrachlorodibenzofuran (-TCDF) Contaminant
1 ,2,3,7, 8-pentachlorodibenzofuran (-PeCDF)
2,3,4,7,8-pentachlorodibenzofuran (-PeCDF)
1 ,2,3,4,7,8-hexachlorodibenzofuran (-HxCDF)
1 ,2,3,6,7,8-hexachlorodibenzofuran (-HxCDF)
1 ,2,3,7,8,9-hexachlorodibenzofuran (-HxCDF)
2,3,4,6, 7,8-hexachlorodibenzofuran (-HxCDF)
1 ,2,3,4,6, 7,8-heptachlorodibenzofuran (-HpCDF)
1 ,2,3,4,7,8, 9-heptachlorodibenzofuran (-HpCDF)
Octachlorodibenzofuran (OCDF)
Polychlorinated biphenyls
3,3\4,4'-tetrachlorobiphenyl (PCB 77)
3,3*,4,4',5-pentachlorobiphenyl (PCB 126)
3,3',4,4',5,5'-hexachlorobiphenyl (PCB 169)
2,3,3',4,4,-pentachlorobiphenyl (PCB 105)
2,3,4,4', 5-pentachlorobiphenyl (PCB 114)
3,3',4,4',5-pentachlorobiphenyl (PCB 118)
2\ 3,4,4', 5-pentachlorobiphenyl (PCB 123)
2,3,3',4,4',5-hexachlorobiphenyl (PCB 156)
2,3,3',4,4',5,-hexachlorobiphenyl (PCB 157)
2,3',4,4',5,5'-hexachlorobiphenyl (PCB 167)
2,3,3',4,4,,5,5,-heptachlorobiphenyl (PCB 189)
2,2',3,4,4',5,5,-heptachlorobiphenyl (PCB 180)
The fish oil with reduced content of contaminants can be obtained preferably by the following process: a) The fish oil is first refined. Oil is heated via a heat exchanger and phosphoric acid is added followed by sodium hydroxide in a short mix refining plant. The oil is then water washed twice and vacuum tried.
b) The oil is then "cold cleared". Refined oil is cooled in a stirred vessel until it deposits a solid fraction referred to in the industry as stearin. The oil slurry is then filtered through a filter press in a cold environment in order to remove the stearin. The liquid filtrate in known as olein and is the "cold cleared" oil.
c) The oil is charged into a batch vessel fitted with steam heating coils, cooling coils, steam ejector vacuum equipment and a vacuum sealed mechanical stirrer. A vacuum of 0.5 to 60 mbar, preferably 2 to 30 mbar, most preferably 5 to 20 mbar, is raised on the vessel and 0.1 to 5.0 %
(w/w), preferably 0.2 to 4.0 % (w/w), most preferably 0.5 to 2.5 % (w/w) powdered activated carbon (of a commercially available grade, e.g. Pulsorb RB ex. Chemviron Carbon Ltd) is added and stirred into the oil.The temperature is then raised to 40 to 100° C, preferably 50 to 80°C.
The oil and the carbon are stirred and held at this temperature for 5 to 240 minutes, preferably for 10 to 100 minutes, most preferably for 20 to 50 minutes.
d) The oil is then cooled to 20 to 40° C. The vacuum is released and the mixture is discharged from the vessel.
e) 0.5 to 2.5 % (w/w) of filter aid (of a commercially available grade) is then added and the mixture is stirred. The mixture is then filtered through a filter, e.g. a vertical leaf "Niagara" type, to remove the carbon and filter aid.
f) The product is then deodorised. The oil is charged into a deodorisation vessel equipment with heating and cooling coils, steam spray coils and a steam ejection vacuum system. A vacuum of 0.5 to 60 mbar, preferably 1 to 20 mbar, most preferably 2 to 5 mbar, is then pulled over the oil and the oil is heated to 100 to 250° C, preferably 140 to 230° C, most preferably 170 to 220° C. Steam is then purged through the oil using the steam spray coils and these conditions are maintained for 0.5 to 20 hours, preferably 1 to 10 hours, most preferably 2 to 6 hours.
g) Steam purging then ceases and the oil is cooled to 40 - 60° C at which time any vitamin or other additions are made. Vacuum is then broken and the oil is discharged to the finished product storage tanks.
Example
The following example demonstrates the reduction in organochlorine contaminants and polycyclic aromatic hydrocarbons achievable using the process as outlined above. Analyses were performed analogous to Food Surveillance Information Sheet, Vol. 106, June 1997, MAFF, London and the references cited therein.
Table 2
Figure imgf000009_0001
Figure imgf000010_0001
The concentrations of PAHs are determined by capillary gas chromatography-mass spectrometry and quantified by reference to 13C internal standards. Results are given in μg/kg (Table 3) for individual compounds and also as benzo-(a)-pyrene (BAP) equivalents (Table 4).
Figure imgf000011_0001
1 = feedstock 2, 3, 4 = level in fully processed oil
Figure imgf000012_0001
* calculated with reference to I.C.T.Nisbet et al. (1992) Toxic Equivalency Factors (TEFs) for Polycyclic Aromatic Hydrocarbons (PAHs). Regulatory Toxicology and Pharmacology 16, 290-300
1 = feedstock 2, 3, 4 = level in fully processed oil

Claims

Patent Claims
1. Process for the preparation of oil of marine origin with reduced content of polychlorinated dioxins, furans, biphenyls, and polycyclic aromatic hydrocarbons, characterized in that the marine oil a) is refined with acid and/or alkali, b) is cold cleared, c) is stirred under reduced pressure in the temperature range of 40 to 100° C with activated carbon, d) is cooled to 20 to 40° C, e) is separated off the activated carbon, f) is deodorised with hot steam under reduced pressure for a period of 0.5 hour to 20 hours, g) and is cooled to 20 to 70° C.
2. Process according to claim 1 , characterized in that fish body oil is used as oil of marine origin.
3. Process according to claim 2, characterized in that cod liver oil is used.
4. Process according to claim 1 , 2 or 3, characterized in that the level of powdered activated carbon is 0.1 to 5.0 % (w/w).
5. Process according to claim 1 , 2, 3 or 4, characterized in that step c) is carried out at a pressure of 0.5 to 60 mbar for 5 to 240 minutes.
6. Process according to claim 1 , 2, 3, 4, 5 or 6, characterized in that the oil is deodorised in the temperature range from 100 to 250° C at a pressure of 0.5 to 60 mbar.
7. Oil of marine origin with reduced content of polychlorinated dioxins, furans and biphenyls obtainable by one of the processes 1 to 6.
8. Oil of marine origin according to claim 7 wherein the oil is cod liver oil.
9. Oil of marine origin according to claim 7 or 8 with a concentration of polychlorinated dioxins in the range 0.01 - 0.3 (ng TEQ/kg oil).
10. Oil of marine origin according to claim 7, 8 or 9 with a concentration of polychlorinated furans in the range 0.01 - 0.1 (ng TEQ/kg oil).
11. Oil of marine origin according to claim 7, 8, 9 or 10 with a concentration of polychlorinated biphenyls in the range 0.01 - 5 (ng TEQ/kg oil).
12. Oil of marine origin according to claim 7 or 8 with combined concentrations of polychlorinated dioxins, furans and biphenyls in the range 0.05 - 6 (ng TEQ/kg oil).
1 . Oil of marine origin according to claims 7 - 12 with a concentration of polycyclic aromatic hydrocarbons in the range 0.005 - 0.4 (BAP- equivalents [μg/kg]).
14. The use of the oil according to one of the claims 7-13 in foodstuffs or pharmaceutical formulations.
PCT/EP1999/003657 1998-06-05 1999-05-27 Contaminant reduced marine oil Ceased WO1999064547A1 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
IL13984799A IL139847A (en) 1998-06-05 1999-05-27 Contaminant reduced marine oil
CA002334022A CA2334022C (en) 1998-06-05 1999-05-27 Contaminant reduced marine oil
US09/701,841 US6469187B1 (en) 1998-06-05 1999-05-27 Contaminant reduced marine oil
DE69933027T DE69933027T2 (en) 1998-06-05 1999-05-27 Marine oil with less impurities
AU43696/99A AU758397B2 (en) 1998-06-05 1999-05-27 Contaminant reduced marine oil
EP99926436A EP1084214B1 (en) 1998-06-05 1999-05-27 Contaminant reduced marine oil
JP2000553537A JP4727039B2 (en) 1998-06-05 1999-05-27 Reduced pollutant fish oil
NZ507936A NZ507936A (en) 1998-06-05 1999-05-27 Contaminant reduced fish oil
IS5689A IS2398B (en) 1998-06-05 2000-10-27 Contaminated marine fish oil
NO20006160A NO322025B1 (en) 1998-06-05 2000-12-04 Fish oil with reduced contaminant content, process for its preparation and use in food or pharmaceutical preparations.

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WO2002006430A1 (en) * 2000-07-19 2002-01-24 Lysi Hf. Marine oils with reduced levels of contaminants
US8680080B2 (en) 2001-07-27 2014-03-25 Neptune Technologies & Bioressources, Inc. Natural marine source phospholipids comprising polyunsaturated fatty acids and their applications
US8278351B2 (en) 2001-07-27 2012-10-02 Neptune Technologies & Bioressources, Inc. Natural marine source phospholipids comprising polyunsaturated fatty acids and their applications
US10028968B2 (en) 2001-07-27 2018-07-24 Aker Biomarine Antarctic As Natural marine source phospholipids comprising polyunsaturated fatty acids and their applications
US8383675B2 (en) 2001-07-27 2013-02-26 Neptune Technologies & Bioressources, Inc. Natural marine source phospholipids comprising polyunsaturated fatty acids and their applications
WO2008054228A1 (en) * 2006-10-31 2008-05-08 Due Miljø As Method of oil purification, and uses thereof for food and feed
WO2009132463A1 (en) * 2008-05-02 2009-11-05 Neptune Technologies & Bioressources Inc. New deodorization method and organoleptic improvement of marine oil extracts
WO2010039037A1 (en) * 2008-10-03 2010-04-08 Dag Arntsen Process for removal of contaminations from organic oils
EP2344614A4 (en) * 2008-10-03 2012-03-28 Dag Arntsen Process for removal of contaminations from organic oils
EP2438819B2 (en) † 2009-06-02 2018-02-14 Golden Omega S.A. Method for producing a concentrate of eicosapentaenoic and docosahexaenoic acid esters
US8981137B2 (en) 2009-06-02 2015-03-17 Golden Omega S.A. Method for producing a concentrate of eicosapentaenoic and docosahexaenoic acids
US10617702B2 (en) 2009-10-29 2020-04-14 Acasti Pharma Inc. Concentrated therapeutic phospholipid compositions
US9475830B2 (en) 2009-10-29 2016-10-25 Acasti Pharma Inc. Concentrated therapeutic phospholipid compositions
US8586567B2 (en) 2009-10-29 2013-11-19 Acasti Pharma, Inc. Concentrated therapeutic phospholipid compositions
US10130644B2 (en) 2009-10-29 2018-11-20 Acasti Pharma Inc. Concentrated therapeutic phospholipid compositions
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US20140275594A1 (en) * 2011-07-14 2014-09-18 Soluciones Extractivas Alimentarias, S.L. New process for reducing pollutants in fats and oils and their derivatives
US9309484B2 (en) 2011-07-14 2016-04-12 Soluciones Extractivas Alimentarias, S.L. Process for reducing pollutants in fats and oils and their derivatives
WO2013007315A1 (en) * 2011-07-14 2013-01-17 Soluciones Extractivas Alimentarias, S.L. New process for reducing pollutants in fats and oils and their derivatives
US12331015B2 (en) 2012-05-14 2025-06-17 Nissui Corporation Highly unsaturated fatty acid or highly unsaturated fatty acid ethyl ester with reduced environmental pollutants, and method for producing same
EP3971165B1 (en) 2012-05-14 2024-08-07 Nissui Corporation Highly unsaturated fatty acid or highly unsaturated fatty acid ethyl ester with reduced environmental pollutants, and method for producing same
US20150247106A1 (en) * 2012-11-02 2015-09-03 Pronova Biopharma Norge As Removal of undesired components from oil compositions
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NO20006160L (en) 2000-12-04
IL139847A0 (en) 2002-02-10
DE69933027D1 (en) 2006-10-12
NO20006160D0 (en) 2000-12-04
ES2272071T3 (en) 2007-04-16
PT1084214E (en) 2007-01-31
IS5689A (en) 2000-10-27
IS2398B (en) 2008-08-15
IL139847A (en) 2004-07-25
DE69933027T2 (en) 2007-03-08
EP1084214A1 (en) 2001-03-21
NO322025B1 (en) 2006-08-07
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AU758397B2 (en) 2003-03-20
ZA200100108B (en) 2002-06-26
EP1655361A1 (en) 2006-05-10
US6469187B1 (en) 2002-10-22
DK1084214T3 (en) 2006-12-04
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AU4369699A (en) 1999-12-30
NZ507936A (en) 2002-12-20

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