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Prosjektnummer
542052
Decontamination of Persistent Organic Pollutants in Fishmeal and Fish Oil (DECONTAM)
Project results
The results from this project were included in a doctoral thesis. The following is an abstract of the thesis:
Persistent organic pollutants (POPs) are fat soluble chemical substances that persist in the environment and bioaccumulate in the food chain. Through long-range environmental transportation by air, water and migratory species they are transferred to new locations distant from the source of release and might cause adverse effects to human health and to the environment. POPs comprise pesticides, industrial chemicals and unwanted by-products. The European Commission has implemented food and feed legislations concerning maximum permitted levels (MPLs) of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), dioxin-like polychlorinated biphenyls (DLPCBs), polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs). Fish and consequently fishmeal and fish oil has been identified as one of the most important contributors to the level of dioxins and DL-PCBs in food and feed products. Fish caught in some of the North-European fishing areas contain high dioxin and PCB levels resulting in fishmeal and oil with WHO-PCDD/F-PCB-TEQ levels above the maximum permitted. To meet the new industrial and socialeconomic challenges there is a need for development of cost-effective decontamination technologies.
Efficiency and limitations of alternative decontamination technologies to reduce the level of PCDD/Fs, DL-PCBs and polybrominated diphenyl ether flame retardants (PBDEs) in fishmeal (i.e., mechanical fat separation, organic solvent extraction and oil leaching) and fish oil (i.e., activated carbon (AC) adsorption and short-path distillation (SPD)) have been studied in this thesis. Factorial design experiments, response surface methodology and quantitative structure property relationships (QSPRs) have been utilized to model and optimize the fish oil decontamination alternatives. The trapping mechanisms for non- and mono-ortho PCBs on AC have been studied by use of molecular dynamics simulations.
Optimization of the existing mechanical fat separation steps in the fishmeal process is expected to be the most cost-effective way to reduce the POPs content. However, the obtainable effects are limited (estimated to maximum 20–30 %) and have to be combined with organic solvent extraction if high decontamination rates are needed. The feasible use of a new oil leaching process has been studied and found to give effects comparable to hexane and isopropanol extraction of fishmeal (i.e., > 75 %).
AC adsorption of PCDD/Fs is highly effective with obtainable WHO-TEQ-reduction of 99 %. Adsorption of DL-PCBs is less effective and dependent on orthosubstitution, i.e., non-ortho-PCBs are adsorbed more effectively than mono-ortho- PCBs, with maximum obtained levels of 87 % and 21 %, respectively. Compliance with present feed and food WHO-PCDD/F-PCB-TEQ legislations in fish oil can be achieved based on AC adsorption. The adsorption process had no effect on PBDEs. The selectivity can be explained based on dispersive electron interaction affected by sorbate planarity and steric effects and presence of electrostatic forces.
Within each of the studied homologue groups, the volatility and reduction after SPD of the individual congeners is linearly dependent on the number of chlorine or bromine substitutions and ortho-substitution. The QSPRs were combined with process parameters to establish decontamination models for each homologue group of POPs. High decontamination efficiency (> 90 %) can be obtained by choice of favorable process conditions giving residual levels considerable below MPLs in feed and food.
AC and SPD did not have any negative effects on fish oil oxidation level. Oxidative stability of the oil after SPD was affected both negative and positive depending on processing conditions. SPD did not affect the level of polyunsaturated fatty acids (PUFA) nor induce geometrical isomerization.
Some co-evaporation and loss of vitamins, cholesterol and unsaponifiables can not be avoided during SPD. The retention level will depend on the applied process conditions and the concentration ratio and difference in vapor pressure between free and ester forms of the respective compounds. A high retention level (>80 %) of volatile nutrients after SPD could be obtained by choice of process conditions giving residual WHO-TEQ-levels in accordance with present feed and food legislations and the voluntary industrial monograph of GOED
The results from this project were included in a doctoral thesis. The following is an abstract of the thesis:
Persistent organic pollutants (POPs) are fat soluble chemical substances that persist in the environment and bioaccumulate in the food chain. Through long-range environmental transportation by air, water and migratory species they are transferred to new locations distant from the source of release and might cause adverse effects to human health and to the environment. POPs comprise pesticides, industrial chemicals and unwanted by-products. The European Commission has implemented food and feed legislations concerning maximum permitted levels (MPLs) of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), dioxin-like polychlorinated biphenyls (DLPCBs), polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs). Fish and consequently fishmeal and fish oil has been identified as one of the most important contributors to the level of dioxins and DL-PCBs in food and feed products. Fish caught in some of the North-European fishing areas contain high dioxin and PCB levels resulting in fishmeal and oil with WHO-PCDD/F-PCB-TEQ levels above the maximum permitted. To meet the new industrial and socialeconomic challenges there is a need for development of cost-effective decontamination technologies.
Efficiency and limitations of alternative decontamination technologies to reduce the level of PCDD/Fs, DL-PCBs and polybrominated diphenyl ether flame retardants (PBDEs) in fishmeal (i.e., mechanical fat separation, organic solvent extraction and oil leaching) and fish oil (i.e., activated carbon (AC) adsorption and short-path distillation (SPD)) have been studied in this thesis. Factorial design experiments, response surface methodology and quantitative structure property relationships (QSPRs) have been utilized to model and optimize the fish oil decontamination alternatives. The trapping mechanisms for non- and mono-ortho PCBs on AC have been studied by use of molecular dynamics simulations.
Optimization of the existing mechanical fat separation steps in the fishmeal process is expected to be the most cost-effective way to reduce the POPs content. However, the obtainable effects are limited (estimated to maximum 20–30 %) and have to be combined with organic solvent extraction if high decontamination rates are needed. The feasible use of a new oil leaching process has been studied and found to give effects comparable to hexane and isopropanol extraction of fishmeal (i.e., > 75 %).
AC adsorption of PCDD/Fs is highly effective with obtainable WHO-TEQ-reduction of 99 %. Adsorption of DL-PCBs is less effective and dependent on orthosubstitution, i.e., non-ortho-PCBs are adsorbed more effectively than mono-ortho- PCBs, with maximum obtained levels of 87 % and 21 %, respectively. Compliance with present feed and food WHO-PCDD/F-PCB-TEQ legislations in fish oil can be achieved based on AC adsorption. The adsorption process had no effect on PBDEs. The selectivity can be explained based on dispersive electron interaction affected by sorbate planarity and steric effects and presence of electrostatic forces.
Within each of the studied homologue groups, the volatility and reduction after SPD of the individual congeners is linearly dependent on the number of chlorine or bromine substitutions and ortho-substitution. The QSPRs were combined with process parameters to establish decontamination models for each homologue group of POPs. High decontamination efficiency (> 90 %) can be obtained by choice of favorable process conditions giving residual levels considerable below MPLs in feed and food.
AC and SPD did not have any negative effects on fish oil oxidation level. Oxidative stability of the oil after SPD was affected both negative and positive depending on processing conditions. SPD did not affect the level of polyunsaturated fatty acids (PUFA) nor induce geometrical isomerization.
Some co-evaporation and loss of vitamins, cholesterol and unsaponifiables can not be avoided during SPD. The retention level will depend on the applied process conditions and the concentration ratio and difference in vapor pressure between free and ester forms of the respective compounds. A high retention level (>80 %) of volatile nutrients after SPD could be obtained by choice of process conditions giving residual WHO-TEQ-levels in accordance with present feed and food legislations and the voluntary industrial monograph of GOED
The doctoral thesis is published by the University of Bergen and is available at BORA: http://hdl.handle.net/1956/5129
In Norwegian
Populærvitenskapelig framstilling
Fjerning av miljøgifter i fiskeolje er tidlig i prosjektet undersøkt ved bruk av aktivt kull adsorpsjon. Prosessbetingelser som påvirker renseeffekten er studert og det er etablert modeller for reduksjon av miljøgiftene. Aktivt kull fjerner effektivt dioksiner, men i mindre grad PCB. I tillegg er det observerte store forskjeller i adsorpsjon av PCB avhengig av fravær eller tilstedeværelse av Cl-substituering i ortho-posisjon. Denne forskjellen er studert nærmere ved bruk av molekylære simuleringsmodeller for absorbsjon av PCB til aktivt kull i samarbeid med prof. Kvamme sin gruppe på Institutt for fysikk og teknologi, Universitetet i Bergen. En molekylærdynamisk modell for slik simulering er utviklet, men modellen har ikke greid å bekrefte de funn som er gjort i eksperimentelle studier. Årsaken til dette ligger trolig bl.a. i den valgte oppbygging av simuleringsmodellen for aktivt kull med tildeling av alternerende ladning på C-atomer. De grunnleggende utfordringer med absorbsjonsmodellen er imidlertid løst og kan videreføres i nye studier. Resultater fremkommet i prosjektet er skrevet sammen til en PhD thesis som ble innlevert mars 2011. I avhandlingen er det foretatt en oppsummering av kjent teknologi for fjerning av miljøgifter i fiskeolje og fiskemel og en sammenfatning av 5 vitenskapelige artikler publisert under prosjektet.
In Norwegian
Populærvitenskapelig framstilling
Fjerning av miljøgifter i fiskeolje er tidlig i prosjektet undersøkt ved bruk av aktivt kull adsorpsjon. Prosessbetingelser som påvirker renseeffekten er studert og det er etablert modeller for reduksjon av miljøgiftene. Aktivt kull fjerner effektivt dioksiner, men i mindre grad PCB. I tillegg er det observerte store forskjeller i adsorpsjon av PCB avhengig av fravær eller tilstedeværelse av Cl-substituering i ortho-posisjon. Denne forskjellen er studert nærmere ved bruk av molekylære simuleringsmodeller for absorbsjon av PCB til aktivt kull i samarbeid med prof. Kvamme sin gruppe på Institutt for fysikk og teknologi, Universitetet i Bergen. En molekylærdynamisk modell for slik simulering er utviklet, men modellen har ikke greid å bekrefte de funn som er gjort i eksperimentelle studier. Årsaken til dette ligger trolig bl.a. i den valgte oppbygging av simuleringsmodellen for aktivt kull med tildeling av alternerende ladning på C-atomer. De grunnleggende utfordringer med absorbsjonsmodellen er imidlertid løst og kan videreføres i nye studier. Resultater fremkommet i prosjektet er skrevet sammen til en PhD thesis som ble innlevert mars 2011. I avhandlingen er det foretatt en oppsummering av kjent teknologi for fjerning av miljøgifter i fiskeolje og fiskemel og en sammenfatning av 5 vitenskapelige artikler publisert under prosjektet.
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Faktaark: Fjerning av persistente organiske miljøgifter i fiskemel og fiskeolje
Forskningsrådet. 2012. Av Åge Oterhals (Nofima)
Background
Fishmeal and fish oil are the most heavily contaminated ingredients in feed production, with products of European fish stocks more heavily contaminated than those from South Pacific stocks. The fish stocks of concern in the north European industry are sprat and herring from the Baltic Sea, and herring, sprat, sand eel and blue whiting in the North Sea. The differences in dioxin and PCB levels reflect the general pollution level in the respective fishing areas and will disfavour the North European fishmeal and oil producers in the world market.
Fishmeal and fish oil are the most heavily contaminated ingredients in feed production, with products of European fish stocks more heavily contaminated than those from South Pacific stocks. The fish stocks of concern in the north European industry are sprat and herring from the Baltic Sea, and herring, sprat, sand eel and blue whiting in the North Sea. The differences in dioxin and PCB levels reflect the general pollution level in the respective fishing areas and will disfavour the North European fishmeal and oil producers in the world market.
The legislation levels were revised in November 2005 to include dioxin-like PCBs. Consideration will be given by 31 December 2008 to significantly reduce the maximum levels. The new levels shall be determined based on the technical possibilities of the most effective, economical viable decontamination procedure. To improve and reinforce the competitiveness of the European industry there is a need for development of new and cost effective decontamination solutions.
Fishmeal is an important ingredient in fish feed and can only to a limited extent be replaced by vegetable proteins without a reduction in feed efficiency and growth. The fatty acid composition in the flesh from farmed fish will also reflect the feed composition and inclusion of low dioxin vegetable oil will significantly reduce the level of long chain n-3 fatty acids.
Objectives
To develop a new oil extraction process to reduce the persistent organic pollutants level in fishmeal. The reseach will aim to identity optimal processing conditions with respect to both decontamination efficiency and preservation of fishmeal and oil quality. The new oil extraction process is expected to have several advantages compared to a standard hexane extraction process. This will include the possibility of easy integration in an existing fishmeal processing line, use of a safe and non-flammable extraction medium and lower investment and operation costs.
Expected project impact
The results should reduce the POPs content in fishmeal without loss of protein quality. Additionally, the project will identify optimal conditions for decontamination of the oil used in the process.
The results should reduce the POPs content in fishmeal without loss of protein quality. Additionally, the project will identify optimal conditions for decontamination of the oil used in the process.
Project design and implementation
The research activity has been performed at the Norwegian Institute of Food, Fisheries and Aquaculture Research (Nofima) in Bergen under the supervision of Prof. Bjørn Kvamme at the University of Bergen, Department of Physics and Technology, and Prof. Ragnar Nortvedt, Department of Biology as a co-supervisor. Collaboration with NIFES and Institute for Environmental Studies, VU University, Amsterdam has been established on the analysis of persistent organic pollutants (POPs). Some POPs analyses have also been performed at Eurofins WEJ Contaminants GmbH, Germany. Quality assessments and analyses of minor components in fish oil and fishmeal have been performed at NIFES and Nofima BioLab in Bergen (both laboratories are accredited according to ISO 17025). Experimental work on short-path distillation was performed in the pilot plant facility at UIC GmbH (Alzenau, Germany). All other process optimization studies have been performed at the laboratory and pilot plant facilities at Nofima in Bergen. This knowledge-building project with user involvement (KMB) has received financial support from Pronova BioPharma (Sandefjord, Norway), Egersund Sildoljefabrikk (Egersund, Norway) and Marine Harvest (Bergen, Norway).
Persistent organic pollutants (POPs) are fat soluble chemical substances that persist in the environment and bio-accumulate in the food chain. Through long-range environmental transportation by air, water and migratory species they are transferred to new locations distant from the source of release and might cause adverse effects to human health and to the environment. POPs comprise pesticides, industrial chemicals and unwanted by-products. The European Commission has implemented food and feed legislations concerning maximum permitted levels (MPLs) of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), dioxin-like polychlorinated biphenyls (DL-PCBs), polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs). Fish and consequently fishmeal and fish oil has been identified as one of the most important contributors to the level of dioxins and DL-PCBs in food and feed products. Fish caught in some of the North-European fishing areas contain high dioxin and PCB levels resulting in fishmeal and oil with WHO-PCDD/F-PCB-TEQ levels above the maximum permitted. To meet the new industrial and social-economic challenges there is a need for development of cost-effective decontamination technologies.
Medieomtale
Matolje kan erstatte løsemidler
nofima.no