1. Removal of dioxin’s and PCB’s from fishmeal and fishoil
FF SKAGEN Klaus H. Kristoffersen November 2007
Removal of dioxin’s and PCB’s from fishmeal and fishoil
November 2007

2. Agenda Introduction What is Dioxin’s and PCB´s ?
FF SKAGEN Klaus H. Kristoffersen November 2007
Agenda
Introduction
What is Dioxin’s and PCB´s ?
What will the future bring regarding contaminants ?
The situation at FF-of-Denmark, today!
Conclusive remark

3. Agenda Introduction What is Dioxin’s and PCB´s ?
FF SKAGEN Klaus H. Kristoffersen November 2007
Agenda
Introduction
What is Dioxin’s and PCB´s ?
What will the future bring regarding contaminants ?
The situation at FF-of-Denmark, today!
Conclusive remark

4. Persistent Organic Pollutant -POP
FF SKAGEN Klaus H. Kristoffersen November 2007
Persistent Organic Pollutant -POP
POP’s belong to a group of Chemicals nominated as PTB compounds. Persistent, Toxic and liable to Bioaccumulation.
POP’s strongly resist break down by photolytic, chemical and biological means
POP’s potential to injure humans and other organism’s is high, even at low concentrations
POP’s dissolved in fat, accumulate in fatty tissues of living organisms
A highly toxic chlorinated formualtion that is
Bio accumulated in the food chain

5. FF SKAGEN Klaus H. Kristoffersen November 2007
Properties of POP’s
Slowly evaporation tend to make them globetrotting freely with a tendency of Polar accumulation due to the cold climate prevailing here
A highly chlorinated formulation serves as toxicant and adds superior persistency towards biological decomposition
They practically don’t dissolve in water, but are readily dissolved in fats, accumulating in the fatty tissue of living organisms, bio accumulating as they travel up the food chain

6. Exposure pathways of POP
FF SKAGEN Klaus H. Kristoffersen November 2007
Inceration Process
Thermal Metal Process
Chlorine Process
Car Exhaust
Beef
Pork
Chicken
Vegetables
Fish
Rain/Deposition
Plant/Field
Water/Soil
Unwanted
by-products
Humans

7. Exposure pathways of POP
FF SKAGEN Klaus H. Kristoffersen November 2007
Exposure pathways of POP
Transformator Oil
Capacitor Oil
Flame retardants
Cable
Beef
Pork
Chicken
Vegetables
Fish
Rain/Deposition
Plant/Field
Water/Soil
Manmade
Humans

8. Are all 210 compounds important?
Dioxin Compounds
FF SKAGEN Klaus H. Kristoffersen November 2007
Dioxins is not an individuals substance, but a group of 210 individuals components
75 PCDD’s
135 PCDF’s
Are all 210 compounds important?

9. FF SKAGEN Klaus H. Kristoffersen November 2007
PCB Compounds
PCB is not a single substance, but a group of 209 individuals components
PCB’s – 12 PCB’s were found to have dioxin –like properties

10. Toxicity definition of Dioxin/PCB
FF SKAGEN Klaus H. Kristoffersen November 2007
Toxicity definition of Dioxin/PCB
Studies performed on animals during the 80th and 90th revealed that the toxicity of the different congeners was differing a lot
TCDD – 2,3,7,8-tetrachlorodibenzo-p-dioxin became the reference as being considered the most potent of all PCCD/F’s and PCB’s
Toxicity of individual congeners was found to be directly related to the above TCDD molecular structure with the four chlorines positioned laterally, inducing extreme persistency
Based on a huge number of scientific evaluations, WHO developed a so-called TEF (TCDD or Toxic Equivalency Factor) ranking the congeners in order of magnitude

11. Toxic Equivalent Factors
FF SKAGEN Klaus H. Kristoffersen November 2007
Toxic Equivalent Factors
Congener
WHO-TEF
PCDDs 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-HxCDD 1,2,3,6,7,8-HxCDD 1,2,3,7,8,9-HxCDD 1,2,3,4,6,7,8-HpCDD OCDD
PCDFs 2,3,7,8-TCDF 1,2,3,7,8-PeCDF 2,3,4,7,8-PeCDF 1,2,3,4,7,8-HxCDF 1,2,3,6,7,8-HxCDF 1,2,3,7,8,9-HxCDF 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF OCDF
Congener
WHO-TEF
Non-ortho-PCBs 3,3’,4,4’-TCB (77) 3,4,4’,5-TCB (81) 3,3’,4,4’,5-PeCB (126) 3,3’,4,4’,5,5’-HxCB (169)
Mono-ortho-PCBs 2,3,3’,4,4’-PeCB (105) 2,3,4,4’,5-PeCB (114) 2,3’,4,4’,5-PeCB (118) 2’,3,4,4’,5-PeCB (123) 2,3,3’,4,4’,5-HxCB (156) 2,3,3’,4,4’,5’-HxCB (157) 2,3’,4,4’,5,5’-HxCB (167) 2,3,3’,4,4’,5,5’-HpCB (189)

12. EU regulation in force of Year 2007
FF SKAGEN Klaus H. Kristoffersen November 2007
EU regulation in force of Year 2007
Maximum levels of dioxins and sum of dioxin + dioxin-like PCB (ng WHO-TEQ/kg; 12% water)
Dioxin
DL-PCB
Sum
Fishoil
6,0 (5)
18,0 (14)
24,0
Fishmeal
1,25 (1)
3,25 (2,5)
4,5
Fishfeed
2,25 (1,75)
4,75 (3,5)
7,0
Action level

13. Agenda Introduction What is Dioxin’s and PCB´s ?
FF SKAGEN Klaus H. Kristoffersen November 2007
Agenda
Introduction
What is Dioxin’s and PCB´s ?
What will the future bring regarding contaminants ?
The situation at FF-of-Denmark, today!
Conclusive remark

14. Upcomming !
FF SKAGEN Klaus H. Kristoffersen November 2007
In the future will organochlorine pesticides be in focus in the fish meal- and oil industri
The species of main interest are Aldrin, Dieldrin, DDT, Endrin, Heptachlor, Chlordane, Hexachloro-benzene, Mirex and Toxaphene
Mostly these pesticides have been manufactured by purpose and specifically applied as insecticides, Hexachloro-benzene and Toxaphene also being present as industrial by-products
Manufacturing and application have ceased during the last decades in developed area’s of the world
Aldrin
Dieldrin
Heptachlor
Chlordane
Mirex
DDT
Hexachlor
Toxaphene
Endrin

15. Agenda Introduction What is Dioxin and PCB´s ?
FF SKAGEN Klaus H. Kristoffersen November 2007
Agenda
Introduction
What is Dioxin and PCB´s ?
What will the future bring regarding contaminants ?
The situation at FF-of-Denmark, today!
Conclusive remark

16. Status of oil/meal purifying at FF of Denmark 1#2
FF SKAGEN Klaus H. Kristoffersen November 2007
Status of oil/meal purifying at FF of Denmark 1#2
Purifying of the fishoil:
Step 1 is absorption with active carbon for removing af dioxins, tracemetals and gummings.
Step 2 is thin film deodorisering for removing of primary PCB’s (and other POP’s) and secondary reduction of FFA and peroxidvalues to zerovalues. The reduction of anisidinvalue is around 50 %, caused by decompostion to miner and more volatile molecules. These molecules is stripped away from the triglycerides together with the PCB’s, free fattyacids, peroxids and other radicals.

17. Status of oil/meal purifying at FF of Denmark 2#2
FF SKAGEN Klaus H. Kristoffersen November 2007
Status of oil/meal purifying at FF of Denmark 2#2
Purifying of the fishmeal (removing contaminants):
We are extracting the organic pollutants from the fish meal by an ”inline” cleaning proces.
This is an method, were we don’t use organic extraction solutions for the extraction. The principle is to extract the organic pollutants with a purified fishoil.
This method have proved to reduce the dioxin content. The method have a reductiondegree of 85 %.

18. FF SKAGEN Klaus H. Kristoffersen November 2007

19. POP’s reduction process at FF
FF SKAGEN Klaus H. Kristoffersen November 2007
POP’s reduction process at FF
Crude Fish oil
Acid
Degumming
Phospholipids,
Trace metals,
proteins
Pre-Absorption
Absorption with active carbon
Dioxins
POP Stripping
PCB’s, pesticides
(POP’s)
Fish Oil

20. FF SKAGEN Klaus H. Kristoffersen November 2007
Conclusive remark
By adjusting conditions of processing, a target degree of removal of not just FFA and PAH’s, but also POP’s can be reached.
Modern pesticides of organophosphate origin is claimed to decompose readily at processing temperatures above 150 oC and consequently should not be of any concern. Irrespective of the above, these compounds are believed to be efficiently removed at normal process conditions in Stripping as intact molecules or decomposed fractions thereof.
Use the fishoil-extraction technology to extract POP’s with a purified oil from fish meal.

21. Thanks for your attention!
FF SKAGEN Klaus H. Kristoffersen November 2007
Thanks for your attention!