Removal of dioxin’s and PCB’s from fishmeal and fishoil

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

2. 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. 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. 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. FF SKAGEN Klaus H. Kristoffersen November 2007 Exposure pathways of POP 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. 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. FF SKAGEN Klaus H. Kristoffersen November 2007 Dioxin Compounds • 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. 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. Congener Congener WHO-TEF WHO-TEF PCDDs2,3,7,8-TCDD1,2,3,7,8-PeCDD1,2,3,4,7,8-HxCDD1,2,3,6,7,8-HxCDD1,2,3,7,8,9-HxCDD1,2,3,4,6,7,8-HpCDDOCDD Non-ortho-PCBs3,3’,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) 110.10.10.10.010.0001 0.00010.00010.10.01 Mono-ortho-PCBs2,3,3’,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) 0.00010.00050.00010.00010.00050.00050.000010.0001 PCDFs2,3,7,8-TCDF1,2,3,7,8-PeCDF2,3,4,7,8-PeCDF1,2,3,4,7,8-HxCDF1,2,3,6,7,8-HxCDF1,2,3,7,8,9-HxCDF2,3,4,6,7,8-HxCDF1,2,3,4,6,7,8-HpCDF1,2,3,4,7,8,9-HpCDFOCDF 0.10.050.50.10.10.10.10.010.010.0001 FF SKAGEN Klaus H. Kristoffersen November 2007 Toxic Equivalent Factors

12. 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) Action level

13. 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. FF SKAGEN Klaus H. Kristoffersen November 2007 Upcomming ! 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. 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. 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. 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. 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. FF SKAGEN Klaus H. Kristoffersen November 2007 • Thanks for your attention!