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

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

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

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

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

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

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

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?

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

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

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 1 1 0.1 0.1 0.1 0.01 0.0001 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 0.1 0.05 0.5 0.1 0.1 0.1 0.1 0.01 0.01 0.0001 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) 0.0001 0.0001 0.1 0.01 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) 0.0001 0.0005 0.0001 0.0001 0.0005 0.0005 0.00001 0.0001

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

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

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

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

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.

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 %.

FF SKAGEN Klaus H. Kristoffersen November 2007

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

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.

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