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

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 ?

• What will the future bring regarding contaminants ?

• The situation at FF-of-Denmark, today!

• Conclusive remark


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 meansPOP’s potential to injure humans and other organism’s is high, even at low concentrationsPOP’s dissolved in fat, accumulate in fatty tissues of living organisms

A highly toxic chlorinated formualtion that isBio accumulated in the food chain


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

Humans

Inceration Process

Thermal Metal Process

Chlorine Process

Car Exhaust

Rain/Deposition

Plant/Field

Water/Soil

Unwantedby-products

Beef

Pork

Chicken

Vegetables

Fish


Exposure pathways of POP

Humans

Rain/Deposition

Plant/Field

Water/Soil

Transformator Oil

Capacitor Oil

Flame retardants

Cable

Manmade

Beef

Pork

Chicken

Vegetables

Fish


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?


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

• 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

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

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

Maximum levels of dioxins and sum of dioxin + dioxin-like PCB (ng WHO-TEQ/kg; 12% water)


Agenda

• Introduction

• What is Dioxin’s and PCB´s ?





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


Agenda

• Introduction

• What is Dioxin and PCB´s ?





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

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 %.


POP’s reduction process at FF

Degumming

Pre-Absorption

Absorption with active carbon

POP Stripping

AcidCrude Fish oil

Phospholipids,Trace metals,proteins

Dioxins

PCB’s, pesticides (POP’s)

Fish Oil


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

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