dioxins & pcbs concerns - alsglobal.es · number of reported 2,3,7,8 - pcdd/f or dioxin-like...
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RIGHT S O L U T I O N S | RIGHT PARTNER
Dioxins & PCBs concerns
Properties, Sources and Formation
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Program
2
• Introduction to dioxins and PCBs
• Sources and formation
• Fate in environmental media
• Exposure pathways
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Dioxins – What are they ?
3
• “Dioxins” are a group of highly toxic, closely related compounds which
exhibit similar chemical and biological characteristics.
• Polychlorinated dibenzo-p-dioxins (PCDDs) and Polychlorinated
dibenzofurans (PCDFs) are generally grouped together as “Dioxins”.
There are 210 of these compounds.
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Dioxins – What are they ?
4
• 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) is the dioxin congener with the highest
acute toxicity. It is considered the most toxic man-made substance and the fifth most
toxic naturally occurring compound known to man.
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Polychlorinated biphenyls (PCBs)
5
• Polychlorinated biphenyls (PCBs) are a complex group of compounds,
some of which show dioxin-like toxic effects. There are 209 PCB
congeners.
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Polychlorinated biphenyls (PCBs)
6
Additives in oils in electrical equipment, hydraulic
machinery
Used for applications where chemical stability has been
required for safety, operation or durability (waxes, inks,
paints, adhesives, plasticizers, joint glues, etc. )
• Polychlorinated biphenyls (PCBs) were used for different
applications, taking advantage from their properties
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PCDD/F and PCBs possible congeners
7
Chlorine substitution
Mono 2 - - 4 - - 3 -
Di 10 - - 16 - - 12 -
Tri 14 - - 28 - - 24 -
Tetra - 22 1 - 38 1 40 2
Penta - 14 1 - 28 2 41 5
Hexa - 10 3 - 16 4 38 4
Hepta - 2 1 - 4 2 23 1
Octa - 1 1 - 1 1 12 -
Nona - - - - - - 3 -
Deca - - - - - - 1 -
Total 26 49 7 48 87 10 197 12
Total PCDD/F and PCBs
PCDFs
135
Total number of PCBs (209)
Number of reported 2,3,7,8 - PCDD/F or dioxin-like PCBs in homologue group
Total number of PCDDs and PCDFs (210)
209
PCB
Total number of non-reported isomers in homologue group
Total number of determinated isomers in homologue group
PCDDs
75
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Properties of Dioxins/PCBs
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• High Toxicity
• High persistence
– difficult degradation
• Bioaccumulation
• Ubiquity
– long range atmospheric transport and deposition
Persistent Organic Pollutants
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A look on 2378 TCDD
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Name 2,3,7,8-tetrachlorodibenzo-p-dioxin
Formula C12H4Cl4O2
Molecular weight 321,98
Melting point 305°C
Water solubility 20 ng/L at 22°C
Log Kow 6,80 at 25°C
Cl
Cl
Cl
Cl
2,3,7,8-Tetrachlorodibenzo-p-dioxin
O
O
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10
Global mobility of POPs
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Dioxins – Why are they of concern ?
11
• Dioxins are highly fat soluble, difficult to metabolise and
tend to accumulate in the fatty tissues of food-producing
animals.
• This leads to bioaccumulation in the food chain,
increasing human exposure levels.
• Dioxins have been found in meat, dairy and fish products
and also in human breast milk.
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Dioxins – Why are they of concern ?
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• Dioxin and related compounds bind to aryl hydrocarbon (Ah)
receptor proteins of cells, causing a toxic response.
• TCDD is classified by IARC as carcinogenic to humans
• Adverse effect to dioxin acute exposure is chloracne
• Acute exposure may cause nausea, vomiting, diarrhoea,
hepatic damages and neurological effects.
• Chronic exposure to dioxins may also cause liver disease,
alterations of thyroid function, impared immune function,
cardiovascular disease, decreased performance in tests of
learning and intelligence, etc.
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Most toxic compounds
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• In total, 7 PCDDs, 10 PCDFs and 12 PCBs exhibit this form of toxicity to
varying degrees. These compounds are assigned “Toxic Equivalence Factors”
(TEFs) based on their toxicity relative to 2,3,7,8-TCDD.
Chlorine substitution
Mono 2 - - 4 - - 3 -
Di 10 - - 16 - - 12 -
Tri 14 - - 28 - - 24 -
Tetra - 22 1 - 38 1 40 2
Penta - 14 1 - 28 2 41 5
Hexa - 10 3 - 16 4 38 4
Hepta - 2 1 - 4 2 23 1
Octa - 1 1 - 1 1 12 -
Nona - - - - - - 3 -
Deca - - - - - - 1 -
Total 26 49 7 48 87 10 197 12
Total PCDD/F and PCBs
Total number of PCBs (209)
Number of reported 2,3,7,8 - PCDD/F or dioxin-like PCBs in homologous group
Total number of PCDDs and PCDFs (210)
209
PCB
Total number of non-reported isomers in homologous group
Total number of determinated isomers in homologous group
PCDDs
75
PCDFs
135
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TEF approach
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• Toxicity Equivalent Factors
• Based on acute toxicity values from in vitro studies
• Based on the comparison of toxicity of specific PCDD/F or PCBs to the most toxic
• The most toxic has factor 1 : TCDD
• Administrative tool for conversion of all data in one number
Total TEQ = Ccongener X TEFcongener
Cl
Cl
Cl
Cl
2,3,7,8-Tetrachlorodibenzo-p-dioxin
O
O
Toxicity Equivalence of
=
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WHO and International TEF
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Congener WHO-TEF
I-TEF (1988) 1997 2005
2,3,7,8-TCDD 1 1 1
1,2,3,7,8-PeCDD 1 1 0,5
1,2,3,4,7,8-HxCDD 0,1 0,1 0,1
1,2,3,6,7,8-HxCDD 0,1 0,1 0,1
1,2,3,7,8,9-HxCDD 0,1 0,1 0,1
1,2,3,4,6,7,8-HpCDD 0,01 0,01 0,01
OCDD 0,0001 0,0003 0,001
2,3,7,8-TCDF 0,1 0,1 0,1
1,2,3,7,8-PeCDF 0,05 0,03 0,05
2,3,4,7,8-PeCDF 0,5 0,3 0,5
1,2,3,4,7,8-HxCDF 0,1 0,1 0,1
1,2,3,6,7,8-HxCDF 0,1 0,1 0,1
1,2,3,7,8,9-HxCDF 0,1 0,1 0,1
2,3,4,6,7,8-HxCDF 0,1 0,1 0,1
1,2,3,4,6,7,8-HpCDF 0,01 0,01 0,01
1,2,3,4,7,8,9-HpCDF 0,01 0,01 0,01
OCDF 0,0001 0,0003 0,001
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Program
• Sources and formation
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Sources and Formation of Dioxins
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Dioxins are not produced commercially but exist as byproducts of combustion
and certain industrial processes.
• Primary Sources (industrial or combustion processes)
Stationery Sources Diffuse Sources
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Sources
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• Secondary Sources (sewage
sludge / biosludge,
compost, contaminated
areas)
– In the past
• Chemical industry
• Pulp and paper industry
– Nowadays
• Thermal processes
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Examples of PCDD/F sources
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Manufacturing, Industry Pentachlorophenol
Paper and cellulose
Printers ´colours from recycled papers
Exhaust gas Fly ash Dry cleaning operations
Wastewater
Distillation residues
Copper extraction Copper slag material
Incomplete combustion
Air
Playgrounds Wood preservative
Treated sludge
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Secondary Sources
20
• Reservoir of PCDD/F with possible release to the
environment
– PCP treated wood
– PCB from transformers, sewage sludge
– Landfills and waste dumps
– Contaminated sites
– Contaminated products such as 2,4,5-T
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Process of formation during incineration
21
• PCDD/F are already present in the
incoming waste
• PCDD/F are formed from
chlorinated precursors
– PCB, PCP, ChlBz
• PCDD/F are formed via de novo
synthesis
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Program
• Fate in environmental media
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Environmental Fate
• Dioxins and Furans, PCBs are found in all media: air,
water, soil, sediments, plants, animals, food.
• Hardly identified in water
• Strong affinity for soil and sediment
• High potential of bioaccumulate in plants, animals and fat
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Fate: Aquatic compartment - Sediment
• Dioxins are resistant to
oxidation and hydrolysis
– low efficiciency of these
processes
• Photodegradation and
microbial transformations
are the most important
routes
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Fate: Soil compartment
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• Absorption on organic carbon in soil
- Immobilisation
• Mobilization if
- Presence of lipophilic solvents
- Erosion, rains
• Soil does not play the main role in environmental
contamination and population exposition, but is an
excellent indicator of contamination
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Air compartment is the most significant for environmental distribution and fate
• Part of Dioxins in gazeous state
– Removal processes include
chemical and photochemical
degradation
• Part of Dioxins bound to
particles
– Transport range depends on ion
particle size
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PCDDs/Fs – Average/country in atmosphere I-TEQ fg/m3
27
Source: National dioxins program – Australia, May 2004
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Monitoring of dioxins in atmosphere
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Source: Dioxin in Danish air – NERI 2004
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Atmosphere - Time trends of PCDD/F - UK
29
Source: Trends in dioxins emissions (1990 – 1999), Partial Regulatory
Impact Assessment – Dioxins and Dioxin-like PCBs in the UK
Environment
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Atmosphere - Time trends of PCDD/F - CR
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Source: Emission of PCDD/F (gram/year) – Czech Republic – Holoubek et al.
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Trends in USA PCDD/F Emission 1987-2000
31
Source: U.S. EPA (Environmental Protection Agency). 2006. An inventory of sources and
environmental releases of dioxin-like compounds in the United States for the years
1987, 1995, and 2000. National Center for Environmental Assessment, Washington, DC;
EPA/600/P-03/002F
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Program
• Exposure pathways
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Exposure pathways
33
• In the past : Occupational exposures
– Chlorophenols production
– Chlorphenoxy herbicides
– Metal production and recycling
– Accidents
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Nowadays : Food chain contamination
– Foodstuffs from animal origin
– Other fatty foodstuffs
– Accidental contamination of food
34