Transcript
Dioxinas y Furanos:Dioxinas y Furanos:una realidaduna realidad
Lic. Claudio Belloso M. Sc.Lic. Claudio Belloso M. Sc.Universidad Católica ArgentinaUniversidad Católica Argentina
Biogroup, Centro de Investigación Científica y Biogroup, Centro de Investigación Científica y TecnológicaTecnológica
Septiembre 2011Septiembre 2011
OUTLINEOUTLINE
Dioxins, Furans:Dioxins, Furans:
A) historyA) history B) chemistryB) chemistry C) biologyC) biology D) EPA Method 23D) EPA Method 23 E) regulationsE) regulations
AIR EMISSIONS
CO2 + H2O
ACID GASES:HCI, HF, SO2
NOx
TOXIC METALS:Pb, Cd, Hg, As, Cr etc
NEW COMPOUNDSNEW COMPOUNDS::PCB’sPCB’sPCDDs (DIOXINS)PCDDs (DIOXINS)PCDFs (FURANS)PCDFs (FURANS)ETCETC
NANONANOPARTICLESPARTICLES
Agente NaranjaAgente Naranja
Herbicidas organoclorados: 2,4-D y 2,3,5-T Herbicidas organoclorados: 2,4-D y 2,3,5-T Contaminados con DIOXINAS y FURANOSContaminados con DIOXINAS y FURANOS
En 1970’ E.E.U.U. usa En 1970’ E.E.U.U. usa A.N.A.N. como deforestador en el como deforestador en el conflicto de Vietnam. Se dispersaron 72.000.000 L conflicto de Vietnam. Se dispersaron 72.000.000 L sobre 1.500.000 hasobre 1.500.000 ha
• Se destruyeron el 14 % de los bosquesSe destruyeron el 14 % de los bosques• Las Dioxinas pasaron a formar parte de las cadenas Las Dioxinas pasaron a formar parte de las cadenas
alimentariasalimentarias• Atención médica para 70.000 personasAtención médica para 70.000 personas• Graves defectos congénitos en hijos de expuestos Graves defectos congénitos en hijos de expuestos
(50.000)(50.000)• Leucemia linfocitaria crónica en militaresLeucemia linfocitaria crónica en militares
2,3,7,8-TCDD2,3,7,8-TCDD
Es 500 veces más tóxico que la Es 500 veces más tóxico que la estricninaestricnina
10.000 veces más tóxico que el 10.000 veces más tóxico que el cianurocianuro
Accidentes con Accidentes con DioxinasDioxinas
1940- Cloracné en plantas industriales de Cl-fenoles y 1940- Cloracné en plantas industriales de Cl-fenoles y herbicidasherbicidas
1957- Se detectó 2,3,7,8-TCDD en herbicidas1957- Se detectó 2,3,7,8-TCDD en herbicidas
1970’- Malformaciones y abortos en Vietnam1970’- Malformaciones y abortos en Vietnam
1976- Escape de 2,4,5-T, afecto a 17.000 personas Seveso1976- Escape de 2,4,5-T, afecto a 17.000 personas Seveso
1977- PCDFs y PCDDs por incineradoras (PCBs) Holanda1977- PCDFs y PCDDs por incineradoras (PCBs) Holanda
Viktor YushchenkoViktor Yushchenko(Before and After)(Before and After)
Major Past Sources of Major Past Sources of Dioxins Dioxins (20th Century Problem – (20th Century Problem – Addressed by Regulations)Addressed by Regulations)
Chloralkali FacilitiesChloralkali Facilities Chlorinated herbicide and biocide Chlorinated herbicide and biocide
ProductionProduction Municipal, Medical, and Hazardous Municipal, Medical, and Hazardous
Waste IncinerationWaste Incineration Chlorine Bleaching of Paper and Pulp Chlorine Bleaching of Paper and Pulp
ProductsProducts
Recently Identified Recently Identified SourcesSources(Minor Compared to (Minor Compared to those in 20th Century)those in 20th Century) Open Burning of Household WasteOpen Burning of Household Waste Uncontrolled CombustionUncontrolled Combustion
– Forest Fires and VolcanoesForest Fires and Volcanoes Metal RefiningMetal Refining Reservoirs – contaminated soils Reservoirs – contaminated soils
and sediments from past releasesand sediments from past releases
IncineraciónIncineración
Las dioxinas y furanos se forman Las dioxinas y furanos se forman por reacción entre compuestos por reacción entre compuestos fenólicos producidos por la fenólicos producidos por la combustión incompleta de la lignina combustión incompleta de la lignina presente en los derivados de la presente en los derivados de la madera (Papel, cartón, etc.) y el HCl madera (Papel, cartón, etc.) y el HCl producido principalmente en la producido principalmente en la combustión de plásticos que combustión de plásticos que contienen cloro, como el PVC.contienen cloro, como el PVC.
1977 -’85 Engineers argue that 1977 -’85 Engineers argue that dioxin problem solved by running dioxin problem solved by running incinerator furnaces at high incinerator furnaces at high temps. temps. They were wrongThey were wrong
1985 - Ozvacic et al. find dioxins 1985 - Ozvacic et al. find dioxins formed formed after after the furnace.the furnace.
Dioxin Emissions from Dioxin Emissions from Tire BurningTire Burning
How do Dioxins Move How do Dioxins Move in the Environmentin the Environment If emitted into air, undergo If emitted into air, undergo
atmospheric transport and atmospheric transport and deposition on land or waterdeposition on land or water
If emitted into water, bind to If emitted into water, bind to sedimentsediment
Bioaccumulate up the food chainBioaccumulate up the food chain Resistance to physical, chemical, Resistance to physical, chemical,
and biological degradationand biological degradation
Dioxins’ Effects in Dioxins’ Effects in PeoplePeople
Cardiovascular Cardiovascular DiseaseDisease
DiabetesDiabetes CancerCancer Porphyria Porphyria EndometriosisEndometriosis Decreased Decreased
TestosteroneTestosterone ChloracneChloracne Biochemical Biochemical
– Enzyme InductionEnzyme Induction– Receptor ChangesReceptor Changes
DevelopmentalDevelopmental– Thyroid StatusThyroid Status– Immune StatusImmune Status– NeurobehaviorNeurobehavior– CognitionCognition– DentitionDentition– Reproductive Reproductive
EffectsEffects– Altered Sex Altered Sex
RatioRatio– Delayed Breast Delayed Breast
DevelopmentDevelopment
Human CancerHuman Cancer
Dioxin is a human carcinogenDioxin is a human carcinogen Exposure to TCDD increases the Exposure to TCDD increases the
risk of cancer at multiple sites, risk of cancer at multiple sites, including lung CAincluding lung CA
Overall increased risk in Overall increased risk in occupational/accident occupational/accident studies is studies is 40-100%40-100%
Human Non-cancer Human Non-cancer EffectsEffects
Good evidence !!!Good evidence !!!
ChloracneChloracneAcute high level or chronicAcute high level or chronicPersists 10 yearsPersists 10 years
Liver enzyme changesLiver enzyme changes
Reproductive hormoneReproductive hormone
changeschangesDecreased testosteroneDecreased testosteroneDecreased libidoDecreased libido
Special PopulationsSpecial Populations
ChildrenChildren may be at greater risk for illness may be at greater risk for illness related to environmental contaminantsrelated to environmental contaminants
Increased outdoor playIncreased outdoor playIncreased hand-to-mouth activitiesIncreased hand-to-mouth activitiesShorter stature - dust, soil, vaporsShorter stature - dust, soil, vaporsHigher intake rate, lower body weight = Higher intake rate, lower body weight = greater dosegreater dose
U.S. Adult Average Daily Intake of U.S. Adult Average Daily Intake of CDDs/CDFs/ Dioxin - Like PCBsCDDs/CDFs/ Dioxin - Like PCBs
21%21%
16%16%
19%19%
14%14%
5%5%
4%4%
7%7%
6%6%
1%1%
Soil ingestionSoil ingestion
Soil dermal contactSoil dermal contact
FreshwaterFreshwater fish andfish andshellfishshellfish
Marine fish and shellfishMarine fish and shellfish
InhalationInhalation
MilkMilk
DairyDairy
EggsEggs
Beef Beef
PorkPork
PoultryPoultry
Other meatsOther meats
Vegetable fatVegetable fat
DIOXINS & FURANSDIOXINS & FURANSThe chemical structuresThe chemical structures
Dioxin like compounds Dioxin like compounds (DLC)(DLC)
3 families3 familiesPCBsPCBsPCDFs (furans)PCDFs (furans)PCDDs (dioxins)PCDDs (dioxins)
BENZENEBENZENE
BIPHENYLBIPHENYL
One of 209 PCBSOne of 209 PCBS
One of 209 PCBSOne of 209 PCBS
PCBs = a family of compounds in which chlorine atoms are substituted for hydrogen
at 1 to 10 positions of BIPHENYL .
Polychlorinated biphenyls
Furans (or PCDFs) have an oxygen atom forminga five membered ring (the furan) between the two benzenes of PCBs. There are 135 furans.
Furans (or PCDFs) have an oxygen atom forminga five membered ring (the furan) between the two benzenes of PCBs. There are 135 furans.
Furans (or PCDFs)
2,3,7,8-TETRACHLORODIBENZO-P-DIOXIN
Dioxins (or PCDDs) have two oxygen atoms linking the two benzene rings, forming the
dioxin ring. There are 75 dioxins.
2,3,7,8-TETRACHLORODIBENZO-P-DIOXIN
Dioxins (or PCDDs) have two oxygen atoms linking the two benzene rings, forming the
dioxin ring. There are 75 dioxins.
Dioxins (or PCDDs)
There are 17 extremely toxic dioxins and furans. They have chlorine at the 2,3,7 and 8 positions: 7 Dioxins 10 Furans
TOXICITY EQUIVALENTS TOXICITY EQUIVALENTS FACTORS (TEFs) FOR DIOXIN FACTORS (TEFs) FOR DIOXIN AND FURANAND FURAN
The biologyThe biology
DioxinDioxinOrOr
Dioxin-likeDioxin-likeCompoundCompound
(DLC)(DLC)
CELLCELL
Ah receptorAh receptor
ArntArntproteinprotein
ComplexComplexWith With
Changed shapeChanged shape
DNADNA
NUCLEUSNUCLEUS
Dioxins Dioxins do not causedo not cause
mutationsmutationsButBut
switch on genesswitch on genes
Switching on a geneSwitching on a gene means producing ameans producing a
specific messenger RNAspecific messenger RNAwhich codes for awhich codes for aspecific proteinspecific protein
messenger RNAmessenger RNAtravels to thetravels to the
ribosomeribosome(= protein(= proteinfactory)factory)
In the ribosomeIn the ribosomethe messenger RNAthe messenger RNA
directs thedirects theproduction of aproduction of aspecific proteinspecific protein
NewNewproteinprotein
NewNewproteinprotein
New protein modifiesNew protein modifies the activity of the cellthe activity of the cell
Two remarkable things Two remarkable things about the about the
1) After 30 years of research scientists do not know 1) After 30 years of research scientists do not know what it is in the cell for. They have not identified its what it is in the cell for. They have not identified its normal ligand or function.normal ligand or function.
??
2) The Ah receptor appears in evolution at the same 2) The Ah receptor appears in evolution at the same time as the backbone appears in fish. Every species time as the backbone appears in fish. Every species above invertebrates has the Ah receptor.above invertebrates has the Ah receptor.
Ah ReceptorAh Receptor
Structure-activity relationshipsStructure-activity relationships
(2)
(1)
0
1
2
3
4
log
ED
50
fo
r T
hym
ic A
tro
ph
y in
Ra
ts
(9) (8) (7) (6) (5) (4)
log Kd for AHR binding
y = 1.119x + 8.374 r 2 = 0.642
The toxic potencies of many halogenated aromatic hydrocarbons The toxic potencies of many halogenated aromatic hydrocarbons are related to their AHR-binding affinities.are related to their AHR-binding affinities.
Data from Safe, S. (1990) Data from Safe, S. (1990) CRC Crit. Rev. Toxicol.CRC Crit. Rev. Toxicol. 2121: 51-88: 51-88. .
Sampling and analytic Sampling and analytic method for dioxin and method for dioxin and furan parameterfuran parameter
For the purpose of these Regulations, emission For the purpose of these Regulations, emission of dioxin and furan into the air shall be sampled of dioxin and furan into the air shall be sampled in accordance with the United States in accordance with the United States Environmental Protection Agency Environmental Protection Agency USEPA USEPA Method 23Method 23 and analysed in accordance with and analysed in accordance with the the USEPA Method 8290 USEPA Method 8290 or in accordance with or in accordance with any other sampling and analytic methods as any other sampling and analytic methods as approved by the Director General.approved by the Director General.
EPA Method 23EPA Method 23
Samples are collected Samples are collected isokinetically using a modified isokinetically using a modified USEPA Method 5 train which USEPA Method 5 train which consists of a glass fiber filter consists of a glass fiber filter containing no organic binders, containing no organic binders, XAD-2 resin trap, and a series of XAD-2 resin trap, and a series of impingersimpingers
XAD-2XAD-2RESINRESIN
HORIZONTAL CONDENSERHORIZONTAL CONDENSER
KNOCKOUT IMPINGERKNOCKOUT IMPINGER
EPA Method 23EPA Method 23
The sampling train is rinsed with The sampling train is rinsed with acetone and/or methylene acetone and/or methylene chloride followed by toluene. chloride followed by toluene.
Acetone and methylene chloride Acetone and methylene chloride rinses can be combined but the rinses can be combined but the toluene rinses need to be kept toluene rinses need to be kept separately.separately.
ENVIRONMENTAL QUALITY ENVIRONMENTAL QUALITY (DIOXIN AND FURAN) (DIOXIN AND FURAN) REGULATIONS 2004REGULATIONS 2004
Permissible air emission limit for new Permissible air emission limit for new facilities.facilities.
Concentration limit for air emission of dioxin Concentration limit for air emission of dioxin and furan for new facilities shall not exceed and furan for new facilities shall not exceed 0.1 0.1 ng/Nmng/Nm33 TEQ.TEQ.
1 ng = 1x101 ng = 1x10-9-9gg
EPA Method 23EPA Method 23
Analytical Methodology: GC/MS (high resolution) by Method GC/MS (high resolution) by Method 2323
ANALISIS DE DIOXINAS Y ANALISIS DE DIOXINAS Y FURANOS EN EMISIONES FURANOS EN EMISIONES GASEOSASGASEOSAS
El Area de Calidad de Aire y Emisiones Gaseosas de Biogroup, ha desarrollado y puesto a punto el método USEPA 23 de análisis de dioxinas y furanos en emisiones de chimeneas.
Convenio Marco de Colaboración
Biogroup, Argentina.Biogroup, Argentina. Keika Ventures LLC, Carolina del
Norte, Estados Unidos.
YOU NEED THREE THINGS TO PROTECT THE PUBLIC FROM TOXIC EMISSIONS.
YOU NEED THREE THINGS TO PROTECT THE PUBLIC FROM TOXIC EMISSIONS.
STRONG REGULATIONS
YOU NEED THREE THINGS TO PROTECT THE PUBLIC FROM TOXIC EMISSIONS.
STRONG REGULATIONS
ADEQUATEMONITORING
YOU NEED THREE THINGS TO PROTECT THE PUBLIC FROM TOXIC EMISSIONS.
STRONG REGULATIONS
ADEQUATEMONITORING
TOUGHENFORCEMENT
YOU NEED THREE THINGS TO PROTECT THE PUBLIC FROM TOXIC EMISSIONS.
STRONG REGULATIONS
ADEQUATEMONITORING
TOUGHENFORCEMENT
IF ANY LINK IS WEAK THE PUBLIC IS NOT PROTECTED
VietnaVietnamm (1962- (1962-1974)1974)
Argentina Argentina 20112011
GRACIAS POR SU GRACIAS POR SU ATENCIÓNATENCIÓN
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