18- Belloso Dioxinas y Furanos

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


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


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.


STRONG REGULATIONS


STRONG REGULATIONS

ADEQUATEMONITORING


STRONG REGULATIONS

ADEQUATEMONITORING

TOUGHENFORCEMENT


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

18- Belloso Dioxinas y Furanos

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