Dioxins & IncinerationDioxins & Incineration

Dr Paul ConnettDr Paul ConnettProfessor Emeritus of ChemistryProfessor Emeritus of Chemistry

St Lawrence University, Canton, NYSt Lawrence University, Canton, NY

PaulPaul@@AmericanAmericanHealthHealthStudies.Studies.oorgrg

OUTLINEOUTLINE

Dioxins & incineration:Dioxins & incineration: A) historyA) history B) chemistryB) chemistry C) biologyC) biology D) health threatD) health threat

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

HistoryHistory 1960s, 1970s Most people hear of dioxins in relation 1960s, 1970s Most people hear of dioxins in relation

to use of Agent Orange in Vietnamto use of Agent Orange in Vietnam 1949 - 1976 dioxins produced in industrial accidents 1949 - 1976 dioxins produced in industrial accidents

in plants making 2,4,5 Trichlorophenol. Most famous in plants making 2,4,5 Trichlorophenol. Most famous Seveso, Italy in 1976.Seveso, Italy in 1976.

1977 dioxins found in trash incinerator emissions 1977 dioxins found in trash incinerator emissions (Olie et al)(Olie et al)

1977 -’85 Engineers argue that dioxin problem 1977 -’85 Engineers argue that dioxin problem solved by running incinerator furnaces at high solved by running incinerator furnaces at high temps. temps. They were wrongThey were wrong

1985 - Ozvacic et al. find dioxins formed 1985 - Ozvacic et al. find dioxins formed after after the the furnace.furnace.

Dioxin 1980s - 1990sDioxin 1980s - 1990s Biggest source of dioxin is from food, Biggest source of dioxin is from food,

particularly animal fat.particularly animal fat. Biggest source of dioxin entering food chains Biggest source of dioxin entering food chains

= combustion= combustion Medical, municipal and hazardous waste Medical, municipal and hazardous waste

incineration, backyard burning (PVC), Fires incineration, backyard burning (PVC), Fires (PVC), copper recycling (PVC), metal smelting(PVC), copper recycling (PVC), metal smelting

1990’s better dioxin control from 1990’s better dioxin control from incineration. Many plants retrofitted and incineration. Many plants retrofitted and older plants closed down.older plants closed down.

DIOXINSDIOXINSThe chemical structuresThe chemical structures

Dioxin like compounds Dioxin like compounds (DLC)(DLC) 3 families3 families PCBsPCBs PCDFs (furans)PCDFs (furans) PCDDs (dioxins)PCDDs (dioxins)

Benzene Benzene

CC

CCC

CH

H

HH

H

H=

C6H6

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)

2,3,7,8-TETRA CHLORO DIBENZO FURAN

1122

33

4455

66

77

88

99

There are 17 extremely toxic dioxins and furans. They have chlorine at the 2,3,7 and 8 positions: 7 Dioxins and 10 Furans

Other Dioxin like Other Dioxin like compoundscompounds PBBs (poly brominated biphenyls)PBBs (poly brominated biphenyls) PBDFs (poly brominated dibenzo furans)PBDFs (poly brominated dibenzo furans) PBDDs (poly brominated dibenzo dioxins)PBDDs (poly brominated dibenzo dioxins) PBCDDs and PBCDFs (mixed brominated and PBCDDs and PBCDFs (mixed brominated and

chlorinated dibenzo dioxins and furans)chlorinated dibenzo dioxins and furans) PBDPE (poly brominated diphenyl ethers)PBDPE (poly brominated diphenyl ethers) Poly brominated and chlorinated napthelenesPoly brominated and chlorinated napthelenes Nitrogen and sulfur analogues!Nitrogen and sulfur analogues!

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

Ah receptorAh receptor

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

Dioxins - major health Dioxins - major health concernsconcerns

• Dioxins accumulate in animal fat. One literDioxins accumulate in animal fat. One liter of of cows’ milk gives the same dose of dioxin as cows’ milk gives the same dose of dioxin as breathing air next to the cows for breathing air next to the cows for EIGHT MONTHSEIGHT MONTHS (Connett and Webster, 1987). (Connett and Webster, 1987).

• In In one dayone day a grazing cow puts as much dioxin a grazing cow puts as much dioxin into its body as a human being would get in into its body as a human being would get in 14 14 yearsyears of breathing (McLachlan, 1995)! of breathing (McLachlan, 1995)!

• Dioxins steadily accumulate in human body fat.Dioxins steadily accumulate in human body fat. The man cannot get rid of them BUT A woman The man cannot get rid of them BUT A woman can…can…

• ……by having a baby!by having a baby!• Thus the Thus the highest dosehighest dose of dioxin goes to the of dioxin goes to the fetus fetus

and then to the and then to the new born infant via new born infant via breastfeeding…breastfeeding…

Dioxins interfere with fetal Dioxins interfere with fetal and infant devlopmentand infant devlopment Dioxins act like fat soluble hormonesDioxins act like fat soluble hormones Disrupt at least six different hormonal Disrupt at least six different hormonal

systems: systems: male and female sex male and female sex hormones; thyroid hormones; insulin; hormones; thyroid hormones; insulin; gastrin and gluocorticoid.gastrin and gluocorticoid.

Linda S. Birnbaum (Linda S. Birnbaum (Health Effects Health Effects Research Laboratory, US EPA) Research Laboratory, US EPA) Developmental Effects of DioxinsDevelopmental Effects of Dioxins Environmental Health PerspectivesEnvironmental Health Perspectives, , 103103: 89-94, 1995: 89-94, 1995

Effects of dioxins on thyroid Effects of dioxins on thyroid function of new born babiesfunction of new born babies H.J. Pluim et al., H.J. Pluim et al., The LancetThe Lancet, May 23, 1992. , May 23, 1992.

(Volume 339, 1303)(Volume 339, 1303) Examined 38 new born babies, divided them Examined 38 new born babies, divided them

into 2 groups:into 2 groups: Low-exposedLow-exposed (mothers had average (mothers had average 18.618.6 pptppt

dioxins in milk fat, range 8.7 - 28)dioxins in milk fat, range 8.7 - 28) High-exposedHigh-exposed (mothers had average (mothers had average 37.537.5 pptppt

dioxins in milk fat, range 29 - 63)dioxins in milk fat, range 29 - 63)

Effect of Dioxins on Neonatal Thyroid Function Effect of Dioxins on Neonatal Thyroid Function after Low-exposure and High-exposure at various after Low-exposure and High-exposure at various agesages

nLow-Low-exposureexposuren(mean)(mean)

nHigh-High-exposureexposuren(mean)(mean)

nP*P*

nAt birthAt birth nT4T4 n122.5122.5 n134.3134.3 n0.0710.071

nT4/TBGT4/TBG n0.2400.240 n0.2320.232 n0.450.45

nTSHTSH n10.410.4 n11.911.9 n0.580.58

n1 week1 week nT4T4 n154.5154.5 n178.7178.7 n0.006*0.006*

nT4/TBGT4/TBG n0.2910.291 n0.3320.332 n0.006*0.006*

nTSHTSH n2.932.93 n2.562.56 n0.510.51

n11weeks11weeks nT4T4 n111.1111.1 n122.2122.2 n0.033*0.033*

nT4/TBGT4/TBG n0.2200.220 n0.2470.247 n0.040*0.040*

nTSHTSH n1.811.81 n2.502.50 n0.044*0.044*

Our Stolen FutureOur Stolen FutureHow Man-made Chemicals are How Man-made Chemicals are Threatening our Fertility, Threatening our Fertility, Intelligence and SurvivalIntelligence and Survival

Theo ColbornTheo ColbornJohn Peterson MyersJohn Peterson MyersDianne DumanoskiDianne Dumanoski19941994

OUT OF OUR BABIES!OUT OF OUR BABIES!

WE WANT DIOXINWE WANT DIOXIN

Institute of Medicine, Institute of Medicine, 20032003Dioxins and Dioxin-like Compounds Dioxins and Dioxin-like Compounds

in the Food Supplyin the Food Supply

Strategies to Decrease ExposureStrategies to Decrease Exposure

July 1, 2003July 1, 2003

Institute of Medicine, Institute of Medicine, 20032003 Fetuses and breastfeeding infants Fetuses and breastfeeding infants

may be at particular risk from may be at particular risk from exposure to dioxin like compounds exposure to dioxin like compounds (DLCs) due to their potential to cause (DLCs) due to their potential to cause adverse neurodevelopmental, adverse neurodevelopmental, neurobehavioral, and immune neurobehavioral, and immune system effectssystem effects in developing in developing systems…systems…

Institute of Medicine, Institute of Medicine, 20032003 ……The committee recommends that the The committee recommends that the

government place a government place a high public health high public health prioritypriority on reducing DLC intakes by on reducing DLC intakes by girls and young women girls and young women in the years in the years well before pregnancy is likely to well before pregnancy is likely to occur.occur.

(by) (by) Substituting low-fat or skim milk, Substituting low-fat or skim milk, for whole milk, for whole milk, (and)…(and)… foods lower in foods lower in animal fat…animal fat…

WE WANT DIOXINWE WANT DIOXIN

OUT OF OUR FOOD!OUT OF OUR FOOD!

Do not build Do not build incinerators within 50 incinerators within 50 km of food production km of food production - particularly grazing - particularly grazing animalsanimals

Promoters say that Promoters say that modern incinerators modern incinerators have solved the dioxin have solved the dioxin problem, but have problem, but have they?they?

Yang & Kim (2004).Yang & Kim (2004). Characteristics of dioxins Characteristics of dioxins and metals emission from radwaste plasma and metals emission from radwaste plasma arc melter system.  arc melter system.  Chemosphere 57: 421-428Chemosphere 57: 421-428

When PVC was fed into the high-temperature When PVC was fed into the high-temperature melter, a significant quantity of PCDD/Fs, melter, a significant quantity of PCDD/Fs, cadmium and lead was emitted.cadmium and lead was emitted.

Wet scrubbing with rapid quenching, as well Wet scrubbing with rapid quenching, as well as a low temperature two-step fine filtration, as a low temperature two-step fine filtration, or both of them together or both of them together cannot cannot effectively effectively control the volatile metal species and gas-control the volatile metal species and gas-phase PCDD/Fs.phase PCDD/Fs.

The removal of PVC from the feed waste The removal of PVC from the feed waste stream must also be effective to reduce the stream must also be effective to reduce the emissions of the PCDD/Fs, cadmium and lead emissions of the PCDD/Fs, cadmium and lead species.species.

While modern While modern incinerators have incinerators have reduced dioxin emissionsreduced dioxin emissionsthere is no real there is no real accountabilityaccountabilityin most countriesin most countries

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

“Even if we made incineration safe we would never make it sensible.It simply does not make sense tospend so much money destroying resources we should be sharing with the future.” (PC)

DIFFERENT TIMES DEMAND DIFFERENT TIMES DEMAND DIFFERENT QUESTIONSDIFFERENT QUESTIONS

2020thth CENTURY CENTURY

WASTE WASTE MANAGEMENTMANAGEMENT

“ “ How do we get rid How do we get rid of our waste of our waste

efficiently with efficiently with minimum damage to minimum damage to our health and the our health and the

environment ?”environment ?”

2121stst CENTURY CENTURY

RESOURCE RESOURCE MANAGEMENTMANAGEMENT

“ “ How do we handle our How do we handle our discarded resources in discarded resources in

ways which do not ways which do not deprive future deprive future

generations of some, if generations of some, if not all, of their value ?”not all, of their value ?”

DIFFERENT TIMES DEMAND DIFFERENT TIMES DEMAND DIFFERENT QUESTIONSDIFFERENT QUESTIONS

2020thth CENTURY CENTURY

WASTE WASTE MANAGEMENTMANAGEMENT

“ “ How do we get rid How do we get rid of our waste of our waste

efficiently with efficiently with minimum damage to minimum damage to our health and the our health and the

environment ?”environment ?”

2121stst CENTURY CENTURY

RESOURCE RESOURCE MANAGEMENTMANAGEMENT

“ “ How do we handle our How do we handle our discarded resources in discarded resources in

ways which do not ways which do not deprive future deprive future

generations of some, if generations of some, if not all, of their value ?”not all, of their value ?”

SAFETYSAFETY

DIFFERENT TIMES DEMAND DIFFERENT TIMES DEMAND DIFFERENT QUESTIONSDIFFERENT QUESTIONS

2020thth CENTURY CENTURY

WASTE WASTE MANAGEMENTMANAGEMENT

“ “ How do we get rid How do we get rid of our waste of our waste

efficiently with efficiently with minimum damage to minimum damage to our health and the our health and the

environment ?”environment ?”

2121stst CENTURY CENTURY

RESOURCE RESOURCE MANAGEMENTMANAGEMENT

“ “ How do we handle our How do we handle our discarded resources in discarded resources in

ways which do not ways which do not deprive future deprive future

generations of some, if generations of some, if not all, of their value ?”not all, of their value ?”

SAFETYSAFETY SUSTAINABILIYSUSTAINABILIY

Incineration is not Incineration is not sustainablesustainable