health and environmental issuses associated with ... _meij.pdf · health and environmental issuses...

Experience you can trust.

Tel Aviv / Israel 23-24 November 2005

Workshop on Environmental and Health Aspects of Coal Ash Utilization1

Health and Environmental issusesassociated with occupational

exposure to pulverized fuel ash

Dr. Ruud Meij


Workshop on Environmental and Health Aspects of Coal Ash Utilization

2

Out line

• Heavy metals

• Research into health aspects CFA in eighties

• Literature study into health aspects CFA in nineties

• Introduction: KEMA and power stations in the NL

• KEMA Research:

• Quartz• PAH’s and Dioxins

• Acute toxicity tests



3

KEMAKEMA

Power Generations Power Generations

& &

SustainablesSustainables

inin

ArnhemArnhem

the Netherlandsthe Netherlands



4

Established in 1927 bythe Dutch Electricity Companies

From Testing Electrical Equipmentvia

National R&D institute to

Independent Independent International Consultancy

Company

History



5

• Annual Revenues US$ 120 Million• Over 1500 Professionals• Serving the World

– 450 clients– in 60 countries

• Main office in The Netherlands

KEMA in figures



6

KEMA Global Presence

Arnhem, the NetherlandsMaastricht, the NetherlandsBonn, GermanyDuisburg, GermanyDresden, GermanyZurich, SwitzerlandWarsaw, PolandMoscow, RussiaAnkara, Turkey

Arnhem, the NetherlandsMaastricht, the NetherlandsBonn, GermanyDuisburg, GermanyDresden, GermanyZurich, SwitzerlandWarsaw, PolandMoscow, RussiaAnkara, Turkey

Jakarta, IndonesiaManila, PhilippinesSydney, AustraliaBeijing, ChinaHong Kong, China

Jakarta, IndonesiaManila, PhilippinesSydney, AustraliaBeijing, ChinaHong Kong, ChinaFairfax, VA

Burlington MAChalfont, PAHorsham, PADenver, COGreenbay, WIMinneapolis, MNSan Jose, CASan Francisco, CAVancouver, Canada

Fairfax, VABurlington MAChalfont, PAHorsham, PADenver, COGreenbay, WIMinneapolis, MNSan Jose, CASan Francisco, CAVancouver, Canada

Bogotá, ColombiaRio de Janeiro, Brazil

Bogotá, ColombiaRio de Janeiro, Brazil

KEMACorp. HQ



7

Fuel consumption of the Dutch Power stations

0,E+00

1,E+05

2,E+05

3,E+05

4,E+05

5,E+05

6,E+05

7,E+0519

65

1967

1969

1971

1973

1975

1977

1979

1981

1983

1985

1987

1989

1991

1993

1995

1997

1999

2001

2003

year

TJ p

er y

ear

biomassUraniumblast furnace gasnatural gasheavy fuel oilcoal



8

1b2b

5b5a

3b

2a

ESP

DeNOx

FGD

3a 1a

Typical Dutch coal-fired power station



9

Origin coal in 2003

COL20.7%

AUS6.0%

Blend1.6%

POL0.8%

SAF43.7%

VS0.5%

CHINA0.4%

SPITS0.1%

IND26.3%



10

Origin coal 1991 -200319

91

1993

1995

1997

1999

2001

2003

China

PolandEastern U

SAA

ustraliaC

olombia

InodnesiaSouth A

frica

0

1 0

2 0

3 0

4 0

5 0%

C h in a P o la n d E a s te rn U S A Au s tra liaC o lo m b ia In o d n e s ia S o u th Africa



11

As and eastern USA coal

01234567

1981/2

1988

1990

1992

1994

1996

1998

2000

2002

year

[As]

mg/

kg

0

10

20

30

40

50

60

% e

aste

rn U

SA c

oal

[As] (mg/kg) eastern USA coal

60

80

100

120

140

160

1981/2

1988

1990

1992

1994

1996

1998

2000

2002

year

[F] m

g/kg

0102030405060

% S

A c

oal

[F] (mg/kg) South Africa (%)

0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0.16

1981/2

1988

1990

1992

1994

1996

1998

2000

2002 ye a r

[Hg]

mg/

kg

0

10

20

30

40

50

60

% P

olis

h co

al

[Hg] (m g/kg) P olish coa l (%)

0

15

30

45

60

75

1988

1989

1990

1991

1992

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

2003

year

[B] (

mg/

kg)

0

10

20

30

40

50

% IN

D co

al

B Indonesian coal

B and Indonesian coalHg and Polish coal

F and South African coal



12

Co-combustion



13

Origin secondary fuel

VEGETABLE ANIMAL Meat and bone meal Animal fat

Municipal waste Citrus pellets Poultry dungRDF Cocoa shells SRF Coffee grounds Heavies Olive residues Petcokes Wood pellets Hydrocarbon gas Palm Kernel

Wheat husk pellets Fresh wood Demolition wood Sewage sludge

Biomass pellets Paper sludge

BIOMASS INDUSTRIAL WASTE



14

Parameters influencing the composition of ashPrimary parameter

Secondary parameter

Fuel Coal (subdivided according to type, origin and ash content), brown coal, peat, industrial waste, domestic waste, paper, etc.

Combustion technique

Grate boilers, pulverised coal boilers with dry ash removal, pulverised coal boilers with wet ash removal, cyclone boilers, gasification, fluidised bed combustion, fluidised gasification, etc.

Temperature and residence time

During combustion and in the flue gas ducts

Type of particle filter

ESPs (high-temperature, low-temperature, dry and wet systems), cyclones, baghouses, wet systems; also filter efficiency

Other flue gas clean-up systems

deNOx, FGD system, etc.



15

FBA PFA

Fly dust

Fly ash



16

Nomenclature applied in the Netherlands to ash flows from coal-fired power stationsTerm Definition % of all ash

producedParticle size

Furnace bottom ash

Collected at bottom of boiler 12 Coarse

Pulverised fuel ash (ESP ash)

Removed from flue gases by E-filter 87,8

50% of the overall mass made up of particles under 30 μm

Fly ash In flue gases after passing through E-filter and (in plants without FGD system) in the stack

0,25

50% of the overall mass made up of particles under 3 μm

Fly dust In flue gases in the stack (after passing through FGD system)

0,0550% of the overall mass made up of particles under 0,3 μm



17

What aspects are important for using a (waste) material as a building material ?

technical & economical aspects technical & economical aspects technical & economical aspects environmental aspectsenvironmental aspectsenvironmental aspects

legal aspectslegal aspectslegal aspects(occupational) healthand safety aspects(occupational) health(occupational) healthand safety aspectsand safety aspects

perception / public supportperception / public support



18




APLEHT x =∗Σ l*),,,(lnThe formula of Meij-Sarabèr

•l = Lamers factor

TTHHEELLPPAA

echnicalechnical propertiesproperties

egislationegislation & guide lines& guide lines

nvironmentalnvironmental propertiesproperties

erceptionerception

cceptancecceptance

ealthealth & safety properties& safety properties



20

Out line

• Heavy metals




• KEMA Research:





21

NOK “Humane toxicological properties of different types of coal ash and the health risks for employees in the fly ash processing industry”.

TNO-report R 87/117b d.d. October 1987of G.J. Vink and J.H.E. Arts “Potential health effects of coal fly ash and risks of occupational exposure”

Work done in the eighties after the reintroduction of coal

• Cell test systems, • animal experiments • and epidemiological studies



22

The conclusion of the report from 1987 is:

“Based on the current, limited available information of a number of small epidemiological studies, it appears that there is no increased health risk involved for the employees in coal-fired power stations and in fly ash processing industry, as long as the requirements laid down for nuisance dust in the occupational environment are met”


dust that do not posses specific toxicalproperties



23

With respect to carcinogenicity the authors concluded in 1987:

“No carcinogenic effects in de lungs or in other organs are observed with exposure to coal fly ash after long term animal tests, as far as two years”




24

Out line

• Heavy metals




• KEMA Research:





25

Prof.Dr. P.J. Borm of the research group Health Risk Analyses and Toxicology of the University of Maastricht, later professor at the University of Düsseldorf and a member of the German TLV committee, has reviewed the literature again.

This review is published in:

BORM, P.J.A., 1997. Toxicity and occupational health hazards of coal fly ash (CFA). A review of data and comparison to coal mine dust. Annals of Occupational Hygiene, 41, pp. 659-676.

Status Report on the Health Issues Associated with Pulverised Fuel ash



26

All information obtained in the nineties, confirms the conclusion of the 1987 report that employees in coal-fired power stations and in fly ash processing industry experience no increased health risk, as long as the requirements laid down for nuisance dust in the occupational environment are met.

.




27

Out line

• Heavy metals




• KEMA Research:





28

.

Mandible

Face

Cranium

Serratus anterior

Obliquus externus abdominis

Rectus abdominis

mediusGlutaeus

Adductor longus

Pectineus

Pronator teres

Gracilis

Adductor longus

Sternocleidomastoid

Brachialis

Flexor digitorum sublimis

Abductor Pol licis longus

Extensor pollicis brevis

Extensor digitorum communisExtensor carpi radialis brevis

Coracobrachialis

Extensor digitorum longus & peronaeus tertius

Clavicle

Scapula

Humerus

Radius

UlnaSacrum

Femur

Patella

Fibula

Tibia

Pelvis

Trapezius

Soleus

Gastrocnemius

Triceps brachi i

Biceps femoris

Peronaeus longus

MUSCLES, DEEP LAYER, ANTERIOR VIEW

Esophagus

Lungs

Heart

Liver

Pancreas

Large intestine

Small intestine

Bladder

Stomach

Brain

SYMPATHETIC NERVOUS SYSTEM

ADDITIONAL RESEARCHTO GAPS IN KNOWLEDGE- KEMA-DAM®- heavy metals in PM50- speciation- particle size and fugitive dust- quartz- dioxins and PAHs- coal- co-combustion

Status Report on the Health Issues Associated with Pulverised Fuel ash version 2



29

Introduction & Summary

1. PFA

2. Fugitive dust

6. Quartz

3. Stack emissions

4. Co-firing

5. Coal

7. Chromium(VI)

8. Radioactivity

9. Dioxins

10. PAHs

10 sections :

Version 2 Version 2




30

Toxicology

Swiss physician Paracelsus (1493-1541)

“Was ist ein Gift? Alle ding ist ein Gift und nichts ist ohne Gift. Allein die Dosis macht das ein Ding Gift ist”



31

Toxicology

Toxicity is determined by:

• doses = concentration x exposure time

• the chemical form or speciation

• the method of exposure: ingestion, inhalation and skin contact

• the individual



32

Toxicology

Toxicity in pulverised fuel ash:

• inorganic compounds (HM and in particular α-quartz)

• organic compounds

• Particle size distribution

• exposure



33


Exposure:•Ingestion•Skin contact•Inhalation



34


1. PFA

2. Fugitive dust

6. Quartz

3. Stack emissions

4. Co-firing

5. Coal

7. Chromium(VI)

8. Radioactivity

9. Dioxins

10. PAHs

10 sections :

Version 2 Version 2




35

KEMA-DAM® dust assessment methodology1. Acceptance maximum allowable exposure = 10 mg•m-3

2. Choice of elements to be considered3. Determination concentrations of elements4. Calculation concentrations of elements in the inhalable fraction5. Determination of element’s speciation6. Determination of the choice of TLVs and conversion into elements7. Calculation exposure per individual element8. Calculation quotient exposure and TLV9. Choice components with similar toxic action on the same organ

system10. Summation of results of step 8 on the basis of step 9 (addition rule)11. Determination of which components are carcinogenic12. Determination of concentration of elements from 11 in the total amount

of dust13. Testing result #8, criterion is < 0.5 (statistic inaccuracies)14. Testing result #10, criterion is < 1 (addition rule)15. Testing result #12, criterion is 0.1% 16. Determination whether the substances in question can be considered

as a nuisance dust

Dust A

ssessment M

ethodology



36

National TLV (PEL)-listThe Directorate of Working Conditions of the Ministery of Social Affairs and Employment publishes every year the National threshold limited value list (TLV in Dutch MAC, in the USA PEL)

The definition of the threshold limited value is:the TLV is de maximum acceptable concentration of a gas, vapour or mist of a solid substances in the air of a working place

The basic assumption, as much as possible, of the assessment of the TLV of a substances is that the concentration during repeated exposure even during a long period or their whole working live –as far as the present knowledge– in general their health,as well as their off spring, does not harm.



37

For a great number of substances TLV-values are given in mg•m-3, not for coal fly ash.Furthermore, TLV-values are given for nuisance dust:

National TLV (PEL)-list

PM fractionTLV-value

mg.m -3

PM 50 Inhalable 10

PM 4 respirable 5



38

1. Acceptance maximum allowable exposure = 10 mg•m-3

2. Choice of elements to be considered

3. Determination concentrations of elements

4. Calculation concentrations of elements in the inhalable fraction

Dust A

ssessment M

ethodologyKEMA-DAM®



39

ac

b

e d

fg-C

g-5

h

i

k

1

2 3

4

5

j

Research performed :

Survey of elemental composition of coal, ash, flue gases, limestone, gypsum, sludge, process water, effluentMass balance studies (quality assurance)Evaluation of leaching behaviourEvaluation of radioactivity



40

Mass Balance studies

• Full coal firing– 1980 – present 42 test series

• Co-firing– 1993 – present 55 test series– 1993 – 2000 <10% m/m– 2000 – present >10% m/m (until 40%)



41

Macro elements Al, Ca, Cl, Fe, K, Mg, Na, P, Si, Ti Main elements C, H, N and S Trace and minor elements

As, B, Ba, Be, Br, Cd, Ce, Co, Cr, Cs, Cu, Eu, F, Ge, Hf, Hg, I, La, Mn, Mo, Ni, Pb, Rb, Sb, Sc, Se, Sm, Sn, Sr, Te, Th, Tl, U, V, W, Zn

Measured elements

In red elements mentioned in the EU WID



42

Parameters deduced from these studies:Parameters used in the KEMA TRACE MODEL® for predicting the emissions and ash compositionAsh: Relative Enrichment factor

RE = [element concentration in ash] • % ash content in coal[element concentration in coal] 100

Gaseous components:- vaporization percentage in boiler/ESP- removal in FGDleaching percentage relation radioactivity and elemental compositionpartition between sludge, gypsum and effluent



43

Classification of elements based on their behaviour during combustion in boiler and ducts with their Relative Enrichment factor (RE)

[X] in ash % ash content in coalREx =

[X] in coal•

100

Class FBA PFA Fly ash 1) behaviour in installation

I ~1 ~1 ~1 Not volatileIIc <0.7 ~1 >4IIb <0.7 ~1 2<..≤4IIa <0.7 ~1 1.3< ≤2

III <<1 <<1 Very volatile: some to hardly any condensation on ash particles in ESP

Volatile in boiler, but complete condensation in ESP on the ash particles

B, Br, C, Cl, F, Hg, I, N, S and SeIII

As, Cd, Ge, Mo, Pb, Sb, Tl and Zn

IIa

Be, Co, Cu, Ni, P, U, V and WIIb

Ba, Cr, Mn, Na and RbIIc

Al, Ca, Ce, Cs, Eu, Fe, Hf, K, La, Mg, Sc, Sm, Si, Sr, Th and Ti

I

classified elementsClass



44

Classification of elements based on their behaviour during combustion in boiler and ducts with their Relative Enrichment factor (RE)


[X] in coal•

100

Class FBA PFA Fly ash 1) behaviour in installation

I ~1 ~1 ~1 Not volatileIIc <0.7 ~1 1.3< ≤2IIb <0.7 ~1 2<..≤4IIa <0.7 ~1 >4

III <<1 <<1 Very volatile: some to hardly any condensation on ash particles in ESP

Volatile in boiler, but complete condensation in ESP on the ash particles


[X] in coal•

100

B, Br, C, Cl, F, Hg, I, N, S and SeIII

As, Cd, Ge, Mo, Pb, Sb, Tl and Zn

IIa

Be, Co, Cu, Ni, P, U, V and WIIb

Ba, Cr, Mn, Na and RbIIc

Al, Ca, Ce, Cs, Eu, Fe, Hf, K, La, Mg, Sc, Sm, Si, Sr, Th and Ti

I

classified elementsClass



45

Geometrical diameter in Geometrical diameter in µµmm

Particle Size Distribution in PFA and fly ash(relatively in %)

PFAPFA

-- 44

PFAPFA

-- 33

PFAPFA

-- 22

PFAPFA

-- 11

Fly ashFly ash



46

RE-factors in bottom ash, PFA1-4, fly ash



47

012345678

Al

Ca

Na As Cr

Se Zn

RE

fact

or

FBAecoPFA-CPFA-5Fly ashFly dust

Enrichment

[concentration in the ash of element x] ash content in %RE (x) =

[concentration in the fuel of element x]•

100

114 25~1 mg/m3 fly ash~1 mg/m3 fly dust

7.1 mg/m3 droplets43% fly ash

Fly ashFly ash



48

Aluminium

R2 = 0,100,0

0,5

1,0

1,5

2,0

0 1000 2000 3000 4000 5000

specific surface (cm2.g-1)

RE-

fact

or

Relation between RE-factor and specific surface 1/2



49

Lead

R2 = 0,790,0

1,0

2,0

3,0

4,0

5,0

6,0

0 1000 2000 3000 4000 5000

specific surface (cm2 .g-1)

RE-

fact

or

Relation between RE-factor and specific surface 2/2



50

0

20

40

60

80

100

1 10 100 1000aerodynamic diameter (µm)

% o

f tot

al s

uspe

nded

mat

ter

PPKVA 98/99

PM2.5 respirabel+

PM4 respirabel

PM10 fijn stof

PM50 inhaleerbaar

Particle size distribution



51

T trace R radioactivityA ashC coal E emissions

TT trace RR radioactivityAA ashCC coal EE emissions

COAL DATABASEelemental composition per country

check BMD

emission(leachate)

leachingparameters

checkEWC

compositionbottom ash

RE-factorbottom ash

check BMD

emission(leachate)

leachingparameters

radioactivity

specificradioactivity

check EWC

compositionPFA (ESP ash)

RE-factorPFA (total)

checkTLV

compositionPFA (inhalable)

RE-factorPFA (inhalable)

check WID

emissioninto air

removalin FGD

compositionfly ash

RE-factorfly ash

check WID

emissioninto air

removalin FGD

concentrationin flue gsses

upstream FGD

Vaporisationpercentage

class III elements

FUEL INPUT SECONDARY FUEL DATABASEelemental composition per biomass

KEMA TRACE Model ®KEMA TRACE Model KEMA TRACE Model ®®

Check BVA



52

Dust A

ssessment M


Cr: Cr (VI)P: Ca

3(PO

4)2

As: Ca3

(AsO4)2

Measurements: Thermodynamicalcalculations

Si: SiO2

etc.

Fact

Outokumpu

4. Calculation concentrations of elements in the inhalable

fraction

5. Determination of element’s speciation



53

ESCA or XPS



54

element gaseousphase 1200C

in PFA remarks

Macro-elementsAl - glass, 3Al2O3·2SiO2 glass, mulliteCa - glass, CaO, CaSO4 ~90% is in the glass en ~10% is “free” CaOCl HCl Cl-

Fe - Fe2O3, FeSO4 hematiteK - glass, KAl(SO4)2, K2O glassMg - glass, Mg(SO4), MgO glassNa - glass, Na2(SO4), Na2O glassP - Ca3(PO4)2 phosphate is determined at KEMA with

XPS, mostly in glassS SO2 SO4

2-

Si glass, SiO2,3Al2O3·2SiO2

mostly in glass, otherwise mullite andquartz

Ti - TiO2 rutile

“Best guess” speciation of the elements 1/2



55

element gaseousphase 1200C

in PFA remarks

Trace- en micro-elementsAs As2O3 Ca3(AsO4)2 As(V) arsenate, determined via LAMMAB B2O3, H3BO3 BO3

3-

Ba - BaSO4

Be - BeSO4, BeOBr HBr Br--

Cd - CdSO4, CdOCo - CoSO4, Co3O4

Cr - Cr2O3 Cr(III) <10% CrO2 Cr(VI), determined via XAFSGe - GeO2

F HF F-

Hg Hg, HgCl2 HgCl2, HgSO4

I ICl I-

Mn - MnO2, MnSO4

Mo - MoO3

Ni - NiSO4, NiOPb - PbSO4

Sb - Sb2SO4, Sb2O5

Se SeO2 CaSeO4(H2O)2

Sn - SnSO4, SnO2

Te - TeO2, TeO42-

Th - ThO2, Th(SO4)2

U - UO3, (U3O8)V - VOSO4, V2O5

W - WO3, WO42-

Zn - ZnSO4, ZnO, ZnAl2O4

“Best guess” speciation 2/2



56

Dust A

ssessment M


7. Calculation exposure per individual element

8. Calculation quotient exposure and TLV

6. Determination of the choice of TLVs and conversion into elements



57

respiratory system

kidneys

ears

central nervousblood

immune systemmucous

eyes

gastroenteric tract

skin

organs generalreproduction

liver

bone tissues

hormone

spleenpancreas

heart

muscles

As

BBa

Be

Cd

Cl

Co

Cr(VI)

Cu

FHg

Mn

Mo

Ni

PbSbSeSiSnTeTIUVZn

9. Choice components with similar toxic action on the same organ system

Dust A

ssessment M

ethodology



58

TC=

TC....+

TC+

TC

i

in..i

n

n

2

2

1

1 ∑

Dust A

ssessment M


10. Summation of results of step 8 on the basis of step 9

(addition rule)

13. Testing result #8, criterion is < 0.5 (statistic

inaccuracies)

14. Testing result #10, criterion is < 1 (addition rule)



59

compositioninhalable PFA

comply to TLVyes/now

fraction of TLV7)component

mean max.

permitted concaccording TLV

at 10 mg.m-3 PM50 mean. max. mean. max.trace elemenents in mg.kg-1 db

B 242 453 312500 yes yes <0.01 <0.01Ba 1.412 3.408 50000 yes yes 0.03 0.07Co 50 74 2000 yes yes 0.03 0.04Cr 130 189 50000 yes yes <0.01 <0.01Cs 7.5 9.9 176991 yes yes <0.01 <0.01Cu 101 178 100000 yes yes <0.01 <0.01F 303 1190 250000 yes yes <0.01 <0.01

Hg 0.33 1.93 5000 yes yes <0.01 <0.01Mn 348 770 100000 yes yes <0.01 0.01Mo 22 59 500000 yes yes <0.01 <0.01

Pb 4) 104 204 15000 yes yes 0.01 0.01Sb 7.6 15.2 50000 yes yes <0.01 <0.01Se 18 49 10000 yes yes <0.01 <0.01

Sn 5) 14 200000 yes <0.01 <0.01Te 5) 3 10000 yes <0.01 <0.01Tl 5) 7 10000 yes <0.01 <0.01U 10 19 20000 yes yes <0.01 <0.01V 259 409 1000 yes yes 0.26 0.41W 12 92 100000 yes yes <0.01 <0.01Zn 261 1195 403226 yes yes <0.01 <0.01

Σ fractions trace elements yes yes 0.42 0.75

Dust A

ssessment M

ethodology



60

Potential carcinogenic:

As, Be, Cd, Co, Cr(VI) en Ni

Comply with the criteria

Dust A

ssessment M


11. Determination of which components are carcinogenic

12. Determination of concentration of elements from #11 in the total amount of dust

15. Testing result #12, criterion is 0.1%



61


1. PFA

2. Fugitive dust

6. Quartz

3. Stack emissions

4. Co-firing

5. Coal

7. Chromium(VI)

8. Radioactivity

9. Dioxins

10. PAHs

10 sections :

Version 2 Version 2




62

0

20

40

60

80

100

1 10 100 1000aerodynamic diameter (µm)

% o

f tot

al s

uspe

nded

mat

ter

PPKVA 98/99

PM2.5 respirabel+

PM4 respirabel

PM10 fijn stof

PM50 inhaleerbaar

Particle size distribution



63

Statistical data of the particle sizedistribution of PFA in the NL

deeltjesgrootteverdeling Fractie van PKVA in % PM4/PM50

D10 (µm) D50 (µm) D90 (µm) PM 2.5 PM 4 PM10 PM 50 %Gem. 6,5 31,0 131,0 1,3 4,6 19,9 54,7 8,4Std.. 0,3 4,8 15,6 0,2 0,5 1,8 2,8 0,6v (%) 5 16 12 12 11 9 5 7min 5,8 23,2 104,8 1,2 4,1 17,1 49,1 7,6max 7,0 43,0 157,5 1,7 5,9 24,0 59,9 9,8n 17 17 17 17 17 17 17 17

gem–2*std 5,9 21,3 99,7 1,0 3,6 16,2 49,2 7,3gem+2*std 7,2 40,6 162,3 1,7 5,6 23,5 60,3 9,5

PFA (EN) = PKVA (NL) = poederkoolvliegas of ESP-as

Average: 21 µm geometrical31 µm aerodynamic55% is inhalable 5% is respirable20% is PM101% is PM2,5



64

Cyclons Ströhlein

Gravicon

PM4 PM50



65

Concentrations suspended inhalable PFA under the ESP

Optical MethodStröhlein GraviconVC25G

inhalable

0

5000

10000

15000

20000

25000

16-09-99 14:24 16-09-99 15:36 16-09-99 16:48 16-09-99 18:00 16-09-99 19:12 16-09-99 20:24 16-09-99 21:36

date/time

conc

entr

atio

n (u

g/m

3 )

Optical methodStröhlein Gravicon VC25G



66

-10,0

0,0

10,0

20,0

30,0

40,0

50,0

60,0

70,0

0 50 100 150 200 250 300

PM 4 concentra tions [ug/m3]

Cd content in PM4 versus [PM4]

Cadmium inrespirable particulates



67

Fugitive dust



68

0

300

600

900

020040

060080

01000

0,0

30,0

60,0

90,0

120,0

µg/m 3

mm

PM10 around PFA storage

90,0-120,060,0-90,030,0-60,00,0-30,0

0

100

200

300

400

500

600

700

800

900

1000

0

100

200

300

400

500

600

700

800

900

1000

µg/m 3m

m

PM10 around PFA storage

0,0-2,0 2,0-4,0 4,0-6,0 6,0-8,0

8,0-10,0 10,0-12,0 12,0-14,0 14,0-16,0

16,0-18,0 18,0-20,0

KEMA 3D Model®: Dust Dispersion & Deposition Model



69

PFA-concentraties around the deposit (24hr percentiles)

x y mean 50,0 90,0 95,0 98,0 99,7 max.days in 3 years 545 109 54 22 3 1

0 0 0,7 0,00 2,5 4,1 5 10 120 100 0,7 0,00 2,7 4,5 7 10 210 200 0,8 0,00 3,1 4,6 7 12 200 300 0,9 0,00 3,3 5,8 8 16 260 400 1,1 0,00 4,0 6,4 10 21 270 500 1,2 0,00 4,4 7,7 10 21 320 600 1,3 0,00 5,0 8,0 13 20 220 700 1,4 0,00 5,5 9,1 14 23 310 800 1,1 0,00 4,3 7,8 11 17 260 900 1,1 0,00 3,9 6,8 11 19 350 1000 0,9 0,00 2,9 5,5 9 15 26

µg.m-3PM10



70


1. PFA

2. Fugitive dust

6. Quartz

3. Stack emissions

4. Co-firing

5. Coal

7. Chromium(VI)

8. Radioactivity

9. Dioxins

10. PAHs

10 sections :

Version 2 Version 2





The Occurrence of QuartzThe Occurrence of Quartzinin Coal Fly Ash ParticlesCoal Fly Ash Particles

Ruud Meij, Siep Nagengast Ruud Meij, Siep Nagengast and Henk te Winkeland Henk te Winkel

77thth International Symposium on Particle ToxicologyInternational Symposium on Particle Toxicology

Maastricht, The NetherlandsMaastricht, The Netherlands

October 13, 14 and 15 1999October 13, 14 and 15 1999

KEMAKEMAKEMA

the Netherlandsthe Netherlandsthe Netherlands



72

Review of research to (quartz in-duced) effects of coal fly ash (PFA) 1/31980 Review five epidemiological studies at 1 970 employees at

coal-fired stations in the UK (Bonnel, Schilling and Massey): no pneumoconiosis, in cytotox. tests non-fibrogenic

1983 Occupational Lung Disorders, standard book of Parkes:Cytological studies indicate that PFA is not fibrogenic, and no lung disease has been observed in animalsnor in man exposed to PFA alone.

1983 In vitro assay of cytotoxicity of PFA (CG-13) to lung macro-phages (Hooftman en Arkesteijn [TNO]): PFA is not toxic.

1983 Idem, but done by Pigott [ICI]: same results.

1985 Idem but done to PFA (CG-13) high in α-quartz (18%) (Hooftman, Arkesteijn and Roza [TNO]: same results.



73

Review of research to (quartz in-duced) effects of coal fly ash (PFA) 2/31987 Review by Vink and Arts[TNO] ..workers do not run in-

creased health risk under circumstances which generally meet the requirements of nuisance dust..after two years of animal exposure no carcinogenic effects in the lungs or other organs have been noticed.

1993 In vitro assay of cytotoxicity of PFA (CG-13) to lung macro-phages and in vivo assay of lungs or rats intratracheallyexposed to low NOx PFA ( Arts [TNO]): PFA induced comparable effects to those of TiO2...

1996 Recent review by Borm confirms the above findings



74

Review of research to (quartz in-duced) effects of coal fly ash (PFA) 3/31997 In vitro effects of PFA (AC-8,9; MV) on lung and blood target

cells (Borm & Schins): • cytotoxicity studies to lung epithelial cells show toxicity

less than neg. controls,• no DNA damage at non toxic concentrations,• release of TNF-α was not stimulated by PFA (10.7 % α-

quartz)• PFA do not show stable surface radicals

The data suggest that quartz in PFA does not act as quartz in silica and does not impose a fibrogenic risk.



75

Questions to be asked:

2.What is the fate of α-quartz in coal during combustion ?

1.What is the amount of α-quartz in coal fired in NL

3.What is the amount of α-quartz in the respirable part of PFA ?

4.How is α-quartz present in PFA ?



76

α-quartz content (XRD) D50 in μmn mean±std.

in %RE-factor aerodynamic

coal 50 2.1±1.4 82.7±14.9PFBA 1 10.8 0.39 coarsePFA-C 13 9.2±3.0 0.47±0.12 30.8±7.9PFA-4 or 5 5 3.6±1.3 0.16±0.02 9.9±6.2CG-slag 4 n.d. coarseCG-fly ash 4 n.d. 4.3

What is the amount of α-quartz in coal fired in NL ?

[quartz] concentration in ash ash content in coal (%)RE = [quartz] concentration in coal • 100



77

Green SiRed Al



78

Cross section of a PFA-particle of AC station unit 9.

The dark grey spots are α-quartz.

EDS was performed along the line



79

0

10 20 29 39 49 59 68 78 88 98

107

117 Al2O3

0

20

40

60

80

100

%

position along the line in µm

Al2O3 SiO2



80

From a qualitativeto a quantitative approach



81

α-quartz content in % (w/w)XRD SEM/XMA

total fraction respirable fraction (PM4)co-de

powerstati-on.

sampletype total total enclo-

sedfree total enclosed free

21 AC-9 p.coal 4.2 4.0±3.2 1.4±1.2 2.6±3.9 0.022±0.023 0.018±0.023 0.004±0.00622 AC-9 PFA-C 14.1 14.5±4.1 4.7±0.9 9.8±4.0 0.10±0.05 0.06±0.02 0.04±0.0323 AC-9 PFA-5 4.4 5.6±1.3 3.9±0.6 1.7±1.5 0.61±0.16 0.55±0.14 0.06±0.0647 CG-13 PFA-C 9.9 11.2±3.6 5.6±1.4 5.6±2.9 0.14±0.07 0.12±0.05 0.02±0.0348 CG-13 PFA-4 5.2 7.1±2.3 4.9±1.2 2.2±1.6 0.17±0.07 0.15±0.05 0.02±0.02

number of particles studiedquartz-containing particles PM4 quartz-containing particles

partPM4

in %w/w

PM4 totaltotal enclosed free total enclosed free

21 0.17 24 217 98 88 10 11 11 022 1.2 346 5,594 1,996 1,636 360 80 73 723 20 616 996 156 149 7 60 59 147 2.3 273 1,822 544 488 56 62 58 448 3.5 347 2,501 646 611 35 67 66 1tot. 1,606 11,130 3,440 3,272 468 280 267 13

CCSEM



82

α-quartz content in %(w/w)

code powerstation.

sampletype

XRD SEM/XRA21 AC-9 p.coal 4.2 4.0±3.222 AC-9 PFA-C 14.1 14.5±4.123 AC-9 PFA-5 4.4 5.6±1.347 CG-13 PFA-C 9.9 11.2±3.648 CG-13 PFA-4 5.2 7.1±2.3

The accuracy of the applied method



83

The statistical foundationnumber of particles studiedcode sample

typepart

PM4 in %w/w

PM4 total

21 p.coal 0.17 24 21722 PFA-C 1.2 346 5,59423 PFA-5 20 616 99647 PFA-C 2.3 273 1,82248 PFA-4 3.5 347 2,501

total 1,606 11,130



84

Partition between free and embeddedα-quartz content in % (w/w)

SEM/XMAtotal fractioncode sample

type total enclosed free21 p.coal 4.0±3.2 1.4±1.2 2.6±3.922 PFA-C 14.5±4.1 4.7±0.9 9.8±4.023 PFA-5 5.6±1.3 3.9±0.6 1.7±1.547 PFA-C 11.2±3.6 5.6±1.4 5.6±2.948 PFA-4 7.1±2.3 4.9±1.2 2.2±1.6



85

Partition between respirable and total and between free and embedded

α-quartz content in % (w/w)SEM/XMArespirable fraction (PM4)code sample

type total enclosed free21 p.coal 0.022±0.023 0.018±0.023 0.004±0.00622 PFA-C 0.10±0.05 0.06±0.02 0.04±0.0323 PFA-5 0.61±0.16 0.55±0.14 0.06±0.0647 PFA-C 0.14±0.07 0.12±0.05 0.02±0.0348 PFA-4 0.17±0.07 0.15±0.05 0.02±0.02



86

Conclusions Quartz

• CG-slag and CG-fly ash is 100% glass and does not contain any crystalline silica forms.

• No cristobalite and tridymite could be found

• α-Quartz in the respirable fraction is <0.2% and pre-dominantly present embedded in the molten particle

• There is no reason to assume that PFA induces PMF, so occupational limits of quartz should not be applicable towards PFA.



87


1. PFA

2. Fugitive dust

6. Quartz

3. Stack emissions

4. Co-firing

5. Coal

7. Chromium(VI)

8. Radioactivity

9. Dioxins

10. PAHs

10 sections :

Version 2 Version 2




88

Conclusions chromium VI

• % Cr (IV) lies between 4 -9 % (mean 6%),so Cr(VI) is no problem

• total Cr is rather constant and low Cr in mg•kg-1

•Coal 18 ± 6•FBA 117 ± 14•PFA total 130 ± 15•PFA-inhalable 130 ± 15•PKVA respirable 182 ± 40•Fly dust (fly ash) 204 ± 130



89


1. PFA

2. Fugitive dust

6. Quartz

3. Stack emissions

4. Co-firing

5. Coal

7. Chromium(VI)

8. Radioactivity

9. Dioxins

10. PAHs

10 sections :

Version 2 Version 2




90

Radioactive aspects

Doses limits:Radiological workers max. 20 mSv/yearOther workers max. 1 mSv/yearpopulation max 0,1 mSv/year per nuclide

Background: + 2 mSv/year (Netherlands)

Exemption of permits for substances1-100 Bq•g-1 per nuclide, since 2000 Euratom Basic Safety Standard(Eur-BSS) 1-10 Bq•g-1 per nuclide



91

Radioactive aspects

Contribution of the annual doses of population and workers of limits

Dosis contribution per yearRoute

population workers

mSv•a-1 in % of limit (0,1) mSv•a-1 in % of limit (1)

Stack emissions 4• 10-6 0,004 nihil

Fugitive dust dump 1•10-4 0,1 1,6•10-2 1,6

Disaster during 1 hr 2•10-5 0,02 3,6•10-4 0,04

TLV inhalable

10 mg•m-3

5,6•10-2 5,6



92


1. PFA

2. Fugitive dust

6. Quartz

3. Stack emissions

4. Co-firing

5. Coal

7. Chromium(VI)

8. Radioactivity

9. Dioxins

10. PAHs

10 sections :

Version 2 Version 2




93

Dioxins

Congeneer dioxinen I-TEF Congeneer furanen I-TEF

PCD

D

2,3,7,8-TCDD 1,2,3,7,8-PCDD 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 octa-CDD

1 1 0,1 0,1 0,1 0,01 0,0001

PCD

F

2,3,7,8-TCDF 1,2,3,7,8-PCDF 2,3,4,7,8-PCDF 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 octa-CDF

0,1 0,05 0,5 0,1 0,1 0,1 0,1 0,01 0,01 0,0001



94

Dioxins

pg I-TEQ•g-1 total Upper bound

PFA (n=10)0 – 0,058 <1,3 - <1,6

FBA (n=1) 0,16 <0,6



95


1. PFA

2. Fugitive dust

6. Quartz

3. Stack emissions

4. Co-firing

5. Coal

7. Chromium(VI)

8. Radioactivity

9. Dioxins

10. PAHs

10 sections :

Version 2 Version 2




96

PAHs polycyclic aromatic hydrocarbonsc a rc in o g e n ite it

V R O M -lijs t B o rn e ff- lijs t E P A -lijs t A rb e id s in -s p e c tie IA R C IE A 4 )

n = 1 0 n = 6 n = 1 6 n = 1 2 2 ) 1 9 8 3 3 ) 1 9 9 3n a fta le e n + +a c e n a fty le e n +a c e n a fte e n +flu o re e n F + -fe n a n tre e n P A + + -a n tra c e e n A + + -flu o ra n te e n F L U + + + -p y re e n P [Y R ] + -3 ,6 -d im e th y lfe n a n tre e ntr ife n y le e nb e n z o (b )f lu o re e n -b e n z o (a )a n tra c e e n B a A + + 5 6 -5 5 -3 + + +c h ry s e e n C H [R ] + + -/+ -/+6 -m e th y lc h ry s e e n -/+b e n z o (e )p y re e n B e P -b e n z o (j)f lu o ra n te e n B jF 2 0 5 -8 2 -3 + + + /+ + +p e ry le e nb e n z o (b )f lu o ra n te e n B b F + + 2 0 5 -9 9 -2 + + + /+ + +b e n z o (k )f lu o ra n te e n B k F + + + 2 0 7 -0 8 -9 + +1 -m e th y lc h ry s e e nb e n z o (a )p y re e n B a P + + + 5 0 -3 2 -8 + + + + + +2 -m e th y lc h ry s e e n -/+d ib e n z o (a ,j)a n tra c e e n -/+ + +d ib e n z o (a ,l)p y re e n 1 8 9 -5 5 -9 + + + +b e n z o (g ,h ,i)p e ry le e n B h g iP + + + -/+d ib e n z o (a ,h )a n tra c e e n D B a h A + 5 3 -7 0 -3 + + + + + /+ + + +in d e n o (1 ,2 ,3 -c ,d )p y re e n IP + + + 1 9 3 -3 9 -5 + + +3 -m e th y lc h o la n tre e n M C A + 5 ) + + +a n ta n tre e n -/+ + /+ +



97

<30FBA (n=1)

<10 PFA (n=10)

Upper boundtotalmg•kg-1

PAHspolycyclic aromatic hydrocarbons



98

Out line

• Heavy metals




• KEMA Research:





99

EcotoxicologyMarine polychaete worm ‘Nereisvirens’Environmental Monitoring and Assessment 21: 85-98 (1992)

Worm ‘Nereis Eisenia fetida’Plant ‘Cyperus esculentus’Ecotoxicology and Environmental Safety 24: 46-57 (1992)

Cockle ‘Cerastoderma edule’Environmental Pollution 85: 191-204 (1994)



100

EcotoxicologyThe bio-availability of compounds present in sold waste is dominated by the water-soluble part. Water is the prevailing mechanism for transport in the environment and intake in the organisms. The bio-availability of a material depends therefore on its leaching behaviour rather than on its chemical composition. So a leaching test is the appropriate first step for a bioassay.

The first experiments were done with the US EPA leaching test. The leachate was assessed by

Duckweed ‘Lemna minor’



101

Duckweed ‘Lemna minor’

Hydrobiologia188/189: 361-366 (1989)Arch. Environ. Contam. Toxicol. 25: 3-11 (1993)

Image processing



102

Leaching test

The availability test serves to determine the maximum fraction of an element available for leaching in the natural environment (‘worst case’). The material is extracted in demineralised water (2 x L/S 50) for two periods of 3 hours. First, at a constant pH of 7 and second, after the liquid is refreshed, at a constant pH of 4.

The choice for the leaching test is very important, e.g. the pH is a main factor. KEMA has chosen for a standardised test: the Dutch availability test (NEN7341).



103

Leaching test + Duckweed

0

2

4

6

8

10

12

14

16

Gro

w fa

ctor

(day

0 =

1.0

0

day 0 day 4 day 7 day 11 day 14medium

25%75%

Surface cover Lemna minorCFA KES/WBR - 13 availabilitymedium

10%

25%

50%

75%



104

Bioassay

We have now a combination of two standardised tests:

Leaching test and bioassay

Duck weed assay takes to much time and is labour intensive, therefore we have chosen for an inexpensive, rapid and generally sensitive and standardised bioassay:

Microtox® test



105

Microtox®-testUsing the knowledge that the flow of electrons in the respiratory chain is an indication of the metabolic state of thecell, the Microtox® test is based on rehydrating the freeze-dried luminescent marine bacteria ‘Photobacterium fischeri’, and measuring the toxicant-induced reductions in bioluminescence in a photometer under defined experimental conditions of temperature, exposure time, and so on. The effect of bioluminescence reduction is proportionate to the toxicity of a diluted sample (NVN 6516). This toxicity is expressed in ‘Effect Concentration’ (EC20,30), the number of sample dilutions which causes 20% bioluminescence reduction in an exposure time of 30 minutes.



106

Microtox®-test

The Microtox®-test is one of the most commonly used microbial toxicity bioassays, which was developed in the late 1970s by Beckman Instruments, Inc. (USA). Today, Microtox® is used in testing various industrial effluents to comply with environmental protection regulations and water quality surveys (KAISER & PALABRICA, 1991).

The pH is set on 6 and NaCl is used for osmotic regulator.TIextract = 100/EC20 and TIsample = TIextract * concentration factor (20 -30)



107

Composition soilsChemical composition in mg/kg (on dry basis) of the soils, as used in this study, with target- and intervention-values, according to the Dutch Guideline for Soil-Protection

ISE-931 ISE-970 RIVM-01 RIVM-02 RIVM-03 RIVM-04 target values

(clean soil)

Interven-tion values

AsBaCdCrCuHgPbNiZn

3.492

0.4517636

0.067.717757

367667.01761322.924751941

50-

2120326

-147328756

7.3-

0.3171102

-13626199

24-

4.215154--

24583

5.2-

1.21334-

12810

1251

292000.8100360.38535

140

5562512

38019010

530210720



108

0

50

100

150

200

250

300IS

E-97

0IS

E-93

1R

IVM

-01

RIV

M-0

2R

IVM

-03

RIV

M-0

4

KES

/WB

R-1

1K

ES/W

BR

-11

(d1)

KES

/WB

R-1

1 (d

2)M

AT/

KST

-71

KES

/WB

R-3

0K

ES/W

BR

-46

KES

/WB

R-8

7

KST

/MA

T-02

2K

ST/M

AT-

023

KST

/MA

T-04

6K

ST/M

AT-

047

KST

/MA

T-04

8K

ST/M

AT-

067(

d)K

ST/M

AT-

069

KST

/MA

T-06

9 (d

)K

ST/M

AT-

070

KST

/MA

T-07

2K

ST/M

AT-

072

(d)

KST

/MA

T-07

4 (d

)K

ST/M

AT-

075

KST

/MA

T-07

7K

ST/M

AT-

079

KPS

/MEC

-090

Toxi

city

Inde

x (T

I

Toxicity Index (relative)

MS-sludge Paper sludgepetcokesWaste wood

15467 1011

Microtox®-test on soils, CFA and sludgeSludge of

WWTP



109

KEMA Databases Trace Elements

1. 1993 Coal2. 1993 Bottom Ash 3. 1993 Pulverised

fuel Ash

7. 1994 Standard Unitand details per lement,update in 2005

4. 1993 Fly Ash, Update in 2003

5. 1993 GaseousComponents

6. 1994 Emissionsheavy fuel oil

8. 1995 Leaching Ashupdate in 2001, 2005

9. 1995 Coal & Ashupdates in 1998-2005

10. 1996 Prediction ofcomposition of ashof blends

11. 1996 Co-firingupdate in 2000

12. 1997 Secondary fuelsupdate in 2001

13. 1999 Radioactivity14. 2005 Gypsum,

lime(stone) and sludge




End sheet

Thank you for your attention.ACKNOWLEDGEMENTS

The projects are carried out within the framework of the Technical service Agreement placed with

KEMA by the six electricity generating companies in the Netherlands: Delta, Electrabel Nederland

N.V., E.ON Benelux, Essent Energie Productie, EPZ and Nuon Power Generation



111

Concentrations suspended inhalable PFA? Frequency of measurements NEN-EN 689

index voorwaarde conclusie aanvullende metingen

< 0,1 representatieve meting tijdens 1dienst

blootstelling onderde norm.

Indien meting representatiefniet nodig

< 0,25 representatieve metingen tijdens 3verschillende diensten


overweeg periodieke metingen(zie annex E NEN-EN 689)

< 1 representatieve metingen tijdens 3verschillende diensten;geometrisch gemiddelde < 0,5


overweeg periodieke metingen(zie annex E NEN-EN 689)

> 1 een meting boven de MAC-waarde blootstelling bovende norm

anderegevallen

geen conclusie meer representatievemetingen

gemeten blootstellingsconcentratie interval< ¼ van de grenswaarde 64 wekentussen ¼ en ½ van de grenswaarde 32 wekentussen ½ van de grenswaarde en degrenswaarde

16 weken

> grenswaarde maatregelen nemen enmeting herhalen



112

Historical View of Dutch and European Standards for Fly Ash in Concrete

The Netherlands Europe

date number description date number description

1991 ASTM C 618 100% coal firing

1991 CUR 26 100% coal firing

1998 CUR 66 co-combustion till10% on mass

1999 CUR 70 idem (adoption)

1995 EN 450 100% coal firing

2001 CUR 83 co-combustion till10% of the total ash

2003 EN450-1 co-combustion till10% of the total ashin (Annex A)

2003 ? CUR 94 total new concept>10% of the total ash

200X EN450-2

????co-combustion >10%of the total ash



113

CUR 94 goes much further, no maximum limit to % co-firing, Just meet the requirements of EN 450 and CUR 94.

Recent developments in the Netherlands

Starting-point is the mineralogical composition of the ash, it must just fit in the normal range of coal fly ash and no introduction of other minerals

health and environmental issuses associated with ... _meij.pdf · health and environmental issuses...

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