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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
Tel Aviv / Israel 23-24 November 2005
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
3
KEMAKEMA
Power Generations Power Generations
& &
SustainablesSustainables
inin
ArnhemArnhem
the Netherlandsthe Netherlands
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
4
Established in 1927 bythe Dutch Electricity Companies
From Testing Electrical Equipmentvia
National R&D institute to
Independent Independent International Consultancy
Company
History
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
8
1b2b
5b5a
3b
2a
ESP
DeNOx
FGD
3a 1a
Typical Dutch coal-fired power station
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
9
Origin coal in 2003
COL20.7%
AUS6.0%
Blend1.6%
POL0.8%
SAF43.7%
VS0.5%
CHINA0.4%
SPITS0.1%
IND26.3%
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
12
Co-combustion
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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.
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
15
FBA PFA
Fly dust
Fly ash
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
18
Experience you can trust.
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization19
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
20
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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”
Work done in the eighties after the reintroduction of coal
dust that do not posses specific toxicalproperties
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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”
Work done in the eighties after the reintroduction of coal
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
24
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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.
.
Status Report on the Health Issues Associated with Pulverised Fuel ash
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
27
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Status Report on the Health Issues Associated with Pulverised Fuel ash
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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”
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
32
Toxicology
Toxicity in pulverised fuel ash:
• inorganic compounds (HM and in particular α-quartz)
• organic compounds
• Particle size distribution
• exposure
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
33
Status Report on the Health Issues Associated with Pulverised Fuel ash
Exposure:•Ingestion•Skin contact•Inhalation
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
34
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
Status Report on the Health Issues Associated with Pulverised Fuel ash
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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.
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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®
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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%)
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
44
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 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 ash % ash content in coalREx =
[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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
46
RE-factors in bottom ash, PFA1-4, fly ash
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
52
Dust A
ssessment M
ethodologyKEMA-DAM®
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
53
ESCA or XPS
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
Tel Aviv / Israel 23-24 November 2005
Workshop on Environmental and Health Aspects of Coal Ash Utilization
56
Dust A
ssessment M
ethodologyKEMA-DAM®
7. Calculation exposure per individual element
8. Calculation quotient exposure and TLV
6. Determination of the choice of TLVs and conversion into elements
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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
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58
TC=
TC....+
TC+
TC
i
in..i
n
n
2
2
1
1 ∑
Dust A
ssessment M
ethodologyKEMA-DAM®
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)
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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
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60
Potential carcinogenic:
As, Be, Cd, Co, Cr(VI) en Ni
Comply with the criteria
Dust A
ssessment M
ethodologyKEMA-DAM®
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%
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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
Status Report on the Health Issues Associated with Pulverised Fuel ash
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Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
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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
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Cyclons Ströhlein
Gravicon
PM4 PM50
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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
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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
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Fugitive dust
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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
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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
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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
Status Report on the Health Issues Associated with Pulverised Fuel ash
Experience you can trust.
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Workshop on Environmental and Health Aspects of Coal Ash Utilization71
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
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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.
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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
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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.
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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 ?
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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
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77
Green SiRed Al
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Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
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Workshop on Environmental and Health Aspects of Coal Ash Utilization
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
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Workshop on Environmental and Health Aspects of Coal Ash Utilization
80
From a qualitativeto a quantitative approach
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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
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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
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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
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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
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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
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Workshop on Environmental and Health Aspects of Coal Ash Utilization
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.
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Workshop on Environmental and Health Aspects of Coal Ash Utilization
87
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
Status Report on the Health Issues Associated with Pulverised Fuel ash
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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
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89
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
Status Report on the Health Issues Associated with Pulverised Fuel ash
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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
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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
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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
Status Report on the Health Issues Associated with Pulverised Fuel ash
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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
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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
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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
Status Report on the Health Issues Associated with Pulverised Fuel ash
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Workshop on Environmental and Health Aspects of Coal Ash Utilization
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 -/+ + /+ +
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<30FBA (n=1)
<10 PFA (n=10)
Upper boundtotalmg•kg-1
PAHspolycyclic aromatic hydrocarbons
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98
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
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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)
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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’
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Duckweed ‘Lemna minor’
Hydrobiologia188/189: 361-366 (1989)Arch. Environ. Contam. Toxicol. 25: 3-11 (1993)
Image processing
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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).
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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%
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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
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Workshop on Environmental and Health Aspects of Coal Ash Utilization
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.
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Workshop on Environmental and Health Aspects of Coal Ash Utilization
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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)
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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
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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
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Workshop on Environmental and Health Aspects of Coal Ash Utilization
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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
Experience you can trust.
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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
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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
blootstelling onderde norm.
overweeg periodieke metingen(zie annex E NEN-EN 689)
< 1 representatieve metingen tijdens 3verschillende diensten;geometrisch gemiddelde < 0,5
blootstelling onderde norm.
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
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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
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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