WHO PAHs Heavy Metal 1988
WHO PAHs Heavy Metal 1988
WHO PAHs Heavy Metal 1988
ENVIRONMENTAL HEALTH
8 8 EM
32
i":-: ORGRGANIZATION
•{'** ilice for ,r.uropc
^
ENVIRONMENTAL HEALTH SERIES
Florence
12-16 October 1987
Michael J. Suess
Regional Officer for Environmental
Health Hazards
CONTENTS
Page
Foreword v
INTRODUCTION 1
HEALTH-RELATED BACKGROUND 30
Technological aspects 36
Populations under consideration 37
Local health impact of cadmium 38
Local health impact of mercury 40
Local health impact of lead 40
Contribution of incinerator emissions to metal
exposure in the general population 41
Environmental release of metals from refuse
incineration compared with other sources 42
Contribution of incinerator emissions to PAH
exposure 47
Emissions of PAH from MSW incinerators compared with
other sources 49
VII
CONCLUSIONS AND RECOMMENDATIONS 50
Conclusions 50
Recommendations 52
REFERENCES 53
Annex 1: List of subgroups 6k
Annex 2: List of participants 65
vm
EHISSIONS OF HEAVY METAL AND PAH COHPOUNDS
INTRODUCTION
As-received MSW
Processed MSW
" [3].
b
Personal communication from experts at the WHO meeting on
PCDD and PCDF Emissions from Incinerators for Municipal Sewage
Sludge and Solid Waste - Evaluation of Human Exposure, Naples, 17-21
March 1986.
NA = Not available.
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
Proximate analysis
ganic and inorganic compounds. MSW can contain the following inor-
ganic compounds: cadmium, as a pigment, a stabilizer in plastics or
a surface coating, or in alloys and batteries; lead, in batteries,
lead-based paints, various metal items, and dusts; mercury, in bat-
teries, and in electrical and control equipment, and organomercuric
compounds in paper manufacturing; beryllium, in fluorescent light
bulbs; and inorganic metallic salts, in paper manufacturing [6].
Some organic compounds can be potentially troublesome: hexane,
toluene, and xylene in oil and acrylic paints, turpentines and other
solvents, and lithographic inks; methylene chloride, in paint
strippers and propellents for spray paint aerosol cans; formal-
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
Gross calorific
value (MJ/kg) 9.2 6.62 11.0 29.6 70.4
Net calorific
value (MJ/kg) 7.91 5.57 9.53 28.9 71.1
Moisture content 31.4 32.1 31.0 41.7 58.3
(X by weight)
Ash content 30.5 42.8 21.9 57.6 42.4
(% by weight)
Volatiles (X by
weight) 31.6 14.4 43.7 18.4 81.6
C (X by weight) 28.8 28.7 29.0 40.8 59.2
H 2 (X by weight) 2.52 1.04 3.55 17.0 83.0
Oz (X by weight) 12.4 4.9 17.6 16.3 83.7
N (X by weight) 0.71 0.65 0.74 38.0 62.0
S (X by weight) 0.28 0.43 0.18 62.0 38.0
Cl (X by weight) 0.35 0.14 0.49 17.4 82.6
Pb (X by weight) 0.011 0.019 0.006 57.8 32.2
Cd (X by weight) 0.0012 0.0004 0.0017 16.4 83.6
Hg (X by weight)* 0.00004 0.00003 0.00004 41.0 59.0
a
Identifiable metal pieces were removed from samples prior
to chemical analysis. Hence metal content and distribution refer
only to nonmetallic sources.
Substance Amount
H20 10 - 18 % by volume
CO* 6 - 12 % by volume
O2 7 - 14 % by volume
CO < 0.1 % by volume
Dust 2 - 15 g/m3
Cl" 250 - 2000 mg/m3 (as HC1)
F" 0.5 - 5 mg/m3 (as HF)
S0 2 + SO3 100 - 1000 mg/m3 (mainly S0 2 )
NO + NOz 100 - 400 mg/m3 (largely as NO)
10
EMISSIONS OF HEAVY HETAL AND PAH COMPOUNDS
11
EMISSIONS OF HEAVY HETAL AND PAH COMPOUNDS
removal system to remove the particles on which the mercury has been
actively absorbed [14,15] (H. Vogg et al., paper presented at Fifth
International Recycling Congress, 1986) are required to achieve high
mercury removal. High mercury removal has also been obtained using
the scrubber/fabric filter and semidry/ESP systems, provided that
the flue gas is adequately cooled [13]. Properly operated wet
scrubbers are also capable of considerably reducing mercury
emissions (Goepfert, Reimer and Partners, unpublished report, 1986).
Data on emissions of PAH and other chlorinated organic com-
pounds are limited. Most sampling programmes for PCDD/PCDF, which
have been fairly extensive, have unfortunately neglected to analyse
for these compounds. The scrubber/fabric filter technology generally
demonstrated removal rates of 80-99X for these compounds [13].
L
Table 6. Participate emissions froa HSU incinerators
1
per Engineers, 1984,
Unpublished reports: Cooper 1984, :1985; Bahn
et al., 1986; Velzy, 1986, 1987).
DS = Dry or semidry scrubber (lime addition).
ESP a Electrostatic precipitator.
FF * Fabric filter (bag house).
gr/dscf a Grains per dry standard cubic foot.
12
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
Traditional
Advanced
13
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
14
EHISSIOHS OF HEAVY HETAL AND PAH COHPOUNDS
15
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
16
Table 9. Emission factors and distribution (X of input) for selected metals
and PAH [22]
Compound Bottom ash Boiler ash Fly and Fly ash from stack
g/t of
waste
% g/t of
waste
boiler ash
g/t of
waste
Tradi-
tional
«as cleaning
Advanced 8
t/»
g/t of
g/t of waste %
waste
a
Distribution in percentage is not based on PAH concentrations in MSW
input.
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
Canada* Canada*
France" France"
Italy0 Italy/
Switzerland" Switzerland"
18
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
Canada* Canada*
France" France"
Italy" Italyc
Switzerland*1 Switzerland"
United States"
19
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
Canada* Canada*
France0 Francec
Italy" Italy"
Switzerland* Switzerland f
United Kingdom"
20
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
USAh USA"
1.2-2.2 mg/Nm3 - 7% 0 2 0.028 mg/Nm3 - 12% C0 2
(dry) MB w/ESP (dry) MB w/wet/dry
0.4-0.6 mg/Nm3 - 7% 02 scrubber and FF
(dry) RDF w/ESP
2.0 mg/Nm3 - 71 0 2 (dry) MB
2.2 mg/Nm3 - 12% C0 2 (dry) SA
21
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
PAH
22
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
23
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
Incinerator ash
24
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
Total PAH
Canada*
Italy
Japan
Sweden"
BaP only
Canada"
Italj
25
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
Japan
United States'
26
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
Government regulations
27
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
28
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
29
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
Total dust 50 a
Heavy metals
Pb + Cr + Cu +Mn 5b
Ni + As l"
Cd + Hg 0.2b
Hydrochloric acid 50 a
Hydrofluoric acid 2b
Sulfur dioxide 300 b
1
These values do not apply to plants designed to burn refuse-
derived fuel and that use such fuels exclusively. The Commission
shall submit to the Council as soon as possible proposals for limit
values to be applied to these plants.
a
100 mg/Nm3 in case of incineration plants of a nominal
capacity less than 3 tonnes per hour.
b
These limits do not apply to incineration plants of a
nominal capacity less than 1 tonne per hour.
HEALTH-RELATED BACKGROUND
30
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
Exposure pathways
Metabolism
31
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
About 500 PAH have been detected in air (Pott, address before
the Federal Council of Environment, Berlin (West), 1983), but re-
ports of ambient air levels of PAH dating from the 1950s to about
1970 are limited only to BaP only. These data are not necessarily
comparable with more recent reports because many different sampling
procedures and analytical methods have been used. The natural back-
ground level of BaP is determined by the production of PAH in vege-
tation [65] . PAH could be detected even in borings out of 140-m
depth more than 100 000 years old [66]. Compared with the anthro-
pogenic load, the natural background level of PAH in air amounts to
not more than 1%.
The annual average of BaP concentrations in urban European
locations often exceeded 100 ng/m3 in the 1960s [67], while more
recent measurements in the Federal Republic of Germany and USA in-
dicate that levels are now mostly below 10 ng/m3 [67,68].
32
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
PAH are highly lipid-soluble and are absorbed across the lungs,
gut, and skin of mammals. As most of the PAH in the ambient air are
attached to fine particles, the potential health effects of PAH
after inhalation depends on the deposition rate in the respiratory
tract, residence time in the lung, the dissolution rate of PAH from
the particles, and the chemical structure. Furthermore, the overall
composition of the particulate matter (i.e. the ratio of the mass of
the carbonaceous core to the mass of the attached organic material)
is a factor in determining the biological half-life of the particle-
related PAH in the lungs. Particles that consist mainly of organic
material, such as coal tar aerosols, will be eliminated from the
lungs almost completely within 24 hours. In contrast, the lung
clearance half-life of soot particles, which consist mainly of car-
bonaceous material, such as diesel soot, is relatively long [77].
PAH associated with the latter particle types may exert a stronger
carcinogenic effect in the lungs because their residence time is
longer.
In general, PAH metabolism consists of a series of oxidation
steps catalysed by monoxygenases and epoxide hydrase. Metabolites
33
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
34
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
35
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
1 ng/m3 BaP in a mixture with all the other PAH and related sub-
stances of coke oven emissions.
Technological aspects
36
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
(b) the indirect impact in the vicinity of the plant, the in-
dicators of which may be the increase of the concentration
in soil and plants grown for human consumption
37
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
General population
38
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
39
EHISSIONS OF HEAVY METAL AND PAH COMPOUNDS
type and about 275 g/ha/y for the same plant after modernization
[25]. Assuming that these data on lead concentrations in ambient air
in rural areas are of the order of 0.1 ug/m 3 , the lead levels near
an incinerator (located in a rural area) could be of the order of
0.2 to 0.3 ug/m3. Such values, if applied to an urban area, would
elevate the background levels by some 0.1 to 0.2 ug/m 3 . Thus,
waste incineration alone does not seem likely to cause locally
significant elevations of the ambient air lead concentration
sufficient to lead to health effects by inhalation.
Other available data [107] do not point to significantly ele-
vated levels of lead in street dust, soil, or grass in the vicinity
of an incinerator in the London area. No impact on human health
from the deposition of lead from incinerators onto locally grown
food is expected.
For children, general contamination of the environment (e.g.
street dust and soil) may play a dominant role in their exposure
pattern. At present, the increased exposure derived from incinerator
emissions via this pathway cannot be quantified but it is not ex-
pected to play a major role in urban areas.
To summarize, in general no local health impact of lead from
incinerator emissions alone should be envisaged. The relative signi-
ficance of lead emissions from incinerators to total exposure levels
among local populations will be greater in more rural areas, where
other sources, particularly motor vehicle emissions, make a smaller
contribution.
Mercury
41
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
Incineration
Atmosphere 5 142 5.9
Landfill 46 3 241 0.7
43
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
ND = not determined.
Atmospheric emission not determined but probably negligible.
44
EMISSIONS OF HEAVY METAL AMD PAH COMPOUNDS
Total 5300
A cadmium inventory survey was carried out in 1980 for the then
nine Member States of the EEC [105]. Table 19 presents a breakdown
of the amounts of MSW incinerated, and the estimated discharges of
cadmium to landfill and the atmosphere. Atmospheric emissions of
cadmium from traditional refuse incineration were estimated to ex-
ceed 30 t in 1977; the largest contributors were, in decreasing
order, the Federal Republic of Germany, France, and the United King-
dom. In comparison with other human activities and natural sources,
traditional refuse incineration emerges as a major source of atmos-
pheric release of cadmium, being responsible for about 25% of the
regional total, and is the second largest single source category.
45
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
• Except Ireland.
Total 7.12
46
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
47
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
Contribution from
incineration (X) 46 -20 27
49
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
Mobile sources
(gasoline and diesel
automobiles) 20 000 47 000 22 000 26 000
Conclusions
50
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
51
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
Recommenda t ions
6. Many PAH are known animal carcinogens and may also be carcino-
genic to humans. As the cancer risk from carcinogenic PAH is assumed
to depend on dose, the emissions of these substances, even at low
levels over a prolonged time, should be kept to a minimum.
52
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
12. Safe handling of ash residues, both in the incinerator plant and
during transport to disposal sites, should be practised to minimize
occupational exposure and fugitive emissions; assessments of the
metal and PAH exposure levels of the operators should be undertaken.
Liquid effluents from wet scrubbers and quenches should be properly
treated prior to discharge to receiving waters.
REFERENCES
53
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
7. Brunner, P.H. & Ernst, W.R. Alternative methods for the analy-
sis of municipal solid waste. Waste management and research, 4:
147-160 (1986).
54
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
16. Brunner, P.H. et al. Total organic carbon emissions from muni-
cipal incineration. Waste management and research, 5: 355-365
(1987).
22. Brunner, P.H. & Moench, H. The flux of metals through municipal
solid waste incinerators. Waste management and research, 4:
105-119 (1986).
55
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
30. Brunner, P.H. & Zobrist, I. Die Mullverbrennung als Quelle von
Metallen in der Umwelt. [Burning of wastes as a source of metals
in the environment]. Mull und Abfall, 9: 221-227 (1983).
39. Donnelly, J.R. & Jons, E. By-product disposal from MSW inciner-
ator flue gas cleaning systems. New York, American Pollution
Control Association, 1987.
56
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
41. Wadge, A. & Hutton, M. The uptake of cadmium, lead and selenium
by barley and cabbage grown on soil amended with refuse in-
cinerator fly ash. Plant and soil, 96: 407-412 (1986).
42. Friberg, L. et al. Cadmium and health. Boca Raton, CRC Press,
1985.
46. Wadge, A. & Hutton, M. The cadmium and lead content of sus-
pended particulate matter emitted from a UK refuse incinerator.
Science of the total environment, 67: 91-95 (1987).
57
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
52. Vostal, J.J. et al. Lead analysis of house dust: a method for
the detection of another source of lead exposure in inner city
children. Environmental health perspectives,!_'.91-97 (1974).
61. Lansdown, R. & Yule, W. The lead debate: the environment, toxi-
cology and child health. London, Croom Helm, 1986.
58
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
59
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
82. Neal, J. & Rigdon, R.H. Gastric tumours in mice fed benzo(a)-
pyrene. A guantitative study. Texas reports in biology and
medicine, 25: 553-557 (1967).
60
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
61
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
103. Dean, R.B. & Suess, M.J., ed. The risk to health of chemicals
in sewage sludge applied to land. Waste management and
research. 3: 251-278 (1985).
62
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
114. Suess, M.J. The environmental load and cycle of polycyclic aro-
matic hydrocarbons. Science of the total environment, £:
239-250 (1976).
63
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
Annex 1
MEMBERSHIP OF SUBGROUPS
Dr Brunner Dr Romanelli
Mr Finkelstein (.Leader) Mr Smith
Mr Kilgroe Mr Velzy (Rapporteur)
Mr Milhau Dr Viviano
Mr Moller Dr Vogg
Dr Nottrodt Mr Woodfield
Dr Bencko Dr Riolfatti
Dr Borneff Dr Schoeny
Dr Dolara Ms Victorin
Dr Heinrich Dr Wadge (Rapporteur)
Dr Hutton Dr van Wijnen
Dr Kostial (Leader) Dr Zapponi
Dr Piotrowski
Mr Finkelstein Dr Suess
Dr Kostial Mr Velzy (Co-Rapporteur)
Dr Piscator (Leader) Dr Wadge (Co-Rapporteur)
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
Annex 2
LIST OF PARTICIPANTS
Temporary advisers
65
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
66
EMISSIONS OF HEAVY METAL AND PAH COMPOUNDS
67