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Ivastc Management & Research
Ivastc Management & Research
Ivastc Management & Research
The leachability of heavy metals in municipal solid waste (MSW) incinerator residues
was evaluated using equilibrium leach tests and the sequential chemical extraction
procedure. Incinerator bottom ash, boiler and economizer fly ashes were sampled
from a full-scale two-stage combustion facility without pollution-control devices. Fly
ashes were also collected from a pilot-plant scale, lime-based flue-gas scrubber
system, connected to a mass burning incinerator facility. Generally, bottom ashes
contained low to moderate concentrations of cadmium, copper, lead and zinc which
are relatively insoluble under normal landfill leaching conditions. Fly ashes contained
relatively moderate concentrations of cadmium and copper and much higher con-
centrations of lead and zinc which are readily available for leaching under normal
landfill conditions. Metal leachability appears to be dependent upon metal
speciation, the pH of the leaching medium and ash particle size.
!. Introduction
E
8
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e,
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Heatg" metal leachability 229
2. Incinerator design
FLUE GASES
I
STAGE ELECTROSTATIC
PREC~ITATOR
STACK
WATER WALL SECTION
AUXILIARY FUEL
VERT!CAL TUBE
BOILER SECTKM
VIBRATING FEEDER
HOPPER
/
1[ REFRACTO Y FU N CE
OUTLET(STACK)......_~ .
2K.L~qAy
INLFT
SAMPUNG ~"
AT~
FILTER
LOCATION
In the wet-dry system, flue gases were contacted with a lime slurry spray in a wet--dry
scrubber vessel for chemical conditioning and cooling. The gases then passed through
the fabric filter unit, bypassing the dry scrubber vessel.
3. Sample collection
Twelve performance tests (PTs) were conducted at the PEI-EFW facility, representing
four sets of operating conditions run in triplicate (Table I). Samples of ash (bottom,
boiler and economizer) were collected from one of the test runs under each set of operating
conditions. Thirteen performance tests were conducted at the FLAKT pilot plant under
six different sets of operating conditions (Table 2). Ashes from the wet-dry scrubber
vessel, the dry scrubber vessel and the fabric filter unit were collected from one of the
test runs under each set of operating conditions. In runs PT7 to PTI0, no dry scrubber
ash was collected because the dry scrubber vessel was bypassed during the wet--dry
system testing.
Detailed information on the operational design and the operating conditions of both
facilities, are given in the NITEP Summary Reports (Environment Canada, 1985, 1986).
4.1. P E I - E F I V ashes
PEI-EFW ashes were subjected to the WTU Multiple Batch Leaching Procedure
(MBLP) (Constable & C6t6, 1986). The test involved exposing the samples to three
ltea O' metal leachabili O' 231
TABLE 1
PEI-EFW incinerator operating conditions
Settings
Operating Primary temp. Secondary temp. Feed cycle Performance
mode (~ (~ (rain) test no.
TABLE 2
Flakt pilot plant operating conditions
Performance
Operating mode Target Actual* test no.
different types of leaching media (distilled water, an acidic solution and a synthetic
municipal landfill ieachate) at a liquid-to-solid ratio of 20: I. The solids and leaching
media were then rotated at 2-3 rpm for a period of 18 h. After a short settling period,
the supernatant was decanted and filtered through a 0.45 ltm membrane filter. Each
leachate was measured for pH, conductivity, and total dissolved solids (TDS) before
being preserved with concentrated nitric acid to a pH of 2 and analyzed for heavy
metals. Results from the M B L P are given in terms of fraction extracted, which is defined
as the ratio of the mass of a metal in a leachate to the mass of that metal in the ash
sample, expressed as a percentage.
50000
ECONOMIZER ASH
~,uz,-,,,,~ BOILER ASH
r,,.,'/,,-J BOTrOM ASH
E 40000
Q.
rl
z 30000
0
I.-
<
r
}-" 20000
z
I.d
Z
0 10000
0
.......... [7771 !
Cd Cu Pb Zn
HEAVY METALS
Fig. 4. Average heavy metal concentrations in ashes from the P E I - E F W facility.
manganese bound metal ions were extracted from the remaining residue using 0.4 r,t
hydroxylamine hydrochloride in 25% (v/v) acetic acid. In Fraction D, the organically.
bound metal ions and sulphides were leached from the residue remaining from Fraction
C by extraction with 0.02 M nitric acid and 30% hydrogen perixode. Finally, Fraction E
was extracted from the remaining residue of Fraction D, using a total digestion with
a~lua-regia/hydrofluoric acid and hydrogen perixode, giving the residual metal ions.
5. Results.and discussion
5.1. P E I - E F W facility
5. I.I Metal concentrations ht ashes
The average concentrations of cadmium, copper, lead and zinc in the MSW ashes from
the PEI-EFW facility are shown in Fig. 4. Typically, the bottom ashes contained low to
moderate concentrations of cadmium, copper, lead and zinc, ranging from 30 ppm for
cadmium to 5900 ppm for zinc. Higher concentrations of copper were found in the
bottom ashes (average of 1500 ppm) than in the fly ashes (average of 555 ppm). In
contrast, the boiler and economizer fly ashes contained very high heavy metal con-
centrations, especially lead and zinc (up to 3.6% for Pb and 5.4% for Zn).
5.1.2. Leachabilio'
The average pH and total dissolved solids (TDS) concentrations of leachates from the
MBLP tests are presented in Table 3. The pH levels of the leachates generated from the
distilled water leach tests on the bottom ashes were all alkaline, and ranged from 7.81
for sample PTI2 to 11.03 for sample PT5. The pH levels of bottom ash leachates
generated using the more aggregsive le,qching media (the acidic and synthetic solutions)
were acidic, and ranged from 4.7 for sample PT5 to 5.45 for sample PTI2. Boiler and
economizer ash leachates were mildly acidic with all three types of leaching media. The
TDS results indicate that the fly ashes were much more soluble than the bottom ashes.
Results from the MBLP tests are shown i~ Fig. 5 and are expressed in terms of
leachable fractions. Leachable fraction is defined as the ratio of the mass of a metal in
lh, ary metal leachabili O" 233
TABLE 3
Average pH and total dissolved solids results for leachates from PEI-EFW
and APC pilot plant ashes
PEI~EFW
Bottom ash 9.10 1085 5.31 5.01
Boiler ash 5.96 26,700 4.58 4.62
Economizer ash 5.92 26,500 4.75 4.76
the leachate to the mass of that metal present in the ash sample. The results of the
distilled water leach test were used to determine the immediate leachability of the
metals in an ash (i.e. the leachability under non-aggressive leaching conditigns). The
immediate leachability of the metals in the PEI-EFW bottom ashes was very low, with
less than 0.059/o of any metal being leached. The use of more aggressive leaching media
increased heavy metal leachability significantly. Up to 6.7~ of the cadmium, 29~ of
copper, 17~ of lead, and 219/o of zinc were leached with the acidic and/or synthetic
leaching media. These increases are primarily due to the mildly acidic pH of the leaching
media. Despite the increased leachability .under the more aggressive leaching conditions,
this is not likely to pose a significant hazard to the environment because of the low
metal concentrations in the bottom ashes. This will be verified in future studies by
subjecting all types of MSW ashes io a regulatory leach test (e.g. the Government of
Ontario (1983) Regulatio n 309 Leachate Extraction Procedure). to determine their
classification as hazardous or non-hazardous wastes.
The immediate leachability of the economizer and boiler fly ashes under both non-
aggressive and aggressive leaching conditions was higher than the bottom ashes. With
the non-aggressive leaching medium, up to 1009/oof the cadmium, 63~ of the zinc, 369/o
of the copper and 0.109/o of the lead in the fly ashes were solubilized. The use of more
aggressive leaching media made little difference to the leachability of cadmium, lead
and zinc. Copper concentrations, however, increased under the more aggressive leaching
conditions with up to 609(,, of the copper present in the ashes being leached. The
difference in leachability between the bottom and fly ashes is consistent with the findings
of a recent study by the State of Washington's Department of Ecology (Knudson 1986).
100
,~ INCINERATOR ASH
I eo
80
40
3o
lO
Od Ou PARAMETER I'b Zn
100 . . . .
IIo
IO
o
8,o
i" 4O
10
0
Od Ou
PARAMt'IXR
lib 7at
zinc were fot, nd to increase from the wet-dry scrubber ash through to tile fabric filter
ashes. This is probably due to the metals condensing out of the flue gases and adsorbing
onto the surfaces of the ash particles, which are subsequently captt, red in the pro-
gressivcly more efficient pollution control devices. Copper concentrations were similar
in all ashes.
I
10000 DRY -:::
SCRUBBER ASH
E
i:i:
n t7777] W ~ - D R Y
o. 8000 SCRUBBER ASH
z
o 6000 :i'i:
%%,
,,.%,
I-- %%,
%%,
n,- %%,
'o'd
I- 'o~
z 4000 'So%
.4~
bJ ,%~
to
Z
0
tO 200O ,%o,
,%o,
Cd Cu Pb Zn
PARAMETERS
Fig. 6. Average heavy metal concentrations in ashes from the Flakt pilot Plants.
100
WET-DRY DRY
80
6 o -
r 40
z
o
F- 20
o
~b_100
Cd Cu Pb Zn
LLI
~
m 8o
I
~ 60
IMMEDIATE LEACHABLE FRACTION
--J FROM BATCH LEACH TEST
4O
SHORT-TERM LEACHABLE
[~'727/2~ FRACTION (SCE:A+B)
20
LONG-TERM LEACHABLE
FRACTION (SCE:A+B+C)
Cd Cu Pb Zn
Fig. 7. Comparison of immediate, short- and long-term leachable fractions for a typical set of pilot plant ashes.
were the most immediately soluble contaminants in the ashes, especially lead from
some of the fabric filter ashes. Up to 36~ of the lead was leached by distilled water
indicating that it may have been in the form of a readily soluble chloride or hydroxide
salt. The relatively low concentrations of cadmium and zinc measured in the leachates
(up to 0.15~ of cadmium and'2.13~ of zinc) was the result of the amphoteric nature of
the metals and the alkalinity of the leachates (Fig. 7).
The pH and TDS concentrations in the leaehates from the distilled water batch leach
tests are presented in Table 3. The pit levels for all of the pilot phmt ash leachates were
highly alkaline, ranging from an average or 1 !.45 to 12.0. A plot of the ieachate pH
versus metal leachable fraction is given in Fig. 8, and ilh, strates how metal solubility
236 S.E. Sawell et al.
40
v
Z 30
0
I-.- COPPER
0 LEAD
t=_ 20 o ZINC
la.i
._1
'1-
C.~ 10
lad
,--I
0
9 10 It 12 13
pH (unlts)
Fig. 8. Metal leachability versus pll in distilled water leachates from fabric filter ashes.
remained relatively constant over the pH range 9.7 to 12.0, then increased above pH
12. Figure 8 is discussed in more detail later.
temperature, excess air addition, recycle rate, etc.) could have affected the heavy metal
concentrations.
6. Conclusions
The results indicate that MSW bottom ashes are relatively insoluble and may be
considered suitable for landfilling. MSW incinerator boiler and economizer fly ashes,
on the other hand, contain high concentrations of heavy metals, especially lead and
zinc, which are readily available for leaching under normal landfill conditions. Even the
addition of lime to the flue-gas stream in the APC system provided only a limited
buffering capacity to the ashes. Contaminant leachability from these ashes appears to
be dependent upon several factors, including combustion temperature, the pH of the
resultant ash, ash particle size, and metal speciation.
7. Recommendations
The results obtained here and-in othel- preliminary studies, such as that by Knudson
(1986), indicate that MSW incinerator fly ash residues may require treatment (e.g.
solidification, vitrification, metal recovery, etc.) prior to landfilling.
Further ash characterization studies are required to identify the potential mobility of
a wide range of contaminants in ashes from ~ wide range of EFW facilities. Research
and development of stabilization techniques for these residues is also warranted.
238 S.E. Sawell et al.
References
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leachability from solid wastes, lVater Scienbe Technology, 19, 1029-1036.
Campbell, H. W., Crescuolo, P. J. & Bridle, T. R. (1982), Fate of heavy metals and potential for
clinker formation during pilot scale incineration of sewage sludge, Water Science Technology,
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Constable, T. W. & C6t6, P. L. (1986), Development and applications of a multiple-batch leaching
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Phung, H. T., Lund, L. J., Page, A. L. & Bradford, G. R. (1979), Trace elements in fly asia and
their release in water and soil, Journal of Enrironmental Qttalit)', 8, 2.
Reiman, D. O. (1985), Erfassung, Transport und Behandlung yon Flugstauben: BambergerModell
(Capture, transport and treatment of flyash: the Bamberger model), VGB Krafit'erkstecknik
65.7, 683-687.