Environment International 29 (2003) 895 – 900

www.elsevier.com/locate/envint

Chemical speciation and phytoavailability of Zn, Cu, Ni and Cd in soil

amended with fly ash-stabilized sewage sludge
D.C. Su a, J.W.C. Wong b,*
a
Department of Plant Nutrition, China Agricultural University, Beijing 100094, PR China
b
Department of Biology, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR, PR China
Received 24 October 2002; accepted 17 February 2003

Abstract

A sequential extraction method was used to determine chemical forms of Cu, Zn, Ni and Cd in fly ash-stabilized sludge. A loamy acid soil
amended with fly ash-stabilized sludge was used to grow corn under greenhouse conditions. Sewage sludge amended with coal fly ash can
reduce the availability of Cu, Zn, Ni and Cd in the sludge. Increasing fly ash amendment rate significantly reduced DTPA-extractable Cu, Zn,
Ni and Cd concentrations. Percentages of Cu, Zn and Ni in residual fraction increased with an increase in fly ash amendment rates. Majority
of Cu was associated with organic form, but Zn and Ni were associated with Fe – Mn oxide and residual forms. Addition of ash-amended
sludge to soil significantly increased dry mass of corn. With coal fly ash amendment rate increasing, concentrations of Zn and Cu in shoot
tissues of corn decreased significantly, but concentrations of Cd and Ni did not change significantly. Significant correlations were found
between concentrations of Cu and Zn in corn shoot and oxide and total Cu fractions, and all chemical fractions of Zn in fly ash-stabilized
sludge, respectively. Hence, ash amendment significantly reduced the availability of heavy metals by chemical modification of their chemical
speciation into less available forms.
D 2003 Elsevier Science Ltd. All rights reserved.

Keywords: Fly ash; Sludge; Heavy metal speciation; Corn; Uptake

1. Introduction Lime is commonly used as an alkaline agent to raise the

Compared to landfilling and incineration, application of
sewage sludge to agricultural land is a more sustainable
treatment because it recycles both nutrients and organic
matter. Sewage sludge has been used as a source of nutrients
for plant growth and as soil conditioner to improve physical
properties in many countries (Wong et al., 1996; Bowen et
al., 1992; Logan and Harrison, 1995). However, land
application of sewage sludge has been limited by its
enriched pathogens and heavy metal contents (Sims and
Kline, 1991). Excessive levels of heavy metals introduced to
soil by sewage sludge can lead to elevated uptake of heavy
metals by plants, which will cause damage to plants and
affect human health upon consumption of crops grown on
the soil. To reduce the availability of heavy metals in
sewage sludge is therefore one of the major concerns in
land application of sewage sludge.
* Corresponding author. Tel.: +852-3411-7056; fax: +852-3411-5995.
E-mail address: jwcwong@hkbu.edu.hk (J.W.C. Wong).
pH of swage sludge to kill pathogens and to reduce the
availability of heavy metals enriched in sludge (Christensen,
1987). Coal fly ash is the residues produced during the
burning of coal for generation of electricity. It is enriched
with CaO, MgO, SiO2 and Fe –Mn oxide and has a pH up to
12 depending on coal sources. Since alkaline coal fly ash
contained a large amount of CaO, it can be used as a
stabilization agent for sewage sludge to reduce pathogens
and heavy metal availability (Wong, 1995; Wong et al.,
1996; Jiang et al., 1999).
Heavy metals present in various forms in soil. Different
forms of heavy metals have different mobility and phytoa-
vailability (Chlopecka, 1996a). Knowledge of the heavy
metal speciation in soil amended with sewage sludge is
important for the understanding of the bioavailability and
mobility of heavy metals in soils. Generally, the plant
uptake of heavy metals is correlated to extractable forms
of the metals rather than to the total metal contents in the
soils (Xian, 1989). Liming, presumably the most widely
known ameliorant in agriculture, decreases the mobility of

0160-4120/$ - see front matter D 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0160-4120(03)00052-7
896 D.C. Su, J.W.C. Wong / Environment International 29 (2003) 895–900

metals and their uptake by plants caused by metal hydrolysis dewatered sludge in a series of proportion of 0%, 5%, 10%,
reactions and/or co-precipitation of carbonate (Chlopecka, 35% and 50% (dry weight basis), and mixed thoroughly
1996a,b). The composition of coal fly ash differs signifi- using a mechanical blender. The ash-sludge mixtures were
cantly from lime; its mechanisms to reduce the availability air-dried, and samples from each mixture were taken for
of heavy metals enriched in sludge are precipitation at high later chemical analysis.
pH and physical adsorption (Wong, 1995). The distribution
of heavy metals among the exchangeable, carbonate, oxide, 2.2. Greenhouse experiment
organic and residual fractions using sequential extraction
analysis could assess the potential phytoavailability of A loamy soil from abandoned farmland in the New
heavy metals in coal fly ash-stabilized sludge. Territories was collected for the plant growth experiment
The objectives of this research were to determine the in a greenhouse. The ash-sludge mixtures prepared above
forms of Cu, Zn, Ni and Cd in fly ash-amended sewage were added to the loamy soil at a ratio of 1:5 (v:v). The
sludge and to better understand the mobility of heavy metals treated soil, then, was packed into pots of 14 cm in diameter.
in soil receiving fly ash-amended sludge and their avail- There were a total of six treatments (five different types of
ability to plants. To gain an understanding of the mechanism ash-sludge mixtures, plus one control pot of loamy soil
by which the phytoavailability of heavy metals in coal fly without sludge treatment) with three replications for each
ash-amended sludge is reduced, sequential extraction pro- treatment. Corn seeds were sown in each pot. Pots were
cedures was used to identify changes associated with metal placed on a bench in a greenhouse, and allowed to grow for
speciation in coal fly ash-amended sludge. a period of 42 days. Then, the plants were carefully removed
from the pots with roots; washed with tap water to remove
any attached particles and then rinsed twice with deionized
2. Materials and methods water. Shoots were separated by cutting at the base of the
shoots and then oven-dried at 70 jC for 72 h. Dry mass of
2.1. Coal fly ash-stabilized sewage sludge the shoot was recorded. The oven-dried shoot tissues were
then ground to pass through a 1-mm sieve using a stainless-
Coal fly ash was collected from the Castle Peak Power steel mill for chemical analysis.
Station of China Light and Power, and anaerobically
digested sewage sludge was collected from the Tai Po 2.3. Chemical analysis
Wastewater Treatment Plant (activated sludge process) in
Hong Kong. Selected physico-chemical properties and A sequential extraction scheme developed by Tessier et
heavy metal contents of the coal fly ash and sewage sludge al. (1979) was used to partition Cu, Zn, Ni and Cd in the
are listed in Table 1. ash-sludge mixtures into several fractions. Each fraction was
Coal fly ash-stabilized sewage sludge was prepared in the defined as: (1) exchangeable (extracted by 1.0 mol l 1
following manner. The alkaline coal fly ash was added to CaCl2), (2) carbonate (extracted by 1.0 mol l 1 NaOAc, at
pH 5.0), (3) Fe – Mn oxides (extracted by 0.04 mol l 1
Table 1 NH4OH.HCl), (4) organic (extracted by 0.02 mol l 1
Physico-chemical properties of coal fly ash, sewage sludge and loamy soil HNO 3 + 30% H 2O 2) and (5) total (digested by conc.
Fly ash Sewage sludge Loamy soil HF + conc. HClO4). Concentrations of Cu, Zn, Ni and Cd
pH (soil/water = 1:5) 12.4 (0.2)* 6.24 (0.23) 4.60 (0.02) were measured using atomic absorption spectrometry (AAS)
EC (dS m 1) 2.02 (0.03) 4.12 (0.18) 0.10 (0.01) or graphite furnace atomic absorption spectrometry
(soil/water = 1:5) (GFAAS) method. Residual concentrations of Cu, Zn, Ni
Organic carbon (%) 0.15 (0.01) 27.8 (0.18) 1.4 (0.02)
Moisture content (%) 0.13 (0.02) 87.3 (0.2) ND
and Cd were calculated by subtracting the first four fractions
Total N (%) 0.047 (0.003) 7.03 (0.02) 0.09 (0.01) from the total.
Soluble NH4 – N 4.46 (0.22) 837 (29.4) 7.11 (0.89) Total metal contents in plant tissues were determined by
(mg kg 1) H2SO4 – H2O2 digestion (Lowther, 1989) method. The con-
Total P (%) 0.33 (0.017) 1.95 (0.09) 0.03 (0.002) centrations of Cu, Zn, Ni and Cd in the digested solutions
Soluble PO4 – P 0.28 (0.02) 218 (11.8) 2.17 (0.26)
(mg kg 1)
were measured using AAS or GFAAS. Citrus leaf standard
Total K (%) 0.14 (0.04) 0.23 (0.01) 0.71 (0.03) reference materials from the National Institute of Standards
Total metals content and Technology were digested and analyzed for the purpose
(mg kg 1) of quality control. The metal contents of the reference
Cd BLD 3.32 (0.2) BLD materials were all within the recommended ranges.
Cu 88.0 (0.8) 979 (41.6) 4.97 (0.01)
Ni 92.5 (0.2) 83.1 (6.1) 1.38 (0.02)
Zn 124.6 (1.5) 1268 (32) 19.1 (1.0) 2.4. Statistical analysis
ND: not determined.
BLD: below detection limit. All data were analyzed using a SAS statistical computer
* Values in parentheses are standard deviation of means of triplicate. package (SAS Institute, 1999). One-way ANOVA was used
 D.C. Su, J.W.C. Wong / Environment International 29 (2003) 895–900 897

Table 2
Physico-chemical properties of fly ash-stabilized sewage sludge#
1
Treatment pH (1:5) EC (dS m ) DTPA-Cu DTPA-Zn DTPA-Ni DTPA-Cd
1
mg kg
Sludge 6.24 e* 4.60 a 328 a 987 a 28.3 a 1.04 a
Sludge + 5% fly ash 7.08 d 3.16 b 241 b 780 b 23.5 b 0.78 b
Sludge + 10% fly ash 7.35 c 2.37 c 215 c 652 c 18.6 c 0.63 c
Sludge + 35% fly ash 8.68 b 1.30 d 122 d 253 d 9.7 d 0.15 d
Sludge + 50% fly ash 9.11 a 1.12 e 96.8 e 159 e 9.6 d 0.15 d
LSD 0.04 0.14 10.2 23.5 3.1 0.06
#
The ash amendment rates for sewage sludge were 0%, 5%, 10%, 35% and 50% (w/w).
* Values followed by the same letter within the same column do not differ significantly at 5% level according to the least significant difference test.

to analyze the significance of treatment effects ( F-test, at
0.05 significance level). The differences between individual
means were tested using the LSD at 0.05 significance level
(Little and Hills, 1978).
3. Results and discussion
3.1. Chemical properties of fly ash-stabilized sludge
Table 2 shows the selected physico-chemical properties
of coal fly ash-stabilized sludge. With an increase in fly ash
amendment rate, pH value increased significantly. This was
due to high content of CaO and MgO in coal fly ash (Wong
et al., 1996). Electrical conductivity decreased with increas-
ing ash amendment rate. The increase in pH after ash
amendment might cause the precipitation of soluble cations
in the ash sludge mixture, which caused the reduction in EC
of the ash-sludge mixture; DTPA-extractable Cu, Cd, Ni and
Zn can be used as an indicator of bioavailability and toxicity
of these heavy metals (Soltanpour, 1991). Increasing the ash
amendment rate significantly reduced the content of DTPA-
extractable Cu, Cd, Ni and Zn. The reduced availability of
heavy metals following ash amendment can be explained by
the pH-dependent characteristics of these metals or change
of more unavailable chemical forms with an increase in pH
for these heavy metals (Sims and Kline, 1991; Chlopecka,
1996b).
3.2. Chemical forms of Cu, Cd, Ni and Zn in fly ash-
stabilized sludge
Chemical forms of metals in soil are affected by pH,
redox potential (Eh), organic matter and other factors
(Chlopecka and Adriano, 1996; Chlopecka, 1996b; Chlo-
pecka et al., 1996). The chemical speciation of Cu changed
when sludge was amended with fly ash (Table 3). As fly ash
amendment rate increased from 0% to 50%, percentages of
Cu in the residual fraction increased from 20.0% to 31.6%,
and that in the organic fraction decreased from 69.8% to
41.3%. The high pH and CaO and MgO contents in the fly
ash caused the organic fraction of Cu converted to residual
form. As a result, we will expect a reduction in the
bioavailability of Cu in the sludge. Percentages of Cu in
carbonates and Fe –Mn oxides fractions did not change
significantly with ash amendment rate increasing. When ash
amendment rate was lower than 10%, percentages of Cu in
the exchangeable fraction did not change significantly with
an increase in ash amendment rates. However, percentages
of Cu in the exchangeable fraction increased significantly
when ash amendment rate was higher than 10%. This is
likely due to the dissolution of Cu in the organic fraction at
high pH condition. Table 3 shows that majority of Cu in fly
ash-stabilized sludge was found in organic and residual
fractions. Since the Cu concentration in sludge was higher
than that of coal fly ash, the concentrations of Cu in each
form decreased significantly with an increase in ash amend-

Table 3
1
Concentration of copper in the various chemical forms of fly ash-stabilized sewage sludge (mg kg )
Treatment Exchange able Carbonate Oxide Organic Residual Total
Sludge 56.5 a* 40.6 a 3.1 a 683 a 196 a 979 a
5.8%# 4.1% 0.3% 69.8% 20.0% 100%
Sludge + 5% fly ash 37.7 b 32.2 b 1.4 b 423 b 152 b 547 b
6.9% 5.9% 0.3% 59.0% 27.9% 100%
Sludge + 10% fly ash 31.4 c 26.4 c 1.3 b 251 c 105 c 415 c
7.6% 6.4% 0.3% 60.5% 25.2% 100%
Sludge + 35% fly ash 42.5 b 11.6 d 1.3 b 101 d 76.7 d 233 d
18.2% 5.0% 0.6% 43.4% 32.9% 100%
Sludge + 50% fly ash 38.3 b 6.9 e 0.93 c 70.1 e 53.6 e 170 e
22.6% 4.1% 0.5% 41.3% 31.6% 100%
LSD 5.02 2.72 0.38 25.1 17.4 18.3
* Values followed by the same letter within the same column do not differ significantly at 5% level according to the least significant difference test.
#
Percentage contributions of each chemical form of Cu in fly ash-stabilized sewage sludge.
898 D.C. Su, J.W.C. Wong / Environment International 29 (2003) 895–900

Table 4
1
Concentration of zinc in the various chemical forms of fly ash-stabilized sewage sludge (mg kg )
Treatment Exchange able Carbonate Oxide Organic Residual Total
Sludge 61.2 a* 152 c 517 a 110 a 329 a 1268 a
4.8%# 12.0% 40.7% 16.5% 25.9% 100%
Sludge + 5% fly ash 25.6 b 183 a 484 a 102 b 352 b 1147 b
2.2% 16.0% 42.2% 8.9% 30.7% 100%
Sludge + 10% fly ash 12.5 c 172 b 357 b 53.3 c 343 b 938 c
1.3% 18.3% 38.1% 5.7% 36.5% 100%
Sludge + 35% fly ash 11.0 c 74.7 d 166 c 9.6 d 179 c 440 d
2.5% 17.0% 37.8% 2.2% 40.6% 100%
Sludge + 50% fly ash 4.2 d 69.0 d 124 d 6.3 d 194 c 398 e
1.1% 17.3% 31.2% 1.5% 48.8% 100%
LSD 2.0 10.3 39.2 6.9 23.6 28.9
* Values followed by the same letter within the same column do not differ significantly at 5% level according to the least significant difference test.
#
Percentage contributions of each chemical form of Zn in fly ash-stabilized sewage sludge.

ment rate due to dilution effect. The DTPA-extractable Cu
(Table 2) was significantly negatively correlated with pH
(r = 0.99; P < 0.01) and positively correlated with carbo-
nate Cu, organic Cu, total Cu, residual Cu, and oxide Cu
(r = 0.99, 0.98, 0.97, 0.96 and 0.83; P < 0.01), but poorly
correlated with exchangeable Cu fraction (Table 3).
Percentage distribution of Zn in the various chemical
forms differed from that of Cu (Table 4). Percentages of Zn
in the residual fraction increased, while that in the organic
fraction decreased with an increase in fly ash amendment
rates. This indicated that fly ash can stabilize Zn in the
sludge. Table 4 shows that majority of Zn was associated
with Fe –Mn oxide form (31.2% to 42.2% of the total) and
residual form (25.9% to 48.8% of the total). Zinc existed in
the exchangeable fraction was least associated with fly ash
amendment. Concentrations of Zn in each chemical form
had the same decreasing trend as Cu with an increase in ash
amendment rate. The DTPA-extractable Zn (Table 2) was
significantly negatively correlated with pH (r = 0.99; P <
0.01) and correlated positively with total Zn, oxide Zn,
organic Zn, residual Zn, carbonate Zn, and exchangeable Zn
(r =0.99, 0.98, 0.97, 0.89, 0.87 and 0.85; P < 0.01) (Table 4).
Distribution of Ni among the different extractants showed
that the greatest amount was in the residual form (51.9% to
80.7% of total), followed by oxide form, while the organic
form contained the lowest (Table 5). Percentages of Ni in the
residual fraction increased with an increase in fly ash amend-
ment rates, but decreased in all other fractions. Concentra-
tions of Ni in each chemical form did not change significantly
with an increase in ash amendment rates except in the organic
form, because concentration of Ni existed in more or less the
same amount in both sludge and fly ash. The significant
increase in Ni in the residual fraction demonstrated the
benefit of the alkaline stabilization process. Metals confined
in the residual fractions are usually not expected to be
released over short period of time under the conditions
usually encountered in nature (Tessier et al., 1979; Chlo-
pecka, 1996b, Chlopecka et al., 1996). The DTPA-extractable
Ni (Table 2) was significantly positively correlated only with
pH (r = 0.97; P < 0.01) and correlated negatively with resid-
ual Ni (r = 0.92; P < 0.01) (Table 5).
Table 6 shows the distribution of Cd in sludge with
different ash amendment rates. Percentage of Cd in the
exchangeable and carbonate fractions increased, but that in
the residual fraction decreased with an increase in fly ash
amendment rates. Concentrations of Cd in each form
decreased with an increase in the ash amendment rates
except in the organic form. The percentage increase in Cd

Table 5
1
Concentration of nickel in the various chemical forms of fly ash-stabilized sewage sludge (mg kg )
Treatment Exchange able Carbonate Oxide Organic Residual Total
Sludge 8.7 a* 6.3 b 14.8 ab 10.2 a 43.1 d 83.1 b
10.5%# 7.6% 17.8% 12.3% 51.9% 100%
Sludge + 5% fly ash 7.7 ab 7.6 b 15.3 a 3.1 b 50.2 cd 83.9 b
9.2% 9.1% 18.2% 3.7% 59.8% 100%
Sludge + 10% fly ash 3.6 b 10.5 a 14.2 abc 2.8 b 54.6 c 85.7 b
4.2% 12.3% 16.6% 3.3% 63.7% 100%
Sludge + 35% fly ash 7.0 ab 1.9 c 10.5 bc 1.7 b 76.1 b 97.2 ab
7.2% 2.0% 10.8% 1.7% 78.3% 100%
Sludge + 50% fly Ash 6.6 ab 2.1 c 10.2 c 2.2 b 88.3 a 109.4 a
6.0% 1.9% 9.3% 2.0% 80.7% 100%
LSD 4.6 2.8 4.6 1.5 10.7 14.6
* Values followed by the same letter within the same column do not differ significantly at 5% level according to the least significant difference test.
#
Percentage contributions of each chemical form of Ni in fly ash-stabilized sewage sludge.
 D.C. Su, J.W.C. Wong / Environment International 29 (2003) 895–900 899

Table 6
1
Concentration of cadmium in the various chemical forms of fly ash-stabilized sewage sludge (mg kg )
Treatment Exchange able Carbonate Oxide Organic Residual Total
Sludge 0.59 a* 0.27 a 0.27 a 0.10 a 2.09 a 3.32 a
17.8%# 8.1% 8.1% 3.0% 63.0% 100%
Sludge + 5% fly ash 0.41 b 0.24 ab 0.18 b 0.09 a 1.15 b 2.07 b
19.8% 11.6% 8.7% 4.3% 55.6% 100%
Sludge + 10% fly ash 0.36 c 0.20 c 0.13 c 0.11 a 0.90 c 1.70 c
21.2% 11.8% 7.6% 6.5% 52.9% 100%
Sludge + 35% fly ash 0.18 d 0.21 bc 0.09 cd 0.11 a 0.19 d 0.78 d
23.1% 26.9% 11.5% 14.0% 24.4% 100%
Sludge + 50% fly ash 0.15 d 0.22 bc 0.07 d 0.09 a 0.03 d 0.56 d
26.8% 39.3% 12.5% 16.1% 5.4% 100%
LSD 0.05 0.03 0.05 0.03 0.21 0.36
* Values followed by the same letter within the same column do not differ significantly at 5% level according to the least significant difference test.
#
Percentage contributions of each chemical form of Cd in fly ash-stabilized sewage sludge.

concentration in the exchangeable form is likely caused by plant growth. Besides, the higher ash content increased soil
the higher pH for treatment groups with higher fly ash pH from 8.7 to 9.1, which will suppress the availability of
amendment rates. DTPA-extractable Cd (Table 2) was sig- nutrients for plant growth.
nificantly negatively correlated with pH (r = 0.98; Uptake of heavy metals by plants are not only influenced
P < 0.01) but positively with exchangeable Cd, residual by their concentrations in soil, their chemical forms, phys-
Cd, total Cd and oxide Cd (r = 0.98, 0.96, 0.95 and 0.90) icochemical properties of the soil, but also by plant nutrition,
(P < 0.01) (Table 6). stage of growth, and other factors (Adriano, 1986; Chlo-
pecka, 1996a,b). With coal fly ash amendment rate increasing
3.3. Effects of fly ash-stabilized sludge on growth and heavy in the ash sludge mixture, concentrations of Zn and Cu in
metal uptake in corn shoot tissues of corn decreased significantly, but concentra-
tions of Cd and Ni showed little changes. This indicated that
Dry mass in the shoot of corn and heavy metal concen- fly ash amendment reduced the phytoavailability of Zn and
trations in the shoot tissues are listed in Table 7. Addition of Cu in the sludge.
coal fly ash-stabilized sludge significantly increased the dry
weight yield of corn compared to the control soil. Dry 3.4. Chemical fractions and heavy metal concentrations in
weight yields in ash-stabilized sludge receiving 5% and plant tissues
10% ash amendment were significantly higher than other
treatments. Improvement of biomass growth following Significant correlation was observed only between con-
sludge or ash-sludge amendment can be explained by an centration of Cu in corn shoot tissue and Cu in the oxide
increase in nutrients and also improved soil physical proper- fraction (r = 0.81*), and total Cu (r = 0.79; P < 0.05) in fly
ties as compared to the control (Wong and Su, 1997). ash-stabilized sludge, when data from all treatments were
However, increasing in ash amendment level of > 10% in combined. No significant correlation was observed between
the ash sludge mixture caused a decrease in nutrients for Cu in corn shoot tissue and Cu in the organic fraction since
Cu bound strongly with the organic fraction. Exchangeable
Zn, residual Zn, total Zn, DTPA-extractable Zn, and organic
Zn in fly ash-stabilized sludge were significantly positively
Table 7 correlated with Zn in corn shoot (r = 0.98, 0.99, 0.90, 0.85
Dry weight yields and heavy metal concentration in shoot tissue of corn and 0.84; P < 0.01). Although exchangeable and DTPA-
growing in soil receiving ash-stabilized sludge
extractable Zn are good indicators of bioavailability of Zn
Treatment Dry weight Cu Zn Ni Cd from fly ash-stabilized sludge, no clear advantage was noted
(g pot 1) 1
mg kg in the present study as compared to other chemical forms.
Sludge 13.1 b* 18.1 a 345 a 2.4 a 0.09 a This may indicate that there is a continuous equilibrium
Sludge + 5% fly ash 29.6 a 13.5 b 140 b 2.0 a 0.04 c process happening in soil, causing the shift of metal forms
Sludge + 10% fly ash 26.5 a 14.2 b 124 b 1.8 a 0.06 b from one chemical species to another. Besides, DTPA-
Sludge + 35% fly ash 15.1 b 12.4 b 82.0 c 1.7 a 0.07 abc
Sludge + 50% fly ash 11.8 b 12.2 b 58.7 c 1.9 a 0.07 ab
extractable Zn showed a lower correlation with tissue Zn
Soil 2.6 c 9.1 c 72.5 c 2.6 a 0.06 b contents as compared to exchangeable Zn. Exchangeable Zn
LSD 4.8 2.8 29.4 0.7 0.03 would be a more reliable form for predicting Zn availability.
* Values followed by the same letter within the same column do not differ Significant negative correlation was observed between Zn
significantly at 5% level according to the least significant difference test. concentration in shoot and pH of the fly ash-stabilized sludge
900 D.C. Su, J.W.C. Wong / Environment International 29 (2003) 895–900
(r = 0.86; P < 0.01). It is well documented that the avail-
ability of Zn depends on soil pH (Adriano, 1986). Concen-
trations of Cd and Ni in corn shoot tissue were in general
poorly correlated with each chemical fraction of Cd and Ni in
fly ash-stabilized sludge.
4. Conclusions
Amending sewage sludge with coal fly ash could reduce
the availability of Cu, Zn, Ni and Cd in the sludge.
Increasing fly ash amendment rates significantly reduced
DTPA-extractable Cu, Zn, Ni and Cd contents in the sludge.
Percentages of Cu, Zn and Ni in residual fraction increased
with an increase in fly ash amendment rate. Majority of Cu
was associated with organic form, but Zn and Ni were
associated with Fe – Mn oxide and residual forms. Addition
of ash-amended sludge to soil significantly increased the
dry weight yields of corn. With increasing coal fly ash
amendment rate, concentrations of Zn and Cu in shoot
tissues of corn decreased significantly, but concentrations of
Cd and Ni showed no significant change. Significant
correlations only noted between shoot tissue content and
some Cu and Zn chemical fractions in fly ash-stabilized
sludge. The present experiment demonstrated that the ash-
stabilized sludge products not only improved the growth of
corn, but also reduced the availability of sludge heavy
metals. Nevertheless, the long-term accumulation of heavy
metals following the application of ash-stabilized sludge
warrants further studies.
Acknowledgements
The work described in this paper was supported by grants
from the Research Grants Council of the Hong Kong
Special Administrative Region, PR China (Project No.
HKBU 2043/98M) and the National Natural Science
Foundation of China (No. 20277045). We would also
express our special thanks to Mr. K.K. Ma for his excellent
technical support throughout the study.
References
Adriano DC. Trace elements in the terrestrial environment. New York:
Spring-Verlag; 1986.
Bowen PT, Jacken MK, Corbitt RA, Conce N. Sludge treatment, utilization
and disposal. Water Environ Res 1992;64:378 – 86.
Chlopecka A. Forms of Cd, Cu, Pb, and Zn in soil and their uptake by
cereal crops when applied jointly as carbonates. Water Air Soil Pollut
1996a;45:297 – 308.
Chlopecka A. Assessment of forms of Cd, Zn and Pb in contaminated
calcareous and gleyed soils in Southwest Poland. Sci Total Environ
1996b;188:253 – 62.
Chlopecka A, Adriano DC. Mimicked in-situ stabilization of metals in a
cropped soil: bioavailability and chemical form of zinc. Environ Sci
Technol 1996;30:3294 – 303.
Chlopecka A, Bacon JR, Wilson MJ, Kay J. Forms of cadmium, lead, and
zinc in contaminated soil from Southwest Poland. J Environ Qual
1996;25:69 – 79.
Christensen GL. Lime stabilization of wastewater sludge. In: Gutschick
KA, editor. Lime for environmental use in ASTM STP 931. Philadel-
phia: American Society for Testing and Materials; 1987. p. 78 – 94.
Jiang RF, Yang CG, Su DC, Wong JWC. Coal fly ash and lime stabilized
biosolids as an ameliorant for boron deficient acidic soils. Environ
Technol 1999;20:645 – 59.
Little TM, Hills JJ. Agricultural experimentation: design and analysis. Chi-
chester: Wiley; 1978.
Logan TJ, Harrison BJ. Physical characteristics of alkaline stabilized sewage
sludge (N-Viro soil) and their effects on soil physical properties. J Envi-
ron Qual 1995;24:153 – 64.
Lowther JR. Use of a single sulfuric acid – hydrogen peroxide digest for the
analysis of Pinus radiata needles. Commun Soil Sci Plant Anal
1989;11:175 – 88.
SAS Institute. Version 8. Cary, NC: SAS Inst.; 1999.
Sims JT, Kline JS. Chemical fractionation and plant uptake of heavy metals
in soil amended with co-composted sewage sludge. J Environ Qual
1991;20:387 – 95.
Soltanpour PN. Determination of nutrient availability and elemental tox-
icity by AB-DTPA soil test and ICPs. Adv Soil Sci 1991;16:165 – 89.
Tessier A, Campbell PGC, Bisson M. Sequential extraction procedure for
the speciation of particulate trace metals. Anal Chem 1979;51:844 – 50.
Wong JWC. The production of artificial soil mix from coal fly ash and
sewage sludge. Environ Technol 1995;16:741 – 51.
Wong JWC, Su DC. Reutilization of coal fly ash and sewage sludge as an
artificial soil-mix: effects of preincubation on soil physico-chemical
properties. Bioresour Technol 1997;59:97 – 102.
Wong JWC, Jiang RF, Su DC. Boron availability in ash-sludge mixture and
its uptake by corn seedlings (Zea mays L.). Soil Sci 1996;161:182 – 7.
Xian X. Effect of chemical forms of cadmium, zinc and lead in polluted
soils on their uptake by cabbage plants. Plant Soil 1989;113:257 – 64.