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ABSTRACT
Determining mobility and availability of metals in sewage sludge
amended soil is an environmental concern. Potential leachability and
bioavailability of metals following sludge applied to agricultural soil
was evaluated. Geochemical forms of metal occurring in sludge-amended
soil were subjected to fractionation for understanding heavy metal transformation and remobilization in sludge-amended soil. Metal leachability
was determined using reconstructed soil proles where dewatered sewage
sludge was incorporated into the surface 010 cm of soil. Two-sludge
application rates; 150 and 300 kgN/ha, equivalent to sludge at 4 and 8
ton/ha, were applied to soil columns representing typical agricultural
clay soils of Thailand (Rangsit acid sulfate soil). The soil columns
were leached with 32 l equivalent to 600 mm of surface water using different leachants (distilled water pH 6, distilled water adjusted to pH 3
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766
PARKPIAN ET AL.
INTRODUCTION
Like many countries in Southeast Asia, Thailand is regarded as an
agricultural country, and the majority of national income comes from agricultural exports. Most of Thai agricultural soils have been used extensively
for crop production for extended periods of time and are usually low in soil
organic matter (SOM) and essential plant nutrients. Added nutrients (chemical fertilizer) are needed for maintaining and increasing crop production.
As a result, the fertilizer applications have increased substantially.
Chemical fertilizers are most commonly imported, being paid for in foreign
currency equivalent to several thousand millions Baht. To reduce such expenditures for chemical fertilizers, sewage sludge (which is considered an organic
fertilizer) is available from wastewater treatment plants in Bangkok for use as
an alternative source of plant nutrients for crops. Agricultural application of
767
768
PARKPIAN ET AL.
Figure 1.
769
the column wall was sanded to increase roughness of the wall for minimizing
any edge eect. To facilitate drainage and soil retainage, 3 cm depth of acidwashed gravel was put over the porous plate. A geotextile was then placed on
the top of the gravel to prevent soil loss during leaching. Washed sand was
placed onto the geotextile to inhibit soil clogging in the geotextile. The soil
was packed into the column and initially rewetted by distilled water to avoid
entrapment of air in the soil pore, until bulk density and water content
reached eld conditions at 1.04 g/cm3 and 47%. Soil thickness after soil
saturation was 10 cm. The quantity of sewage sludge applied to the soil
columns was determined according to AIT recommendation (16) for sludge
application rates for agricultural soils. Dewatered sewage sludge under wet
condition was applied and mixed with topsoil (02 cm depth) at an application rate of 150 and 300 kgN/ha as a dry weight basis. The columns were
rested to stabilize for 1 week, while water content was maintained at 70%
eld capacity during stabilization. The soil columns were leached using leachants shown in Table 1.
Eight liters of a leachant, which was equivalent to 150 mm of simulated
rainfall on a monthly basis, was continuously passed downward through the
soil columns. A second leaching was conducted after gravitational ow
ceased 3 days afterward. A total of four leachings (32 l as being equivalent
to 600 mm, representing average annual rainfall statistics in Pathum Thani
provinces during the rainy season for 4 months) was sprayed onto topsoil in
each soil column. Leachate following each leaching episode was collected in
plastic bottles by gravity ow. Volume, pH, and dissolved organic carbon
(DOC) were immediately measured and recorded. One liter of aliquot was
ltered through Whatman no. 5 lter paper and stored in a refrigerator until
770
PARKPIAN ET AL.
Table 1.
Treatment
Leachants
analyzed. The columns, following a 1-week rest after the last leaching, were
dismantled. The soil core was subsequently removed from the column cut
into ve portions: 02, 24, 46, 68, and 810 cm.
Sample Analysis
All samples were characterized for selected parameters utilizing a specic standard method (Table 2) prior to the leaching experiments. In addition, geochemical forms or metal speciation was conducted from the sludgeamended soil samples after leaching soil columns were completed.
Parameter
Particle size
distribution
pH
Total nitrogen
Total phosphorous
Available phosphorous
Organic carbon
Cation exchange capacity
Exchangeable cations
Water soluble trace metal
Total trace metal
concentrations
Metal speciation
Leachate
771
pH
Dissolved organic carbon
Soluble trace metals
Method
Hydrometer method described by Sheldrick
and Wang (47)
Electrometric method described by
Hendershot, Lalande, and Duquette (47)
Semi-micro kjeldahl method described by
McGill and Figueiredo (47)
HC1O4 acid digestion method described by
OHalloran (47)
Bray II method described by Olsen and
Sommer (48)
Walkley-Black method described by
Rhoades (48)
Ammonia saturation method described by
Rhoades (48)
Ammonium Acetate Method described by
Hendershot, Lalande, and Duquette (48)
Extract by 0.01 M CaCl2
AAs after using CEM MDS-2000 microwave
for digestion
Sequential extraction procedure described by
Tessier et al. (13)
pH meter
Shimadzu 5000A TOC analyzer
Shimadzu AA-6701F atomic absorption
spectrometer
previous application of lime and fertilizer. Soils with high clay content, such
as Rangsit soil, have a high cation exchange capacity (35 meq/100 g). The
water-soluble fraction of heavy metals was low in this soil. Total heavy metal
content of the soil was also relatively low due to no previous history of
receiving metals in the form of sludge application.
Characteristics of Sewage Sludge
Sewage sludge from Bangkok Wastewater Treatment Plant was also
analyzed for selected parameters, which are shown in Table 4. Sludge pH
(6.94) was near neutral using a 1 : 5 sludge-to-water ratio. Total nitrogen
in sewage sludge was approximately 3.60%, with available nitrogen being
approximately 755 mg/kg. Such a nitrogen level is sucient for maintaining plant growth. The sewage sludge used in the study is an excellent
source of many plant nutrients. High amounts of calcium in sludge
resulted from liming in a dewatering process. The Ca could increase the
adsorption of metals by exchanging with cations and coprecipitation as
772
PARKPIAN ET AL.
Table 3.
Parameter
Analyzed Value
3
1.04
4.58
0.05
360
7.75
35
109
1419
266
0.23
0.51
2.99
1.03
2.52
0.29
0.72
21
13
23
24 831
15
16
31
53
773
Parameter
Sludge pH (1 : 5 sludge : water)
Moisture content (%)
Total N (%)
Available N (mg/kg)*
Total P (mg/kg)
Available P (mg/kg)
Organic matter (%)
Alkalinity (g/cm3)*
Exchangeable cations (mg/kg)
K
Ca
Mg
Analyzed Value
6.94
85
3.60
755
13 536
476
46
750
1307
5387
355
0.19
20.58
14.16
3.94
2.29
12.45
1.89
1437
107
1607
23 852
1841
39
1500
420
2800
Zn Cd Ni
Fe
Cu
Zn
Cd
Ni
Fe
Mn
1166 20 455
Mn Cd>Cu>Ni>Zn>Fe
Mn Cd>Ni>Zn>Cu>Fe
Mn Cd>Cu>NiZn>Fe
Mn Cd>Cu>Zn>Fe>Ni
*Input of metals metals from sludge metals from soil metals from distilled water or rainwater.
4.47 31.42
2.37
3667
4601 25 581
Mn
23 291 892
Fe
2.58 26.28
4133
2393 23 256
Ni
2.37
0.25
3.63 22.11
3800
Cd
1002 11 905
Zn
The Sequence of
Leachability
9.10 35.18
0.40
4.36 24.03
2835
Cu
2.21
0.18
Mn
Cu
At 300 kgN/ha
180 197 4.3 77 140 060 159 1.69 3.18 0.31
5. Rangsit
soil sludge
leached by
DW (pH 6)
6. Rangsit
180 197 4.3 77 140 060 159 1.94 3.59 0.26
soil sludge
leached by
DW pH 3
7. Rangsit
180 197 4.4 75 140 060 159 1.77 2.59 0.30
soil sludge
leached by rainwater
(pH 5)
At 150 kgN/ha
1. Rangsit soil
(no sludge)
leached by
DW (pH 6)
2. Rangsit
soil sludge
leached by
DW (pH 6)
3. Rangsit
soil sludge
leached by
DW pH 3
4. Rangsit
soil sludge
leached by
rainwater (pH 5)
Treatment
Metal Leachability at 150 and 300 kgN/ha of Sludge Applied (Based on Dry Metal Weight)
Table 5.
5275
8572
5303
3851
4012
3598
3438
DOC in
Leachate
(mg/kg)
774
PARKPIAN ET AL.
775
776
PARKPIAN ET AL.
777
Nickel
In addition to Cu, Ni is another transition metal that tends to form
covalent bonds with organic ligands (35), but the bond is not as strong as Cu.
In general, Ni is controlled with pH-dependent solubility and complexation
with soluble carbon (28). However, under acid sulfate soil such as Rangsit
soil, the form of Ni is mainly in Ni-sulfate in soil solution. As pH of leachant
was increased, Ni leachability was decreased. This was because H ions
in low pH leachant are strongly attracted to the soil surface (negative
charges), and they have the power to replace Ni. The sequence of metal
leachability in soil column leached with DW pH 3 showed that Ni mobility
was dierent from the other sludge-amended soil leachates. This was because
Ni solubility was aected by the low pH (pH 3). Low pH metal binding
competed with H ions, resulting in fewer sites available for binding (30).
Therefore, under acid soil Ni, with water solubility (2.99 mg/kg) higher
than Cu (0.51 mg/kg), had more leachability than Cu in the soil column
leached by DW pH 3.
778
PARKPIAN ET AL.
779
Treatment
Cu
Zn
Cd
Ni
Fe
Mn
At 150 kgN/ha
1. No sludge leached by DW
2. Sludge leached by DW
3. Leachability of
sewage sludge (3) (2) (1)
2835
3800
955
1002
2393
1391
11 905
23 256
11 351
Trace
2400
2400
23
31
8
291 892
200 250
At 300 kgN/ha
4. Sludge leached by DW
5. Leachability of
sewage sludge (5) (4) (1)
9389
6554
16 142
15 140
72 093
60 188
28 701
28 701
65
42
221 258
780
Table 7.
PARKPIAN ET AL.
Metal Concentrations in the Leachate from Soil Column Leached by Rainwater
Control1
1501
3002
Maximum Level
Groundwater
Quality Standard3
0.012
0.005
0.002
Trace
0.114
0.861
0.017
0.006
0.008
0.008
0.081
0.821
0.056
0.083
0.029
0.076
0.143
1.004
1.5
15.0
0.01
1.0
0.5
Under acid sulfate soil (clay soil) in these leachate studies, Mn showed
the highest concentration in the leachate. Whereas in other studies, Zn concentration from sewage sludge applied to sandy loam soil and silty clay loam
soil was the highest concentration in the leachate (36,37). The dierence of
those metal concentrations or movement in the soil prole was associated
with dierence in soil type and background metal contents in sludge.
Copper and Zinc Mobility in Sludge-Amended Soil
The concentrations of Cu and Zn remain in a sludge-amended soil
prole after leaching soil columns were analyzed to quantify depth metals
penetrated following sludge application. Mobility of Cu and Zn within
soil depth is present in Figures 3 and 4. At the 150 kgN/ha application rate
to the Rangsit soil, there was no evidence of Cu movement from sludgesoil
layer (02 cm depth) with depth into the soil column. As mentioned previously, microbial oxidation of organic components in sewage sludge is an
important aspect governing the movement of sludge in soil. When organic
material is degraded, both fulvic (soluble) and humic (insoluble) acids
are produced. Insoluble organic material eectively inhibits uptake of
metal cations such as Cu, which binds strongly with organic material, preventing plant uptake. Conversely, soluble organics increased the carrying
capacity of soil solution for Cu (38). Therefore, DOC containing fulvic
acids resulting from the origin sludge application could signicantly inuence
the mobility of Cu. However, Cu movement was restricted to surface 4 cm
below sludgesoil layer. Beyond 4-cm depth, Cu concentration was still in
line with native Rangsit soil Cu (21 mg/kg) concentration. When sludge
application was doubled (300 kgN/ha), two soil columns leached with DW
0-2
4-6
20.81
8-10
19.64
20
40
0-2
80
68.59
43.94
18.52
17.75
4-6
19.72
18.16
8-10
0
20
40
Cu Conc (mg/kg)
60
Cu Conc (mg/kg)
(b)
60
80
58.28
0-2
45.98
23.8
20.78
4-6
20.12
18.71
8-10
0
10
20
(c)
30
40
50
60
70
Cu Conc (mg/kg)
Sludge Applied at 150 kgN/ha
71.69
0-2
39.14
4-6
21.44
19.76
8-10
21.42
20.94
0
(d)
781
22.87
(a)
20
40
60
80
Cu Conc (mg/kg)
Sludge Applied at 150 kgN/ha
PARKPIAN ET AL.
0-2
22.78
4-6
21.57
8-10
21.86
20
40
46.22
35.92
4-6
24.89
27.05
8-10
15.55
20
40
Zn Conc (mg/kg)
80
67.78
0-2
(b)
60
80
68.94
0-2
49.04
25.54
21.53
4-6
29
8-10
16.84
(c)
20
40
Zn Conc (mg/kg)
60
80
0-2
52.71
32.45
4-6
24.52
29.84
8-10
15.31
0
(d)
60
Zn Conc (mg/kg)
(a)
782
20
40
Zn Conc (mg/kg)
60
80
783
and rainwater showed that Cu still accumulated only in such layer (04 cm),
the same as the 150 kgN/ha application rate. However, soil columns leached
with DW pH 3, which had the highest amount of DOC (4012 mg/kg) Cu
reached down to the 6-cm depth of a 10 cm depth packed soil column.
Mobility of Zn in Rangsit (Figure 4) after receiving sludge at a low rate
(150 kgN/ha) seemed to be restricted to the surface 08 cm layer. Beyond
8-cm depth in the soil column, Zn concentration of sludge-treated soil was
similar to values found for background Zn concentration (23 mg/kg) in soil.
When sludge application rate was increased (300 kgN/ha), Zn concentration
below 8-cm depth in all soil columns increased above background levels.
Increase in the sludge application rate inuenced Zn mobility more than
Cu mobility under acid sulfate soil. This was due mainly to the linkage form
of Zn that is favorable to remobilization, whereas Cu was mainly accumulated in the topsoil as predominated by less mobilizable forms. However, Cu
and Zn concentrations were recovered close to 100% within 10-cm soil depth
because re-adsorption and precipitation of metals occurred during their
movement from the sludgesoil layer.
Other reported research observed similar results, which showed that the
majority of sludge applied accumulated in the soil surface. As a result, the
movement of metals from the application site was typically minimal.
Following are a few examples of such observations; no sludge-borne metals
were detected below the 15-cm depth in the soil columns, even on the
Plaineld sand with a pH of 4.9 (39). Over 90% of the deposited heavy
metals (Cd, Cr, Ni, Pb, and Zn) were found in the 015 cm soil depth,
where sludge was incorporated, and no statistically signicant increase in
heavy metal content of the soil was detected below the surface 30 cm of the
soil prole after 6 years of continued annual sludge application in coarse and
loamy soil (40). Similar to the work in California that found that the metals
include Cd, Cu, Zn, and Hg, which had concentrations in sludge that were
markedly greater than those in the untreated soil that had moved in small
amounts into the 2530 cm depth over the 9-year period (41). Metals transported from soil surface in grassland soil treated with sewage sludge also did
not go below 10 cm. Most of the 7 metals (Cd, Cr, Cu, Mo, Ni, Pb, and Zn)
(60100%, mean 87%) remained in the upper 5 cm of soil (42). These earlier
studies showed soil below the topsoil layer (015 cm depth) had no signicant
enrichment in heavy metals following sludge application. Less than 1% of the
metal applied had moved below the topsoil layer.
Soil pH at 02 cm depth in sludge-amended Rangsit soil increased over
background topsoil pH (Figure 5). Generally, sewage sludge is treated with
lime to control odor at wastewater treatment plants during sludge processing.
Corresponding organic biodegradation under the acidic condition takes
place, and no acidic products are produced to further decrease soil pH.
The increased soil pH resulted from calcium content of sludge, as such,
would alleviate metal leaching in the soil prole, helping to neutralize soil
PARKPIAN ET AL.
0-2
4.48
4-6
4.51
8-10
4.59
4.4
4.5
4.6
4.7
(a)
4.9
4.97
0-2
4.61
4.78
4-6
4.57
8-10
4.57
4.64
4.4
4.5
4.6
4.8
Soil pH
(b)
4.7
Soil pH
4.8
4.9
4.48
4.48
0-2
4.52
4.5
4-6
4.52
4.54
8-10
4.4
4.5
4.6
(c)
4.7
4.8
4.9
Soil pH
Sludge Applied at 150 kgN/ha
784
4.74
4.72
0-2
4.69
4.68
4-6
4.67
8-10
4.56
4.4
4.5
4.6
(d)
4.7
4.8
4.9
Soil pH
Sludge Applied at 150 kgN/ha
785
Treatment
Soil Depth
(cm)
(a) Copper
Sewage
sludge
Rangsit soil No sludge leached
by DW (pH 6) (control)
With sludge leached
by DW (pH 6)
With sludge leached
by DW3
With sludge leached
by rainwater (pH 5)
Carb
Ox
Org
Res
11.98
10.40
12.18
59.35
6.09
02
810
02
810
02
810
02
810
10.77
16.74
10.14
16.13
14.28
14.60
12.18
11.20
13.48
11.09
7.73
10.08
7.60
11.24
7.47
8.14
9.49
10.37
9.97
9.84
11.83
13.53
15.16
12.60
12.49
9.04
14.67
11.3
15.72
15.46
12.78
13.37
53.77
52.75
57.49
52.64
50.57
45.17
52.40
54.69
11.71
24.95
52.98
6.12
4.25
02
810
02
810
02
810
02
810
7.94
13.17
62.36
20.16
59.63
19.89
54.99
13.99
4.14
6.05
7.76
3.91
4.69
2.54
4.61
4.61
8.10
11.08
11.60
12.01
15.45
10.68
20.83
13.99
7.00
10.40
6.16
6.23
4.88
9.75
4.71
4.28
72.82
59.30
12.12
57.68
15.35
57.14
14.86
63.12
(b) Zinc
Sewage
sludge
Rangsit soil No sludge leached
by DW (pH 6) (control)
With sludge leached
by DW (pH 6)
With sludge leached
by DW3
With sludge leached
by rainwater (pH 5)
Exch
786
PARKPIAN ET AL.
787
CONCLUSIONS
The leachability of metal from the soil prole depended on pH of leachant, rate of sludge applied, chemical nature of metal and metal species, and
fraction. Properties such as organic matter, CEC, soil pH, and minerals in
soil increased the buering capacity of soils, favoring higher metal retention
in the surface layer. Results of this study showed that for Cu and Zn, less
than 0.5% of the two metals applied at 150 kgN/ha and less than 1.8% of
each metal applied at 300 kgN/ha were detected in the leachate. Whereas,
close to 100% of the added metals from sludge were recovered within 10 cm
of the soil column from both sludge application rates. Sequential extraction
of sludge-amended soil after leaching at a high application rate revealed that
Cu was associated with organic and residual fractions, which are not easily
788
PARKPIAN ET AL.
ACKNOWLEDGMENTS
The author would like to thank Mr. Somchai Sornwanee, Ms. Jarirat
Srinatpat, and Ms. Noppawan Jantavee for their excellent technical support
and assistance on sample analyses throughout the experiment at the Department of Drainage and Sewerage, Bangkok Metropolitan Administration
(BMA). The Royal Thai Government provided the nancial support for
this research.
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791