heavy metals and nutrients chemistry in sewage sludge amended thai soils
TRANSCRIPT
This article was downloaded by: [University of Southern Queensland]On: 11 October 2014, At: 07:07Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number:1072954 Registered office: Mortimer House, 37-41 Mortimer Street,London W1T 3JH, UK
Journal of EnvironmentalScience and Health,Part A: Toxic/HazardousSubstances andEnvironmental EngineeringPublication details, including instructions forauthors and subscription information:http://www.tandfonline.com/loi/lesa20
Heavy metals and nutrientschemistry in sewage sludgeamended Thai soilsP. Parkpain a , S. Sirisukhodom a & A. A.Carbonell‐Barrachina b
a Space Technology Application andResearch Program , SERD, Asian Instituteof Technology , P. O. Box 4, Klongluang,Pathumthani, 12120, Thailandb Departamento de Agroquímica yBioquímica, Facultad de Ciencias ,Universidad de Alicante , Apartado decorreos 99, Alicante, 03080, SpainPublished online: 15 Dec 2008.
To cite this article: P. Parkpain , S. Sirisukhodom & A. A. Carbonell‐Barrachina(1998) Heavy metals and nutrients chemistry in sewage sludge amendedThai soils, Journal of Environmental Science and Health, Part A: Toxic/Hazardous Substances and Environmental Engineering, 33:4, 573-597, DOI:10.1080/10934529809376749
To link to this article: http://dx.doi.org/10.1080/10934529809376749
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of allthe information (the “Content”) contained in the publications on ourplatform. However, Taylor & Francis, our agents, and our licensorsmake no representations or warranties whatsoever as to the accuracy,completeness, or suitability for any purpose of the Content. Anyopinions and views expressed in this publication are the opinions andviews of the authors, and are not the views of or endorsed by Taylor& Francis. The accuracy of the Content should not be relied upon andshould be independently verified with primary sources of information.Taylor and Francis shall not be liable for any losses, actions, claims,proceedings, demands, costs, expenses, damages, and other liabilitieswhatsoever or howsoever caused arising directly or indirectly inconnection with, in relation to or arising out of the use of the Content.
This article may be used for research, teaching, and private studypurposes. Any substantial or systematic reproduction, redistribution,reselling, loan, sub-licensing, systematic supply, or distribution in anyform to anyone is expressly forbidden. Terms & Conditions of accessand use can be found at http://www.tandfonline.com/page/terms-and-conditions
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
J. ENVIRON. SCI. HEALTH, A33(4), 573-597 (1998)
HEAVY METALS AND NUTRIENTS CHEMISTRY IN SEWAGE
SLUDGE AMENDED THAI SOILS
Key Words: Bioavailability, heavy metal, sewage sludge
P. Parkpain1, S. Sirisukhodom1 and A. A. Carbonell-Barrachina2
1 Space Technology Application and Research Program. SERD, Asian Institute ofTechnology, P. O. Box 4, Klongluang, Pathumthani. 12120. Thailand
2Departamento de Agroquímica y Bioquímica. Facultad de Ciencias. Universidadde Alicante. Apartado de correos 99, 03080-Alicante, Spain
ABSTRACT
Sludge from the Sipraya treatment plant (Thailand) was mixed at 1090, 1340,
and 2680 ton/ha with two representative Thai soils (Rangsit and Thonburi) to
study sludge-soil chemistry (heavy metals and nutrients solubility and availability).
Mean concentrations of cadmium (Cd), copper (Cu), zinc (Zn), iron (Fe), and
manganese (Mn) in this sewage sludge were within the norms for application to
agricultural soils as reported by the US Environmental Protection Agency; both
soils contained low indigenous concentrations of heavy metals. Soil-solution data
573
Copyright © 1998 by Marcel Dekker, Inc.
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
574 PARKPAIN, SIRISUKHODOM, AND CARBONELL-BARRACHINA
indicated that chemical properties of a sludge-soil mixture depended not only on
the soil, sludge, and its application rate, but also on the sludge-soil interactions.
Soil pH increased and tended to hold steady near neutrality in the Rangsit soil; pH
value more suitable for plant growth than the initial one. Sludge application
significantly increased available concentrations of plant macronutrients:
phosphorus (P), potassium (K) and heavy metals: Cd, Cu, Zn, Fe, and Mn in both
soils; it is important to point out the fact that Cu, Zn, Fe, and Mn are also essential
plant nutrients. When heavy metal fractionation was studied, most of these
chemical elements initially present as easily mobile pools were later (12 weeks of
incubation) converted into sparingly mobile fractions, decreasing risks of heavy
metal toxicity.
INTRODUCTION
Domestic sewage discharges into the environment is a major urban
environmental problem in Thailand. The government will spend more than 600
million US. dollars between 1991 to 1998 for construction of wastewater
treatment plants (BMA, 1995). By the year 2000, sludge production in Bangkok is
predicted to reach approximately 172 ton dry solid/day (AIT, 1995). Disposal
space is limited and the cost for disposal is certainly increasing. This will lead to
additional environmental problems unless safe and environmental-concerned
disposal options for sludge material are developed.
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
METALS AND NUTRIENTS IN SLUDGE-AMENDED SOILS 575
Sludge due to high nutrient content could be utilized as soil amendment or
fertilizer. Increasing cost of commercial fertilizers have made sludge application to
crop and forest lands an attractive alternative for waste disposal and a seemingly
responsible means for resource reuse and recycling. Agricultural application was
ranked as the first disposal choice to be promoted in Bangkok areas (AIT, 1995).
Waste application on agricultural lands, however, has caused concerns. It is
often argued that heavy metals such as cadmium (Cd), nickel (Ni) or lead (Pb) in
sludge, when applied to soils, may enter the food chain through plants or animals,
contaminate surface and ground water, and thus cause health hazards. In reality,
metal concentrations in sewage sludge vary widely (Hue and Ranjith, 1994),
depending on several factors, including: (i) sewage origin (e.g. industrial wastes
usually contain higher levels of heavy metals than residential wastes), (ii) sewage
treatment process (e.g. each process reduce heavy metal differently), and (iii)
sludge treatment process (e.g. aerobic versus anaerobic treatment). In addition,
when applied to soils, the bioavailability of sludge-borne metals is further
influenced by soil properties (e.g., pH, redox potential (Eh), sesquioxide content,
and organic matter) as well as sludge application rate (Hue and Ranjith, 1994).
This explains the lack of metal accumulation in plants grown on certain sludge-
amended soils and the beneficial effects of sludge on soil fertility and plant
nutrition (Hue, 1988). Given this background, a better understanding of the basic
chemistry of wastes and their interactions with soils will help sludge managers
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
576 PARKPAIN, SIRISUKHODOM, AND CARBONELL-BARRACHINA
make reasonable decisions on the use of sludges on lands. Unfortunately,
understanding about Thailand's sludges and their reactions with highly acidic soils
is inadequate.
Studies on bioavailability of heavy metals from sewage sludge amended soils
were conducted to determine fate and transport of metals in two typical
agricultural soils of Thailand. Data collected in this studies will be used to develop
guidelines for sludge application on agricultural lands. A series of laboratory
experiments were conducted on sludge amended soils at various application rates
and equilibration times. Specific objectives of this study were to evaluate: (i)
metals availability in selected agricultural soils after sludge application, and (ii)
chemical fate, transport, and accumulation of heavy metals and nutrients (Cd, Cu,
Zn, Mn, and Fe) in agricultural soils treated with sludge.
MATERIALS AND METHODS
Characterization of Soils and Sewage Sludge
The two major agricultural soil series ( plough layer, 1-20 cm) found in the
Bangkok region and elsewhere in Thailand: Rangsit and Thonburi, were used in
this study. Sewage sludge (after thickening and dewatering processes) with a 20 %
dry solid content, from Sipraya wastewater treatment plant, was selected for soil
amendment.
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
METALS AND NUTRIENTS IN SLUDGE-AMENDED SOILS 577
Soils and sludge were sampled, air dried at ambient temperature (25-35 °C),
crushed by hand in a porcelain mortar, and sieved through a 2-mm screen. Initial
chemical and physical properties are summarized in Table 1.
Soil particle size analysis was determined using the hydrometer method
(Sheldrick and Wang, 1993). Clay minerals content in the soil was determined by
x-ray diffraction (Whittig and Allardice, 1986). Soil pH values were measured in a
1:2.5 soil:water mixture (Hendershot et al., 1993a). Soil cation exchange capacity
(CEC) was determined using the ammonium saturation procedure (Rhoades,
1982). Organic matter was analyzed by the Walkley-Black method (Schnitzer,
1982). Humic substances were extracted and fractionated with NaOH and N a ^ O ?
respectively, and quantified by the permangametry method (Suzuki et al., 1980).
Total nitrogen was determined by semi-micro Kjeldahl method (McGill and
Figueiredo, 1993). Total and available phosphorus (P) were analyzed by digestion
with concentrated HC1O4 and extraction with Bray II solution respectively; P was
then measured colorimetrically (O'Halloran, 1993). Exchangeable cations:
potassium (K), magnesium (Mg), and calcium (Ca) were extracted with 1 M
NH40AC (pH 7.0) and analyzed by atomic absorption spectrophotometer (AAS)
(Hendershot et al., 1993b). Iron and manganese oxides were determined by citrate
dithionite extraction and analyzed by AAS (Ross and Wang, 1993). Total metals
cadmium (Cd), copper (Cu), zinc (Zn), manganese (Mn), and iron (Fe) were
digested with a mixture of HC1O4:HNO3 at 2:1 (v:v) and measured by AAS (Soon
and Abboud, 1993).
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
578 PARKPAIN, SIRISUKHODOM, AND CARBONELL-BARRACHINA
Metal Bioavailabilitv in Sludge Amended Soils
Sludge was added to soils at rates of 100.00, 122.95, and 245.90 g/100 soil
(1090, 1340, and 2680 ton/ha). Reaction time for sludge amended and unamended
soil (control) treatments was 0, 5, 8, 10, and 12 weeks. All treatments were
incubated at constant room temperature (25 °C). Soil moisture content was
maintained at approximately 60 % field capacity by frequently adding distilled-
deionized water.
Metal bioavailability in the treatments was measured with time and it was
compared with that found in controls. At end of each reaction period, selective
dissolution techniques were used to quantify metal concentrations in various pools
(plant available, water soluble, exchangeable, organically bound, and amorphous
oxides bound forms). Several chemical extradants were used to extract metals of
interest (Cd, Cu, Zn, Mn, and Fe) according to Soon and Abbound (1993): DTPA
pH 7.3 and 0.1 N HC1 (plant available), 0.01 M CaCl2 (water soluble), 1 M
NH40AC pH 7.0 (exchangeable), 0.1 M Na4P2O7 (organically bound), and acid
ammonium oxalate (bound to amorphous oxides). A 10-g (dry soil basis) soil
sample was equilibrated with 25 mL of each extractant solution. Samples were
horizontally shaken at 150 rpm for 2 h, and then filtered. Metals in the filtrate were
measured by AAS. Soil pH and selected plant nutrients (P and K) at each reaction
time were also monitored.
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
METALS AND NUTRIENTS IN SLUDGE-AMENDED SOILS 579
RESULTS AND DISCUSSION
Characteristics of Studied Soils
Chemical and physical characteristics of soils and sludge material studied are
presented in Table 1. Rangsit soil contained 68 % clay as compared to 57 % clay
in Thonburi soil. These two soils studied fall into the same "clay texture" class as
classified by the textural triangle method (USDA, 1970). Based on a higher
content of monmorillonite, Thonburi soil would be expected to have a greater
metal sorption capacity than Rangsit soil because monmorillonite can sorb higher
amount of cations than any other clay minerals (Srivastava et al., 1989).
Rangsit soil pH was quite low (4.6) due to its parent material: estuarine
sediment. This pH value is below the reported suitable pH range (6.5-7.5) for
general plant growth (Mengel and Kirkby, 1982). Soil pH below 6.5 may also pose
metal toxicity problems (U.S. EPA, 1983). Thonburi soil pH, on the other hand,
was high (7.9), though its parent materials were also marine sediment, because of
frequent liming and amendments. According to the low pH, the soil could
potentially has heavy metals toxicity problem if amended with sewage sludge
containing high heavy metals concentrations.
Organic matter (OM) of Rangsit soil was rated as moderately high (3.18%)
whereas Thonburi soil was rated as moderately low (1.21%) (USDA, 1970).
Cation exchange capacity (CEC) values for the soils were related to OM and clay
types and contents (USDA, 1970). Heavy texture soil such as Rangsit had higher
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
580 PARKPAIN, SIRISUKHODOM, AND CARBONELL-BARRACHINA
TABLE 1
Chemical and Physical Properties of Soils and Sewage Sludge Samples.
Parameter
Particle size distribution, %SandSiltClay
Clay mineral content, %KaoliniteIlliteMontmorillonite
pHOrganic matter, %Cation exchange capacity, meq/100 gsoilHumic substances;
Total humus (Ht), mlExtracted humus (He), mlTotal humic acid (HA), mlTotal fiilvic acid (FA), ml
Total nitrogen, %Total phosphorus, mg/kgAvailable phosphorus, mg/kgExchangeable cations, mg/kg
KMgCa
Total free oxides, mg/kgFeMn
Total heavy metal, mg/kgCdCuZnMnFe
RangsitSoil
16.6715.0768.265-20High
MediumLow4.683.18
20.43
46.008.667.451.210.39
5718
50610171094
546638
Trace275168
10551
ThonburiSoil
9.6233.0257.365-20
MediumLowHigh7.941.21
17.44
17.501.591.340.250.1711520
182926
4951
11559190
Trace2264
21120486
SewageSludge
-
-6.82
19.89-
288.508.685.193.493.431151979
87032738332
218503743
1.22801
13262621
16706
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
METALS AND NUTRIENTS IN SLUDGE-AMENDED SOILS 581
CEC than Thonburi due in part to the higher soil OM and clay content. The CEC
values of Rangsit and Thonburi soils were rated high (20 meq/100g soil) and
moderately high (17 meq/100g soil), respectively, according to the standard USD A
determination (USDA, 1970).
As illustrated in Table 1, both soils contained low quantities of extracted humus
and more humic acid than fulvic acid. The humic acid present could play a major
important role in forming complexes with nieta! ions. Since both solubility of metal
ions and humic acid complexes are pH dependent (Sparks, 1995), the pH level of
Rangsit and Thonburi soils would be important in determining metal availability.
Iron and Mn oxides found in soil can strongly govern metal behavior (Mengel
and Kirkbly, 1987). This oxides bind with variety of trace metals, influence soil
acidity, and govern metal solubility and toxicity. Iron and Mn oxides were clearly
higher in Thonburi soil than in Rangsit soil.
Native heavy metal content in the two soils were quite low and were lower than
acceptable maximum concentration for metals in agricultural soils in European
countries (Webber et al., 1984).
Characteristics of Sewage Sludge
Average pH value of sewage sludge was 6.82. This value was slightly higher
than recommended ceiling pH (6.5) limit for use in agricultural application (U.S.
EPA, 1983). Organic matter in sludge was rather high (19.89 %) due to the
original organic substances from wastewater and microbial cells. Although sludge
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
582 PARKPAIN, SIRISUKHODOM, AND CARBONELL-BARRACHINA
contained a higher amount of total humus (Table 1) than the soils studied, it
yielded the lowest percent of extracted humus in total humus (He/Ht), indicating
that most of organic substances in this sludge had not stabilized yet and would be
subjected to further mineralization.
This sludge contained large amounts of N (3.43 %), P (0.12%) ,and cations (K,
Mg, Ca, Cu, Zn, Mn, and Fe) which can serve as a source of plant nutrients.
Mineralization of OM in the applied sludge could induce metal solubilization and
release into soil solution. Fortunately, sludge chemical properties, such as pH
buffering capacity and high levels of exchangeable cations, would help suppress
release of metals into solution (Khalid, 1980).
Concentrations of all individual heavy metals (except Fe) in the sludge material
were high when compared to those of agricultural soils. Thus, application of
sludge to soil would result in an increase in heavy metals content of the soil. All
metals in the sludge were, however, within the acceptable or allowable range for
agricultural use (Webber et al., 1984).
Fate of Heavy Metals in Sludge Amended Soils
Soils were amended with various rates of sludge application and incubated for
0, 5, 8, 10, and 12 weeks. Changes in soil pH, plant nutrients (P and K), and metal
solubility (Cd, Cu, Zn, Mn, Fe) were as follows.
Application of sewage sludge resulted in a significant increase in pH of the
Rangsit acid soil (Figure la). Other studies have reported similar pH changes
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
METALS AND NUTRIENTS IN SLUDGE-AMENDED SOILS 583
resulting from sludge application (Cavallaro et al., 1993 and Hue, 1992). This
effect was not observed, however, in the neutral or alkaline soil (Thonburi) (Figure
lb). After 12 weeks, all Rangsit soil treatment combinations amended with sludge
approached an alkaline pH (Figure la), with measured pH being higher than 7.5.
Similar results have also been reported by Siriratpiriya (1989). This change of soil
pH from very strong acid (4.6) to neutral or slightly alkaline would be more
suitable for crop production due to a reduction in the risk of heavy metals toxicity.
Sludge application rates at 1090, 1340, and 2680 ton/ha are equivalent to
additions of 978, 1203, and 2406 mg P/kg soil, and 870, 1070, 2140 mg K/kg soil,
respectively. Available P significantly increased after sludge application (week 0),
and continued to increase with time in all sludge-treated soils (Figure 2). Gillies et
al. (1989) reported that when sludge is applied to soil, soil organic matter and
plant nutrients will significantly increase. After 8 weeks, P concentration started to
level off Plant available P was, however, more than adequate even at the lowest
sludge application rate (1090 ton/ha) and significantly higher than in control soils.
Since the soils used for this incubation study have high CEC and clay content, P
toxicity would not occur.
A significant increase in exchangeable K induced by sludge application was also
found in Thonburi soil (Figure 3b). The availability of K (Figure 3) in both soils
slightly decreased after 8 weeks, following a pattern similar to that of available P.
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
584 PARKPAIN, SIRISUKHODOM, AND CARBONELL-BARRACHINA
10.00
0 5 8 10 12 0 5
(a) (b)
FIGURE 1
Soil Reaction Change: (a) Rangsit Soil, (b) Thonburi Soil.
- Control -•— Application rate 1090 ton/ha
- Application rate 1340 ton/ha -*— Application rate 2680 ton/ha
5 8 10Reaction Tiire, wk
5 8 10Reaction Türe, wk
(a) (b)
FIGURE 2
Soil Available P: (a) Rangsit Soil, (b) Thonburi Soil.
• Control
• Application rate 1340 ton/ha
• Application rate 1090 ton/ha
- Application rate 2680 ton/ha
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
METALS AND NUTRIENTS IN SLUDGE-AMENDED SOILS 585
1000.00
900.00 ¡r~~J*.'«''"*~-'800.00 • ; - - . •^••^^^j^^sxl^
-^ 700.00 \ r - ^ 7 * ^ * ^ " •"•"'-£ 600.00 • -/-
£. 500.00 f "
% 400.00300.00
200.00-•
100.00 • •
0.00
1000.00
0.00
800.00-
TDO 700.00 pT—j.•£ 600.00 iE 500.00 4- ~
S 400.00 - — — - -
300.00-
200.00 -,
100.00--
H 1 H5 8 10
Reaction Time, \vk5 8 10Reaction Tine, wk
(a) (b)
FIGURE 3
Soil Exchangeable K: (a) Rangsit Soil, (b) Thonburi Soil.
• Control
- Application rate 1340 ton/ha
• Application rate 1090 ton/ha
- Application rate 2680 ton/ha
Results depicted in Figures 2 and 3 showed that sludge application to soils
would provide a significant source for two essential macronutrients (P and K).
Although P and K concentrations tended to decrease after 8 weeks of incubation,
the remaining concentrations in the soil, as plant available, were above vegetables
and crops requirements.
In this study, data using DTPA pH 7.3 extraction are presented since this
extractant solution is reported to be the most appropriate for evaluating
bioavailable forms of metals, including Cd (Haq et al., 1980).
Only-low concentrations of plant available Cd were measured in both soils
(Rangsit and Thonburi) after sludge application (Figure 4). Plant available Cd did
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
586 PARKPAIN, SIRISUKHODOM, AND CARBONELL-BARRACHINA
5 8 10Reaction Tims, wk
(a)
5 8 10Reaction Time, wk
(b)
FIGURE 4
Plant Available Cd (DTPA Extract): (a) Rangsit Soil, (b) Thonburi Soil.
-Control
• Application rate 1340 ton/ha
- Application rate 1090 ton/ha
• Application rate 2680 ton/ha
not increase proportionally to sludge application rate (1090, 1340, and 2680 ton
sludge/ha which was equivalent to 1.22, 1.50, and 3.00 mg Cd/kg soil,
respectively) because several sludge properties, such as OM, pH, and
exchangeable cations, increase soil Cd sorption capacity, decreasing Cd release to
the soil solution. Furthermore, concentration of Cd released from the sludge
amended soils did not increase with time, implying that after sludge application to
the soils, most of the added Cd remained in non-bioavailable forms. The low
concentrations of plant available Cd found (below the maximum threshold for
available Cd in agricultural soils, <0.5 )ig/mL) indicated that its phytotoxicity
would be minimum (Geiger et al., 1993).
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
METALS AND NUTRIENTS IN SLUDGE-AMENDED SOILS 587
Since Cu and Zn behave similarly to Cd in soil, they could possibly compete
with each other for the available sorption sites in soil (Nriagu, 1980). Application
rate of sludge 1090, 1340, 2680 ton/ha are equivalent to addition of 801, 985, and
1970 mg Cu/kg soil, 1326, 1630, and 3260 mg Zn/kg soil, respectively. Sludge
application significantly increased soil Cu and Zn concentrations (Figure 5 and 6).
Copper and Zn concentrations increased with increasing sludge application rate but
tended to decrease with time.
Metal speciation in soil samples treated with sewage sludge analyzed at zero
incubation time indicated that large amounts of these two metals (Cu and Zn)
existed mainly as organically and amorphous oxides bound forms (Table 2 and 3).
Cu fractions existed in the following order of relative distribution; organically
bound, plant available (DTPA extract), and amorphous oxides/hydroxides bound
forms (Table 2). Only small portions were presented in the water soluble, 0.1 N
HC1 extract, and exchangeable forms. Geiger et al. (1993) reported similar results
and concluded that Cu was strongly bound to soil OM.
Zinc exhibited similar distribution patterns to Cu (Table 3). Plant available Zn
(DTPA extract) was the main Zn fraction, followed by amorphous
oxides/hydroxides bound Zn and organically bound Zn, both with similar
concentrations. Exchangeable and water soluble forms were only found in trace
amounts.
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
588 PARKPAIN, SIRISUKHODOM, AND CARBONELL-BARRACHINA
5 8 10Reaction Time, wk
5 8 10Reaction Time, wk
(a) (b)
FIGURE 5
Plant Available Cu (DTPA Extract): (a) Rangsit Soil, (b) Thonburi Soil.
- • - Control -•— Application rate 1090 ton/ha
-*— Application rate 1340 ton/ha -*— Application rate 2680 ton/ha
— .3
_ 120.00
•á looooE- 80.00
5 8 10Reaction Time, wk
(a)
5 8 10
Reaction Time, wk
(b)
FIGURE 6
Plant Available Zn (DTPA Extract): (a) Rangsit Soil, (b) Thonburi Soil.
• Control
• Application rate 1340 ton/ha
- Application rate 1090 ton/ha
• Application rate 2680 ton/ha
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
METALS AND NUTRIENTS IN SLUDGE-AMENDED SOILS 589
TABLE 2
Cu Fractions (mg/kg) of the Studied Soils at 0 and 12 Weeks of Incubation.
Cu Fraction (extractant)
Plant available (DTPA)Water soluble (CaCl2)Exchangeable (NHioAc)Plant available (HC1)Organic bound
(Na4P2O7)Amorphous. Oxide bound(Am. Oxalate)
RangsitOwk
R.
963
112
150
69
R2
1144
163
182
101
Soil12
Ri
611.01.90.847
141
wkR2
711.82.51.767
146
ThonburiOwl
Ri
1245
153
185
79
c
R2
1347
184
210
95
Soil12
R,
841.94.31.969
117
wk
R2
862.14.82.076
157
Note: Ri and R2 stand for sewage sludge application rates at 1340 and 2680ton/ha, respectively.
TABLE 3
Zn Fractions (mg/kg) of the Studied Soils at 0 and 12 Weeks of Incubation.
Zn Fraction (extractant)
Plant available (DTPA)Water soluble (CaCl2)Exchangeable (NHtoAc)Plant available (HC1)Organic bound
(Na4P2O7)Amorphous. Oxide bound(Am. Oxalate)
Rangsit SoilOwk
R!
1230.36.90.255
55
R2
1310.37.80.353
55
12
Ri
1070.01
1.00.185
105
wk •
R2
1260.02
1.10.2110
150
Thonburi SoilOwk
Ri
1380.14.80.155
53
R2
1460.15.20.154
53
12
Ri
1130.11.1
0.0286
124
wk
R2
1170.11.7
0.03111
156
Note: Ri and R2 stand for sewage sludge application rates at 1340 and 2680ton/ha, respectively.
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
590 PARKPAIN, SIRISUKHODOM, AND CARBONELL-BARRACHINA
Sludge-added Cu and Zn initially partitioned into easily mobile pool (plant
available, water soluble, and exchangeable forms) was converted into immobile
pools (organically bound and amorphous oxides/hydroxides bound forms) after 12
weeks of incubation (Tables 2 and 3).
Although concentration of readily available Cu and Zn in amended soils
decreased with time, Cu and Zn concentrations at 12 weeks were still higher than
those found in non-amended soils. This could possibly induce Zn toxicity in Zn-
sensitive plants and create antagonistic effects with P, causing a reduction in P
uptake by plants (Mengel and Kirkby, 1982). Concentrations of both Cu and Zn in
sewage sludge in conjunction with the Cd level should be considered before
applying sludge to agricultural soils.
Iron and Mn can be adsorbed or bound with a number of trace metals, induce
soil acidity, and become toxic at high concentrations (Vega et al., 1992). Their
chemistry was similar to that of Cu and Zn. Sludge application at rates of 1090,
1340, and 2680 ton/ha were equivalent to addition of 16706, 21225, and 42450
mg Fe/kg soil, and 2621, 3330, 6660 mg Mn/kg soil, respectively. Soils presented
high concentrations of Fe and Mn (Table 4 and 5) after sewage sludge application.
The increase in Fe and Mn concentration, however, was not proportional to the
sewage sludge application rate.
Iron fractions in soils occurred in the following decreasing order at zero weeks
after sludge application: organically bound > amorphous oxides/hydroxides > plant
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
METALS AND NUTRIENTS IN SLUDGE-AMENDED SOILS 591
TABLE 4
Fe Fractions (mg/kg) of the Studied Soils at 0 and 12 Weeks of Incubation.
Fe Fraction (extradant)
Plant available (DTPA)Water soluble (CaCl2)Exchangeable (NHioAc)Plant available (HC1)Organic bound
Amorphous. Oxide bound(Am. Oxalate)
Oi
Ri
580.04
0.6Tr.
248
97
Rangsitvk
R2
410.30.6Tr.
250
106
Soil12
Ri
7.3Tr.0.60.3
294
839
wkR2
7.0Tr.0.80.4
349
967
Thonburi SoilOwk
R.
270.10.5Tr.
211
106
R2
250.20.5Tr.
245
113
12Ri
6.9Tr.0.60.3
325
893
wkR2
5.2Tr.0.70.4
352
994
Note: Ri and R2 stand for sewage sludge application rates at 1340 and 2680ton/ha, respectively.
TABLE 5
Mn Fractions (mg/kg) of the Studied Soils at 0 and 12 Weeks of Incubation.
Mn Fraction (extractant)
Plant available (DTPA)Water soluble (CaCl2)Exchangeable (NHtoAc)Plant available (HC1)Organic bound
(Na4P2O7)Amorphous. Oxide bound(Am. Oxalate)
RangsitOwk
Ri
675.265
7.7121
209
R2
614.562
4.2117
203
Soil12 wk
Ri
19410.8
718.1176
205
R2
21623.3100
14.4203
274
Thonburi SoilOwk
Ri
883.5
. 524.2115
211
R2
712.648
3.6113
207
12 wkRi
1768.272
5.5191
207
R3
21020.8105
18.9243
280
Note: Ri and R2 stand for sewage sludge application rates at 1340 and 2680ton/ha, respectively.
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
592 PARKPAIN, SIRISUKHODOM, AND CARBONELL-BARRACHINA
available (DTPA extract) (Table 4). Soils contained small concentrations of Fe in
the exchangeable form and trace amounts of both water soluble and plant available
Fe (HC1 extract). During incubation, plant available Fe (DTPA extract) and water
soluble Fe significantly decreased with time while Fe bound to organic matter and
amorphous oxides significantly increased in both soils (Table 4). Most of the Fe
added with the sludge was immobilized into lesser available pools with time.
Mn existed in the soils mainly as amorphous oxides/hydroxides, followed by
organically bound forms (Table 5). Plant available Mn (DTPA extract) was similar
in concentration to exchangeable Mn. Water soluble and plant available (HC1
extract) Mn were low compared to the other Mn fractions. Major Mn fractions
increased with reaction times. At 12 weeks, in contrast to Cu, Zn, and Fe, the
applied sewage sludge still continued supplying Mn to the soils (Table 5). Vega et
al. (1992) reported similar results; they indicated that added OM from sewage
sludge may create a reduced environment which in turn increases Mn solubility.
The high concentrations of Fe resulting from sewage sludge application could
initially induce Fe toxicity in plants, however, this Fe-induced toxicity would
decrease with time as shown by Fe concentration reduction with time (Figure 7).
Manganese, on the other hand, appeared to have a greater potential for plant
toxicity as shown by the measured increase in Mn with time (Figure 8). Risk of Mn
toxicity depend on the Mn content of the soil and the amount of easily oxidizable
carbon (Vega et al., 1992). Therefore, precaution should be taken regarding
potential Mn toxicity resulting from sewage sludge application to agricultural soils.
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
METALS AND NUTRIENTS IN SLUDGE-AMENDED SOILS 593
70.00 30.00 i
25.00 *
20.00-
15.00 •
10.00
5.00 •
0.00-
y
0 5 8
Reaction Time.
„ ,
- * = 1- • - X ]
t10 1
wk5 8 10
Reaction Time, wk
(a) (b)
FIGURE 7
Plant Available Fe (DTPA Extract): (a) Rangsit Soil, (b) Thonburi Soil.
• Control
- Application rate 1340 ton/ha
• Application rate 1090 ton/ha
• Application rate 2680 ton/ha
250.00 25003-
5 8 10Reaction Time, wk
T5 8 10
Reaction Time, wk
(a) (b)
FIGURE 8
Plant Available Mn (DTPA Extract): (a) Rangsit Soil, (b) Thonburi Soil.
- Control
- Application rate 1340 ton/ha
• Application rate 1090 ton/ha
- Application rate 2680 ton/ha
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
594 PARKPAIN, SIRISUKHODOM, AND CARBONELL-BARRACHINA
CONCLUSIONS
Sludge from the Sipraya treatment plant (Thailand) was mixed at three different
rates with two representative Thai soils (Rangsit and Thonburi) to study heavy
metals and nutrients solubility and availability. Heavy metals concentrations (Cd,
Cu, Zn, Fe, and Mn) in this sewage sludge were within the norms for sludge heavy
metals application to agricultural soils as reported by the US E.P.A. Application of
sewage sludge increased pH of the acid soil (Rangsit) and improved both soils
fertility by increasing available concentrations of plant nutrients. Heavy metals
concentration generally increased with sludge application to soils. Most of metals
from the sludge amended soils became immobile with time. Further research on
metal toxicity risks from sludge application are needed before the practice of
sewage sludge application to Thailand agricultural soil can be recommended.
These studies should include metals and nutrients uptake by plants as related to
sludge application rate.
ACKNOWLEDGEMENTS
This research was supported by a grant from The Swedish International
Development Cooperation Agency (SIDA), The Royal Thai Government (RTG)
and World Health Organization (WHO).
REFERENCES
AIT (Asian Institute of Technology), "Master Plan on Treatment and Disposal of
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
METALS AND NUTRIENTS IN SLUDGE-AMENDED SOILS 595
Domestic Sewage Sludge Including Nightsoil and Oil and Grease Residues forBangkok Metropolitan" Final Report, Paper Prepared for BMA (1995).
BMA (Bangkok Metropolitan Administration), "Sipraya Wastewater TreatmentPlant Project, Water Quality Control Division, Drainage and Sewerage Dept.,BKK (1995).
Bingham, F. T., Garrison, S. and Strong, J. E., J. Environ. Qual., 13, 71-74(1984).
Bradley, J. et al., Worldwide Sludge Management Practices. In: C. Lue-Hing et al.(eds.), "Municipal Sewage Sludge Management: Processing, Utilization, andDisposal", Water Quality Management Library, vol. 4, Technomic Publishing Co.,Inc., Lancaster (1992).
Cavallaro, N., Padilla, N. and Villarrubia, J., Soil Sci., 156, 63-70 (1993).
Geiger, G., Federer, P. and Sticher, H., J. Environ. Qual. 22, 201-207 (1993).
Gennaro, M. C. et al., The Effect of Sewage Sludge on Sorption Process of HeavyMetals by Soil. In: S. P. Vamavas (ed.), "Environmental Contamination", 6th
International Conference, Delphi, Greece, CEP Consultants Ltd., UK (1994), pp.86-88.
Haq, A. U., Bates, T. E. and Soon, Y. K., Soil Sci. Soc. Am. J. 44, 772-777(1980).
Hendershot, W. H., Lalande, H. and Duquette, M., Soil pH. In M. R. Carter (ed.),"Soil Sampling and Method of Analysis", Lewis Publishers, Boca Raton, Fla, US(1993a).
Hendershot, W. H., Lalande, H., and Duquette, M., Exchangeable cations. In M.R. Carter (ed.), "Soil Sampling and Method of Analysis", Lewis publishers, BocaRaton, Fla, US (1993b).
Hue, N. V., Commun. Soil Sci. Plant Anal. 19, 1633-1643 (1988).
Hue, N. V., Commun. Soil Sci. Plant Anal. 23, 241-264 (1992).
Hue, N.V. and Ranjith, S.A., Water, Air, and Soil Pollution. 72, 265-283 (1994).
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
596 PARKPAIN, SIRISUKHODOM, AND CARBONELL-BARRACHINA
Khalid, R. A., Chemical Mobility of Cadmium in Sediment-Water Systems. In: J.O. Nriagu (ed.), "Cadmium in the Environment Part I: Ecological Cycling", JohnWiley & Sons, Inc., New York, NY, US (1980), pp. 257-304.
Lindsay, W. L. and Norvell, W. A., Soil Sci. Soc. Am. J. 42, 421-428 (1978).
Mcgill, W. B. and Figueiredo, C. T., Total Nitrogen. In: M. R. Carter (ed.), "SoilSampling and Method of Analysis", Lewis Publishers, Boca Raton, Fla, US(1993).
Mengel, K. and Kirkby, E. A., "Principles of Plant Nutrition", International PotashInstitute, Worblaufen-Bem, Switzerland (1982).
Nriagu, J. O., Production, Uses, and Properties of Cadmium. In: J. O. Nriagu(ed.), "Cadmium in the Environment Part I: Ecological Cycling", John wiley &sons, Inc., New York, NY, US (1980), pp. 35-70.
O'Halloran, I. P., Phosphorus. In: M. R. Carter (ed.), "Soil Sampling and Methodof Analysis", Lewis Publishers, Boca Raton, Fla, US (1993).
Rhoades, J. D., Soil Cation Exchange Capacity. In: A. L. Page, R. H. Miller andD. R. Keeney, (eds.), "Methods of Soil Analysis Part II: Chemical andMicrobiological Properties", 2nd Edition, ASA and SSSA, Inc. Publisher, Madison,WI, US (1982).
Ross, G. J. and Wang, C., Iron and Manganese Oxides. In: M. R. Carter (ed.),"Soil Sampling and Method of Analysis", Lewis Publishers, Boca Raton, Fla, US(1993).
Schnitzer, M., Soil Organic Matter. In: A. L. Page, R. H. Miller and D. R. Keeney,(eds.), "Methods of Soil Analysis Part II: Chemical and MicrobiologicalProperties", 2nd Edition, ASA and SSSA, Inc. Publisher, Madison, WI, US (1982).
Sheldrick, B. H. and Wang C., Soil Particle Size Analysis. In: M. R. Carter (ed.),"Soil Sampling and Method of Analysis", Lewis Publishers, Boca Raton, Fla, US(1993).
Soon, Y. K. and Abboud, S., Total Heavy Metals. In: M. R. Carter (ed.), Soil"Sampling and Method of Analysis", Lewis Publishers, Boca Raton, Fla, US(1993).
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014
METALS AND NUTRIENTS IN SLUDGE-AMENDED SOILS 597
Sparks, D. L., "Environmental Soil Chemistry", Academic Press Inc., CA, US(1995).
Srivastava, S. K. et al., Environ. Technol. Letters. 10, 275-282 (1989).
Suzuki, M. et al., "Soil Chemical Studies on Rotting Process of Plant Remains inRelation to Fertility of Upland Soils in Thailand", The Cooperative Research WorkBetween Thailand and Japan, DOA, Ministry of Agriculture and Cooperatives,Bangkok, Thailand (1980).
US EPA (US Environmental Protection Agency), "Municipal SludgeManagement", EPA 430/9-77-004, US EPA, Washington, D. C. (1983).
USDA (US Department of Agriculture), "Soil Taxonomy of the NationalCooperative Soil Survey", DOA, US (1970).
Vega, S., Calisay, M. and Hue, N. V., J. Plant Nutr. 15, 219-231 (1992).
Webber, M. D., Kloke, A. and Jell, J. C., A Review of Current Sludge UseGuideline for the Control of Heavy Metal Contamination in Soils. In: P. L.Hermite and H. Ott (eds.), "Processing and Use of Sewage Sludge", D. ReidalPublishing Company, Holland (1984), pp. 371-385.
Whittig, L. D. and Allardice, W. R., X-ray Diffraction Techniques. In: R. Arnoldet al. (eds.), Methods of Soil Analysis. Part I: Physical and Mineralogical Methods.2nd Edition. ASA, Inc. and SSSA, Inc. Publisher, Madison, WI, US (1986).
Received: October 22, 1997
Dow
nloa
ded
by [
Uni
vers
ity o
f So
uthe
rn Q
ueen
slan
d] a
t 07:
07 1
1 O
ctob
er 2
014