heavy metals and nutrients chemistry in sewage sludge amended thai soils

27
This article was downloaded by: [University of Southern Queensland] On: 11 October 2014, At: 07:07 Publisher: Taylor & Francis Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK Journal of Environmental Science and Health, Part A: Toxic/Hazardous Substances and Environmental Engineering Publication details, including instructions for authors and subscription information: http://www.tandfonline.com/loi/lesa20 Heavy metals and nutrients chemistry in sewage sludge amended Thai soils P. Parkpain a , S. Sirisukhodom a & A. A. CarbonellBarrachina b a Space Technology Application and Research Program , SERD, Asian Institute of Technology , P. O. Box 4, Klongluang, Pathumthani, 12120, Thailand b Departamento de Agroquímica y Bioquímica, Facultad de Ciencias , Universidad de Alicante , Apartado de correos 99, Alicante, 03080, Spain Published online: 15 Dec 2008. To cite this article: P. Parkpain , S. Sirisukhodom & A. A. CarbonellBarrachina (1998) Heavy metals and nutrients chemistry in sewage sludge amended Thai 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

Upload: a-a

Post on 13-Feb-2017

212 views

Category:

Documents


0 download

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