J. ISSAAS Vol. 20, No.

2:43-50 (2014)

EFFECTS OF SILICATE APPLICATION ON THE RELEASE PATTERN

OF NATIVE INORGANIC PHOSPHORUS FROM ANDISOL SOIL IN LEMBANG,
INDONESIA USING SUCCESSIVE RESIN EXTRACTION

Arief Hartono1 and Ridho Bilhaq2

1
Department of Soil Science and Land Resource, Faculty of Agriculture,
Bogor Agricultural University, Jalan Meranti, Kampus IPB Darmaga 16680.
2
Alumni of Land Resource Management, Faculty of Agriculture, Bogor Agricutural University
Corresponding author: [email protected]

(Received: December 27, 2013; Accepted: November 28, 2014)

ABSTRACT

Andisol is soil order which covers a wide area in Lembang, West Java, Indonesia. Lembang is
a horticultural crops area with intensive phosphorus fertlization for years. The efforts to mine
phosphorus in Andisol soil in Lembang is necessary to increase the efficiency of phosphorus
fertilization and to decrease phosphorus enrichment in water bodies. Trials on the effect of silicate
application on the release pattern of native inorganic phosphorus from Andisol soil in Lembang using
successive resin extraction were conducted in the laboratory of Department of Soil Science and Land
Resource, Faculty of Agriculture, Bogor Agricultural University from March to July 2011. Sodium
silicate (Na2SiO3) with the rates 0, 18, 45, 90 g were added to the three hundred g (oven-dry weight)
soil and incubated for one month. After one month of incubation, ten times successive resin extraction
and phosphorus fractionation were conducted. Data of successive resin extraction were simulated
using first order kinetic equation. The results showed that application of sodium silicate increased
maximum phosphorus release. The application of sodium silicate with the rate of 90 g resulted in the
highest maximum phosphorus release. However the application of sodium silicate decreased the rate
constant of phosphorus release. The changes of phosphorus fractions after successive resin extraction
showed that NaOH-phosphorus inorganic (Al-P and Fe-P) and HCl-phosphorus inorganic (Ca-P) were
P fractions contributed to phosphorus release. The results suggested that silicate can be used to mine
phosphorus from Andisol soil in Lembang.

Key words: contribution, fractionation, maximum, mining, rate constant

INTRODUCTION

Andisol is soil order which covers wide area in Lembang, West Java, Indonesia. The land in
Lembang is mostly cultivated for horticultural crops. The application of phosphorus fertilizers is
very intensive in Andisol soil in Lembang. It is indicated by relatively high total phosphorus
(Hartono, 2007). Hartono (2007) reported that total phosphorus of Andisol in Lembang was about
5000 mg phosphorus kg-1 and distributed mostly in inorganic phosphorus fractions namely Al-P, Fe-P
and Ca-P. Similar results concerning the phosphorus accumulation in inorganic phosphorus were
reported in Chilean volcanic soils (Briceño et al. 2004). The value of total phosphorus in Andisol
soil in Lembang was very high compared to that of other upland soils in Indonesia (Hartono et al.,
2005). Therefore efforts to mine phosphorus in this soil is very important to increase phosphorus
fertilization efficiency and to decrease phosphorus eutrophication in water bodies.

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 Effects of silicate application on the release patterns.....

The parent material of Andisol soil in Lembang is tuff andesitic derived from mount
Tangkuban Perahu. The clay fractions are short-range-order minerals dominated by allophane
(Hartono, 2007; Tan, 1984; Wada, 1959). Theoritically, phosphorus mostly sorbed by hydrous oxides
of aluminium (Al) and iron (Fe) on allophane, however the excess phosphorus sorbed on allophane
was supposed to decrease the bonding energy of sorption. Meason et al. (2009) reported that addition
of triple super phosphate (TSP) increased the sodium hydroxide phosphorus (Al-P and Fe-P)- and
hydrochloric acid-extractable phosphorus (Ca-P) pools suggesting that phosphorus sorption sites were
blocked by phosphorus from TSP decreasing the phosphorus sorption capacity and bonding energy.

One way to mine phosphorus is to replace phosphorus position on sorption sites with the ion
relatively having the same behaviour with phosphorus. It was reported that the sulfate was only
significant at pH < 4.5 to compete with phosphorus on the sorption sites. At pH > 4.5 the ability of
sulfate to compete with phosphorus on sorption site was not significant (Pigna and Violante, 2003).
The humic substances extracted from peat soil and Andisol were inconsistent in decreasing
phosphorus sorption maxima and bonding energies of the soils high in Al and Fe oxides (Hartono et
al. 2013) meaning that the humic substances were inconsistent to compete with phosphorus on
sorption sites. On the other hand, the use of silicate markedly reduced phosphorus sorption maximum
of low pH Greenville soil from the Coastal Plain of Georgia (Owino-Gerroh and Gascho, 2005). The
silicate was also reported to enhance the phosphorus transformation from moderately resistant
phosphorus (Al-P and Fe-P) to labile phosphorus (Hartono, 2007). These reports indicated that
silicate could compete with phosphorus and it could replace previously sorbed phosphorus on sorption
sites.

The research on how silicate replaces phosphorus on sorption sites and the amount of total
phosphorus replaced by silicate in Andisol soil in Lembang is not yet evaluated. Therefore the
objective of this research was to evaluate the effect of silicate on the native inorganic phosphorus
releasing pattern in Andisol soil in Lembang and which inorganic phosphorus fractions contribute to
the phosphorus released.

MATERIALS AND METHODS

Soil sample

Soil sample of Andisol soil was collected in plots belonging to Indonesian Vegetables
Research Institute, Lembang, West Java.in March 2011. The trials were conducted in the laboratory
of Department of Soil Science and Land Resource, Faculty of Agriculture, Bogor Agricultural
University from March to July 2011. Soil sampls were air-dried and crushed to pass through a 2-mm
mesh sieve. Prior to experiments, initial analyses of the soil samples were carried out to determine
soil pH, total organic carbon (C), total phosphorus, cation exchange capacity (CEC), exchangeable
calcium (Ca), exchangeable magnesium (Mg), exchangeable potassium (K), exchangeable sodium
(Na), and oxalate-extractable iron and aluminum (Feo and Alo).

Methods of initial analyses

Initial analyses were described by Hartono (2007). The pH was measured in a 1:1.5 (w/v)
water solution using a pH meter (EUTECH INSTRUMEN type pH 2700). Soil texture was
determined by the pipet method (Gee and Bauder, 1986). Total organic C in soil was determined by
a NC analyzer (Sumigraph NC analyzer NC-800-13 N, Sumika Chem. Anal. Service). Total
phosphorus was obtained by digesting the soil sample using concentrated percloric acid and nitric acid
as described by Kuo (1996). Their absorbance at 693 nm was determined using a UV-VIS
spectrophotometer (UV-1200, Shimadzu Corporation, Japan). Cation exchange capacity was
detrermined by extraction with 1 mol L-1 NH4OAc pH 7.0 and the contents of exchangeable bases

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 J. ISSAAS Vol. 20, No. 2:43-50 (2014)

calcium (Ca2+) and magnesium (Mg2+) were obtained by atomic absorption spectrophotometry (AA-
640-12, Shimadzu Corporation, Japan) while those of exchangeable potassium (K+) and sodium (Na+)
were obtained by flame emission spectrophotometry (AA-640-12, Shimadzu Corporation, Japan).
Base saturation was defined as the ratio of total exchangeable bases to cation exchange capacity,
expressed as a percentage. Oxalate-extractable iron and aluminum (Feo and Alo) were obtained by
extraction with 0.3 mol L-1 ammonium oxalate, at pH 3 for 4 h in a dark room (McKeague and Day,
1966). The extracted iron and aluminum of Feo and Alo were filtered through a syringe filter with a
0.45 µm pore size (Minisart RC 15, Sartorius, Hannover, Germany). The extracted iron and
aluminum were then determined by inductively coupled plasma-atomic emission spectroscopy
(SPS1500, SEIKO Instruments Inc., Tokyo, Japan ).

Incubation experiment

Three hundred g (oven-dry weight) soil was weighed into a plastic pot and incubated with
sodium silicate, with the rates 0, 18, 45 and 90 g for one month. A completely randomized design in
double replication was set up. Deionized water was added to the pots to maintain the soil moisture
around 85 % of water holding capacity every second day gravimetrically. After the period of
incubation, the soil samples were air-dried.

Successive resin extraction experiment

Successive resin extraction experiment was performed to release phosphorus from sorption
sites. Successive resin extraction mimics the phosphorus uptake by plant root (Mc Kean and Warren,
1996). Two resin strips oversaturated with bicarbonate were put into the 50 mL centrifuge tubes
containing containing 1 g soil and 30 mL distilled water. It was shaken for 16 h, afterwhich the resin
strips were removed and washed with distilled water. Any soil trapped in the resin strips was
collected and dried. This lost soil was weighed and taken into account in the calculations of the
amount of phosphorus extracted. Resin strips were placed in a clean 50 mL tube and applied 20 mL
0.5 mol L-1 HCl and shaken for 16 h. After that resin-phosphorus inorganic was determined. The
resin strips was removed, washed and regenerated for further use as described by Saggar et al. (1990)
and Tiessen and Moir (1993). The extraction of phosphorus from each sample was continued by
placing a regenerated resin strip in the original centrifuge containing the soil and water suspension
and the procedure was repeated. A set of ten successive extractions was performed.

Phosphorus fractionation

Initial phosphorus fractionation were conducted before successive resin extraction experiment.
phosphorus fractionation after successive resin extraction experiment was conducted to evaluate the
changes of phosphorus fractions. phosphorus fractionation procedure was described in Figure 1
(Hartono, 2008). Characterization of sequential soil phosphorus extraction was explained as follows:
(i) resin-phosphorus inorganic was interpreted as phosphorus that is readily available to plant, (ii)
NaHCO3-phosphorus inorganic, were interpreted as phosphorus which are strongly related to
phosphorus uptake by plants and microbes and bound to mineral surface, (Mattingly, 1975; Tiessen
and Moir, 1993) (iii) NaOH-phosphorus inorganic, were interpreted as phosphorus which are more
strongly held by chemisorption to Fe and Al components of soil surface (Fe-P and Al-P) and (iv) HCl-
phosphorus inorganic was interpreted as Ca-P of low solubility.

Calculation of contribution of NaHCO3-Phosphorus inorganic, NaOH- Phosphorus inorganic

and HCl- Phosphorus inorganic to the total P released as resin- Phosphorus inorganic

Contribution of NaHCO3-Pi, NaOH-Phosphorus inorganic and HCl-Phosphorus inorganic to

the total phosphorus released as resin-Phosphorus inorganic in percentage was determined by the

45
 Effects of silicate application on the release patterns.....

values of inital NaHCO3-Phosphorus inorganic, or NaOH- Phosphorus inorganic or HCl- Phosphorus

inorganic was subtracted by the values of NaHCO3- Phosphorus inorganic, or NaOH- Phosphorus
inorganic or HCl- Phosphorus inorganic after successive resin extraction of each treatment and
divided by the total P released as resin- Phosphorus inorganic of each treatment.

Duplicate 1 g soil
samples
A set of ten successive Determine phosphorus inorganic: Resin-
resin extraction Phosphorus inorganic

-1
Add 30 mL 0.5 mol L NaHCO3 and then shaken for 16 h
Bicarbonate extractable phosphorus

Precipitate organic matter Determine phosphorus inorganic:

NaHCO3-Phosphorus inorganic
-1
Add 30 mL 0.1 mol L NaOH and then shaken for 16
h OH extractable phosphorus

Determine phosphorus inorganic:

Precipitate organic matter
-1 NaOH-Phosphorus inorganic
Add 30 mL 1 mol L HCl and then shaken for 16 h
Determine phosphorus inorganic:
HCl extractable phosphorus
HCl-Phosphorus inorganic

Fig. 1. Flow chart of the phosphorus fractionation into various inorganic phosphorus fractions

Data analyses

Data from successive resin extraction were simulated using first order kinetic as written below:

Resin- Phosphorus inorganic = a (1-e-k(number of extraction))

where the constant a is the maximum phosphorus released and k is the rate constant. Analyses of
variance followed by a Tukey’s test were applied to evaluate the effect of silicate to the parameters.

RESULTS AND DISCUSSION

Physico-chemical properties of Andisol soil in Lembang

Physico-chemical properties of Andisol soil in Lembang are presented in Table 1. The status
of selected chemical properties was based on the methods as described by Hartono (2007) and
classified according to the criteria published by Soepratohardjo et al. (1983). Soil pH of Andisol soil
in Lembang was acid. Total organic carbon was very high. Cation exchange capacity was high
however the base saturation was low. Sum of percentage of aluminum plus half of iron extracted by
ammonium oxalate acid more than 2% typifies for Andisol soil. Total phosphorus were very high
indicating that phosphorus in Andisol soil in Lembang was very accumulated.

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 J. ISSAAS Vol. 20, No. 2:43-50 (2014)

The initial phosphorus fractionation showed that phosphorus was accumulated in the NaOH-
Phosphorus inorganic, HCl-Phosphorus inorganic, NaHCO3-Phosphorus inorganic and resin-
Phosphorus inorganic. The values of NaOH-Phosphorus inorganic, HCl-Phosphorus inorganic,
NaHCO3-Phosphorus inorganic and resin-Phosphorus inorganic were 968, 790, 391, 97.9 mg
phosphorus kg-1, respectively.

Table 1. Physico-chemical properties of Andisol soil in Lembang (Hartono, 2007).

Soil Properties Value Status

pH (H20) 4.74 acid
Total Organic Carbon (C) (%) 6.06 very high
-1
Total-Phosphorus (P) (mg kg ) 4783 very high
Total-Nitrogen (N) (%) 0.44 medium
Calcium (Ca) (cmolc kg-1) 2.64 low
Magnesium (Mg) (cmolc kg-1) 0.34 low
-1
Potassium (K) (cmolc kg ) 0.1 low
-1
Sodium (Na) (cmolc kg ) 0.21 low
-1
Cation Exchange Capacity (CEC) (cmolc kg ) 30.1 high
Base saturation (BS) (%) 10.9 low
Clay (%) 24.9 -
Oxalate: -
Aluminium (Alo) (%) 5.97 -
Iron (Feo) (%) 2.11 -
Alo+1/2Feo (%) 7.03 -

Successive resin extraction

The pattern of phosphorus released is presented in Figure 2. Maximum phosphorus released

and the constant rate of first order kinetic is presented in Table 2. The increasing rates of silicate in
the form of sodium silicate increased phosphorus release. The application of silicate in the form of
sodium silicate significantly increased maximum phosphorus release. The application of sodium
silicate with the rate 90 g resulted in the highest maximum phosphorus release compared to other
treatments. The maximum phosphorus released from the application of sodium silicate, with the rates
0, 18, 45 and 90 g, were 274, 479, 744 and 1050 mg phosphorus kg-1, respectively.

Table 2. Maximum phosphorus release (a) and rate constant (k) derived from first order kinetics

Rates of sodium
k (number of extraction-1) a (mg Phosphorus kg-1) R2
silicate (g pot-1)
0 (control) 0.442 a* 274 a 0.99
18 0.311 ab 479 a 0.99
45 0.283 bc 744 b 0.99
90 0.248 bc 1050 c 0.99
*Means followed by the same letter within a column are not significantly different (Tukey`s test, P < 0.05)

47
 Effects of silicate application on the release patterns.....

Fig. 2. Phosphorus release pattern (mg kg-1) of Andisol soil in Lembang after successive
resin extraction as influenced by the amount of Na2SiO3

The maximum phosphorus released by application of sodium silicate with the rate 90 g was
about 22% of total phosphorus. This finding confirmed that silicate could be used to mine phosphorus
in Andisol soil in Lembang. The application of silicate in the form of sodium silicate significantly
decreased the rate constant. The least value of rate constant was the application of sodium silicate
with the rate 90 g. It indicated that slow release of phosphorus sorbed in sorption sites occured with
the presence of silicate. Although the application of silicate increased the maximum phosphorus
release but the rate of phosphorus release was slow. It could increase the efficiency of phosphorus
uptake by plant. The results also confirmed that the transformation of resistant phosphorus to labile
phosphorus occured with the application of silicate (Hartono, 2007).

Phosphorus fractionation after successive resin extraction

Phosphorus fractionation after successive resin extraction is presented in Table 3. Compared

to initial phosphorus fractionation the values of NaHCO3-Phosphorus inorganic, NaOH-Phosphorus
inorganic and HCl- Phosphorus inorganic in Table 3 decreased after successive resin extraction
experiment. It indicated that those fractions contributed to the phosphorus release. The samples
treated by sodium silicate showed the higher decrease of those phosphorus fractions compared to
those of the control sample.

Table 3. Phosphorus fractionation after successive resin extraction.

NaOH- HCl-
Rates of sodium silicate NaHCO3- Phosphorus
Phosphorus Phosphorus
(g pot-1) inorganic
inorganic inorganic
-1
……………………mg Phosphorus kg …………………
0 (control) 316 851 689
18 238 758 583
45 282 682 461
90 175 564 466

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 J. ISSAAS Vol. 20, No. 2:43-50 (2014)

Percentage of the contribution from NaHCO3-Phosphorus inorganic, NaOH-Phosphorus

inorganic and HCl-Phosphorus inorganic is presented in Table 4. NaOH-Phosphorus inorganic
fraction and HCl-Phosphorus inorganic fraction which are interpreted as phosphorus strongly held by
chemisorption to iron and aluminum components of soil surface and Ca-P of low solubility
respectively were the main contributors for phosphorus release. Their contibution varied from 33.7%
to about 46.9%. It indicated that NaOH- Phosphorus inorganic and HCl-Phosphorus inorganic were
not stable phosphorus fractions. Phosphorus was released when phosphorus in the soil solution
decreased.

Table 4. The percentage of contribution to the value of resin-Pi from NaHCO3- Phosphorus
inorganic, NaOH- Phosphorus inorganic and HCl- Phosphorus inorganic

Rates of sodium NaCHO3- NaOH- Phosphorus HCl- Phosphorus

silicate Phosphorus inorganic inorganic inorganic
(g pot-1) ..............................................%.............................................

0 (control) 28.0 43.7 37.7

18 33.3 45.7 45.0
45 15.6 40.8 46.9
90 22.5 42.1 33.7

CONCLUSIONS

Total phosphorus of Andisol soil in Lembang were very high. They mostly accumulated in
NaOH-Phosphorus inorganic (Al-P and Fe-P) and HCl-Phosphorus inorganic (Ca-P). The application
of silicate increased maximum phosphorus release in successive resin exraction. However the
application of silicate decreased the rate constant of phosphorus release.

Successive resin extraction experiment sugested that silicate could be used to mine phosphorus
in Andisol soil in Lembang to save phosphorus fertilizer. NaOH-Phosphorus inorganic and HCl-
Phosphorus inorganic were phosphorus fractions which contributed to phosphorus release. Materials
containing silicate are promising to be used as ameliorant for releasing native phosphorus of Andisol
soil. It is necessary to make calibration experiments in the field to select which materials are good as
ameliorant in Andisol soil.

ACKNOWLEDGEMENT

The authors thank the Indonesian Vegetables Research Institute, Lembang West Java, for
helping in the soil samples collection and the Graduate School of Agriculture, Kyoto University for
funding the chemical reagents.

REFERENCES

Briceño, M., M. Escudey, G. Galindo, D. Borchardt, and A. Chang. 2004. Characterization of

chemical phosphorus forms in volcanic soils using 31P-NMR spectroscopy. Commun. Soil
Sci. Plant Anal. 35: 1323-1337.

Gee, G. W. and Bauder J. W. 1986. Particle-size analysis, pp 383-411. In G. S Campbell, R. D.

Jackson, M. M. Mortland, D. R. Nielson and, A. Klute (eds.). Methods of Soil Analyses Part
1 Physical and Mineralogical Methods. 2nd ed. Am. Soc. Agron.

49
 Effects of silicate application on the release patterns.....

Hartono, A. 2008. Releasing pattern of applied phosphorus and distribution change of phosphorus
fractions in the acid upland soils with successive resin extraction. J. Trop. Soil. 13:87-94.

Hartono, A. 2007. The effect of calcium silicate on the selected chemical properties and
transformation of inorganic and organic phosphorus in Andisol Lembang. Gakuryoku, 33: 1-9.

Hartono, A., L.T. Tri Indriyati and Selvi. 2013. Effects of humic substances on phosphorus sorption
and desorption characteristics of soils high in iron and aluminum oxides. J. ISSAAS. 19:86-92.

Hartono, A., S. Funakawa and T. Kosaki. 2005. Phosphorus sorption-desorption characteristics of

selected acid upland soils in Indonesia. Soil Sci. Plant Nutr. 51, 787-799.

Kuo, S. 1996. Phosphorus, 869-919 pp. In D. L. Spark, A. L. Page, P. A. Helmke, R. H. Loeppert,

P. N. Soltanpour, M. A. Tabatai, C. T. Johnston, and M. E. Sumner, (eds.). Methods of Soil
Analyses Part 3 Chemical Methods. ASA and SSSA, Madison, WI.

Mattingly, G. E. G. 1975. Labile phosphorus in soils. Soil Sci. 119: 369-375.

McKeague, J. A. and J. H. Day. 1966. Dithionite and oxalate extractable Fe and Al as aids in
differentiating various classes of soils. Can. J. Soil Sci. 46: 13-22.

McKean, S. J. and G. P. Warren. 1996. Determination of phosphate desorption characteristics in

soils using successive resin extractions. Commun. Soil Sci. Plant Anal. 27: 2397-2417.

Meason, D. F., W. I. Travis, J. B. Friday and P.G. Scowcroft. 2009. Effects of fertilization on
phosphorus pools in the volcanic soil of a managed tropical forest. Forest Ecology and
management. 258:2199-2206.

Owino-Gerroh, C. and G. J. Gascho. 2005. Effect of silicon on low pH soil phosphorus sorption and
on uptake and growth of maize. Commun. Soil Sci. Plant Anal. 35:2369-2378.

Pigna, M. and A. Violante. 2003. Adsorption of sulfate and phosphate on Andisols. Commun. Soil
Sci. Plant Anal. 34:2099-2113.

Saggar, S., M. J. Hedley and R. E. White 1990. A simplified resin membrane technique for
extracting phosphorus from soils. Fert. Res. 24: 173-180.

Soepratohardjo, M., H. Subagjo, Suhardjo, Ismangun, D. S. Marsoedi, A. Hidayat, Y. Dai, A. Adi, M.

Supartini, Mursidi, and J. S. Adiningsih. 1983. Terms of reference survey of soil capability.
Center for Soil Research, Bogor (In Indonesian). 52 p.

Tan, K.H, 1984. The Andosol in Indonesia. In Tan K.H. Andosols. A Hutchinson Ross Bencmark
Book. New York. 418 p.

Tiessen, H. and J. O. Moir. 1993. Characterisation of available P by sequential extraction, pp. 75-86.
In Soil Sampling and Methods of Analysis. M. R. Carter, (ed.). Can. Soc. of Soil Sci. Lewis
Publ.

Wada, K. 1959. Reactions of phosphate with allophane and halloysite. Soil Sci., 87:325-330.

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