A Contemporary Overview of Silicon Availability in Agricultural Soils

J. Plant Nutr. Soil Sci. 2014, 177, 831–844 DOI: 10.1002/jpln.
201400202 831
Review Article
A contemporary overview of silicon availability in agricultural soils
Richard J. Haynes1*
1 School of Agriculture and Food Science/CRC CARE, The University of Queensland, St Lucia, Queensland 4072, Australia
Abstract
Our current understanding of silicon (Si) availability in agricultural soils is reviewed and knowl-
edge gaps are highlighted. Silicon is a beneficial rather than essential plant nutrient and yield re-
sponses to its application have been frequently demonstrated in Si-accumulator crops such as
rice and sugarcane. These crops are typically grown on highly weathered (desilicated) soils
where soil solution Si concentrations are low. Increased yields are the result of simultaneous
increases in plant tolerance to a wide range of biotic (plant pathogens, insect pests) and
abiotic (water shortage, excess salts, metal toxicities) stresses. Traditionally, soil solution Si is
viewed as being supplied by dissolution of primary and secondary minerals and buffered by ad-
sorption/desorption of silicate onto Al and Fe hydrous oxide surfaces. In recent years it has be-
come recognized that phytogenic cycling of Si [uptake of Si by plants, formation of phytogenic
silica (SiO2 × nH2O) mainly in leaves and subsequent return of this silica to soils in plant litter] is
the main determinant of soil solution Si concentrations in natural forests and grasslands. Consid-
erable diminution of the phytogenic Si pool in agricultural soils is likely due to regular removal of
Si in harvested products. A range of extractants (unbuffered salts, acetate-based solutions, and
acids) can provide valuable information on the Si status of soils and the likelihood of a yield re-
sponse in rice and sugarcane. The most common Si fertilizers used are industrial byproducts
(e.g., blast furnace slag, steel slag, ferromanganous slag, Ca slag). Since agriculture promotes
soil desilication and Si is presently being promoted as a broad spectrum plant prophylactic, the
future use of Si in agriculture is likely to increase.
Aspects that require future research include the role of specific adsorption of silicate onto hy-
drous oxides, the significance of phytogenic Si in agricultural soils, the extent of loss of phyto-
genic Si due to crop harvest, the role of hydroxyaluminosilicate formation in fertilized soils, and
the effect of soil pH on Si availability.
Key words: silicon / phytoliths / soil Si pools / soil desilication / fertilizer Si / biogenic Si
Accepted September 19, 2014
1 Introduction agricultural systems is creating a new removal mechanism for

Si which is substantially changing the terrestrial and, thus,
Silicon (Si) is the second most abundant element of the global Si cycle (Vandevenne et al., 2012). Indeed, from the
earth’s crust with a mean content of 28.8% (Wedepohl, viewpoint of managing agricultural ecosystems, Si is an agro-
1995). It occurs in more than 370 rock-forming minerals and nomically important nutrient.
is a basic component of most soils. In recent times the global
Si cycle has received increased attention because of its inter- Although Si is still not considered as an essential nutrient, its
relationship with the C cycle. Indeed, biogeochemical cycling beneficial effects on plant growth and yields have been re-
of Si regulates atmospheric CO2 concentrations via several peatedly demonstrated particularly for crops such as sugar-
mechanisms including (1) chemical weathering of minerals in cane and rice (Savante et al., 1997; 1999). Positive yield re-
the terrestrial environment, with consumption of CO2, and the sponses occur particularly in soils containing low concentra-
eventual precipitation of CaCO3 as marine sediments, (2) oc- tions of Si in soil solution including highly weathered Oxisols
clusion of C in phytogenic silica deposited in soil, and (3) bio- and Ultisols and organic soils (e.g., Histisols). The main
genic sequestration of C in oceanic phytoplankton (Si is an mechanisms of yield increase are through improving plant re-
essential nutrient for growth of diatoms) and their subsequent sistance against abiotic (metal toxicities, water stress, salin-
sedimentation (Street-Perrott and Barker, 2008; Struyf et al., ity) and biotic (plant pathogens and insect pests) stresses
2009; Carey and Fulweiler, 2012; Frings et al., 2014). Of late, (Ma and Yamaji, 2006; Meena et al., 2014; Tripathi et al.,
the importance of Si to plant ecology in terrestrial systems 2014). The Si status of agricultural soils has come under re-
has been recognized (Cooke and Leishman, 2011) and it has cent scrutiny due to the realization that phytogenic cycling of
been suggested that removal of Si in harvested products in Si (through the formation of phytogenic silica in plants and its
* Correspondence: Prof. R. J. Haynes; e-mail: r.haynes1@uq.edu.au
ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.plant-soil.com

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832 Haynes J. Plant Nutr. Soil Sci. 2014, 177, 831–844
subsequent return to the soils in plant litter) drives soil solu- of their production is on highly weathered Ultisols and Oxisols
tion Si concentrations in natural ecosystems; and this expor- (Savante et al., 1997; 1999), which have a characteristically
tation of harvested product in agriculture severely depletes low Si status.
soils of their phytogenic Si pool (Keller et al., 2012). Indeed,
because the continual removal of Si in harvested product is The main determinant of concentrations of Si in soil solution
promoting desilication of soils, addition of fertilizer Si may be- is the solubility of primary and secondary minerals (Karatha-
come a more common practice for a wide range of crops in nasis, 2002; Sommer et al., 2006). Silicon in soil solution is
the future (Meena et al., 2014). In addition, because of its mainly present as monomeric silicic acid (H4SiO4) (Drees et
known effect in protection of plants against biotic stresses, Si al., 1989; Dove, 1995; Dietzel, 2000) although at high pH
is now being promoted and researched as a broad spectrum, (> 9) silicic acid dissociates to form H3SiO4 and above pH 11
environmentally friendly plant prophylactic which can estab- to H2SiO24 . Silicon concentrations in soil solution have been
lish a broad spectrum resistance to diseases and pests in a reported to range from 0.01 to 2.0 mM (Karathanasis, 2002)
wide range of plants (Keeping and Kvedaras, 2008; Van but are commonly in the range of 0.1 to 0.6 mM (Epstein,
Bockhaven et al., 2013). 2001; Sommer et al., 2006). In general, Si concentration in
soil solution decreases with increasing soil development
Little work has concentrated on the fertility aspects of Si avail- (Karathanasis, 2002; Sommer et al., 2006). As a result, the
ability in agricultural soils. Modern textbooks on soil fertility soluble Si content of tropical soils, such as Ultisols and Oxi-
normally mention Si in passing and there is no definitive cov- sols, is generally 5–10 times less than that of most temperate
erage of its availability and crop use. The purpose of this pa- soils (McKeague and Cline, 1963; Juo and Sanchez, 1986;
per is to provide a contemporary view of Si availability in agri- Foy, 1992). Where a large group of soils in a region of a coun-
cultural soils and to point out where gaps in our knowledge try is surveyed, there is generally a positive relationship be-
exist. tween pH and Si solubility/extractability (Fox et al., 1967;
Cheong et al., 1968; Oya and Kina, 1989; Oya et al., 1989;
Miles et al., 2014). For example, the positive relationship be-
2 Silicon status of soils
tween pH and CaCl2-extractable Si for 112 sites on the South
A major consequence of the chemical weathering of primary African sugar belt is shown in Fig. 1. The more weathered
silicate minerals is desilication. Weathering releases highly soils with lower soluble Si are also those with lower pH val-
mobile basic cations (Ca2+, Mg2+, K+, and Na+), moderately ues.
mobile Si(OH)4, and relatively immobile Al and Fe into soil
solution (White, 1995; Karathanasis, 2006). Part of the Si Silicate can be adsorbed to the surfaces of variably charged
released from the mineral structure reacts with Al (and to a soil colloids such as Fe and Al hydrous oxides. Such adsorp-
lesser extent Fe and Mg) to form secondary clay minerals, tion is highly pH-dependent because with increasing pH (up
while the remainder is subjected to leaching. As a conse- to pH 9.8; the pK1 for silicic acid) an increasing proportion of
quence, most soils experience a loss of Si and basic cations total Si in solution is present as H3SiO4 rather than H4SiO4.
during weathering (White, 1995). Desilication is most pro- Because Si is preferentially adsorbed in the anionic H3SiO4 -
nounced in humid tropical environments and occurs to a less- form, maximum Si adsorption occurs at a soil pH of about 9.8
er extent in temperate regions (Karathanasis, 2006). From (Bowden et al., 1980). The relationship between pH and ionic
the viewpoint of this review, it is important to note that rice strength on the adsorption of silicate by the iron oxide goe-
and sugarcane are tropical/subtropical crops and the majority thite is shown in Fig. 2. As a result, in short-term equilibrium
4
CaCl2-extractable Si / mg kg–1
Silicate adsorbed / mol cm–2 ×
3 5 7 9 11
Soil pH
pH
Figure 1: Relationship between pH and CaCl2-extractable Si for 112
soils collected from sugarcane production fields in South Africa. Figure 2: Effect of pH and ionic strength on adsorption of silicate by
Redrawn from Miles et al. (2014). goethite. Redrawn from Bowden et al. (1980).

J. Plant Nutr. Soil Sci. 2014, 177, 831–844 Silicon availability in agricultural soils 833
experiments Si solubility in soils decreases with increasing horticultural crops such as garlic, onion, cucumber, chinese
pH (Hingston and Raupach, 1967; Hingston et al, 1972; cabbage, strawberries, and potatoes (Epstein, 1999; Voogt
Goldberg and Glaubig, 1988; Haynes et al., 2013). Thus, if and Sonnenveld, 2001; Kang and Jung, 2002).
adsorption reactions are the major factor determining soil sol-
ution Si concentrations then Si solubility and availability will Silicon has been shown to protect plants against a suite of
decrease with increasing pH. pathogens (mainly fungi but also some bacteria) (Currie and
Perry, 2007; Guntzer et al., 2012a; Van Bockhaven et al.,
2013). The increased resistance to disease occurs through
3 Silicon uptake and use by crops two main mechanisms. Firstly, impregnation of epidermal cell
walls with silica creates a hard outer barrier which mechani-
Plants differ greatly in their ability to accumulate Si and con-
cally impedes penetration by fungi and thereby disrupts the
centrations in above-ground parts can range from 1 to 100 g
infection process. Secondly, soluble Si can act as a modulator
kg–1 (they are normally present in concentrations of similar or-
of host resistance to pathogens through physiological and
der to those of macronutrients such as N and K) (Epstein,
biochemical/molecular mechanisms (Fauteux et al., 2006;
1999; Ma and Takahashi, 2002). The process of Si uptake
Brunings et al., 2009; Ghareeb et al., 2011; Van Bockhaven
can be classified as active, passive or rejective, and accord-
et al., 2013). Similarly, Si applications can enhance plant re-
ingly plants can be classified as accumulators, intermediates,
sistance to insect pests (Laing et al., 2006; Kvedaras and
and excluders. Plants are considered as Si accumulators
Keeping, 2007; Keeping and Kvedaras, 2008; Kvedaras et
when the tissue Si concentration is > 10 g kg–1 and as ex-
al., 2010). The deposition of silica in epidermal layers offers a
cluders when they have concentrations < 5 g kg–1 (Ma and
physical barrier to sucking insects and leaf-eating caterpillars
Takahashi, 2002). Seven (sugarcane, rice, wheat, barley, sug-
and, in addition, Si plays a role in the induction of chemical
ar beet, soybean,s and tomatoes) out of the 10 most impor-
defences against herbivores (Correa et al., 2005; Gomes et
tant crops (ranked by global production) are classified as ac-
al., 2005; Ye et al., 2013).
cumulators (Guntzer et al., 2012a).
It has been widely reported that the addition of Si can in-
The distribution of Si within shoot organs and tissue is deter-
crease drought tolerance in crops including rice, sorghum,
mined primarily by the transpiration rate of the organ. Most of
wheat, sunflower, cucumber, and pepper (Liang et al., 2007;
the Si remains in the apoplast and is deposited at the termini
Sacala 2009; Tripathi et al., 2014; Zhu and Gong, 2014). Sili-
of the transpiration stream, mainly in the outer walls of the ep-
con additions have also been shown to increase salinity toler-
idermal cells in the shoots. The deposited silicic acid is con-
ance in a similar range of crops (Meena et al., 2014; Tripathi
centrated by transpiration loss of water and polymerizes as
et al., 2014; Zhu and Gong, 2014). Such Si-stimulated toler-
amorphous silica (SiO2 × nH2O) to form deposits known as
ance to drought/salinity is achieved by a range of physiologi-
phytogenic Si (Smithson, 1956). These silica deposits can
cal (e.g., modulation of transpiration rates, increased photo-
contain small amounts of impurities such as Al, Fe, Ti, Mn, P,
synthesis, decreased uptake of Na+ and Cl–) and biochemi-
Cu, N, and C (Clarke, 2003). Silica can also accumulate in
cal/molecular (e.g., improved antioxidant defences, osmotic
the vascular system and the endodermis of roots (Mitani and
adjustment with organic solutes) mechanisms (Zhu and
Ma, 2005). Amorphous phytogenic Si is immobile within the
Gong, 2014).
plant and so Si tends to accumulate in older plant tissues.
Silicon applications can be effective at alleviating toxicity of
The application of Si often improves plant resistance to a
metals including Al, Mn, Fe, Cd, Pb, and Zn (Gu et al., 2012;
range of biotic and abiotic stresses (Epstein, 1999; Ma and
Maksimović et al., 2012; Bharwana et al., 2013; Dufey et al.,
Yamaji, 2006; Liang et al., 2007; Meena et al., 2014). The
2013; Nhan and Hai, 2013). The responsible mechanisms are
main biotic stresses alleviated include pathogen and insect
complex and can be divided into external (e.g., co-deposition
pest damage, while the most important abiotic stresses are
of metals and Si in soil solution) and internal (e.g., co-deposi-
drought, salinity, and metal toxicities. Since plants growing in
tion of metals and Si in roots, inhibition of root-to-shoot trans-
the field are constantly subjected to an array of stresses, yield
port of metals) (Liang et al., 2007).
increases due to fertilizer Si applications are not surprising on
Si-deficient soils. Silicon is typically applied as slag (see be-
low) to rice at about 225–300 kg Si ha–1 annually and to sug-
4 Importance of phytogenic Si
arcane at about 600–1125 kg Si ha–1 every 4–5 y (at replant-
ing) (Kingston, 2008). Yield responses under field conditions As already noted, Si accumulates in plants as silica deposits
to Si fertilizer additions in sugarcane have been reported as particularly in the shoots. This silica is returned to the soil
10–50% in Hawaii (Ayres, 1966; Clements, 1965; Fox et al., mainly in plant litter, and as the organic matter (OM) is de-
1967), 6–14% and 20% in Florida (Gascho and Andreis, composed the silica is released. Extraction and analysis of
1974; Raid et al., 1992), 7–12% in Brazil (Korndörfer and phytogenic Si in soils is often restricted to silt-sized particles
Lepsch, 2001), and 21–41% in Australia (Kingston et al., (this fraction is classified as phytolith Si) and the < 5 mm frac-
2005). Similarly, for rice yield responses have been reported tion is not included (Sommer et al., 2006). The term phytogen-
as 1–4% and 10–30% in Japan (Yoshida, 1981; Mizuochi, ic Si is used here to describe all of the silica returned in plant
2002), 0–400% and 8–29% in China (Wang et al., 2001; material. Due to the recycling of Si in the litter, the distribution
Wang, 2005), and 17% in South Korea (Ali et al., 2008). Yield of phyogenic silica through the soil profile is typically similar
increases have also been observed in a wide range of grain to that of organic C. Under natural forest or grassland there is
crops including wheat, barley, rye, and sesame, as well as a pronounced accumulation at the soil surface and a rapid de-

crease with depth (Alexandre et al., 1997; Saccone et al., the phytogenic Si pool in forest soils due to disequilibrium
2007; 2008), while under arable cultivation (with regular inver- caused by loss of Si-rich grasses during canopy closure and
sion of the plough layer) both OM and phytogenic Si are more logging of trees. For agriculture, disequilibrium is mainly at-
evenly distributed within the surface layer (Guntzer et al., tributable to the high uptake of Si by some crops and the an-
2012b; Seyfferth et al., 2013). nual removal of much of this Si in the harvested product. In-
deed, Matichenkov and Bocharnikova (2001) calculated that
In recent years, the importance of cycling of Si through the 210–224 m tonnes of Si are removed from agricultural soils
phytogenic Si pool in the soil of natural ecosystems has be- each year.
come recognized (Cornelis et al., 2011; Sommer et al., 2013;
Frings et al., 2014). Indeed, in natural forests and grasslands The uptake by rice and sugarcane of 200–400 kg Si ha–1 y–1
nutrients are characteristically cycled from soil to plant and is well above that normally absorbed in natural systems (e.g.,
then back to the soil, and losses are relatively small compar- 20–100 kg Si ha–1 y–1) and, furthermore, the bulk of this phy-
ed to the quantities continually being cycled. The flux of Si togenic Si is removed from the system at harvest rather than
through the plant in temperate and tropical forests ranges being returned to the soil. In S and SE Asia, where most of
from 5–76 (often 20–50) kg ha–1 y–1 (Bartoli, 1983; Lucas et the rice is grown, rice straw and husks are typically removed
al., 1993; Alexandre et al., 1997; Cornelis et al., 2010; from the field and used for a range of purposes, including ani-
Meunier et al., 2010) and in grasslands it is in the same order, mal fodder and fuel, so that all the above-ground vegetation
12–127 kg ha–1 y–1 (Blecker et al., 2006; Alexandre et al., (and phytogenic Si) is removed from the field. This depletes
2011; White et al., 2012). the soil of Si and accelerates soil desilication (Seyfferth et al.,
2013). For rice, retention of straw on the field (rather than
Studies in various temperate and boreal forests have reveal- straw removal) is an important management tool for recycling
ed that the immediate source of silicic acid taken up by the Si. This is because a large proportion of the above-ground Si
trees is predominantly phytogenic silica and that this is then uptake (about 80%) is retained in the straw rather than the
converted back to phytogenic Si in tree foliage and then re- harvested grain. Dobermann and Fairhurst (2000) calculated
turned to the soil as tree litter (Farmer et al., 2005). Alexandre that 40–70 kg ha–1 Si was held in 1 Mg of rice straw. For sug-
et al. (1997), using a steady-state approach, showed that arcane, return of bagasse (the crushed cane) or bagasse fly
about 74% of soil solution Si under a rainforest in the Congo ash (if bagasse is used as a fuel source at the mill) and filter
originated from phytogenic Si, while Bartoli (1983) found 85% mud to the fields can be important in maintaining the Si status
of Si uptake by a deciduous forest originated from dissolution of soils (Savante et al., 1999).
of phytogenic Si. Alexandre et al. (1997) calculated that about
92% of phytogenic Si is rapidly recycled, while only about 8% Several workers have recently attempted to quantify the loss
are sequestered in a stable phytogenic pool. Gérard et al. of phytogenic Si from soils under agriculture. Clymans et al.
(2008) found 60% of the biogeochemical cycle of Si in a (2011) compared phytogenic Si in soils under boreal forest
Douglas fir forest originated from phytogenic Si. However, as with those under agriculture and measured larger quantities
noted by Cornelis et al. (2011), the importance of the phyto- under forest. They attributed the depletion under agriculture
genic cycling of Si will be highly dependent on the extent to to systematic removal of crop residues (and therefore a re-
which mineral weathering has taken place. In a humid tropical duced return of phytogenic Si). Similar findings were reported
climate, in which there has been strong depletion of litho-pe- by Struyf et al. (2010) for temperate forest soils converted to
dogenic Si, phytogenic cycling of Si will supply the bulk of soil agriculture. On the classical Broadbalk continuous wheat ex-
solution Si and therefore that taken up by the plants. periment at Rothamsted, Guntzer et al. (2012b) measured a
decrease in phytogenic Si in the surface 23 cm of soil of be-
The quantities of phytogenic Si measured in the soil varies tween 19 and 66% between 1893 and 2000 (depending on
greatly between studies and may well be affected by the method of estimation). Keller et al. (2012) found that on a
method of measurement and soil type, as well as vegetation long-term trial in Boigneville, France, a period of 12 y of wheat
cover (Keller et al., 2012). The range for natural forests (gen- straw removal (compared to straw returned) resulted in a re-
erally reported to a soil depth of 30–50 cm) is 7,000–31,262 duction of 41–64% in phytogenic Si in the surface 20 cm of
(often 1,000–18,000) kg Si ha–1 (Alexandre et al., 1997; soil. Keller et al. (2012) calculated that, assuming that phyto-
Gérard et al., 2008; Saccone et al., 2008; Clymans et al., genic Si was the only source of Si for crops and with an ex-
2011) and that for native grasslands 18,000–71,100 kg Si portation of 50–100 kg Si ha–1 y–1 and an initial pool of phyto-
ha–1 (Blecker et al., 2006). The range for the small number of genic Si of 1 Mg ha–1, under a temperate climate and an initial
studies on agricultural land is 800–13,458 kg Si ha–1 (Des- forest setting the phytogenic Si pool would be depleted within
planques et al., 2006; Clymans et al., 2011; Guntzer et al., a few decades. Desplanques et al. (2006) measured an ex-
2012b). Some diminution of phytogenic Si is to be expected portation of Si from a rice field in the Camargue, France, by
in agricultural soils (Keller et al., 2012; Struyf et al., 2010; Van- grain and straw as 270 kg ha–1 y–1 and calculated that if phy-
devenne et al., 2012). That is when a soil is converted to agri- togenic Si was considered the only source of Si for plants
culture—the phytogenic Si pool (accumulated under natural then the stock of available Si would be exhausted after only
vegetation) is in disequilibrium with the current vegetation. 5 y. However, there were significant inputs of Si by irrigation
For example, after deforestation, Struyf et al. (2010) con- water. Yet, no workers have attempted to quantify the effects
cluded that there are likely to be increased Si fluxes, depletion of sugarcane monoculture on the phytogenic Si content of
of phytogenic Si, and eventually reduced Si fluxes. Similarly, soils. Nonetheless, Berthelsen (1997) compared a site under
Sommer et al. (2013) observed considerable dissolution of rainforest with an adjacent long-term (30 y) sugarcane site in

N Queensland and found CaCl2-extractable Si levels were that cause the breaking of siloxane bonds, >Si–O–Si<, at the
13.1 mg kg–1 under forest and only 5.3 mg kg–1 under sugar- particle surface (Dove et al., 2008). Increasing pH leads to
cane. Such results demonstrate that under sugarcane there the deprotonation of surface silanol groups, thereby facilitat-
was a decrease in Si supplying ability of the soil, which could ing the further breaking of the bridging siloxane bonds. Base-
well be due to a decrease in phytogenic Si. promoting dissolution occurs when the solution pH exceeds
the point of zero charge (for SiO2 in the pH range 1.2–4.0)
(Fraysse et al., 2006). Fraysse et al. (2009) calculated the
5 Solubility/availability of phytogenic Si half-life of phytogenic Si in soil, assuming 100% water satura-
As discussed above, phytogenic Si is now recognized as one tion over the year, to be 26–156 weeks at pH 4–5 and only
of the most important sources of Si in soil solution among all 7–10 weeks at pH 6–7. Similarly, Nguyen et al. (2014)
soil minerals (Fraysse et al., 2006; 2009; 2010; Nguyen et al., showed that Si release from phytogenic Si in rice straw was
2014; Seyfferth et al., 2013; Gocke et al., 2013). It is, how- an order of magnitude greater at pH 6.5 than at 3.0.
ever, important to note here that phytoliths can be highly re-
sistant to dissolution and may remain in soils for thousands of The sorption of di- and trivalent metals (Al3+, Fe3+, Zn2+,
years, thus, contributing to C sequestration (Parr and Sulli- Cu2+) to the surfaces of phytogenic Si is known to markedly
van, 2005) and their use in paleobotanical and archaeological reduce its solubility (McKeague and Cline, 1963; Wilding et
studies (Rovner, 1971; Santos et al., 2010). Fraysse et al. al., 1979; Dove, 1995; Van Bennekom et al., 1991), and Al3+
(2009) compared the Si release rate from phytogenic Si to has been shown to be particularly effective (Nguyen et al.,
that of typical primary [olivine, diopside (pyroxene), albite-or- 2014). The cations are adsorbed on deprotonated Si-O– sites
thoclase (feldspar)] and secondary (e.g., illite, kaolinite and and mitigate water attack on Si–O–Si bonds. Fe3+ has a simi-
smectite) silicate minerals and found that at common soil pH lar effect to Al3+ and a lowered decomposition rate of phyto-
values (i.e., 4–8) phytogenic Si was 102 to 104 times more genic Si in soils over time has been attributed to adsorption of
soluble than the other minerals (Fig. 3). While the dissolution Al3+ and Fe3+ to its surfaces (Wickramasinghe and Rowell,
rate of litho-pedogenic Si, in the form of primary and secon- 2006; Nguyen et al., 2014). Since the solubility of Al and Fe
dary minerals, decreases markedly with increasing pH (and is increase greatly with decreasing pH (particularly below pH
greatly favored by acidic soil conditions), the reverse is the 5.5), their adsorption to the surfaces of phytogenic Si will be
case for phytogenic Si (Figs. 3 and 4). Dissolution of phyto- favored at low soil pH. This will further reduce the solubility of
genic Si increases with decreasing particle size due to the in- phytogenic Si at low soil pH and reinforce the trend for its in-
crease in surface area (Drees et al., 1989) and is promoted creasing solubility with increasing pH. The adsorption of Al
by moist soil conditions and removal of soil solution Si. and Fe to phytolith surfaces may partly explain why some can
be so persistent in soils.
Dissolution of phytogenic Si, measured between pH 2 and
12, was found by Fraysse et al. (2006) to be intermediate be- Under field conditions, high rainfall conditions (as occur in
tween that of quartz and of amorphous silica (Fig. 4). Dissolu- tropical regions where crops such as sugarcane and rice are
tion rates of phytogenic Si originating from different plants grown) will favor dissolution of phytogenic Si and dissolution
(larch, elm, fern, horsetail, and bamboo) over the same pH will occur most rapidly from smaller silica particles. A logical
range were very similar (Fraysse et al., 2006; 2009). Dissolu- extension of the above discussion is that liming will tend to in-
tion of SiO2 is due to nucleophilic attack of water molecules
1,E-12
Quartz
Amorphous silica
1,E-13 Soil phytoliths
R / mol Si cm–2 sec–1
Log R / mol Si g–1 day–1
Heated phytoliths
Fresh phytoliths
1,E-14
1,E-15
1,E-16
1,E-17
0 2 4 6 8 10 12 14
pH pH
Figure 3: Comparison of the effect of pH on the solubility of some typ- Figure 4: Comparison of the dissolution of phytogenic Si with that of
ical soil clay minerals and parent rock primary minerals with that of amorphous silica and quartz as a function of pH. Redrawn from
phytogenic Si. Redrawn from Fraysse et al. (2009). Fraysse et al. (2006).

crease the solubilization and plant-availability of phytogenic dispersion of soil particles (Berthelsen and Korndörfer, 2005)
Si. Yet, no such relationship between liming, phytogenic Si meaning that the extracted solution may require filtering
solubility and plant availability of Si has been demonstrated. through a micropore filter (after centrifugation) prior to analy-
Indeed, an increasing pH will also favor an increased adsorp- sis. Unbuffered salt solutions such as 0.01 M CaCl2 are fa-
tion of silicate by Al and Fe hydrous oxide surfaces and de- vored (Berthelsen et al., 2003; Höhn et al., 2008; Miles et al.,
creased weathering of primary and secondary minerals so 2014) since they have an ionic strength similar to that of the
the overall effect is unclear. Further work in this area is war- soil solution and the dominant cation is Ca2+, as is the case in
ranted. most soil solutions. Their ionic strength also prevents disper-
sion and facilitates easy extraction and analysis.
6 Estimation of plant-available Si Ammonium- and Na-acetates (buffered at low pH with acetic

There are three key parameters that are likely to be important acid) as well as acetic acid itself have been extensively used
in relation to the plant- availability of Si. These are (1) the in- as extractants for soil Si (Sauer et al., 2006). The acid extrac-
tion would result in dissolution of amorphous Al and Fe oxides
tensity (concentration of Si in soil solution), (2) the capacity
(the reserve supply in solid phase that supplies the soil solu- and hydroxides with release of adsorbed Si (Sauer et al.,
tion), and (3) the retention capability of the soil (Si adsorption 2006; Höhn et al., 2008) plus dissolution of amorphous alumi-
nosilicates and any highly soluble crystalline aluminosilicate
capacity). For example, for soil P a soil test extractant is gen-
erally used to measure a combination of intensity and ca- material, while the presence of the acetate anion might favor
pacity and, thus, whether P fertilizer is required or not, while a desorption of adsorbed silicate. In some cases phosphate
P retention test is used to modify the fertilizer recommenda- has been added to the Na-acetate extractant in order to dis-
tion (the greater the P retention the more P needs to be place more adsorbed silicate from adsorption surfaces (Fox
added) (Haynes, 1984). However, for Si the relative impor- et al., 1967). In this regard, Heinai and Saigusa (2006) suc-
tance of various soil pools in relation to capacity is much less cessfully used a phosphate buffer extraction (Na2HPO4) to
displace adsorbed Si for soil testing in paddy rice.
clear than for P and probably differs in different situations
(e.g., dissolution of amorphous silicates, crystalline phyllosili-
cates, phytogenic Si or residual fertilizer Si), while the role of Citric acid has been suggested by some workers (Acquaye
Si adsorption is also unclear. For example, its adsorption and Tinsley, 1965), and the modes of extraction are likely to
maximum is at pH 9.8, yet most soils, in which Si is deficient, include solubilization of Al and Fe hydrous oxides and alumi-
are in the pH range of 5–6. In contrast to P, as phosphate is nosilicates, displacement of adsorbed silicate by citrate and
held by soil colloids so strongly that it is highly immobile in complexation of Fe and Al by citrate, thus, preventing forma-
soils, leaching of silicic acid from soils is a common phenom- tion of Al and Fe complexes with Si during extraction (Sauer
enon (Sommer et al., 2006; Gérard et al., 2008; Frings et al., et al., 2006). In addition, sulfuric acid has been used by a
2014). Although Gallez et al. (1977) developed a method for number of workers (Hurney, 1973; Fox et al., 1967; Meyer
measuring Si retention by soils (at pH 9.2) and Herbillon et al. and Keeping, 2001). This is a modification of the Truog ex-
(1977) developed an ‘‘index of Si saturation’’ based on both tractant for soil P, and in some cases both available P and Si
the Si adsorption and Si release characteristics, these param- are determined on the same extract.
eters have not met with wide acceptance. In acid soils, precip-
itation of added Si in form of hydroxyaluminosilicates (see be- In general, acids such as sulfuric and citric acid extract more
low) might well be a more important sink for Si than adsorp- Si than the Na- and NH4-acetate-based extractants, which in
tion to soil colloids. There is a need for more detailed studies turn extract more Si than water and CaCl2 (Fox et al., 1967;
into the chemistry of Si in soils before factors and interactions Berthelsen et al., 2003; Barbosa Filho et al., 2004; Wang et
influencing Si availability are fully understood. al., 2004; Kanamugire et al., 2006; Haynes et al., 2013). It
has been pointed out (Haynes et al., 2013) that acid extrac-
Given the above uncertainties, it is not surprising that there is tants can remove very large amounts of Si from soils treated
no universally accepted method to evaluate plant-available Si with slags since these materials are acid-soluble. Some of
in soils. Information summarized in Table 1 illustrate the diver- the Si extracted originates from residual unreacted slag
sity of extractants that have been used. These tests have present in the soil. Similar observations have been made re-
been developed by groups of workers in different countries garding the Na-acetate buffer (pH 4.0) method (Imaizumi and
and regions to meet the specific needs of the climates, soils, Yoshida, 1958) by both Sumida (2002) and Wang et al.
and crops (mainly sugarcane or rice) in their locality. Many (2001). These strongly acidic extractants should therefore be
other extractants have also been used although critical values avoided on Si-fertilized soils.
have not necessarily yet been derived (Berthelsen and Korn-
dörfer, 2005; Sauer et al., 2006). Many different extractants can provide valuable information
as to the Si status of soils and the likelihood of a yield re-
Water has been used by some workers to estimate readily- sponse in rice or sugarcane. Indeed, when a range of differ-
soluble Si (Fox et al., 1967; Elawad et al., 1982). However, ent extractants are compared over a range of soils and ferti-
extracting with water dilutes the ionic strength of the soil solu- lizer histories there is frequently a very strong correlation be-
tion greatly so that the amounts extracted will differ from those tween extractable Si values derived from different extractants
present in soil solution. For example, as shown in Fig. 2, Si (Berthelsen, 2000; Berthelsen et al., 2003, Wang et al., 2004;
adsorption onto metal hydrous oxides increases with increas- Kanamugire, 2007). This occurs even though extractants
ing ionic strength. In addition, the low ionic strength results in may remove widely different quantities of Si from the soil

Table 1: Some selected methods used to determine extractable soil Si along with suggested critical levels below which a crop response can
be expected.
Extractant Extraction ratio and period Suggested critical level Reference
H2 O 1:10 for 4 h < 0.90 Fox et al. (1967);

Elawad et al. (1982)
0.01 M CaCl2 1:10 for 16 h < 20 Haysom and Chapman

(1975); Berthelsen et al.
(2003)
0.5 M NH4-acetate (pH 4.8) 1:50 for 1 h < 20 Fox et al. (1967)
0.5 M acetic acid 1:10 for 1 h < 15 Snyder (1991)
0.18 Na-acetate (plus 0.87 M acetic acid, pH 4.0) 1:10 for 5 h < 60 Imaizumi and Yoshida (1958)
0.005 M sulfuric acid 1:200 for 16 h < 100 Hurney (1973);

Berthelsen et al. (2003)
0.025 M sulfuric acid 1:10 for 20 min < 40–70 Meyer and Keeping (2001);
Kanamugire (2007)
0.04 M Na2HPO4 (pH 6.2) 1:10 for 24 h < 200–300 Heinai and Saigusa (2006)
(Table 1). They still extract more Si from soils with a higher Si tive Si source for crops, diatomaceous earth has limited solu-
status and more from Si-fertilized rather than unfertilized soils. bility in acidic conditions and its solubility increases greatly at
Nevertheless, Berthelsen et al. (2001; 2005) suggested that pH > 9.0 (as with phytogenic Si). Berthelsen et al. (2003)
the best single measure of Si availability was that extracted showed that diatomaceous earth was generally an ineffective
with 0.01 M CaCl2. In a survey of 200 sugarcane sites in N source of Si for sugarcane grown in soils of pH 4.8–6.0.
Queensland, Berthelsen et al. (2003) found a close relation-
ship between leaf Si and 0.01 M CaCl2-extractable Si, while The most common Si fertilizers are various industrial by-prod-
no relationship was obtained when 0.005 M H2SO4 was used ucts. Useful materials from the steel industry include blast fur-
as the extractant. Similarly, in a survey of 28 sites in South nace slag, steel slag, converter slag, ferromanganous slag,
Africa, Miles et al. (2014) found a close correlation between and silica fume. Calcium silicate slag is also produced as a
soil and leaf Si when 0.01M CaCl2 was used as an extractant by-product of the manufacture of phosphorus in electric arc
(R2 = 0.77) and a much weaker one (R2 = 0.48) when 0.02 M furnaces. These slag materials contain various amounts of
H2SO4 was used. Ca- and/or Mg-silicates and are very effective fertilizer materi-
als as long as they do not contain significant amounts of
heavy metal contaminants (Gascho, 2001; Korndörfer and
7 Fertilizer Si
Pereira, 2011). Slags also act as liming materials since dis-
There is a range of silicate-containing materials suitable for solved OH– ions are released. The dissolution of akermanite,
use as fertilizers (Gascho, 2001). In general, their usefulness a major mineral component of blast furnace slag, is shown
is dependent on reactivity rather than total Si content. There below:
are a few naturally occurring mineral materials such as wol-
lastonite (21–25% Si; CaSiO3), olivine (ca. 20% Si; MgSiO3) Ca2MgSi2O7 + 7 H2O > 2 H4SiO4 + Mg2+ + 6 OH– + 2 Ca2+
and diatomaceous earth (38–42% Si) that can be mined from
the earth’s surface and used. Availability often limits their use. Registration of Si slags as fertilizers in Japan requires the ma-
For example, the use of wollastonite is restricted because of terial to contain not less than 20% SiO2 and to have a neutral-
its relatively high cost, which is attributable to other major in- izing capacity of > 35%, 100% of particles < 200 mm and
dustrial uses for the material (ceramics, friction products, met- > 60% of particles < 600 mm, and to conform to standards for
allurgy, paint, and plastics) as well as the cost of transport acid soluble and total loadings of Ni, Cr, and Ti (Takahashi,
from isolated mined deposits to agricultural areas. Wollaston- 2002; Owa, 2002). Standards developed in other countries
ite is, however, a very effective source of fertilizer Si (Berthel- are similar (Kingston, 2008). A range of these slag materials
sen et al., 2003; Korndörfer et al., 2005; Pereira and Cabral, have been used very successfully as Si fertilizers for both rice
2005; Buck et al., 2011). Wollastonite is also a liming material and sugarcane (Takahashi, 2002; Kingston, 2008).
since its dissolution releases OH– ions:
There are also some manufactured fertilizer Si products in-
CaSiO3 + 3 H2O > Ca2+ + H4SiO4 + 2 OH– cluding fused Mg-phosphate (7.5–9.4% acid soluble Si),
which is made by fusing a mixture of phosphate rock and oli-
Diatomaceous earth is the fossilized remains of diatoms (phy- vine or serpentine, and fused K-silicate (11–12% acid soluble
toplankton that are enclosed in a cell wall made of silica) and Si), which is made from calcining coal fly ash with K- and Mg-
is found in sedimentary rock. While wollastonite solubility is hydroxide. Silica gel is manufactured from Na-silicate and sul-
favored in the acidic pH range and therefore can be an effec- furic acid, and its solubility can be increased by small particle

size and raising the pH during gel preparation (Vogelsberger strated that for a range of Si sources; the water/amberlite H+
et al., 1992). Like diatomaceous earth and silica fume, its sol- resin method showed highest correlations with plant Si up-
ubility is increased greatly above pH 9.0. It has been used take. Nonetheless, in a similar experiment, Buck et al. (2011)
successfully in both paddy rice and wheat (Mecfel et al., found the Na2CO3/NH4NO3 method was best correlated with
2007; Gocke et al., 2013). Potassium silicate is manufactured plant Si uptake. At present, most regulatory systems for Si
by calcining silica sand with K-carbonate and can be used as fertilizers use the total Si content of the materials.
a solid fertilizer product (Ma and Takahashi, 2002). Its high
solubility means it can be also used to supply plants with Si in Since wollastonite and slags are effective liming materials,
hydroponics or as foliar applications (Menzies et al., 1992; their application increases both soluble Si concentrations and
Kanto et al., 2004). soil pH. This can result in a strong positive relationship be-
tween soluble or extractable Si and pH (Berthelsen et al.,
As noted above, the total Si content of a fertilizer material 2003; Haynes et al., 2013). The relationship between pH and
does not give any indication of its solubility or how much of CaCl2-extractable Si in a soil, when blast furnace slag was
the Si is potentially plant-available. A number of different applied at increasing rates to a Si-deficient soil, is shown in
chemical extractants for estimating available Si in silicate Fig. 5. Such a relationship is often likely to be observed in
fertilizer materials have been suggested (Kato and Owa, soils treated with varying amounts of wollastonite, blast fur-
1997a; 1997b; Haynes et al., 2013). These include 0.5 M HCl nace or steel slags. Adsorption of Si to soil colloids in the pH
(Savante et al., 1999), 0.5 M NH4-acetate (pH 4.8) (Hagihara, range 5–6 is not strong, therefore any increased adsorption
1981), water/amberlite resin in H+ form (Kato and Owa, caused by the increased pH is masked by the large increase
1997b), and Na2CO3/NH4NO3 (Pereira et al., 2003). As al- in Si supply.
ready noted, dissolution of wollastonite and slag results in
consumption of H+ ions, and as pH rises further Si dissolution Even where non-liming fertilizer Si sources (e.g., acidulated
is depressed. For this reason, acid extractants promote slag wollastonite) are applied to soils, increasing pH can cause an
dissolution (by removing OH– from solution) and are believed increase in Si solubility (Tavakkoli et al., 2011). In such cases,
to extract unrealistically large amounts of Si (Imaizumi and decreased solubility at low pH may be a factor. For example,
Yoshida, 1958; Kato and Owa, 1997a). The H+ resin method silicic acid can readily combine with Al to form colloidal hy-
used by Kato and Owa (1997b) buffers the extraction be- droxyaluminosilicates (HASs) (Farmer et al., 1979; Doucet et
tween pH 6 and 7 (similar values to those in soil). The al., 2001; Schneider et al., 2004). The precipitation of such
Na2CO3/NH4NO3 extractant was developed with the specific species has been forwarded as one mechanism by which ad-
aim of promoting dissolution of water-insoluble CaSiO3 dition of silicates to soils alleviates Al toxicity (Liang et al.,
(Pereira et al., 2003). 2001; 2007). Doucet et al. (2001) showed that an excess of
Al over Si(OH)4 (as would typically occur in an acid soil) re-
Working with a range of fertilizer Si materials and a range of sults in the formation of an imogolite-like phase termed HASA,
extractants, both Berthelsen et al. (2003) and Haynes et al. which has a Si:Al ratio of 0.5. When Si(OH)4 is present in ex-
(2013) concluded that there is no extractant that is reliable cess (e.g., after Si application to a soil) then further reactions
over a range of Si sources. For example Na2CO3/NH4NO3 is occur to form HASB, which has a Si:Al ratio of 1.0. Both forms
effective at extracting Si from wollastonite but ineffective for are known to occur in soils (Doucet et al., 2001). The practical
slags, while the water/amberlite H+ resin method is effective significance of such reactions from the viewpoint of Si avail-
for slags but not for wollastonite (Haynes et al., 2013). Both ability is that at soil pH values < 5.5 there are typically sub-
Pereira et al. (2003) and Berthelsen et al. (2003) demon- stantial concentrations of exchangeable and soluble Al
present, and added Si is likely to react with Al to form insolu-
ble HASs. For example, addition of silicic acid to two acid
soils was shown by Matlou (2006) to lower exchangeable and
soil solution Al concentrations significantly.
8 Foliar applications
There has been commercial interest in developing silicon-
containing solutions (normally K or Na-metasilicate or silicic
acid) for foliar applications, particularly in relation to disease
and pest control (i.e., environmentally friendly fungicides and
pesticides). Their use has met with limited success. For ex-
ample, there have been some reports of control of powdery
mildews on cucumber, muskmelon, zucchini, and grape
(Bowen et al., 1992; Menzies et al., 1992). As already noted,
plants (especially Si-accumulators) absorb Si in quantities
similar to those for macronutrients (e.g., N and K), and by
comparison with plant-requirement or the quantities that can
be soil-applied, the amounts that can be applied in foliar
Figure 5: Relationship between pH and CaCl2-extractable Si in a soil sprays are very small. Thus, Matlou (2006) found that regular
treated with increasing rates of blast furnace slag. Redrawn from foliar applications of Si to sorghum on a Si-deficient soil did
Haynes et al. (2013).

not significantly influence tissue Si application while soil appli- erable primary and secondary minerals (since the return of
cation of Ca-silicate was very effective. phytogenic Si will be limited). Globally, seven out of the 10
most important crops are Si-accumulator plants, so that in the
Since it is the Si status of the plant that influences plant toler- future crops other than rice and sugarcane (e.g., wheat, bar-
ance to biotic and abiotic stress, soil applications are gener- ley, soybeans, sugar beet, tomatoes) will very likely require Si
ally more effective. Guével et al. (2007), for instance, found applications to maintain maximum yields. Since crops in the
that soil applications of Si increased leaf Si concentrations field are constantly subjected to an array of stresses and plant
and reduced powdery mildew severity in wheat by as much tolerance to many stress factors can be greatly improved by
as 80% but foliar applications had a very small effect. Similar Si applications, a lack of Si may well be contributing to a glob-
observations were made by Liang et al. (2005) working with al yield decline which has been noted in recent times for a
powdery mildew on cucumber. In rice, brown spot incidence range of crops. In addition, Si is now being promoted as an
was greatly reduced by soil application of Si, but there was environmentally-friendly plant, prophylactic for a very wide
only a small effect of foliar-applied Si (Rezende et al., 2009). range of crops, and soil applications have been shown to be
It was suggested by Guével et al. (2007) that foliar sprays of much more effective than foliar sprays. A much better under-
K2SiO3 might inhibit powdery mildew severity by having os- standing of the Si fertility of soils is therefore required.
motic effects on spores germinating on the leaf surface. Liang
et al. (2005) suggested that foliar Si applications do not elicit There is a wide range of issues encompassing the solubility
physiological and biochemical/molecular mechanisms of host and availability of Si in agricultural soils that need further re-
resistance to pathogens that occur with soil applied applica- search. Firstly, the relative importance of various solid phase
tions. Thus, present evidence suggests that soil applications pools supplying the soil solution needs greater understand-
of Si are required to achieve increased plant tolerance to bi- ing. For example, the significance of adsorption/desorption
otic and abiotic stress and thus increased crop yields. reactions is unclear since Si is preferentially adsorbed as
H3SiO4 (pK1 = 9.8) with an adsorption maximum at pH 9.8,
9 Irrigation water yet Si in soil solution, at common soil pH values of 5–6, is
present predominantly as H4SiO4. The fact that leaching of Si
The amount of Si supplied in irrigation water may well be an from soils and its transport in streams to the sea are important
important management consideration (Kingston, 2008). In components of the biogeochemical cycling of Si suggests
Hawaii, Fox et al. (1967) showed that the response of sugar- that it is highly mobile in most soils. Limited research sug-
cane to Si applications was markedly greater in areas irri- gests that at soil pH values < 5.5, addition of Si can result in
gated with mountain runoff waters containing 2.5 mg Si L–1 the formation of insoluble hydroxyaluminosilicates (due to the
than where crops were irrigated with lower altitude ground- initially high soluble and exchangeable Al present), thus low-
water containing 30 mg L–1. Takahashi (2002) observed that ering Si availability. The significance of this reaction is, how-
Si concentrations in irrigation waters in rice paddies in Japan ever, still unclear. The importance of phytogenic Si as a
ranged between 1.9 and 28.9 mg L–1. In average, 10.2 mg Si source of soluble Si in agricultural soils also needs much
L–1 resulted in a supply of 142 kg Si ha–1 (30% of the crop greater attention. A few studies have suggested that diminu-
needs) when irrigated with 4 ML ha–1. Ma and Takahashi tion of phytogenic Si is the main reason for the very low solu-
(2002) also stressed the importance of Si input from irrigation ble Si concentrations in some agricultural soils. That is, phyto-
for paddy rice. Desplanques et al. (2006) measured an input genic Si is removed at harvest rather than being returned to
of 100 kg Si ha–1 in irrigation water in a rice field in France. the soil. Much more research is necessary to confirm the ex-
They suggested that most of this Si originated from fresh- tent of this and to quantify the role of Si removal in harvested
water diatoms present in the irrigation water. This Si would crops as a factor in the accelerated desilication of agricultural
therefore be present as silica in the frustules of diatoms rather soils. The magnitude and form of inputs of Si in irrigation
than as soluble silicic acid, and the silica would need to dis- water also needs greater consideration.
solve before becoming plant-available. On the other hand, de-
pletion of Si from irrigation water in some parts of Japan has
The effects of pH on the availability of soil Si needs greater
been attributed to rising densities of diatoms in reservoirs.
understanding due to the competing and interacting pro-
Flushes of diatom growth in reservoirs, caused by N and P
cesses involved. Unlike litho-pedogenic minerals, in which Si
contamination of surface waters, results in removal of soluble
solubility is highest at low pH for phytogenic Si, solubility in-
Si from the water and decreases in concentrations of soluble
creases markedly with increasing pH. As already noted, like-
Si in irrigation water downstream (Husnain et al., 2009).
wise does specific adsorption of Si to hydrous oxide surfaces.
However, when fertilizer Si is applied as slag materials, soil
Thus, the nature and magnitude of input of Si in irrigation
pH is also greatly increased since they are liming materials as
water needs further study. It should certainly be measured
well as Si sources. As a result, both soluble Si and pH in-
and considered when considering applying Si fertilizers.
crease. Where non-liming Si sources are used, formation of
hydroxyaluminosilicates at low pH might limit Si availability.
10 Conclusions Thus, the effect of pH on Si availability is, at present, unclear
and warrants further research.
In the future, Si is likely to be applied to agricultural soils on a
much more extensive and frequent basis. This is because
continual removal of Si in harvested products will, over time,
decrease the Si status of many agricultural soils low in weath-

Acknowledgments Brunings, A. M., Datnoff, L. E., Ma, J. F., Mitani, N., Nagamura, Y.,
Rathinasabapathi, B., Kirst, M. (2009): Differential gene
expression of rice in response to silicon and rice blast fungas
I thank the late Professor K. M. Goh, to whom this paper is
Magnaporthe oryzae. Ann. Appl. Biol. 155, 161–170.
dedicated, for stimulating my interest in the fertility of agricul-
tural soils. Buck, G. B., Korndörfer, G. H., Datnoff, L. E. (2011): Extractors for
estimating plant available silicon from potential silicon fertilizer
sources. J. Plant Nutr. 34, 274–282.
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J. Plant Nutr. Soil Sci. 2014, 177, 831–844 DOI: 10.1002/jpln.

Accepted September 19, 2014

1 Introduction agricultural systems is creating a new removal mechanism for

* Correspondence: Prof. R. J. Haynes; e-mail: r.haynes1@uq.edu.au

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Silicate adsorbed / mol cm–2 ×

ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.plant-soil.com

ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.plant-soil.com

ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.plant-soil.com

ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.plant-soil.com

6 Estimation of plant-available Si Ammonium- and Na-acetates (buffered at low pH with acetic

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Extractant Extraction ratio and period Suggested critical level Reference

H2 O 1:10 for 4 h < 0.90 Fox et al. (1967);

0.01 M CaCl2 1:10 for 16 h < 20 Haysom and Chapman

0.5 M acetic acid 1:10 for 1 h < 15 Snyder (1991)

0.005 M sulfuric acid 1:200 for 16 h < 100 Hurney (1973);

ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.plant-soil.com

ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.plant-soil.com

ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.plant-soil.com

ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.plant-soil.com

ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.plant-soil.com

ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.plant-soil.com

ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.plant-soil.com

ª 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.plant-soil.com

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