The Si in shoots can be returned to the soil (recycling) through plant residue incorporation. There are conflicting reports on the turnover rates of plant-available Si from decomposition of plant materials. Ma and Takahashi (2002) noted that the positive effect of rice straw incorporation on plant-available soil Si is long term in nature and is not fully realized immediately after straw incorporation. However, Marxen et al. (2016) reported that phytoliths from fresh rice straw are soluble at a rate of 2% to 2.5% per day during the first 33 days of their experiment; this was followed by decreasing Si release rates, suggesting that phytolith solubility decreases over time in soil. The findings of Fraysse et al. (2009) were similar wherein phytoliths extracted from horsetail had a dissolution rate of approximately 0.6% and 3% phytolith-Si d−1 at pH 6 and 8.6, respectively. Most Si in the soil is in an inert form, and only a small fraction is soluble and available for plant uptake, whereas most Si in mineral soils is held in the crystalline structure of sand, silt, and clay particles, a Si form unavailable for plant uptake. Soils vary significantly in their ability to supply plant-available Si. In general, soils in which Si fertilization will likely result in increases in crop yields are typically highly weathered, leached tropical soils with low pH, base saturation, and silica-sesquioxide ratios (Silva, 1973). These soils are classified as Ultisols and Oxisols. Their clay minerals are predominantly hydrated Al and Fe oxides and kaolite, characterized as high P-fixing soils. Soils that are less weathered or geologically young have the capacity to supply higher amounts of plant-available Si than highly weathered soils.
Soils known to have limiting plant-available Si content found in the United States generally belong to the following soils orders: Histosols, Ultisols, Spodosols, Inceptisols, and Entisols. Ultisols are common in the Eastern United States, occupying approximately 9.2% of the total US land area (Fig. 3). These are acidic soils characterized by having a low amount of plant-available Ca, Mg, and K. These soils have undergone intense weathering and leaching as is commonly found in warm, humid regions of the United States with high average annual rainfall and are not suited for continuous crop production unless treated with fertilizer and lime. Accumulated clay and the presence of Fe oxides are common in the subsurface horizon of these soils. Plant-available Si in Ultisols is generally low in contrast to the Mollisols that are common in the US Great Plains. Histosols of the EAA of south Florida are composed mainly of organic materials (20%–30% by weight) and are known to have low quantities of plant-available Si. Production areas in this region are known to respond significantly to Si fertilization. Histosols occupy approximately 1.6% of the United States’ land area (Fig. 3). Spodosols are acid soils characterized by a subsurface accumulation of Al- and Fe-humus complex. Similar to Ultisols, these soils require liming in order to be agriculturally productive. These soils are typically formed from coarse-textured parent material and occupy approximately 3.5% of the US land area (Fig. 4). Many regions in the United States have soils belonging to the weakly developed Entisols and Inceptisols that are believed to have low levels of plant-available Si as well (Fig. 5). Entisols generally have little or no evidence of pedogenic horizons development; many are sandy or very shallow (Soil Survey Staff, 1999). This is the most extensive soil order occupying approximately 12.3% of the US land area. Soils belonging to Inceptisols are commonly found in humid and subhumid regions, widely distributed in the US land area (approximately 9.7%), often found on fairly steep slopes, young geomorphic surfaces, and on resistant parent materials. Horizons of these soils are altered and known to have many diagnostic horizons. Soil texture and the duration of cropping systems are criteria other than soil order, which can provide an overview of plant-available Si status. Soils with large fractions of quartz sand that have been farmed for many decades are likely to have low quantities of plant-available Si (Datnoff et al., 1997).
The most common method to quantify the concentration of Si in water, soil extracts, and plant digest samples is via the molybdenum blue colorimetry (Hallmark et al., 1982). Monosilicic is the only form of silicic acid that is molybdate reactive, forming an intense blue color in solution, which increases with H4SiO4 concentration. The presence of other forms of Si (e.g., polysilicic acid) does not affect the formation of Si-molybdate blue complex. Silicon in solution can be measured by inductively coupled plasma-optical emission spectrometry, which can also measure all other forms of Si in solution including those that are not plant available. Thus, this limitation should be considered when estimating plant-available soil Si. Conversely, for quantifying total Si content in plant samples, inductively coupled plasma-optical emission spectrometry analysis may not pose any complications (Frantz et al., 2008).
From the vast amount of literature in the last 50 years, many procedures have been established and standardized for extracting different Si forms, not only plant-available forms, but also Si from amorphous silica and allophane in soils and sediments (Sauer et al., 2006). However, the abundance of Si in soil is interpreted differently when it comes to fertilization guidelines, where the most important fraction of Si is the form available for plant uptake. Plant-available Si is composed of H4SiO4 both in liquid (soil solution) and adsorbed phase (to soil particles). Tubana and Heckman (2015) summarized solutions, which have been used to extract and estimate plant-available Si, including water, calcium chloride (CaCl2), acetate, acetic acid, sulfuric acid (H2SO4), and citric acid (Table 4). The extraction procedures associated with these solutions have undergone a series of modifications, which generally resulted in shorter extraction time requirements. The choice of solution is critical because the amount of plant-available Si estimated by these extraction procedures differs, and so would be the interpretation of results and fertilizer recommendation. For example, Fox et al. (1967) used H2SO4, acetic acid, water, and Ca(H2PO4)2 to extract Si from soils of Hawaii. Water consistently extracted the least amount of Si, whereas those soils dominated by montomorillonite, kaolinite, goethite, and gibbsite contained the highest amount of Si based on the Ca(H2PO4)2 procedure. The H2SO4 procedure extracted the highest Si content from soils, which contained large fractions of allophane, whereas the Si content of soils determined by the acetic acid procedure fell between water and Ca(H2PO4)2/H2SO4. Recent works by Tubana et al. (2012) and Babu et al. (2013) have also demonstrated that the amounts of Si determined using different extractors for Midwest and southern US soils varied significantly. According to Babu et al. (2013), the amount of extractable Si was in the order of citric acid > acetic acid (24-h rest + 2-h shaking > 1-h shaking) > Na acetate > ammonium acetate > CaCl2 > water for soils representing some 130 mineral soils of Louisiana currently farmed to different field crops. The soil Si determined by 0.5 M acetic acid solution ranged from 3 to 300 mg kg−1. Similar study was done by Wang et al. (2004) except that they included Mehlich-3 solution. The amount of extracted Si was in the order of Mehlich-3 > citric acid > 0.1 M HCl > acetic acid > acetate buffer > ammonium acetate > water, suggesting that Mehlich-3 solution likely extracts solution, exchangeable, and adsorbed Si fractions.
Establishment of soil Si test interpretation and fertilization guidelines require knowledge of the critical Si concentrations in the soil, defined as the point on an economic crop response curve corresponding to plant-available soil Si concentrations at which maximum crop yield is attainable. Beyond this critical Si concentration, it is expected that crop response to Si fertilization will not result in further significant yield increases, whereas below this concentration there is the likelihood of a crop significantly responding to Si fertilization. It is expected that critical Si concentrations, just like any other plant-essential nutrients, will vary with soil type, crop species, and soil testing procedure. The critical Si level established for the organic and mineral soils in south Florida (characterized by having low clay, Al, and Fe contents) was based on 0.5 M acetic acid procedure (1-h shaking). Using sugarcane as a test crop, the critical Si level was determined to be 32 g m−3 (McCray et al., 2011) and 19 mg Si kg−1 for a rice crop (Korndörfer et al., 2001). Elsewhere in the world, depending on soil type and extraction procedure, the critical Si concentration varied significantly. For example, the critical level ranged between 71 and 181 mg kg−1 for wheat grown on calcareous soils using Na acetate–acetic acid as the extracting solution, (Liang et al., 1994; Xu et al., 2001). Narayanaswamy and Prakash (2009) showed large differences in critical Si concentrations for rice grown on acidic soils in India because of extracting solutions: 54 versus 207 mg Si kg−1for 0.5 M acetic acid (1-h shaking) versus 0.005 M H2SO4, respectively. For select mineral soils from the Midwest and southern United States Tubana et al. (2012) suggested that critical Si concentrations ranged between 120 and 150 mg Si kg−1 when using ryegrass biomass as the plant response variable.
Standardization of procedures in plant tissue Si testing has not encountered as many challenges as the standardization of soil Si testing. Only a few procedures are established for determining total Si content in plant tissue: gravimetric method, hydrofluoric acid solubilization, autoclave-induced digestion with strong NaOH solution, or microwave digestion assisted with nitric acid–hydrofluoric acid (Yoshida et al., 1976; Novozamsky et al., 1984; Elliott and Snyder, 1991; Feng et al., 1999). The most widely used method was the autoclave-induced digestion method developed by Elliott and Snyder (1991) because it is relatively rapid and does not require costly, specialized instrumentation. However, there were many reports regarding low precision of the method and at times underestimation of Si value in the plant (Taber et al., 2002; Haysom and Ostatek-Boczynski, 2006). Excessive foaming caused some undigested samples to adhere to the walls of plastic tubes, and during autoclaving, the sample particles had lower or no contact at all with the NaOH and H2O2, which resulted in incomplete digestion. This was later addressed by Kraska and Breitenbeck (2010a) with the addition of octyl-alcohol, which eliminates the excessive foaming caused by H2O2 addition. The stability of color development was prolonged as well with the addition of 1 mL of 5 mM ammonium fluoride, and the method was simplified by using a bench-top oven (95°C) over an autoclave. After these modifications, the procedure is now called the oven-induced digestion procedure (Kraska and Breitenbeck, 2010a). Recently, nondestructive, accurate, and high-throughput methods in assessing Si in plants were evaluated. Reidinger et al. (2012) assessed Si in plants using a portable x-ray fluorescence spectrometer with a detection limit of 0.014% Si. Smis et al. (2014) calibrated plant Si extracted by wet alkaline (0.1 M Na2CO3) solution according to Meunier et al. (2013), with the values near-infrared reflectance spectroscopy technique.
Silicon content of plant tissue is an accepted parameter for evaluating plant-Si status. Currently, there are few published plant tissue critical Si concentrations, not only in the United States, but also elsewhere in the world. The published concentrations are mainly for rice and sugarcane. The critical Si level established by Snyder et al. (1986) for rice grown on organic soils of the EAA of south Florida using straw was 3.0%. Recent work by Korndörfer et al. (2001) established critical concentrations for rice (between 1.7% and 3.7%) using similar straw sampling material. Using the most recent fully expanded leaf in rice (Y-leaf) at mid-tillering, Kraska and Breitenbeck (2010b) noted 5.0% as a concentration used to indicate sufficient Si for rice in Louisiana. Using sugarcane top visible dewlap leaf as sampling material, Anderson and Bowen (1990) identified the critical Si content was 1.0%, whereas McCray and Mylavarapu (2010) set a lower value of 0.5%. To maximize sugarcane yield, the Si content in leaf tissue should be more than the reported critical Si concentration (Snyder et al., 1986). It is important to note that the critical Si concentrations are very specific to crop species, location, and sampling material, underscoring the need to establish site-specific plant-Si content interpretations.
The first patent for using Si-rich slag as fertilizer was obtained in the United States in 1881 (Zippicotte, 1881). While the naturally occurring wollastonite Ca silicate is more soluble and contains high amounts of Si, the refining process of this mineral is labor-intensive and expensive, which limits its mass production as a fertilizer (Park, 2001; Maxim et al., 2008). Using this process, high application rates alone can make this Si fertilizer extremely expensive on top of its transportation cost to the field and machinery costs for application. In the United States, the expenses allotted to transportation and machinery may be affordable because of relatively good infrastructure and crop subsidies, but these expenses could be more problematic elsewhere in the world, particularly in developing countries. Nowadays, byproducts of industrial procedures such as the smelting of wollastonite, Fe, and Mg ore, and electric production of P are commonly used as Si fertilizers (Elawad and Green, 1976; Snyder et al., 1986). These are relatively inexpensive sources of Si for crop production. Compared with wollastonite, silicate slags contain smaller fractions of easily soluble Si, but they have added benefits such as liming agents, typically with similar Ca carbonate equivalent and as sources of some plant-essential nutrients (Heckman et al., 2003; Gascho, 2001; White et al., 2014). In addition, some slags, unlike wollastonite, can provide a balanced supply of Ca and Mg.
The amount of plant-available Si and composition of silicate slags differ because of differences in speeds of cooling and granular size of the material (Takahashi, 1981; Datnoff et al., 1992; Datnoff et al., 2001). While silicate slags are more economical to use as Si fertilizer versus wollastonite as Si fertilizer, producers should not overlook the amount of plant-available Si present in the silicate slag. Several methods for quantifying plant-available Si from industrial byproducts have been tested and thus far identified that the Na2CO3 + NH4NO3 extraction methods have been identified as suitable for solid Si sources, whereas the HCl + HF digestion was suitable for liquid sources (Buck et al., 2011). Recently, the 5-day Na2CO3-NH4NO3 soluble Si extraction method was developed for solid fertilizer products (Sebastian, 2012; Sebastian et al., 2013). Total Si and soluble Si of some industrial byproduct sources are reported in Table 5. Included in the list are organic sources: biochar, rice hull ash, and livestock manure composts. Straw from wheat and other small grain crops contains high amounts of Si; wheat straw Si concentrations range from 1.5 to 12 g kg−1 (Heckman, 2012). In addition to this, fresh rice straw can be a potential source of Si. The potential of fresh straw as source of Si is encouraging based on recent findings by Marxen et al. (2016), indicating that this plant material contains large amount of highly soluble phytoliths. This in turn can replenish the amount of plant-available Si taken up by plant from the soil solution.
The use of Si-containing solution applied as foliar spray has an advantage in terms of ease of application at manageable rates and not altering soil pH brought about by high application rates of solid Si sources with high liming potential (Tubana et al., 2012; Haynes et al., 2013). While there is a growing interest on the use of foliar Si solution, limited studies have been conducted in the United States (Kamenidou, 2002; Kamenidou et al., 2009; Lemes et al., 2011; Tubana et al., 2013; Agostinho et al., 2014). In addition, even if there was a positive plant response to foliar Si, the foliar absorption of Si remains questionable because no transport mechanisms have been found to occur in this plant organ to date (Rodrigues et al., 2015).
Analytical methods are available to determine soluble Si analysis for liquid and solid Si fertilizers; however, soil is a dynamic entity, which unfortunately is understudied in Si research. Tubana et al. (2014) reported that the amount, time, and duration of release of plant-available Si from added silicate slag (12% Si) determined by the 0.5 M acetic acid extraction procedure were influenced by clay and organic matter content of the soil. They used soils from Indiana, Louisiana, Michigan, Mississippi, and Ohio that varied in soil pH (5.0–7.4), organic matter content (0.3%–5.0%), and texture (fine sandy loam to silty clay), with initial plant-available Si ranging from 22 to 165 mg kg−1. Increases in plant-available Si were seen 30 days after application across all soil types. However, different trends were observed following this release of plant-available Si: (a) a drastic decline throughout the 120-day period was observed for soils containing high sand and clay fractions, presumably due to leaching and adsorption, respectively; and (b) continuously increased up to 90 days after application then declined for silt loam–textured soil containing moderate amounts of organic matter. Across all soils 120 days after application, the level of plant-available Si was found to remain substantially higher than the control (no Si added). A laboratory incubation study was conducted by Babu et al. (2014) to evaluate the release pattern of H4SiO4 from wollastonite and Ca silicate slag (12% Si) applied to soils of Louisiana varying in clay content and chemical properties. They concluded that the amount of H4SiO4 measured in solution (0.1 M NaCl) was influenced by the adsorption capacity of soils, which was highly determined by soil pH, organic matter, and clay content.
The establishment of Si fertilization as an agronomic practice in crop production is perceived to be pursued only in regions where there is lack of sufficient supply of plant-available Si. Perhaps the oldest reason justifying fertilization in agricultural lands was a compelling circumstance related to sugarcane production in the geologically old soils of Hawaii and the organic and sandy soils of the south Florida EAA. The overwhelming published literature about the beneficial contributions of Si fertilization to crop productivity in production areas where disease and insect pressure is high and abiotic stresses are present has prompted research on Si to proliferate in the United States in the 1990s (Datnoff et al., 2001).
The principal crops in US agriculture collectively can take up 9.55 million tons Si in shoots annually (Table 2) or remove as much as 11.1 million tons from the soils planted to these crops (Table 3). The estimated amount of Si taken up in a given area by each crop showed that removal rates of Si from the soil can be substantial and even higher than primary essential nutrients (e.g., P, K) especially for rice (329 kg Si ha−1), sugarcane (160 kg Si ha−1), and wheat (108 kg Si ha−1). These crops are classified as high–Si-accumulating plants. From the limited information collected in this review, it appears that the estimated shoot Si uptake is significantly much higher (1,408 kg ha−1) than the rest of the crops in the list, even though this crop is a dicotyledon, which are considered to be low–Si-accumulating plants. The shoot Si used in the computation was based on the research of Draycott (2006), indicating that sugar beet top dry matter can contain as much as 115 g Si kg−1. Nevertheless, the estimated amount of Si removed annually by these crops is generally substantial and faster than in natural ecosystems. Based on the total cropland area in the United States (USDA-NASS, 2007) and the average plant Si (Bazilevich, 1993), the total amount of Si removed annually is approximately 21.1 million tons. This is about 10% of the world annual Si removal rate by crops of 210 to 224 million tons reported earlier (Bazilevich, 1993; Reimers, 1990; Savant et al., 1997a). The amount of plant-available Si in solution is characterized as low, ranging from 0.1 to 1.6 kg Si ha−1 in the upper 20-cm soil layer; this is either due to the desilication (leaching) process common in highly weathered soils (Oxisols, Ultisols) or simply due to the fact that the solubility of most Si-bearing minerals in soils is low. The replenishment of plant-available Si in soil solution is critical and may be characterized as slow based on soil Si dissolution kinetics and Si release from organic sources, including crop residues and burned rice husk. The latter, however, was reported to have long-term positive effects. Faimon (1998) studied the kinetics of release of Si from feldspar, grandiorite, and amphibolite, revealing solutions can attain supersaturation with respect to Si; consequently, this may lead to Si flowing out from the solution forming secondary minerals or their amorphous equivalent. This process essentially reduces the amount of plant-available Si.
Silicon chemical dynamics in soils have been understudied until recently. The research thus far reveals that the chemical dynamics between Si and many soil components influence the amount of plant-available Si released to soil solution. This could challenge the assumption that based on the amount of 2:1 layered silicate clay minerals that most soils in the United States are capable of supplying high concentrations of plant-available Si to crops. A recent study showed a significant increase in grain yield of rice even when grown on a soil rich in 2:1 layered silicate clays with high initial levels of 0.5 M acetic acid–extractable Si at 160 μg g−1 (Tubana et al., 2014). Babu et al. (2014) pointed out that the release of H4SiO4 to soil solution is critical to the amount of soil solution plant-available Si and is influenced by different processes (e.g., desorption, polymerization) and soil properties other than pH. This explained the unexpected response to Si of rice grown on soil despite high initial Si level and clay content. In this context, the need for Si fertilization not only may be justified by having low plant-available Si, but also could be based on the soil’s ability to replenish the Si removed by plants from the soil solution, especially for soils under continuous, intensive farming systems. Clearly, a soil’s clay content, pH, organic matter content, and Al and Fe oxide content are essential factors to consider when making a recommendation for a Si fertilizer.
The success of US agriculture as an industry has been attributed to modernization and adoption of intensive crop farming approaches that have enabled the country to become a net exporter of food (USDA-ERS, 2013). This trend is likely to continue, and so will the removal of Si from US cropland soils. Climate change is foreseen to bring more challenges and limitations to crop production in the forms of higher disease pressure, drought, waterlogged conditions, and salt stress. In addition, continuous cropping is always accompanied by removal of basic cations and fertilization, which in turn will eventually lead to soil acidification, making liming programs indispensable in crop production to secure maximum yield. For all these reasons, Si fertilization using low-cost industrial byproduct sources with high liming potential may become an agronomic practice in many crop production systems in the United States, especially for the purpose of alleviating biotic and abiotic stresses that may limit yields as well as for correcting soil pH.
Published with the approval of the Director of the Louisiana Agricultural Experiment Station as publication 2016-306-27516.
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