Agronomic and Environmental Aspects of Phosphate Fertilisers Varying in Source and Solubility An Update Review

Nutr Cycl Agroecosyst (2011) 89:229255 DOI 10.
1007/s10705-010-9390-4
ORIGINAL ARTICLE
Agronomic and environmental aspects of phosphate fertilizers varying in source and solubility: an update review
S. H. Chien L. I. Prochnow S. Tu C. S. Snyder
Received: 8 April 2010 / Accepted: 17 July 2010 / Published online: 28 July 2010 Springer Science+Business Media B.V. 2010
Abstract This review discusses and summarizes the latest reports regarding the agronomic utilization and potential environmental effects of different types of phosphate (P) fertilizers that vary in solubility. The agronomic effectiveness of P fertilizer can be inuenced by the following factors: (1) water and citrate solubility; (2) chemical composition of solid watersoluble P (WSP) fertilizers; (3) uid and solid forms of WSP fertilizers; and (4) chemical reactions of P fertilizers in soils. Non-conventional P fertilizers are compared with WSP fertilizers in terms of P use efciency in crop production. Non-conventional P fertilizers include directly applied phosphate rock (PR), partially acidulated PR (PAPR), and compacted mixtures of PR and WSP. The potential impacts of the use of P fertilizers from both conventional (fully
acidulated) and non-conventional sources are discussed in terms of (1) contamination of soils and plants with toxic heavy metals, such as cadmium (Cd), and (2) the contribution of P runoff to eutrophication. Best practices of integrated nutrient management should be implemented when applying P fertilizers to different cropping systems. The ideal management system will use appropriate sources, application rates, timing, and placement in consideration of soil properties. The goal of P fertilizer use should be to optimize crop production without causing environmental problems. Keywords Phosphate fertilizers Agronomic effectiveness Cadmium P runoff Eutrophication
S. H. Chien (&) Formerly afliated with IFDC, Muscle Shoals, AL, USA e-mail: nchien@comcast.net Present Address: S. H. Chien 1905 Beechwood Circle, Florence, AL, USA L. I. Prochnow IPNI Brazil Program, Piracicaba, SP, Brazil S. Tu IPNI Southwest China Region, Chengdu, China C. S. Snyder IPNI Nitrogen Program, Conway, AR, USA
Introduction Phosphorus (P) is an essential macronutrient that can limit normal plant growth if not provided by the soil or by appropriate quantities of fertilizers. For soils low in available P, the nutrient must be applied in either organic or inorganic form to obtain optimal crop yield. Organic P sources, such as crop residues and animal manure, generally have low P content. These organic P sources must be supplied in massive amounts to provide adequate P rates, rendering their application economically unfeasible in many locations and conditions. Furthermore, plants often absorb
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about 50% of their seasonal P requirements by the time they have accumulated 25% of their total seasonal dry mass (Black 1968). Thus, plants early P requirements are critical. Unlike nitrogen (N), which can be top-dressed as fertilizer 23 times during the growing season, generally P fertilization entails a one-time basal application to the soil before or soon after plant emergence. Because organic P must be converted to inorganic P through a relatively slow mineralization process before it becomes available to plants, organic fertilizers may not meet plants early P requirements, often resulting in lower crop yield (Nachimuthu et al. 2009). Furthermore, unlike conventional chemical N fertilizers which are all water soluble, P fertilizers vary widely in solubility that can inuence the initial and residual P effects. For this and other reasons, inorganic P fertilizers remain the major sources of P application used by farmers in both developed and developing countries. Inappropriate or excessive use of P fertilizers has been linked to environmental pollution, including heavy metal contamination in soils, and P runoff can contribute to the eutrophication of water bodies (Chien et al. 2009). In this review, we extract and synthesize information concerning the P source varying in solubility, agronomic effectiveness, and environmental impact of inorganic P fertilizer use from recent literature reports, especially those published from 1999 to 2009.
Solubility characteristics of various phosphate fertilizers Solubility measurement methods In general, the solubility of P fertilizers is measured according to three categories: water-soluble P, citrate (neutral ammonium citrate or NAC)-soluble P, and citrate-insoluble P. Methods of solubility measurement, however, vary among countries. In the United States, the AOAC procedure (AOAC 1999) is most commonly used. In this procedure, a sample of fully acidulated P fertilizer [single superphosphate (SSP), triple superphosphate (TSP), monoammonium phosphate (MAP), or diammonium phosphate (DAP)] is extracted with water to determine water-soluble P. This step is followed by ltration and extraction of the residue with NAC solution to determine
citrate-soluble P. The remaining P in the residue after citrate extraction is then digested to determine its total P content, which is termed citrate-insoluble P. The combined water-soluble and citrate-soluble P is considered as available P. The amount of citrateinsoluble P can also be indirectly calculated by subtracting available P from total P. In other countries [e.g., the European Community (EC)], direct NAC extraction of fully acidulated P fertilizers (without pre-extraction with water) is often used to measure available P. In general, the two procedures (with or without pre-extraction of WSP) produce only minor differences in the measured amount of available P. For example, Johnsonton and Richards (2003a) reported that the average available P content of four TSP samples was 20.0% P according to one method and 19.4% P according to the other. Therefore, it appears that the use of a single extraction step or sequential extractions for determining available P is not a major issue for fully acidulated P fertilizers. Although the two methods provide similar results for available P, there has been some concern within the fertilizer-production community that these small differences could contribute to challenges in manufacturing and labeling P fertilizers (Falls 1991). Because the water-soluble P fraction represents a signicant portion of total P in most fully acidulated P fertilizers, we refer to fully acidulated P fertilizer interchangeably with water-soluble P (WSP) fertilizer hereafter. In partially acidulated phosphate rock (PAPR) fertilizers or compacted (PR ? WSP) fertilizers, which contain a mixture of un-acidulated phosphate rock (PR) and partially acidulated WSP, the citrate solubility of the un-acidulated PR may be decreased by the Ca common-ion depressive effect on apatite solubility due to the presence of water-soluble monocalcium phosphate (MCP). Therefore, the available P in these types of P fertilizers can be underestimated if a single citrate extraction step is used (Chien 1993). Compacted (PR ? WSP) fertilizers are produced by mixing PR with WSP at certain P ratios. The mixture is compacted, crushed, and screened until the desired granular sizes are reached (Menon and Chien 1996). Similarly, the citrate solubility of apatite in directly applied PR can be underestimated if the PR contains a signicant amount of free carbonates (calcite and/or dolomite). Free carbonates are more soluble than apatite,
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resulting in the same Ca common-ion depressive effect (Chien 1993). In this case, a sequential second extraction and measurement of citrate solubility should be performed to determine the actual available P in the PR after the rst citrate extraction has removed the free carbonates. In one study, for example, the citrate solubility of Huila PR (Colombia) increased from the rst extraction (0.6% P) to the second extraction (1.9% P) because this PR contained 6% CO2 in the form of free carbonates rather than apatite-bound carbonate. Consequently, the second citrate solubility measurement was better correlated with crop response to PR than the rst citrate solubility measurement (Chien and Hammond 1978). Chien (2003a) reported that PAPR produced from PR sources containing low Fe2O3 ? Al2O3 content with 50% acidulation by H2SO4 had the same water solubility as compacted (PR ? WSP) fertilizer made from the same materials at a 1:1 total P ratio. However, when the PR sources had high Fe2O3 ? Al2O3 content, the water solubility of the resulting PAPR fertilizer was lower than that of the compacted fertilizer. This effect occurred because partial acidulation of PR with high Fe2O3 ? Al2O3 content produces WSP and soluble Fe and Al ions that precipitate WSP as water-insoluble FeP and Al P. However, un-acidulated Fe2O3 ? Al2O3 minerals do not adsorb WSP in physically compacted products. Furthermore, the compaction process is preferable to the wet granulation process, which requires drying. During drying, WSP can be precipitated with the associated free carbonates in the PR, resulting in reduced water solubility. As will be discussed below, compaction is preferred to partial acidulation for PR sources that have high Fe2O3 ? Al2O3 content (Chien 2003a). Expression of phosphate solubility The water solubility of fully acidulated P fertilizers can be expressed as a percentage of fertilizer material, total P, or available P. Johnston and Richards (2003a) pointed out different conventions for expressing the water solubility of P fertilizers might result in a distorted view of P water solubility. They compared the conventions used to express water solubility for two US and two UK TSP products. Table 1 shows that the UK2 and US1 samples differed by 11.2% if water solubility was expressed as a percentage of total
Water-soluble P as % of available P 90.5 92.6 96.6 96.9
P (95.2 - 84.0% = 11.2%), 6.4% if water solubility was expressed as a percentage of available P (96.9 90.5% = 6.4%), and only 1.5% if water solubility was expressed as a percentage of TSP (18.9 17.4% = 1.5%). Therefore, the convention used to express P solubility should be considered when comparing the water solubility of fully acidulated P fertilizers. This consideration is relevant to the fertilizer P regulations adopted by different countries. For example, the minimum water solubility of EC-type TSP products has been decreased from 93 to 85% as a percentage of available P in the 2004 EC Commission Regulations (European Community 2004). In Brazil, the minimum water solubility of fully acidulated P fertilizers is about 90% of available P (Chien et al. 2009). When comparing the solubility of various PR sources that have different total P contents, solubility is more appropriately expressed as a percentage of rock than as a percentage of total P. The latter convention gives misleading comparisons when PR sources of varying P content are used. For example, Chien and Hammond (1978) showed that Pesca (Colombia) PR was lower in both total P and citrate solubility as a percentage of rock than Central Florida PR (8.6 vs. 14.2% for total P and 0.8 vs. 1.4% for citrate solubility as a percentage of rock). However, when solubility was expressed as a percentage of total P, the citrate solubility of Pesca PR was the same as that of Central Florida PR (4.0%).The agronomic effectiveness of Central Florida PR, however, was greater than that of Pesca PR, consistent with the citrate solubility values expressed as percentages of rock rather than with those expressed as percentages of total P (Chien and Hammond 1978). Lehr and McClellan (1972) demonstrated that when total P content of North Carolina PR was diluted by half from 13.0 to 6.5% with quartz, the citrate solubility
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remained relatively constant (5.7%) when the solubility was expressed as % of material (PR ? quartz) whereas the solubility increased from 9.1 to 16.0%. This is due to the fact that apatite mineral in a PR has its maximum solubility xed by a solubility-product constant (Chien and Black 1976). Thus, PR solubility can be mathematically increased for one PR source containing low total P content as compared to another PR source containing high total P content when the two PR sources have the same reactivity. Therefore, the solubility of PR in NAC, 2% citric acid (CA), or 2% formic acid (FA) is better expressed as a percentage of rock. The use of PR solubility measurements from the second extraction and the expression of solubility as a percentage of rock are key principles used in a recently developed Phosphate Rock Decision Support System (PRDSS), which compares the relative agronomic effectiveness (RAE) of PR to that of WSP (Smalberger et al. 2006; Chien et al. 2009). This comparison procedure will be discussed below. Chemical and mineralogical composition and solubility characteristics of phosphate fertilizers In fully acidulated commercial-grade P fertilizers, the P compounds within the WSP fraction are mostly in the forms of MCP [Ca(H2PO4)22H2O] in SSP and TSP, NH4H2PO4 in MAP, and (NH4)2HPO4 in DAP. In general, commercial-grade SSP, TSP, MAP, and DAP fertilizers are not 100% water-soluble. Normally, at least 8590% of the total P in these fertilizers is water-soluble, and the remaining P is citrate-soluble. However, some poor-quality SSP sources may contain as little as 5060% watersoluble P. Single superphosphate also contains a signicant amount of CaSO4 as a result of the acidulation of PR with H2SO4. The chemical and mineralogical composition of the remaining waterinsoluble P fraction depends strongly on the source of the PR and the processes used during acidulation. The most common water-insoluble P impurities are the generic P compounds H8 [(Fe,Al)3NaH8(PO4)6 6H2O] in SSP and H14 [(Fe,Al)3NaH14(PO4)84H2O] in TSP (Prochnow et al. 2003a, b, c). According to Prochnow et al. (2003a, b), studies prior to 1999 showed that about 20% of the total P content in Australian SSP fertilizers was in the form of residual apatite and two water-insoluble
P compounds [Ca(Fe,Al)H(HPO4)2F22H2O and (Fe,Al)(K,Na)H8(PO4)66H2O] and that water-insoluble P occurred in the forms of MgAl(NH4)2H (PO4)2F2, AlNH4HPO4F2, and FeNH4(HPO4)2 in MAP fertilizers produced from North Carolina, Florida, and Idaho PR sources. The compound MgAl(NH4)2H(PO4)2F2 was the most abundant of several citrate-insoluble P compounds that remained after citrate extraction of these MAP fertilizers. Prochnow et al. (2003a) identied Fe3NaH8(PO4)6 6H2O as the major water-insoluble P compound in three Brazilian SSP fertilizers. The water solubility of these SSP products as a percentage of available P was 46, 80, and 86%. As will be discussed below, the water-insoluble but citrate-soluble compounds (and citrate-insoluble P impurity compounds) that are present in fully acidulated P fertilizers do have some agronomic value when compared to 100% WSP compounds such as MCP. In terms of providing P to plants, agronomic performance differs among various fertilizers with low percentages of water-soluble P. Some of these fertilizers are very good sources of this essential nutrient.
Agronomic aspects of phosphate fertilizers varying in source and solubility Effects of the chemical and mineralogical composition of P fertilizers on their reactions and agronomic effectiveness in soils Major solid water-soluble P fertilizers include SSP, TSP, MAP, and DAP. All of these compounds are readily soluble in soil and provide P in the soil solution for plant uptake. However, water-soluble P in the form of orthophosphate can be readily converted to water-insoluble P through reactions with soil minerals. In acidic soils, FeAl oxides can convert P in the soil solution to water-insoluble Fe AlP on the surface of mineral particles. In calcareous soils, P in the soil solution can be surfaceadsorbed by CaCO3. Furthermore, P in the soil solution can precipitate with cations as amorphous FeP and/or AlP compounds in acidic soils and as CaP compounds in alkaline or calcareous soils. All of these reactions can result in decreasing P availability over time (Hedley and McLaughlin 2005;
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Table 2 Available P (measured by the Olsen method) in calcareous soil treated with DAP or SSP according to placement method (Lu et al. 1987) Fertilizer Placement methoda Rate of P added (mg P/kg soil) 27 (mg P/kg soil) DAP Broadcast Incorporation Deep placement SSP Broadcast Incorporation Deep placement Control (no fertilizer P) Fertilizer 9 placement 9 rate LSD (0.05) CV(%) 13.35 18.80 9.4 5.2 6.3 22.3 8.3 11.3 (1.5 mg P/kg) 55 (mg P/kg soil) 13.6 6.7 10.6 27.9 17.2 18.9 110 (mg P/kg soil) 18.4 12.3 20.8 39.8 28.6 31.6 220 (mg P/kg soil) 32.9 27.0 33.6 63.6 55.3 70.9
a Values for the incorporation method should not be directly compared to those for broadcast and deep placement because of the effect of placement method on fertilizer concentrations in the soil
Syers et al. 2008). Several terms, such as P sorption, adsorption, retention, xation, precipitation, and immobilization, have been used to describe this process (Chien et al. 2009). In general, only about 1020% of applied P is taken up by the rst crop. However, Syers et al. (2008) concluded that the efciency of water-soluble P fertilizer can be up to 90% when evaluated over an adequate time scale (at least a decade) using the balance method to calculate P recovery. The balance method simply considers yield and P uptake relative to the amount of P applied. Thus, it takes into account residual P from previously applied fertilizer. This method differs from the traditional difference method, which compares crop yield and P uptake between soils with and without added P. Consequently, P recovery calculated by the balance method is higher than that calculated by the difference method. In general, all high-quality WSP fertilizers should be equally effective in providing available P to plants. Therefore, only a limited amount of research has been reported in the literature regarding the agronomic effectiveness of different fully acidulated P fertilizers in terms of source (e.g., SSP, TSP, MAP, and DAP) and solubility. Most published reports on this topic have focused on water-insoluble and partially watersoluble P sources [e.g., PR, PAPR, and compacted (PR ? WSP) fertilizer]. However, because P reaction products vary in solubility (Hedley and McLaughlin 2005; Syers et al. 2008), different sources of fully
acidulated P fertilizers may not be equally effective under certain conditions. For example, Lu et al. (1987) reported that SSP was more effective than DAP for maize grown in a calcareous soil in terms of drymatter yield, P uptake, and available P (Table 2), regardless of the P placement method (broadcast, incorporation, or deep placement). In their study, sulfur (S) was not limiting for plant growth. The major initial reaction product of MCP, which is the main P component of SSP, is dicalcium phosphate dihydrate (DCPD; CaHPO42H2O) in calcareous soils, whereas the principal reaction products of DAP are octacalcium (OCP) [Ca8H2(PO4)53 H2O] and hydroxyapatite (HA) [Ca10(PO4)5(OH)2]. In addition, various types of Ca-NH4-P, such as Ca(NH4)2(HPO4) H2O and CaNH4PO4H2O, may be produced when DAP reacts with calcareous soils (Lindsay 1979). Because DCPD is more soluble than other CaP compounds, SSP performs better than DAP in calcareous soil, as reported by Lu et al. (1987). However, some researchers have claimed that the nitrication of NH4N in MAP and DAP fertilizers to NO3N (which increases acidity levels around fertilizer granules in the soil) and the root absorption of NH4N (which increases rhizosphere acidity) may increase the dissolution of precipitated CaP compounds. This increased dissolution enhances the P availability of SSP or TSP (Terman 1971). Researchers often use SSP and/or TSP as standard WSP sources in comparison with other CaP sources,
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such as PR, PAPR, or compacted fertilizer (PR ? WSP). Use of poor-quality SSP or TSP as a P reference to compare other CaP sources (e.g., PR or PAPR) might result in misleading information and over-estimate the relative effectiveness of those CaP sources. Therefore, it is recommended that researchers check the quality of SSP or TSP before starting the agronomic experiments. It also should be pointed out that SSP contains signicant amount of S that may under-estimate the relative effectiveness of PR against SSP in the S-decient soils if S is not added to the PR treatment. Similarly, the same problem could also be encountered when comparing with other fully acidulated P fertilizers (e.g., TSP, MAP, or DAP) that contain little or no S. For example, Bationo et al. (1995) showed that SSP performed better than TSP as P source for pear millet grown on a sandy soil (pH 5.7) in West Africa. There is no reason to expect that SSP is better than TSP as P source since both contain the same WSP compound (MCP). In this study, no other nutrients except N were applied. It is most likely that the crop responded to P and S so that SSP was better than TSP as reported. Reactions and agronomic effectiveness of uid and solid WSP fertilizers in soils Numerous studies have compared the agronomic effectiveness of uid versus granular or non-granular WSP fertilizers. For a valid comparison of uid and solid P fertilizers, the P should be supplied by the same chemical compounds in both cases, and it should be similarly placed. However, many reported greenhouse and eld trials do not comply with these requirements, and the results often conict. For example, many studies have claimed that uid ammonium polyphosphates (APP) are agronomically superior to ammonium phosphates because of the different P compounds in the two P sources (polyphosphates in APP vs. orthophosphates in ammonium phosphates). Most results in the United States and other countries show equal P availability from these two P sources to crops grown on most soils (Chien et al. 2009). Ottman et al. (2006) also found no signicant differences in alfalfa yield obtained with uid APP and granular MAP on a calcareous soil over 3 years. Some favorable results for APP on neutral to alkaline soils may have been caused by appreciable amounts of micronutrients, such as Fe or
Zn, in the APP (Engelstad and Terman 1980). It is now recognized that the P in APP becomes available to plants only when the polyphosphates are hydrolyzed to orthophosphate in the soil. This process depends largely on soil biological activity. If the hydrolysis of polyphosphate to orthophosphate is slow, soil P xation may decrease over time through the sequestration of polyphosphate, keeping it from being adsorbed by soil minerals. This process may increase the agronomic effectiveness of polyphosphates compared to orthophosphates. Recently, renewed interest in research on uid versus granular forms of the same WSP fertilizers has been reported, especially in Australia. Holloway et al. (2001) showed that commercial uid P fertilizers (e.g., MAP, DAP and APP) were more effective than the corresponding commercial granular P fertilizers in increasing crop yield in calcareous and alkaline soils. Lombi et al. (2004), Hettiarachchi et al. (2006) used highly sophisticated instruments to study the P mobility of surface-applied granular versus uid MAP in a calcareous soil at 60% of eld moisture capacity. They found that total and labile P from liquid MAP diffused farther (1.35 cm) from the initial site of P application than total and labile P from granular MAP (0.75 cm). This difference may explain the better agronomic performance of uid MAP compared to granular MAP in eld trials reported by Holloway et al. (2001), who claimed that the P diffusion and isotopic lability of granular MAP were reduced compared to those of an equivalent liquid MAP because precipitation reactions osmotically induced the ow of soil moisture into MAP granules. In addition, a signicant amount of the initial P remained in the granules even after some time of dissolution due to the presence of waterinsoluble FeAlP minerals in the granule and the in situ precipitation of similar minerals resulting from the diffusion of Ca and Al into the granule. In contrast, there was signicantly less P xation from uid P fertilizers and hence a greater concentration of labile P (Lombi et al. 2004). It should be noted that P diffusion depends strongly on soil moisture content (% of eld capacity) and on the water content of liquid P fertilizers. Furthermore, in studies conducted in Australia, the researchers reported only the total P content. They did not report the proportions of WSP and water-insoluble P content when comparing corresponding uid and granular P fertilizers. For
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example, Lombi et al. (2004) compared commercial granular MAP with commercial uid technical-grade MAP, but they did not report whether the two sources contained the same P compounds or had the same water solubility. One potential benet of applying uid ortho-or polyphosphate sources rather than solid P sources may be that uid P sources can increase the soil concentration of available P with depth (Kovar 2006). This increased concentration is especially important under no-till cropping conditions because the downward movement of orthophosphate is signicantly limited in soil-surface application. By increasing P movement to subsurface depths, application of uid P fertilizers can enhance P recovery and response for deep-rooted cereal crops like maize. Downward P movement should also reduce the surface runoff risk that is responsible for eutrophication in aquatic environments, as will be discussed below. In light of the recently renewed interest in research comparing the agronomic effectiveness of uid and granular WSP fertilizers in Australia (Evans 2008; Holloway et al. 2006), it may be worthwhile to conduct similar research on different soils in other countries. Agronomic effectiveness of controlledrelease coated WSP fertilizers Compared to research on slow-release (mainly N-polymers) and controlled-release (mainly coated urea) N fertilizers, limited information is available in the literature regarding controlled-release WSP fertilizers (mainly MAP and DAP). Most reports on controlled-release soluble P fertilizers concern polymer-coated soluble NPK compound fertilizers and are limited to laboratory studies (Shaviv 2000; Du et al. 2006). Pauly et al. (2002) conducted a greenhouse study with polymer-coated MAP and DAP (thin-coated, 1.8% by weight or thick-coated, 2.2% by weight) to test the growth response and P uptake of barley. Thincoated MAP showed greater dry-matter yield, P uptake, net P fertilizer efciency and net fertilizer release efciency than thick-coated and uncoated MAP. The coating of DAP fertilizer did not consistently improve any of the above-mentioned parameters. Additional information on polymer-coated WSP fertilizers can be found in a recent review paper by Chien et al. (2009). More research, particularly eld
trials, is needed to test whether polymer-coated WSP fertilizers have the potential to improve P fertilizer efciency and crop production. Agronomic effectiveness of water-insoluble and partially water-soluble non-conventional P fertilizer sources According to the AOAC denition (AOAC 1999), citrate-soluble P (including water-soluble P) in P fertilizers is available to plants and is called available P. However, some water-insoluble or partially watersoluble P fertilizers that vary in citrate-soluble P may be as agronomically effective as water-soluble P fertilizers under certain conditions. Chien and Friesen (1992) showed that a high-reactivity ground North Carolina (NC) PR with only 4.2% citrate-soluble P as a percentage of rock was equally effective for maize grown on an acidic soil as almost 100% citrate-soluble TSP. The less-reactive Jordan PR (2.9% P) and Togo PR (1.8% P), however, were less effective than TSP (Fig. 1). In Tanzania, new data indicate that the most reactive Minjingu PR in Sub-Saharan Africa exhibits good agronomic effectiveness (Smithson et al. 2003; Msolla et al. 2005; Szilas et al. 2007a, b). In general, the agronomic effectiveness of different PR sources correlates well with the citrate solubility of the PR (Chien 2003a; Truong 2004). In India, a combination of local low-reactive Mussoorie PR (MPR) with P solubilizing bacteria (PSB) was compared with DAP with respect to productivity and P balance in a ricerapeseed-mungbean cropping system for 3 years. The
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Dry-Matter Yield of Maize, g/pot
TSP
NC PR
Jordan PR
Togo
25 20 15 10
NAC Solubility, % P of Rock

5 0 0 200 400 600 800 1000 1200
NC PR = 4.2 Jordan PR = 2.9 Togo PR = 1.8
Rate of P2O5 Applied, lb/acre
Fig. 1 Dry-matter yield of maize grown with P sources varying in citrate solubility (Hartsells soil; pH 4.8) (Chien 2003a)
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RAE of (MPR ? PBS) in relation to DAP as judged by total productivity was 5365% in the rst cycle but reached 69106% in the third cycle of the cropping system (Sharma et al. 2010). Among crop species, rape is highly efcient in utilizing PR. The exudation of malic acid and citric acid by the plants roots is thought to be responsible for the dissolution of PR. Habib et al. (1999) were probably the rst to report that rape was able to utilize a medium-reactive Ain Layloun PR (Syria) in calcareous soils. In a follow-up study with nine different PR sources varying widely in reactivity for rape grown on an alkaline soil (pH 7.8), Chien et al. (2003a) found that the RAE of PR increased from 0 to 88% as the 2% citric acid (CA) solubility of PR increased from 0.9 to 5.7% P as a percentage of rock (Table 3). These ndings suggest that medium- to high-reactivity PR sources can be used for rape in alkaline soils. This conclusion has important implications for countries that have medium- to highreactivity PR deposits and alkaline soils. For example, several countries in North Africa (e.g., Tunisia, Algeria, and Morocco) have highly reactive PR sources. Farmers in these countries cannot use these low-cost indigenous sources of PR for their current crops (e.g., wheat, barley, and maize) in alkaline soils. The feasibility of growing a high-value crop, such as rape for cooking oil, could translate into a signicant economic benet for farmers if the cost/ benet ratio of using PR is higher than that of using WSP fertilizers. An interesting new eld of PR research involves the increased use of PR for organic farming worldwide because chemical P fertilizers cannot be used on
certied organic farms (Nelson and Mikkelsen 2008). Mixing elemental S, which is allowed as an input for certied organic farming, with PR may provide a source of both nutrients. The oxidation of elemental S to H2SO4 may enhance PR dissolution for organic farming, as reported by Evans et al. (2006), Evans and Price (2009). It should be noted that the effective use of PR with or without elemental S for certied organic farming, as for conventional farming, depends on the reactivity of the PR sources used. Thus, organic farmers should be aware that not all PR sources have the same reactivity. The general rule is that the higher the reactivity of PR, the more likely it is to be an effective P source for organic farming. For example, an indigenous igneous PR from Ontario, Canada, with very low reactivity has been marketed for organic farming due to its high P content (Chien et al. 2009). However, total P content is irrelevant to PR reactivity for direct application. In fact, most igneous PR sources are high in P content but very low in reactivity due to little CO3/PO4 substitution in the apatite structure (Chien 2003a) and are therefore unsuitable for direct application in organic farming. Another example is an organic strawberry farm in Canada that used a highly reactive PR imported from North Africa. However, the crop was grown on alkaline soils, making the PR ineffective as a P source (Chien et al. 2009). The many factors affecting the agronomic effectiveness of PR for organic farming should be considered more or less the same way as for conventional farming. One major exception is in cases where PR is used with composting of either crop residues or animal manures. Composting is likely to produce a neutral to alkaline rather than an
Table 3 Characteristics of different P sources and their RAE values for rape grown to maturity in an alkaline soil (pH 7.8) (Chien et al. 2003a)
P source TSP Gafsa PR (Tunisia) Ain Layloun PR (Syria) Chelesai PR (Kazakhstan) Tilemsi PR (Mali) El-Hassa PR (Jordan) Kenegesepp PR (Russia) Kodjari PR (Burkina Faso) Kaiyang PR (China) Panda Hills PR (Tanzania)
Total P 20.1 13.1 12.2 7.4 11.4 13.6 13.0 11.0 14.1 10.8
2% CAa 100 5.7 5.3 3.6 4.5 3.9 3.4 2.6 2.2 0.9
Reactivityb High Medium Medium Medium Medium Low Low Low Very low
RAE (%) 100 88 82 74 72 64 64 60 42 0
Solubility of P in 2% citric acid as a percentage of rock

b
Based on CO3/PO4 substitution in the apatite structure as measured by X-ray diffraction
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acidic soil environment (Chien et al. 2009). For example, Kuo et al. (2004) reported that pH of a composting pile dropped from initial 65 in the mesophilic phase only for a few days, and soon after the pH began to increase and stayed constant around pH 78 in the thermophilic, cooling, and nally to maturing phase of the composting. Therefore, in the cases of composting organic materials with PR, it is likely that the chelation of organic matter by Ca ions derived from apatite, similar to the mechanism of the dissolution of apatite by neutral citrate solution, is primarily responsible for PR dissolution rather than soil acidity as in the conventional farming. More research is needed to explore these PR reactions and crop responses to the composting of PR in the eld. Lim et al. (2003) used a process called mechanomilling in which six different PR materials were ballmilled at high energy to allow enhanced chemical and physical reactivity. Lim and Gilkes (2001) found that milling increased the solubility of PR in 2% CA by increasing the proportion of X-ray amorphous P and reducing the size of the remaining apatite crystals. However, the surface area of PR was reduced, and the unit-cell a-value of apatite increased toward that of uorapatite, which has the lowest solubility and least surface area among apatite minerals. The increased unit-cell a-value of apatite was likely due to the gradual driving-off of apatite-bound CO3 as CO2 gas as a result of the high energy used during mechanomilling; this process is similar to the calcination of francolite containing apatite-bound CO3 to uorapatite (Chien and Hammond 1991). Lim and Gilkes (2001) attributed the increased solubility and agronomic effectiveness of the processed PR to the dominant amorphous materials formed during mechano-milling. More work is needed to understand the inconsistent effects of mechanical milling on the physical and chemical reactions and agronomic effectiveness of PR. Although hundreds of agronomic trials of PR have been conducted worldwide, it is essential to integrate all important factors affecting the agronomic effectiveness of PR into a comprehensive system to better understand these processes. One way of solving this problem is to use PRDSS. Because it is designed to be practical, PRDSS can be used in developing countries, especially in countries endowed with indigenous PR deposits, to help choose between WSP fertilizers and PR. Recently, IFDC has developed and published its
own PRDSS model for PR sources varying in reactivity for different crop species (Smalberger et al. 2006). Based on this model, the FAO/IAEA has posted the PRDSS on the IAEA web site (http://www.iswam.iaea.org/dapr/srv/en/home). The current PRDSS version can be used to estimate both the initial and residual RAE of PR and the relative economic effectiveness (REE) of PR compared to WSP fertilizers. This PRDSS can be a useful tool to researchers, extension workers, fertilizer companies, and government decision makers who must determine the feasibility of the agronomic use of PR, whether locally produced or imported, compared to that of WSP fertilizers. Figure 2 shows that the latest validation of the updated PRDSS based on initial and residual RAE values is consistent with the predicted and observed RAE values (within 10% of a 1:1 line) across different PR sources, types of soil, and crop species (Chien et al. 2009). It should be noted that the current residual RAE of PR in the updated PRDSS version represents only the average residual RAE values of a PR over several years with the same residual crop. In the future, more work will be needed to model a residual RAE of PR for a given residual crop over a given period of time. Sikora (2002) conducted a theoretical and experimental study to calculate and quantify the liming potential of different PR sources by laboratory titration and incubation with an acidic soil (pH 4.2). The relationship between the calcium carbonate equivalent percentage (CCE) of PR and the percentage of dissolved P followed a quadratic model, where % CCE = 8.47 ? 0.0078 (% dissolved P)2 (r2 = 0.84). Thus, the more P dissolved from PR, the higher the liming value of PR. For example, 50% of the total P dissolved from PR would be 28% as effective as CaCO3 in terms of its liming effect. In a long-term (16 years) eld study with a pastoral soil treated with two PR sources at a P rate of 30 kg P/ha/year, Loganathan et al. (2005) found that soil D pH (pH of PR-treated soilpH of control soil) values ranged from 0.28 at a 05-cm depth to 0.17 at a 2030-cm depth for North Carolina PR and from 0.15 to 0.11 at corresponding depths for Jordan PR. The total liming values were 640 and 414 kg CaCO3/ha for North Carolina PR and Jordan PR, respectively. The results from this long-term eld study show that the continuous use of medium- to high-reactivity PR sources can signicantly reduce the rate of acidication in pastoral soils.
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PR had been applied alone. Prochnow et al. (2004) showed that P uptake from Patos PR in the presence of WSP was higher than that from Patos PR alone, indicating the benecial starter effect of watersoluble P on the effectiveness of Patos PR. Many studies have provided valuable information on the factors affecting the agronomic effectiveness of mixtures of PR and WSP, either by partial acidulation or by compaction of PR with WSP. These factors include the reactivity, degree of acidulation, and degree of Fe and Al impurities of the PR source; the effect of soil properties, such as pH and P-xing capacity; the starter effect of water-soluble P on PR effectiveness; the crop species grown; and the initial and residual P effects (Chien 2003b). Figure 3 shows PAPR and compacted (PR ? TSP) products that performed equally well using Huila PR (Colombia), which contains low amounts of (Fe2O3 ? Al2O3) impurities (2.3%). The compacted product (PR ? TSP) was more effective than PAPR made with Capinota PR (Bolivia), which contains a signicant amount of (Fe2O3 ? Al2O3) impurities (8.8%).
Fig. 2 Comparison of observed and predicted relative agronomic effectiveness (RAE) for (a) initial and (b) residual applications of PR and WSP. The spread (10%) along the one-to-one line (dashed line) is shown by dotted lines (Chien et al. 2009)
Under certain conditions, such as low PR reactivity, high soil pH, or short-term crop growth, the agronomic use of PR may not be as feasible as that of WSP. Mixing PR with WSP can sometimes be agronomically and economically effective under these conditions. Partial acidulation of low-reactive PR (PAPR), which consists of un-acidulated PR and acidulated WSP, is one way to achieve this goal. Another way is to mix PR with WSP by dry granulation (compaction). In one study, the agronomic effectiveness of a low-reactive Patos PR (Brazil) compacted with SSP at a 50:50 P ratio was equal to that of SSP based on the dry-matter yield of wheat and ryegrass (Prochnow et al. 2004). This method was effective because the WSP was able to provide available P to the plants initially (starter effect), resulting in better plant root development, which in turn allowed the plants to utilize the PR more effectively later in their development than if the
Fig. 3 Dry-matter yield of maize grown with TSP and modied PR products made from (a) Huila PR and (b) Capinota PR (Chien et al. 2003b)
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Fig. 4 Relationship between soil P-xing capacity and relative agronomic effectiveness (RAE) based on dry-matter yield and P uptake of maize grown with PAPR (PR acidulated at 50% with H2SO4) (Chien et al. 2003b)
Figure 4 shows that the RAE of PAPR increases with the soils P-xing capacity and that PAPR can be more effective than SSP in soils with very high P-xing capacities. The chemistry of soil reactions as explained by Chien (2003b) is as follows. When MCP, which is the P component in SSP or TSP, dissolves in the soil solution, it is hydrolyzed to DCPD and H3PO4 in the meta-stable triple-point solution (Lindsay 1979). The released H3PO4 can lower soil pH to as low as 1.5 and thus can dissolve Fe and Al minerals, which in turn react with WSP to form water-insoluble FeAlP. These soil reactions decrease the P availability from SSP or TSP because of the P sorption effect of the FeAl minerals. With PAPR, which contains both WSP and PR, part of the H3PO4 produced by MCP hydrolysis will be neutralized by the unacidulated PR. This reaction of H3PO4 with unacidulated PR not only reduces the P xation of the WSP component in PAPR by reactions with FeAlminerals but also allows additional P to be released into the WSP pool. The results indicate that some of the citrate-insoluble P of certain P fertilizers might also be available to plants. These studies raise doubts about the ability of the AOAC procedure to accurately extract plant-available P compounds (Chien et al. 2009). Many studies on the agronomic use of apatitic PR, PAPR, and compacted (PR ? WSP) products have been reported in the literature since 1998. For the readers information, we list some additional reports categorized by the alphabetical order of country
name: (1) Djebel Onk PR (Algeria) by Nemeth et al. (2002), (2) Kaiyang PR (China) and Gafsa PR by Satter et al. (2006), (3) Jinxiang PR (China) by Xiong et al. (2002), (4) China PAPR by Aye et al. (2009), (5) Trinidad de Guedes PR (Cuba) and PAPR by Rodriguez and Herrera (2002), (6) compacted Jamakotra PR (India) with MAP by Nair et al. (2003); Begum et al. (2004), (7) Timemsi PR (Mali) by Babana and Antoun (2005), Babana and Antoun (2006), Somado et al. (2006) (8) Ben Guerir PR (Morocco) by Rivaie et al. (2008), (9) Ogun PR (Nigeria) by Akintokun et al. (2003), (10) Sokoto PR (Nigeria) by Agbenin (2004); Sokoto and Singh (2008), (11) North Carolina PAPR by McLay et al. (2000), (12) North Carolina PR by Rajan (2002), (13) Phalanowa PR (South Africa) by Loganathan et al. (2004), (14) Eppawala PR (Sri Lanka) by Zoysa et al. (1999), (15) Minjingu PR (Tanzania) by Mutuo et al. (1999), (16) Hahotoe PR (Togo) and PAPR by Agyin-Birikorang et al. (2007), (17) Gafsa PR (Tunisia) and Arad (Israel) by Gatiboni et al. (2003); Mendoza et al. (2009), and (18) Riecito PR (Venezuela) by Casanova et al. (2002). Several books on these subjects have also been published since 1998 by the IAEA (2002a, b, 2006), the IFDC (2003), and the FAO (2004). Calcination at high temperature is a non-conventional process for increasing the solubility and agronomic effectiveness of non-apatite PR containing crandallite minerals in the form of CaFe-AlP, which are not suitable for acidulation because of their high FeAl content. In a recent study, Francisco et al. (2008) characterized and conducted agronomic evaluations of two non-apatite PR sources (Sapucaia and Juquia) from Brazil. After calcination at 500C for 4 h, the citrate solubility of these two PR sources increased signicantly from almost none to a maximum of 90 and 51% of total P, respectively. X-ray diffraction showed that the crystalline crandallite mineral was transformed to an amorphous form after calcination. Without calcination, both PR sources were totally ineffective for upland rice grown on an acidic soil (pH 5.4). The two calcined P sources and the highly reactive Gafsa PR were 83, 89, and 100% as effective as TSP, respectively, in increasing the grain yield of upland rice. For ooded rice, the corresponding values were 72 and 68% for the two calcined P sources, respectively, and 0% for the Gafsa PR. This study suggests that there is agronomic
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potential in calcined non-apatite PR sources that cannot otherwise be used for direct application or chemical acidulation. Interest is growing in the use of magnesium phosphates as P sources for crops in the form of struvite (MgNH4PO46H2O) and dittmarite (MgNH4 PO4H2O), which can be recovered from municipal, industrial, and agricultural wastewaters. Both are water-insoluble but citrate-soluble P compounds. Massey et al. (2009) found that recovered struvite and dittmarite were as effective as TSP for wheat grown in a neutral soil (pH 6.5), even when the soil was limed (pH 7.6). These results support previous studies showing recovered magnesium phosphates to be effective in acidic soils, and they provide evidence that recovered phosphates are also effective in slightly alkaline soils (Johnston and Richards 2003b). More research is needed to determine whether recovered Mg phosphates could become useful alternative P fertilizer sources in conventional and organic farming operations. The new concept of effective P availability of water-insoluble P compounds in fully acidulated P fertilizers Although water-insoluble P compounds often do not provide P to plants as effectively as WSP compounds, they do have certain agronomic values compared to WSP compounds (Prochnow et al. 2003a, b, c; Prochnow et al. 2008). Johnston and Richards (2003a) studied the agronomic effectiveness of water-insoluble P residues isolated from four TSP products produced in the US and the UK using ryegrass (8 cuts) as the test crop, which was grown on 13 soils with widely varying properties. The relative effectiveness (RE) of these water-insoluble P residues
with respect to MCP, as calculated by the substitution-rate method, ranged from 44 to 87% in drymatter yield. Johnston and Richards (2003a) also advocated a new concept of calculating the effective availability of water-insoluble P residues compared to WSP. Table 4 shows the calculated effective P as a percentage of total P in the four TSP products. The concept takes into account the equivalent water solubility of the water-insoluble P residues, which is calculated from the RE of the water-insoluble residue. For example, the total P of the water-insoluble P residues of the US1 product was 3.3% (20.7 17.4% = 3.3%). Because its RE based on dry-matter yield was 63% of that of WSP (MCP), the equivalent available P in the water-insoluble P residues was 3.3% 9 0.63 = 2.1%. Thus, the total effective watersoluble P was 17.4 ? 2.1% = 19.5%, and the effective water-soluble P as a percentage of total P was (19.5/20.7) 9 100 = 94%. The US and UK products exhibited similar ranges of effective water-soluble P as a percentage of total P (9497 and 9498%, respectively), as shown in Table 4. However, the range of actual water solubility values for the US products (84.085.5%) was smaller than that of the UK products (90.495.2%), as shown in Table 1. Based on the calculated effective water solubility as a percentage of total P, there was no systematic difference between the US and UK products (Table 4), but the calculated actual water solubility of the US products (average 84.8%) was lower than that of the UK products (average 92.8%), as shown in Table 1. In short, Johnsonton and Richards (2003a) concluded that there is little difference in the agronomic effectiveness of TSP products with water solubility values greater than 85% of the available P2O5. This threshold value was ofcially adopted by the EC in 2004.
Table 4 Calculated effective water solubility as a percentage of total P2O5 in four TSP products (Johnston and Richards 2003a)
Source % total P % water-soluble P REa of water-insoluble P residue (%) Effective available P in water-insoluble P residue (%)
US1 20.7 17.4 63 4.8 19.5 94
US2 21.0 17.9 82 5.7 20.4 97
UK1 20.4 19.1 46 2.5 19.6 94
UK2 19.9 18.9 59 1.3 19.5 98
a RE = Relative effectiveness with respect to TSP
Total effective water-soluble P (%) Effective water-soluble P as % of total P
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Environmental aspects of phosphate fertilizers varying in source and solubility Cadmium in soils and plants from application of various P fertilizers There is increasing concern over the use of P fertilizers containing heavy metals, especially cadmium (Cd), for crop production. Heavy metal uptake by plants is one possible avenue of entry into the human food chain through direct or indirect consumption. Numerous greenhouse and eld studies have been conducted with Cd because it is the heavy metal of most environmental concern in terms of adverse effects from long-term application of fertilizers. There have also been numerous review articles on the issue of Cd impacts from the use of P fertilizers (Alloway and Steinnes 1999; Grant et al. 1999; Morvedt 2005). Grant et al. (1999) noted that the Cd concentration of P fertilizers, application rate, soil type, and crops grown are important factors when considering the relationship between added Cd and plant uptake. The source of Cd in P fertilizers is PR. Depending on the sources of PR, the Cd content associated with P in apatite minerals can vary widely (Table 5). It should be noted that the expression of Cd
Table 5 Range of Cd concentrations in PR from various sources (adapted from Alloway and Steinnes 1999) Source of PR Russia (Kola) South Africa China (Yunam) Jordan Australia (Duchese) Mexico Egypt (Quseir) Peru (Sechura) Israel (Arad) Tunisia (Gafsa) Israel (Zin) Morocco (Boucraa) Australia (Christmas Island) USA (North Carolina) Banaba (Ocean Island) Nauru mg Cd/kg PR 0.2 4 4 6 7 8 8 11 12 38 32 38 43 47 99 100 mg Cd/kg P 1 23 35 27 50 57 61 84 85 108 228 240 275 311 563 641
concentration as mg Cd/kg of PR differs from that as mg Cd/kg of P because P content varies among PR sources. Because the Cd rate applied depends on the P rate used, expression of Cd concentration as mg Cd/ kg of P is more appropriate in discussions of the Cd issue than mg Cd/kg of P fertilizer. Cd in PR originates from the substitution of Cd for Ca in the apatite structure (Iretskaya and Chien 1999). If a PR source contains a signicant amount of Cd, all of the Cd will remain in SSP produced by acidulation of the PR with H2SO4. In the production of H3PO4-based P fertilizers, H3PO4 is rst produced by acidulation of PR with H2SO4 followed by separation of H3PO4 and precipitation of phosphogypsum. As much as 3050% of the Cd in PR is transferred to phosphogypsum and the remaining Cd stays in the H3PO4 during the process (Wakeeld 1980). Unlike SSP which uses 100% PR-P as P source, TSP uses only 2430% of PR-P and 7076% of H3PO4P (Davister 1998). Thus if H3PO4 is used to acidulate the same PR, the resulting TSP may contain 4050% of the TSP-Cd from the PR-Cd and the remaining Cd from H3PO4Cd. Ammoniation of Cd-containing H3PO4 will produce DAP and MAP products that also contain Cd, but less Cd will be present than Cd in TSP because no PR is used. The chemical forms of Cd in acidulated P fertilizers are Cd(H2PO4)2 and CdHPO4, which are Cd analogs of the Ca and NH4 compounds found in commercial, fullyacidulated P fertilizers (Morvedt 2005). It has been suggested that the soil factors affecting Cd availability may be similar to those affecting the P availability of CaP. For example, the dissolution of both CdP and CaP increases with decreasing soil pH. Thus, Cd uptake by crops is higher in acidic soils than in alkaline soils (Iretskaya and Chien 1999). The plant availability of Cd in P fertilizers also depends on soil texture and plant species. Cd uptake is greater in leafy vegetables than in maize or wheat (Morvedt 2005). Grant et al. (1999) stated that Cd availability may be greater with MAP use than with DAP use because MAP is initially acidic whereas DAP is alkaline. Because the actual rate of Cd application based on the P rate from P fertilizers is rather low and Cd uptake by most crop plants is rather limited, gradual accumulation of Cd usually occurs in soils only after long-term application of Cd-containing P fertilizers. Therefore, long-term experiments may be the most
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meaningful to assess the environmental effects of Cd in P fertilizers. Morvedt (2005) summarized the results of long-term eld experiments with TSP made from Florida PR and applied at an annual P rate of 1530 kg/ha after [50 years. He concluded that minimal increases occurred in total Cd concentrations in soil in the short term due to the addition of Cd in P fertilizers applied for crop production. Bolan et al. (2005) calculated that at an annual application rate of 20 kg P/ha, it would take from 214 years (with Gafsa PR containing 70 mg Cd/kg) to 2,250 years (with DAP containing 10 mg Cd/kg) to exceed the threshold limit of 3 mg Cd/kg soil that has been set for Cd application in sewage sludge in New Zealand. These authors concluded that although P fertilizer addition represents the major source of Cd input to soils, at a normal annual rate of fertilizer input (20 kg P/ha), the rate of Cd accumulation appears to be slow. Nevertheless, some countries have enacted regulatory controls on Cd limits in P fertilizers to reduce the potential long-term effects of Cd on soil and plant quality. Table 6 shows the proposed limits of Cd in P fertilizers in various countries. Cadmium inputs in P fertilizers containing the maximum allowable Cd limits range from 0.7 g/ha in The Netherlands to 6.9 g/ha in Japan. Efforts to establish allowable limits of Cd in P fertilizers in the United States began in the mid-1990s. Because fertilizer regulations in the United States are enacted on a state-by-state basis, there is no standard limit of maximum allowable Cd in P fertilizers for the whole country. The US
Table 6 Cadmium limits for P fertilizers in various countries and estimated Cd inputs to soils from P fertilizers at the maximum Cd limits (Morvedt 2005) Country Cd limit (mg kg-1 P) 300 120 200 50 200 343 50 100 50 35 Cd input (g ha-1 with 20 kg ha-1 P) 6.0 2.4 4.0 1.0 4.0 6.9 1.0 2.0 1.0 0.7
Australia Austria Belgium Finland Germany Japan Norway Sweden Switzerland The Netherlands
Environmental Protection Agency (EPA) has set national cumulative ceiling concentration limits for land application of biosolids at 85 mg Cd/kg of soil and a maximum loading rate of 1.9 kg Cd/ha per 365day period (US EPA 2007). The Association of American Plant Food Control Ofcials (AAPFCO), comprising the fertilizer regulatory ofcials in each state, suggested in 2005 that the standard Cd limit in P fertilizers should be 4.4 mg Cd/kg per percent of P content (Morvedt 2005). This is equivalent to a Cd input to soil of 8.8 g Cd/ha at a fertilizer application rate of 20 kg P/ha, which is higher than the 0.74.0-g Cd/ha range in maximum allowable Cd inputs imposed by Western European regulations (Table 6). Grant et al. (1999) suggested that reducing the amount of Cd in P fertilizer might be one method of reducing the long-term accumulation of Cd in the soil. As noted above, several countries have imposed limits on the total Cd concentration that may be present in fertilizer materials. The selection of PR sources that are low in Cd should reduce the concentration of Cd in nished P products after the manufacturing process. However, global reserves of PR containing low levels of Cd are relatively limited. Removing Cd from PR during processing may not be economically viable at current fertilizer prices, despite the technologies that may be available. Restricting P production to low-Cd fertilizer will certainly increase the cost of fertilizer and may limit the amount of P fertilizer available for trade. This could have important implications for food production, particularly in developing countries (Grant et al. 1999). Many researchers have proposed that Cd uptake may be reduced by increasing soil pH with liming because Cd availability decreases with increasing soil pH (Grant et al. 1999). This recommendation is based primarily on greenhouse and growth-chamber studies. However, Grant et al. (1999) pointed out that the efcacy of liming under eld conditions is less consistent and of a smaller magnitude than that noted in container-growth studies. Numerous studies have shown little or no effect of liming on crop Cd uptake under eld conditions. The interaction between pH and organic matter in their effects on Cd in soils may explain these differences. Soil organic matter can reduce the toxic effects of Cd in contaminated soils under acidic conditions. In contrast, at pH 68, higher Cd concentrations were measured for soil samples
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with higher organic matter content because of the complexation of Cd by soluble organic matter (Grant et al. 1999). However, more research is needed, especially long-term experiments under eld conditions, to unravel these conicting reports on the effects of liming on Cd uptake as inuenced by soil properties, agro-climatic conditions, and crop species. Most published research reports and reviews on Cd contamination associated with the use of P fertilizers focus exclusively on commercial, fully acidulated P fertilizers (SSP, TSP, MAP, and DAP). Little information is available regarding the effect of the degree of acidulation of PR on Cd uptake from P fertilizers varying widely in water and citrate solubility. Because Cd and P are present in the same apatite structure, it is expected that acidulation of PR will release soluble P simultaneously with soluble Cd. Table 7 shows that both available P (water ? citrate extractable) and available Cd (extracted by DTPA) increased with increasing acidulation levels in two PR sources (North Carolina and Togo) with high Cd content. Just as the total P content of P fertilizer is irrelevant to crop P uptake, and just as crop uptake of P is determined by the available P content of a fertilizer (Chien 2004a), crop Cd uptake is related to
the available Cd content of the P fertilizer and not to the total Cd content (Chien 2004b) However, laws that regulate the maximum permissible Cd content of fertilizers are based on total Cd, not available Cd. This discrepancy is a serious issue that lawmakers and environmental regulators may need to reconsider. A study by Iretskaya et al. (1999) showed that Cd uptake by upland rice was increased by raising the degree of acidulation of Togo PR, which had signicant Cd content (Table 8). The results showed that the Cd concentration in upland rice grains was 0.051 mg/kg Cd with 50% acidulation with H2SO4 compared to 0.114 mg/kg Cd with 100% acidulation, whereas the two P sources produced the same rice grain yield (Table 8). The study also showed that a high-Cd reactive North Carolina PR was as agronomically effective as a fully acidulated SSP produced from the same PR in increasing rice grain yields, but Cd uptake was lower from the directly applied PR (Table 8). The results showed that Cd uptake by rice was more related to DTPA-extractable Cd than to the total amount of Cd added. For example, the total Cd added was only slightly less from NC-PR than NC-SSP (70.5 vs. 79.0 mg Cd/kg), but Cd uptake from NC-PR was much lower than that
Table 7 Properties of P and Cd contents of various P fertilizers (Iretskaya and Chien 1999) P Source NC-PRa NC-SSPa Togo-PR Togo-PAPRb Togo-SSP
a b
Total P (%) 13.3 6.3 16.0 12.3 9.2
H2O-P (%) 0 5.8 0 4.8 8.7
Citrate-P (%) 2.8 0.5 2.0 1.8 0.5
(H2O ? Citrate)-P (%) 2.8 6.3 2.0 6.6 9.2
Total Cd (mg kg-1) 47.0 24.7 54.0 35.7 31.5
DTPA-Cd (mg kg-1) 0.2 18.7 1.7 6.8 19.7
NC = North Carolina PAPR = PR acidulated at 50% level with H2SO4
Table 8 Upland rice grain yield and Cd uptake by grain from various P sources applied at 200 mg/kg P to an acidic soil (pH 5.6) (Iretskaya and Chien 1999) P sourcea Cd rate added (lg g-1) 70.5 79.0 57.8 69.3 Grain yieldb (g pot-1) 25.3A 24.5 25.6
A
Uptake of Cd by grainb (lg pot-1) 1.68B 3.25 2.88

A
Concentration of Cd in grainb (lg pot-1) 0.066B 0.135A 0.051B 0.114A
NC-PR NC-SSP Togo-PAPR Togo-SSP

a b
27.6A
A
1.44B
A
NC = North Carolina; PAPR = PR acidulated at 50% with H2SO4; SSP = 100% acidulation of PR with H2SO4 Means followed by the same letter within columns are not signicantly different at P \ 0.05
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Table 9 Seed yield of soybean and Cd concentrations in soybean seeds, straw and roots (Chien et al. 2003b) PK source Seed yielda, (g pot-1) 27.1A 29.5
A b
Cd concentrationsb Seeds (mg kg-1) 0.54A 0.35

B
Strawc (mg kg-1) 1.66A 0.88

B
Root (mg kg-1) 1.34A 0.99B 0.27C
Granulated (SSP ? KCl) Bulk-Blended (SSP) ? (KCl) Bulk-Blended (MCP) ? (KCl)

a b c
23.8A
0.06C
0.26C
Seed yield of control plants (no P and K) = 1.4 g/pot Means followed by the same letter within columns are not signicantly different at P \ 0.05 Combined leaf, stem, and pod samples
from NC-SSP (1.68 vs. 3.25 lg Cd/pot). The Cd uptake data reected the much lower content of DTPA-Cd in NC-PR than in NC-SSP (0.2 vs. 8.7 mg Cd/kg), as shown in Table 7. The results also suggest that if PR and PAPR are as agronomically effective as fully acidulated P sources, the former may contribute less to Cd uptake by crops than WSP sources. McLaughlin et al. (1997) reported that increased chloride (Cl) content in irrigated waters imposes a high risk of producing crops with high Cd concentrations. It is believed that Cl ions form relatively strong complexes with Cd2? in the form of CdCl1? and CdCl0 in solution, and these reactions result in 2 enhanced Cd uptake. Based on these observations, Chien et al. (2003b) hypothesized that if a WSP fertilizer has a high Cd content, granulation of this WSP fertilizer with KCl may result in greater Cd uptake by crops compared to an equivalent bulkblended PK fertilizer. In granulated PK fertilizers, KCl and Cd-containing P fertilizers are present within the same granule and are thus in close contact, thereby increasing the possibility of forming CdCl0 2 and CdCl1? complexes. These complexes would be less likely to form when KCl and Cd-containing P granules are physically separated in soil-applied bulkblended PK fertilizers. The above hypothesis was tested and conrmed by Chien et al. (2003b) in a preliminary greenhouse study. In this study, all sources of P and K, whether produced by granulation or bulk-blending, had the same granule size (1.683.36 mm in diameter). Upland rice and soybean were grown to maturity and Brachiaria grass was cut 4 times in an acidic soil (pH 5.2). The results showed that the agronomic effectiveness in increasing crop yield was equal for Cd-containing SSP and reagent-grade MCP (0% Cd),
whether granulated or bulk-blended with KCl. Concentrations of Cd in plant tissue samples of all crops were much lower for MCP than for SSP. In all plant tissue samples, Cd concentrations obtained with granulated PK fertilizer (SSP ? KCl) were signicantly higher than those obtained with bulk-blended PK (SSP ? KCl) fertilizers. One example using a soybean crop is shown in Table 9. The bulk-blending of Cd-containing P fertilizers with KCl can thus reduce Cd uptake by crops compared equivalent granulated PK fertilizers. Although PK fertilizers, not NPK fertilizers, were used in the study, it was expected that the inclusion of N would not affect the results (Chien et al. 2009). If this assumption holds true, the superiority of bulk blending compared to granulation in decreasing Cd uptake would also apply to NPK compound fertilizers. Due to the simplicity of bulk blending and its relatively low investment and operating costs, this process has become popular worldwide. Researchers and fertilizer companies should further develop this process for the future production and use of NPK compound fertilizers while minimizing Cd uptake by crops. Use of P fertilizers to remediate soils contaminated by lead Lead (Pb) in its soluble ionic form is a toxic element that contaminates water and soil, mainly as a result of human activities. Lead contamination in soils is of concern not only because of its toxicity to humans and animals but also because of its ease of exposure through ingestion or inhalation. A soil is generally considered contaminated with Pb when its total concentration exceeds 400 mg Pb/kg, and remediation is required at this level (Yoon et al. 2007). There are many reports in the literature on the use of P fertilizers
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to immobilize Pb by converting less stable Pb compounds, such as cerrusite (PbCO3), to more stable Pb compounds with very low solubility and bioavailability, such as chloropyromorphite [Pb5(PO4)3Cl] (Lindsay 1979). There are many studies on the use of different WSP and PR sources that contain low amounts of heavy metals and that are useful for immobilizing Pb in soils. The following additional references have been reported since 1998: Ma and Rao 1999; Cao et al. 2002; Chen et al. 2003; Bolan et al. 2003; Lin et al. 2005; Bosso et al. 2008; Miretzky and Fernandez 2009. In general, WSP fertilizers (e.g., SSP and TSP) are more effective than PR in reducing soluble Pb content in the Pb-contaminated soils because of their higher water solubility and their ability to react with Pb to form more stable PbP compounds. However, PR may be more economically feasible than WSP for large-scale soil remediation operations because PR is usually more cost effective (Ma and Rao 1999; Chen et al. 2003). It should be emphasized that, as for the agronomic use of PR in conventional or organic farming (Chien et al. 2009), the effectiveness of PR in immobilizing soil Pb depends strongly on the reactivity or solubility of the PR used. Application of phosphate fertilizers in relation to eutrophication Importance of P in water eutrophication Eutrophication (natural and anthropogenic) is the enrichment of surface waters with nutrients that were previously limiting, stimulating aquatic plant life. In the late 1960s, it became clear that changes were occurring in many lakes and reservoirs, especially in industrialized countries, resulting from increasing nutrient loads. These increased nutrient levels promoted undesirable algal growth. Among plant nutrients, P is perhaps more critical than N for algal growth because some species of algae, such as bluegreen algae (Cyanobacteria), can biologically x atmospheric N2. However, P is essential for biological N xation and the support of algal growth. Phosphorus enrichment of surface waters can result in intensied cultural eutrophication problems and overall degradation of water quality. Such waterquality degradation may impair water use for
sheries, recreation, industry, and drinking because of the increased growth of undesirable algae and aquatic weeds and the oxygen shortages caused by their death and decomposition (Sharpley et al. 2003; Foy 2005). The resulting anaerobic condition in marine systems caused by this depletion of oxygen is known as hypoxia. Loss of P from agricultural practices has been identied as a major cause of impaired surface-water quality (US EPA 2009). The use of WSP fertilizers is one of the potential agricultural practices contributing to the eutrophication of water bodies (Alexander et al. 2008). These contributions occur mainly through surface runoff of P in dissolved water (Heathwaite et al. 1998; Preedy et al. 2001; Sharpley et al. 1992; Torbert et al. 1999), the presence of P in eroded sediments (Baker and Laen 1983; Daverede et al. 2003, 2004), and leaching of P into the groundwater in sandy soils (Maguire and Sims 2002). Effects of P fertilizer application on P runoff and eutrophication Many recent experiments investigating P losses have focused on overland ow pathways, comparisons between P fertilizers and other P amendments (especially livestock manures and slurries), and methods of P application (Bundy et al. 2001; Withers et al. 2005). Some recent examples of P losses in overland ows following the land application of P fertilizers and livestock manures are shown in Table 10. Data on P export in terms of total P loss, dissolved P loss, and ow-weighted total P reect the amount of available P for the promotion of eutrophication. The results indicated that P export was less when P fertilizers were incorporated instead of broadcast; that P export increased with increasing P fertilizer application rate; that there was more P runoff from irrigated pasture (Australia); and that P export was greater when P fertilizers were used than when livestock manures were used. Similarly, P runoff from pastures in Britain was reported to be higher with WSP than with manure (Preedy et al. 2001). In a study near Ames, Iowa that compared P runoff losses from ammonium polyphosphate fertilizer to those from liquid swine manure with and without soil incorporation, Tabbara (2003) observed higher concentrations and losses of all P forms with the fertilizer treatment. The higher losses that occurred with the
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Table 10 Recent examples of P losses in overland ow following application of P fertilizers as compared to livestock manures (Withers et al. 2005) Site P Sourcea Amount of P applied (kg ha-1 P) P export Flow (mm) TPb loss (g ha-1 P) Dissolved P loss (% of TP) FWTPc conc. (mg L-1 P) P loss (% of TP applied) \0.1 1.4 13.4 4.2 6.2 6.0 0.9 1.7 30 23 20 14
UK
Control TSP(I) TSP(B)
0 90 90 158 158 0 29 29 0 87 87 0 22 44 66 88
5.4 5.0 5.7 68.2 57.9 48 48 48 7.6 7.6 7.6 0 22 17.5 14.6 11.3
32 45 1,332 24,010 10,630 60 1,863 1,804 1,210 1,980 2,680 6,600 10,100 13,200 12,300
22 40 86 11 11 36 74 45 1,210 1,980 2,680 90 90 90 90
0.60 0.70 23.2 35.2 18.4 0.12 3.88 3.76 15.9 26.0 35.2 30 58 90 109
Iowa UK
APP(B) APP(I) Control TSP Slurry
USA
Control Manure TSP
Australia (pasture)
Control SSP SSP SSP SSP
a b c
I = incorporated, B = broadcast, APP = liquid ammonium polyphosphate, Slurry = cow manure, Manure = poultry manure TP = total P FWTP = ow-weighted total P
fertilizer were attributed to the greater water solubility of P in the fertilizer. More detailed discussions on the factors affecting P runoff risks from soil treated with WSP fertilizers are described below Landscape and rainfall characteristics The runoff of P from soil varies strongly with landscape characteristics. On sloping lands in Yunnan Province, China, P losses were greatest from farmlands with slopes of 68128 and gradually decreased beyond this slope range (Duan et al. 2005). Orchards cultivated on sloping lands lost far more P through runoff than did paddy rice elds. This difference in the orchards and paddy rice eld was closely related to the amounts of soil and water lost (Huang et al. 2004). Phosphorus loss signicantly increased during the fallow period and was intensied by heavy rain-induced runoff events (Udawatta et al. 2004). Soil P accumulation increases the loss of particulate P when soil particles are detached and
transported in runoff. The amounts of P lost through runoff are also dependent on factors related to soil erosion risk, such as soil erodibility, topography, land cover, and cultivation practices (Sharpley et al. 2000; Harrod and Theurer 2002). Phosphorus loss from soils is highest after dry seasons or at the beginning of rain events and gradually decreases as the rainy season or rain event proceeds upland crops (Xu et al. 2007) and paddy rice elds (Jiao et al. 2007). These observations indicate that the amount of P lost from soil through runoff is related to the amount of soluble P in soil that can be leached out by rainwater (Pote et al. 1999). Studies indicate that fertilizers left on the soil surface are most prone to loss, especially if applied to grassland soils, sloping lands, or wet soils; if applied just before a storm or irrigation event; and in many high rainfall areas (Torbert et al. 1999). Fertilizer P sources and management The sources of acidulated P fertilizers may also affect the export of P to water resources. Nash et al. (2003, 2004)
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247 Table 11 Cumulative loss of dissolved reactive and total P in surface runoff from three soils treated with phosphate rock (PR) or triple superphosphate (TSP) (Shigaki et al. 2007) Soils P sources Control North Carolina PR TSP
reported that P losses following the application of DAP were higher than losses from SSP in soils to which water was subsequently added to generate overland ow. These authors showed that lower P availability of SSP than that of DAP after P application to soil could be attributed to the formation of waterinsoluble reaction products, such as CaHPO4, as a result of the hydrolysis of water-soluble MCP in SSP (Lindsay 1979). If this were the case, TSP, which also contains MCP, should exhibit P export results similar to those of SSP. However, data from Hart et al. (2004) showed that both dissolved reactive P and particulate P, which are related to bioavailable P for algal growth and eutrophication (Sharpley et al. 1992), were higher from TSP than from SSP at the same rate of P application (35 kg P/ha). The greater P export from TSP than from SSP was likely due to the greater water solubility of TSP. Therefore, the greater P export from DAP was likely due not to the formation of waterinsoluble P from SSP, as explained by Nash et al. (2003, 2004), but to the greater water solubility of DAP. Another possible factor may be the effect of fertilizer particle size on P runoff. Many SSP fertilizers are produced in an irregular, non-granular form, whereas commercial-grade DAP is always in a granular form. Soil P adsorption of non-granular SSP may be faster than that of granular DAP, resulting in less P export from SSP. More research is needed to investigate the effects of different acidulated P fertilizers (SSP, TSP, MAP, and DAP) that vary in solubility, granular form, and particle size on P runoff risks. Kovar (2006) suggested that uid P sources applied to the soil surface would move into the soil prole, where they may be less subject to loss through runoff or erosion. This process would be especially important for polyphosphates, which are thought to be less subject to soil adsorption. Such soil inltration may help minimize the environmental impact of P during the winter months while maintaining available P for plants in the following growing season. Thus, polyphosphates may present less runoff risk than orthophosphates when applied to the surface. Most research and review reports on the use of P fertilizers in relation to eutrophication are exclusively concerned with conventional fully acidulated P fertilizers. Little information is available on the use of non-conventional P fertilizers, such as reactive PR
Cumulative dissolved reactive P (DRP) loss (kg ha-1) Alvira Berks Watson Averagea 0.28 0.18 0.23 0.23C 0.52 0.39 0.43 0.45B
-1
32.2 14.5 16.2 20.9A 33.2 15.5 19.6 22.7A
Cumulative total P loss (kg ha ) Alvira 0.35 0.83 Berks Watson Averagea 0.30 0.31 0.32C 0.68 0.72 0.74B
a Average DRP and total P loss values in the same row followed by the same letter are not signicantly different at P \ 0.05
or PAPR, to sustain crop productivity and their inuence on P runoff. Studies done in New Zealand and the United States have suggested that the use of reactive PR can not only sustain crop productivity but also minimize runoff losses better than WSP sources because of lower P availability from PR for algal growth (Hart et al. 2004; Shigaki et al. 2006, 2007). Table 11 shows that both cumulative total and dissolved reactive P losses from surface runoff from the three soils were signicantly lower with reactive North Carolina PR than with TSP, indicating that reactive PR may pose a lower eutrophication risk (Shigaki et al. 2007). More work, including eld studies, is needed to validate this conclusion, especially for soils with relatively high P fertility. A positive correlation between fertilizer P rates and P losses through runoff has been observed by a number of researchers (Zhang et al. 2003; Cao and Zhang 2004; Xia et al. 2008). In a paddy eld, application of 0, 25, 60, 120, and 240 kg P/ha resulted in losses of 0.13, 0.50, 0.94, 3.02 and 5.97 kg P/ha to runoff water, respectively (Xia et al. 2008). This result indicates that an overdose of P fertilizer will impose a high risk of P runoff from paddy elds to watercourses during rainy seasons or in water drainage practices that are adopted in paddy rice production for controlling overgrown rice tillers. Large P losses (5.59.0 kg P/ha) in overland ow from pasture soils in Australia were observed when P
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fertilizer was applied prior to irrigation. It has been suggested that the time interval between P application and irrigation is crucial, requiring a minimum of three to 4 days without rain or irrigation to avoid excessive P losses (Bush and Austin 2001; Nash et al. 2004). In a study investigating the export of P from farmlands to the Tai Lake region of China, it was found that the amount of P lost increased with P fertilizer rate, decreased with time after P fertilizer application, and was smaller in soil with better water inltration than in soil with poor inltration. The period of greatest risk for P losses from paddy elds was within 12 months after P application (Zhang et al. 2007). A number of experiments have shown that incorporating fertilizers into the soil minimizes P loss (Withers et al. 2005). However, soil P incorporation via soil mixing is not applicable to no-till cropping systems. The rate and magnitude of soil P release to runoff and soil leachates are determined by the soils P sorption properties and the depth and time of soil water contact. Thus, fresh application of P fertilizer resulting from inadequate contact time for equilibration between the fertilizer and the soil invariably leads to elevated P runoff losses (Haygarth et al. 1998; Hart et al. 2004). These losses are most commonly observed when rain events occur soon after P fertilizer is applied to the land surface. Although generally small in relation to the P fertilizer added, incidental losses occur in rapid ow pathways, namely overland ow and drain ow. These losses are characterized by very high P concentrations, mostly in the form of dissolved P (Withers et al. 2005). Mixing WSP fertilizers into the soil signicantly decreased P losses relative to surface P application such that DRP losses from amended, mixed soils were not signicantly different from those of un-amended soil (Kleinman et al. 2002). Effects of cropping systems on P runoff losses Phosphorus runoff losses vary greatly among cropping systems. Cao et al. (2005) studied P losses from different cropping systems, including mulberry, vegetables, and wheat-rice rotation, for 5 years. Phosphorus losses were greatest in mulberry elds (1.1 kg/ha in 4 months), followed by wheat and paddy rice (0.84 kg P/ha) and vegetables (0.6 kg P/ha). Phosphorus loss was mostly incidental from paddy elds, open from vegetable elds, and intensied from mulberry elds. In the ricewheat rotation
system, however, the amounts of total P lost from the system as a function of both soil P content and P application rates were much higher during the wheat seasons than during the rice seasons in a two-year study (Zhang et al. 2003). Zhu et al. (2007) reported that P losses varied greatly with P rates and cropping systems in the Tai Lake region. The greatest N and P losses occurred in the winter dry season due to irrigation in the paddy rice-rape rotation. The lowest P losses occurred in the ricewheat or rice-green manure rotation. Phosphorus lost through runoff from vegetable elds was 0.27% of applied P, which was two times higher than that lost from the ricewheat rotation system (Zhang et al. 2005). In irrigated areas in semiarid northwestern China, fall irrigation caused considerable P losses to drainage water, while summer irrigation induced little P loss. This minor P loss in summer was attributed to ourishing crops that removed available P from soils and to the small irrigation quota imposed in the summer. In fall, however, crop growth rates generally slowed while irrigation quotas increased, raising P concentrations up to 0.17 mg/l in drainage water across the growing season (Zeng et al. 2008). Kimmell et al. (2001) studied the inuence of tillage and P placement on P losses in runoff water from a somewhat poorly drained soil (Woodson silt loam, 1.01.5% slope) in a grain sorghumsoybean rotation. They found signicant interactions between tillage and P placement for soluble P losses. Broadcast P applications increased P losses from ridge-till to no-till systems. However, the inuence of tillage system was inconsistent. In fertilized grasslands or forests, P losses in runoff often surpass P losses in farmlands. Wu et al. (2008) reported that P runoff losses inuenced by vegetation followed an order of turf grass [ secondary forest [ sloping land [ bamboo. The lack of soil inversion in grasslands and no-till elds causes preferential accumulation of P at the surface, where most of the soil-rainfall interaction occurs (Haygarth et al. 1998; Howard et al. 1999; Turtola and Yli-halla 1999). On sloping lands in southwestern China, however, P losses in runoff from farmlands were much higher than from nonfarmlands that did not receive fertilizers. The order observed in this region was farmland [ articial forest [ grassland with bushes [ secondary forest (Song et al. 2008).
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Soil test phosphorus in relation to eutrophication Traditional soil test phosphorus (STP) methods have been developed and used for P fertilizer recommendations to achieve optimum crop growth, P uptake, and yield. Many STP methods have been developed for specic soils with a particular range of soil properties and for different cropping systems. In general, most STP methods attempt to measure the socalled available soil P, which correlates well with actual P uptake or crop yield. Some well-known STP methods include Bray-1, Bray-2, Olsen, Mehlich-1, Mehlich-2, Mehlich-3, and resin (Beegle 2005; Fixen and Grove 1990). Some of these agronomic STP methods are also used for environmental P risk assessment because of the link between P fertilizer application, STP, and P losses from agricultural lands. Consequently, the idea of controlling P applications by setting an environmental STP threshold above which P applications from fertilizers or manures are either limited or not permitted has been explored in many US states (Maguire et al. 2005). An environmental P workgroup (SERA-17) has been established in the United States with a stated mission to minimize P losses from agriculture. The workgroup meets annually, publishes summaries of recent advances in research, develops position papers, and advises federal and state service and regulatory agencies. Further information can be found in the website http://www. sera17.ext.vt.edu/SERA_17_Publications.htm. Bundy et al. (2001) reported that in no-till corn, both dissolved reactive P concentrations and runoff loads from simulated rainfall (76 mm/h) increased as the Bray-1 P soil test value increased from 8 to 62 mg/kg. Hooda et al. (2000) reported that runoff P concentrations increased considerably when soils were more than 2535% P saturated. They explained that this increase was related to the change from highenergy to low-energy P binding sites. The peak point for P pollution risk in paddy rice elds in the Tai Lake region of China ranged from 25 to 30 mg P/kg of soil available Olsen P (Cao et al. 2005), though few paddy soils in this area reached these values. Daverede et al. (2003) reported that the relationship between dissolved reactive P and Bray-1 P extraction values was approximated by a logistic function (S-shaped curve) for no-till plots and by a linear function for tilled plots. No signicant differences were observed between tillage systems for total
P and algal-available P in runoff. Bray-1 P soil extraction values and sediment concentrations in runoff were signicantly related to the concentrations and amounts of algal-available P and total P. These results suggest that soil Bray-1 P extraction values and runoff sediment concentrations are both easily measured variables for the adequate prediction of P runoff from agricultural elds. However, Pote et al. (1996) showed that a wide range of P tests were similarly related to P concentrations in runoff. A non-conventional P test using paper impregnated with iron oxide (FeO strip) to estimate bioavailable P in agricultural runoff was rst reported by Sharpley (1993). Since then, many researchers have reported results using this new technique (Hooda et al. 2000; Westermann et al. 2001). Fang et al. (2005) compared Bray-1, Mehlich-3, NaOH, oxalate, and FeO strip methods to estimate soil algal-bioavailable P, which is the P fraction that contributes most directly to eutrophication in freshwater bodies affected by agricultural nonpoint-source pollution. Among these methods, the FeO strip method approximated algalbioavailable P most accurately, particularly for calcareous soils. The most current procedure using the FeO strip to estimate bioavailable P in runoff is described by Meyers and Pierzynski (2009). The main advantage of using the environmental STP threshold approach over other more complex P loss assessment tools, such as the P site index, is that it is quick and inexpensive and the agronomic STP data may already be available (Maguire et al. 2005). However, as Maguire et al. (2005) have noted, there are numerous disadvantages in using a simple STP threshold to represent complex and interactive hydrologic, chemical, and management factors that determine actual P loss from sites where P is applied to water bodies by surface-water run-off or erosion of soil sediments. A recent report by Buda et al. (2009) afrms the importance of critical source areas and hydrology in a practical P-Index when estimating risks of soil P runoff losses. That study underscores the need to better understand chronic diffuse P transport. Many states in the United States have established environmental STP threshold guidelines. Table 12 shows some examples of the agronomic and environmental STP threshold values recommended by several of these states. The STP threshold guidelines and P recommendations vary widely among states. It should be noted that, in general,
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Table 12 Soil test phosphorus (STP) threshold values and P management recommendations in several states of the US (Maguire et al. 2005) State STP threshold values (mg P/kg) Agronomic Colorado Kansas Ohio Maryland Texas Pennsylvania 15 50 40 25 44 50 Environmental 20 200 150 75 200 200 Olsen Mehlich-3 Bray-1 Mehlich-1 Texas A & M Mehlich-3 [20 mg P/kg: use P Index [200 mg P/kg: no P addition regardless of P Index rating [40 mg P/kg: no fertilizer P addition; [150 mg P/kg: apply no P until soil test is \150 mg P/kg [75 mg P/kg: use P Index; soils with high index ratings must reduce or eliminate P additions [200 mg P/kg: P addition not to exceed crop removal [200 mg P/kg and \150 ft from stream: use P Index Soil test method Management recommendations for water quality protection
implemented when applying P fertilizers to soils that have different properties and that support different cropping systems. The selection of appropriate sources of P fertilizer and rates, timing, and placement of application should be carefully considered. The goal of P fertilizer management is to optimize crop production while minimizing the risks of environmental impacts, such as toxic Cd accumulation in soils and eutrophication of water bodies.
References
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Conclusions As Withers et al. (2005) have pointed out two underlying principles govern the optimum use of P fertilizers. One is linked to agronomic considerations, while the other is linked to environmental concerns. Together, these two principles provide the foundation for sustainable fertilizer use. The best practices of integrated nutrient management should be
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Agronomic and Environmental Aspects of Phosphate Fertilisers Varying in Source and Solubility An Update Review

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Nutr Cycl Agroecosyst (2011) 89:229255 DOI 10.

Nutr Cycl Agroecosyst (2011) 89:229255

Nutr Cycl Agroecosyst (2011) 89:229255

Water-soluble P as % of available P 90.5 92.6 96.6 96.9

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Dry-Matter Yield of Maize, g/pot

NAC Solubility, % P of Rock

Rate of P2O5 Applied, lb/acre

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RAE (%) 100 88 82 74 72 64 64 60 42 0

Solubility of P in 2% citric acid as a percentage of rock

Based on CO3/PO4 substitution in the apatite structure as measured by X-ray diffraction

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Nutr Cycl Agroecosyst (2011) 89:229255

Nutr Cycl Agroecosyst (2011) 89:229255

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US1 20.7 17.4 63 4.8 19.5 94

US2 21.0 17.9 82 5.7 20.4 97

UK1 20.4 19.1 46 2.5 19.6 94

UK2 19.9 18.9 59 1.3 19.5 98

a RE = Relative effectiveness with respect to TSP

Total effective water-soluble P (%) Effective water-soluble P as % of total P

Nutr Cycl Agroecosyst (2011) 89:229255

Nutr Cycl Agroecosyst (2011) 89:229255

Nutr Cycl Agroecosyst (2011) 89:229255

Total P (%) 13.3 6.3 16.0 12.3 9.2

H2O-P (%) 0 5.8 0 4.8 8.7

Citrate-P (%) 2.8 0.5 2.0 1.8 0.5

(H2O ? Citrate)-P (%) 2.8 6.3 2.0 6.6 9.2

Total Cd (mg kg-1) 47.0 24.7 54.0 35.7 31.5

DTPA-Cd (mg kg-1) 0.2 18.7 1.7 6.8 19.7

NC = North Carolina PAPR = PR acidulated at 50% level with H2SO4

Uptake of Cd by grainb (lg pot-1) 1.68B 3.25 2.88

Concentration of Cd in grainb (lg pot-1) 0.066B 0.135A 0.051B 0.114A

NC-PR NC-SSP Togo-PAPR Togo-SSP

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Cd concentrationsb Seeds (mg kg-1) 0.54A 0.35

Strawc (mg kg-1) 1.66A 0.88

Root (mg kg-1) 1.34A 0.99B 0.27C

Granulated (SSP ? KCl) Bulk-Blended (SSP) ? (KCl) Bulk-Blended (MCP) ? (KCl)

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Nutr Cycl Agroecosyst (2011) 89:229255

Control TSP(I) TSP(B)

22 40 86 11 11 36 74 45 1,210 1,980 2,680 90 90 90 90

APP(B) APP(I) Control TSP Slurry

Control Manure TSP

Control SSP SSP SSP SSP

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32.2 14.5 16.2 20.9A 33.2 15.5 19.6 22.7A

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Nutr Cycl Agroecosyst (2011) 89:229255

Nutr Cycl Agroecosyst (2011) 89:229255

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