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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 Ó 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 inﬂuenced by the following factors: (1) water and citrate solubility; (2) chemical composition of solid watersoluble P (WSP) fertilizers; (3) ﬂuid 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 efﬁciency 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 Á Agronomic effectiveness Á Cadmium Á P runoff Á Eutrophication
S. H. Chien (&) Formerly afﬁliated with IFDC, Muscle Shoals, AL, USA e-mail: email@example.com 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 2–3 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 inﬂuence 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 ﬁltration 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 signiﬁcant 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 signiﬁcant amount of free carbonates (calcite and/or dolomite). Free carbonates are more soluble than apatite,
however. When comparing the solubility of various PR sources that have different total P contents. WSP can be precipitated with the associated free carbonates in the PR.5%). and only 1. 1. the second citrate solubility measurement was better correlated with crop response to PR than the ﬁrst citrate solubility measurement (Chien and Hammond 1978). Table 1 shows that the UK2 and US1 samples differed by 11.2 19. As will be discussed below.9 P (95. which requires drying.Nutr Cycl Agroecosyst (2011) 89:229–255 231 Table 1 Chemical analysis of two US and two UK TSP products (Johnston and Richards 2003a) Source % total P % water-soluble P % available P Water-soluble P as % of total P US1 US2 UK1 UK2 20.9% P) because this PR contained 6% CO2 in the form of free carbonates rather than apatite-bound carbonate. 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). This consideration is relevant to the fertilizer P regulations adopted by different countries. the minimum water solubility of fully acidulated P fertilizers is about 90% of available P (Chien et al.9 19. 14.4 17. was greater than that of Pesca PR.5% with quartz.0 20. 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.5% if water solubility was expressed as a percentage of TSP (18. when the PR sources had high Fe2O3 ? Al2O3 content. compaction is preferred to partial acidulation for PR sources that have high Fe2O3 ? Al2O3 content (Chien 2003a). total P. Furthermore.9 90.6 96.9 17.84. the citrate solubility 123 .9 19.6 vs. for example. In one study.2%).6% P) to the second extraction (1. 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).0%). the citrate solubility of Huila PR (Colombia) increased from the ﬁrst extraction (0. the water solubility of the resulting PAPR fertilizer was lower than that of the compacted fertilizer.3 19. un-acidulated Fe2O3 ? Al2O3 minerals do not adsorb WSP in physically compacted products. Expression of phosphate solubility The water solubility of fully acidulated P fertilizers can be expressed as a percentage of fertilizer material. For example. 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 Fe–P and Al– P.1 18.2 resulting in the same Ca common-ion depressive effect (Chien 1993).2% for total P and 0. a sequential second extraction and measurement of citrate solubility should be performed to determine the actual available P in the PR after the ﬁrst citrate extraction has removed the free carbonates.2% if water solubility was expressed as a percentage of total Water-soluble P as % of available P 90. the convention used to express P solubility should be considered when comparing the water solubility of fully acidulated P fertilizers.4%).5 90.9 17. the compaction process is preferable to the wet granulation process. The latter convention gives misleading comparisons when PR sources of varying P content are used. In this case. Therefore.4% if water solubility was expressed as a percentage of available P (96. Consequently. the citrate solubility of Pesca PR was the same as that of Central Florida PR (4. resulting in reduced water solubility.4 19.0 to 6.1 19. 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. or available P. However.7 21.4% for citrate solubility as a percentage of rock).2 .6 96.The agronomic effectiveness of Central Florida PR. Lehr and McClellan (1972) demonstrated that when total P content of North Carolina PR was diluted by half from 13.4% = 1. 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 (8.5% = 6.0 85.4 95. They compared the conventions used to express water solubility for two US and two UK TSP products. For example. During drying. 2009). when solubility was expressed as a percentage of total P.8 vs. solubility is more appropriately expressed as a percentage of rock than as a percentage of total P.5 92.5 84. In Brazil.0% = 11. However. However. 6.
232 Nutr Cycl Agroecosyst (2011) 89:229–255 remained relatively constant (5. This comparison procedure 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. and DAP. 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.Na)H8(PO4)6Á6H2O] and that water-insoluble P occurred in the forms of MgAl(NH4)2H (PO4)2F2. at least 85–90% of the total P in these fertilizers is water-soluble. Prochnow et al. and 86%. In general.Al)3NaH14(PO4)8Á4H2O] in TSP (Prochnow et al. 2% citric acid (CA). (2003a) identiﬁed Fe3NaH8(PO4)6Á 6H2O as the major water-insoluble P compound in three Brazilian SSP fertilizers. P in the soil solution can precipitate with cations as amorphous Fe–P and/or Al–P compounds in acidic soils and as Ca–P compounds in alkaline or calcareous soils. In acidic soils. In calcareous soils. water-soluble P in the form of orthophosphate can be readily converted to water-insoluble P through reactions with soil minerals.0%. 123 .Al)3NaH8(PO4)6Á 6H2O] in SSP and H14 [(Fe. some poor-quality SSP sources may contain as little as 50–60% watersoluble P. 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. All of these reactions can result in decreasing P availability over time (Hedley and McLaughlin 2005. Therefore. All of these compounds are readily soluble in soil and provide P in the soil solution for plant uptake. 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. and Idaho PR sources. and FeNH4(HPO4)2 in MAP fertilizers produced from North Carolina. This is due to the fact that apatite mineral in a PR has its maximum solubility ﬁxed by a solubility-product constant (Chien and Black 1976). (2003a. TSP. Single superphosphate also contains a signiﬁcant amount of CaSO4 as a result of the acidulation of PR with H2SO4. 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). 2006. c). MAP. 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. commercial-grade SSP.1 to 16. 2009). Furthermore. Chemical and mineralogical composition and solubility characteristics of phosphate fertilizers In fully acidulated commercial-grade P fertilizers. MAP.Al)(K. Chien et al. Thus. However. As will be discussed below. 80. agronomic performance differs among various fertilizers with low percentages of water-soluble P. Fe–Al oxides can convert P in the soil solution to water-insoluble Fe– Al–P on the surface of mineral particles. In terms of providing P to plants. Normally.Al)H(HPO4)2F2Á2H2O and (Fe.7%) when the solubility was expressed as % of material (PR ? quartz) whereas the solubility increased from 9. the P compounds within the WSP fraction are mostly in the forms of MCP [Ca(H2PO4)2Á2H2O] in SSP and TSP. and DAP fertilizers are not 100% water-soluble. b. and (NH4)2HPO4 in DAP. the solubility of PR in NAC. TSP. and the remaining P is citrate-soluble. which compares the relative agronomic effectiveness (RAE) of PR to that of WSP (Smalberger et al. Some of these fertilizers are very good sources of this essential nutrient. The most common water-insoluble P impurities are the generic P compounds H8 [(Fe. or 2% formic acid (FA) is better expressed as a percentage of rock. b). P in the soil solution can be surfaceadsorbed by CaCO3. Florida. The water solubility of these SSP products as a percentage of available P was 46. According to Prochnow et al. NH4H2PO4 in MAP. AlNH4HPO4F2. 2003a. 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. However.
80 9. TSP. Because DCPD is more soluble than other Ca–P compounds.9 110 (mg P/kg soil) 18.6 63. This increased dissolution enhances the P availability of SSP or TSP (Terman 1971). CaHPO4Á2H2O) in calcareous soils. Therefore.Nutr Cycl Agroecosyst (2011) 89:229–255 233 Table 2 Available P (measured by the Olsen method) in calcareous soil treated with DAP or SSP according to placement method (Lu et al. and available P (Table 2).6 27. which is the main P component of SSP.3 11.4 12. (1987) reported that SSP was more effective than DAP for maize grown in a calcareous soil in terms of drymatter yield. PR. SSP. whereas the principal reaction products of DAP are octacalcium (OCP) [Ca8H2(PO4)5Á3 H2O] and hydroxyapatite (HA) [Ca10(PO4)5(OH)2]. have been used to describe this process (Chien et al.2 6. 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. as reported by Lu et al.. various types of Ca-NH4-P.9 17. SSP performs better than DAP in calcareous soil. and DAP) and solubility. (2008) concluded that the efﬁciency 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. and immobilization. Researchers often use SSP and/or TSP as standard WSP sources in comparison with other Ca–P sources. However. because P reaction products vary in solubility (Hedley and McLaughlin 2005. In addition.3 22. Most published reports on this topic have focused on water-insoluble and partially watersoluble P sources [e.2 18. For example. all high-quality WSP fertilizers should be equally effective in providing available P to plants. such as P sorption. 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. (1987).8 39.3 8. Consequently. which compares crop yield and P uptake between soils with and without added P. In general. and compacted (PR ? WSP) fertilizer]. ﬁxation. The major initial reaction product of MCP. P recovery calculated by the balance method is higher than that calculated by the difference method.35 18. adsorption. or deep placement).6 220 (mg P/kg soil) 32. In their study.6 31.3 (1.6 55. Syers et al. 2009).6 6. incorporation.4 5. Thus. precipitation. Lu et al.g.g.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. However. P uptake.. However. 123 . 2008).3 20. retention. Syers et al. 2008).8 28.7 10.05) CV(%) 13. The balance method simply considers yield and P uptake relative to the amount of P applied.5 mg P/kg) 55 (mg P/kg soil) 13. PAPR. regardless of the P placement method (broadcast.3 70. some researchers have claimed that the nitriﬁcation of NH4–N in MAP and DAP fertilizers to NO3–N (which increases acidity levels around fertilizer granules in the soil) and the root absorption of NH4–N (which increases rhizosphere acidity) may increase the dissolution of precipitated Ca–P compounds. MAP. In general. different sources of fully acidulated P fertilizers may not be equally effective under certain conditions. This method differs from the traditional ‘‘difference method’’.0 33. such as Ca(NH4)2(HPO4) H2O and CaNH4PO4ÁH2O. only about 10–20% of applied P is taken up by the ﬁrst crop. it takes into account residual P from previously applied fertilizer. may be produced when DAP reacts with calcareous soils (Lindsay 1979). sulfur (S) was not limiting for plant growth.9 27. is dicalcium phosphate dihydrate (DCPD. Several terms.
. (2001) showed that commercial ﬂuid P fertilizers (e.g. (1995) showed that SSP performed better than TSP as P source for pear millet grown on a sandy soil (pH 5. (2001).g. a signiﬁcant amount of the initial P remained in the granules even after some time of dissolution due to the presence of waterinsoluble Fe–Al–P minerals in the granule and the in situ precipitation of similar minerals resulting from the diffusion of Ca and Al into the granule. They found that total and labile P from liquid MAP diffused farther (1. MAP. the P should be supplied by the same chemical compounds in both cases. (2004). and it should be similarly placed. There is no reason to expect that SSP is better than TSP as P source since both contain the same WSP compound (MCP).7) in West Africa. it is recommended that researchers check the quality of SSP or TSP before starting the agronomic experiments. many reported greenhouse and ﬁeld trials do not comply with these requirements.35 cm) from the initial site of P application than total and labile P from granular MAP (0. This process may increase the agronomic effectiveness of polyphosphates compared to orthophosphates. or compacted fertilizer (PR ? WSP). Ottman et al. Bationo et al. or DAP) that contain little or no S. However. such as Fe or Zn. DAP and APP) were more effective than the corresponding commercial granular P fertilizers in increasing crop yield in calcareous and alkaline soils. Holloway et al. In this study. For example. For example. soil P ﬁxation may decrease over time through the sequestration of polyphosphate. In contrast. 2004). TSP. This difference may explain the better agronomic performance of ﬂuid MAP compared to granular MAP in ﬁeld trials reported by Holloway et al. Reactions and agronomic effectiveness of ﬂuid and solid WSP fertilizers in soils Numerous studies have compared the agronomic effectiveness of ﬂuid versus granular or non-granular WSP fertilizers. PAPR. in the APP (Engelstad and Terman 1980). 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 ﬂow of soil moisture into MAP granules.234 Nutr Cycl Agroecosyst (2011) 89:229–255 such as PR. especially in Australia.75 cm). Lombi et al. It also should be pointed out that SSP contains signiﬁcant amount of S that may under-estimate the relative effectiveness of PR against SSP in the S-deﬁcient soils if S is not added to the PR treatment. Recently. It should be noted that P diffusion depends strongly on soil moisture content (% of ﬁeld capacity) and on the water content of liquid P fertilizers. For 123 . This process depends largely on soil biological activity. In addition. and the results often conﬂict. (2006) used highly sophisticated instruments to study the P mobility of surface-applied granular versus ﬂuid MAP in a calcareous soil at 60% of ﬁeld moisture capacity. there was signiﬁcantly less P ﬁxation from ﬂuid P fertilizers and hence a greater concentration of labile P (Lombi et al. the researchers reported only the total P content.. Furthermore. keeping it from being adsorbed by soil minerals. (2006) also found no signiﬁcant differences in alfalfa yield obtained with ﬂuid APP and granular MAP on a calcareous soil over 3 years. in studies conducted in Australia. It is now recognized that the P in APP becomes available to plants only when the polyphosphates are hydrolyzed to orthophosphate in the soil. no other nutrients except N were applied. MAP. Therefore. 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. It is most likely that the crop responded to P and S so that SSP was better than TSP as reported. Hettiarachchi et al. Use of poor-quality SSP or TSP as a P reference to compare other Ca–P sources (e.. many studies have claimed that ﬂuid ammonium polyphosphates (APP) are agronomically superior to ammonium phosphates because of the different P compounds in the two P sources (polyphosphates in APP vs. Some favorable results for APP on neutral to alkaline soils may have been caused by appreciable amounts of micronutrients. For a valid comparison of ﬂuid and solid P fertilizers. renewed interest in research on ﬂuid versus granular forms of the same WSP fertilizers has been reported. orthophosphates in ammonium phosphates). If the hydrolysis of polyphosphate to orthophosphate is slow. They did not report the proportions of WSP and water-insoluble P content when comparing corresponding ﬂuid and granular P fertilizers.g. the same problem could also be encountered when comparing with other fully acidulated P fertilizers (e. 2009). PR or PAPR) might result in misleading information and over-estimate the relative effectiveness of those Ca–P sources. Similarly.
The less-reactive Jordan PR (2. Holloway et al. 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. Du et al.9% P) and Togo PR (1. 1. One potential beneﬁt of applying ﬂuid ortho-or polyphosphate sources rather than solid P sources may be that ﬂuid P sources can increase the soil concentration of available P with depth (Kovar 2006). (2004) compared commercial granular MAP with commercial ﬂuid technical-grade MAP. (2009). particularly ﬁeld trials. Pauly et al. 2007a. Szilas et al. the agronomic effectiveness of different PR sources correlates well with the citrate solubility of the PR (Chien 2003a.8% P). (2002) conducted a greenhouse study with polymer-coated MAP and DAP (thin-coated. g/pot TSP NC PR Jordan PR Togo 25 20 15 10 NAC Solubility. net P fertilizer efﬁciency and net fertilizer release efﬁciency than thick-coated and uncoated MAP. 2006).Nutr Cycl Agroecosyst (2011) 89:229–255 235 example. Chien and Friesen (1992) showed that a high-reactivity ground North Carolina (NC) PR with only 4. 2005. application of ﬂuid P fertilizers can enhance P recovery and response for deep-rooted cereal crops like maize. b). but they did not report whether the two sources contained the same P compounds or had the same water solubility.8% by weight or thick-coated. were less effective than TSP (Fig. Agronomic effectiveness of controlled–release coated WSP fertilizers Compared to research on slow-release (mainly N-polymers) and controlled-release (mainly coated urea) N fertilizers. % P of Rock 5 0 0 200 400 600 800 1000 1200 NC PR = 4. citrate-soluble P (including water-soluble P) in P fertilizers is available to plants and is called available P. In Tanzania. This increased concentration is especially important under no-till cropping conditions because the downward movement of orthophosphate is signiﬁcantly limited in soil-surface application. Msolla et al. The 30 Dry-Matter Yield of Maize. 2006). Lombi et al. Most reports on controlled-release soluble P fertilizers concern polymer-coated soluble NPK compound fertilizers and are limited to laboratory studies (Shaviv 2000. In general. is needed to test whether polymer-coated WSP fertilizers have the potential to improve P fertilizer efﬁciency and crop production. lb/acre Fig. In India.8) (Chien 2003a) 123 . Thincoated MAP showed greater dry-matter yield. The coating of DAP fertilizer did not consistently improve any of the above-mentioned parameters. By increasing P movement to subsurface depths. Additional information on polymer-coated WSP fertilizers can be found in a recent review paper by Chien et al. Downward P movement should also reduce the surface runoff risk that is responsible for eutrophication in aquatic environments. More research. limited information is available in the literature regarding controlled-release WSP fertilizers (mainly MAP and DAP). Agronomic effectiveness of water-insoluble and partially water-soluble non-conventional P fertilizer sources According to the AOAC deﬁnition (AOAC 1999). Truong 2004). However.2 Jordan PR = 2. however. 2003.8 Rate of P2O5 Applied. In light of the recently renewed interest in research comparing the agronomic effectiveness of ﬂuid and granular WSP fertilizers in Australia (Evans 2008.2% citrate-soluble P as a percentage of rock was equally effective for maize grown on an acidic soil as almost 100% citrate-soluble TSP.9 Togo PR = 1. 1 Dry-matter yield of maize grown with P sources varying in citrate solubility (Hartsells soil. 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. P uptake. 1). it may be worthwhile to conduct similar research on different soils in other countries. new data indicate that the most reactive Minjingu PR in Sub-Saharan Africa exhibits good agronomic effectiveness (Smithson et al.2% by weight) to test the growth response and P uptake of barley. pH 4. as will be discussed below. 2.
5 3.0 11.to high-reactivity PR sources can be used for rape in alkaline soils.6 2. several countries in North Africa (e.1 12. Algeria. with very low reactivity has been marketed for organic farming due to its high P content (Chien et al.7 5.g. Evans and Price (2009). making the PR ineffective as a P source (Chien et al.1 10.9 3. Farmers in these countries cannot use these low-cost indigenous sources of PR for their current crops (e. 2010). 2009). The oxidation of elemental S to H2SO4 may enhance PR dissolution for organic farming. with PR may provide a source of both nutrients.. such as rape for cooking oil. 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. The feasibility of growing a high-value crop.2 7. an indigenous igneous PR from Ontario. Mixing elemental S.to highreactivity PR deposits and alkaline soils.g. One major exception is in cases where PR is used with composting of either crop residues or animal manures. An interesting new ﬁeld of PR research involves the increased use of PR for organic farming worldwide because chemical P fertilizers cannot be used on certiﬁed organic farms (Nelson and Mikkelsen 2008). Habib et al. For example. The general rule is that the higher the reactivity of PR.1 13. (1999) were probably the ﬁrst to report that rape was able to utilize a medium-reactive Ain Layloun PR (Syria) in calcareous soils. (2003a) found that the RAE of PR increased from 0 to 88% as the 2% citric acid (CA) solubility of PR increased from 0.. the crop was grown on alkaline soils. which is allowed as an input for certiﬁed organic farming. Thus. and maize) in alkaline soils. as for conventional farming. In a follow-up study with nine different PR sources varying widely in reactivity for rape grown on an alkaline soil (pH 7. 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. In fact.2 0. However.8) (Chien et al. could translate into a signiﬁcant economic beneﬁt for farmers if the cost/ beneﬁt ratio of using PR is higher than that of using WSP fertilizers. Among crop species.3 3. the more likely it is to be an effective P source for organic farming. For example.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 a Based on CO3/PO4 substitution in the apatite structure as measured by X-ray diffraction 123 .4 2. The exudation of malic acid and citric acid by the plants’ roots is thought to be responsible for the dissolution of PR.0 14. Another example is an organic strawberry farm in Canada that used a highly reactive PR imported from North Africa.6 4.6 13. Tunisia. However. 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.236 Nutr Cycl Agroecosyst (2011) 89:229–255 RAE of (MPR ? PBS) in relation to DAP as judged by total productivity was 53–65% in the ﬁrst cycle but reached 69–106% in the third cycle of the cropping system (Sharma et al. It should be noted that the effective use of PR with or without elemental S for certiﬁed organic farming. barley.4 11. These ﬁndings suggest that medium. wheat.9 to 5. 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. depends on the reactivity of the PR sources used.7% P as a percentage of rock (Table 3). This conclusion has important implications for countries that have medium. Canada.4 13. total P content is irrelevant to PR reactivity for direct application. and Morocco) have highly reactive PR sources. rape is highly efﬁcient in utilizing PR. 2009). as reported by Evans et al. Chien et al. (2006).8). organic farmers should be aware that not all PR sources have the same reactivity.8 2% CAa 100 5.
50% of the total P dissolved from PR would be 28% as effective as CaCO3 in terms of its liming effect.0078 (% dissolved P)2 (r2 = 0. Recently. The total liming values were 640 and 414 kg CaCO3/ha for North Carolina PR and Jordan PR. fertilizer companies. the higher the liming value of PR. Based on this model. the FAO/IAEA has posted the PRDSS on the IAEA web site (http://www. PRDSS can be used in developing countries. 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. Although hundreds of agronomic trials of PR have been conducted worldwide. 2009). types of soil.11 at corresponding depths for Jordan PR. whether locally produced or imported. and crop species (Chien et al.15 to 0. which has the lowest solubility and least surface area among apatite minerals. In the future. and the unit-cell a-value of apatite increased toward that of ﬂuorapatite. (2003) used a process called mechanomilling in which six different PR materials were ballmilled at high energy to allow enhanced chemical and physical reactivity. it is likely that the chelation of organic matter by Ca ions derived from apatite. 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. 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. This PRDSS can be a useful tool to researchers. cooling. One way of solving this problem is to use PRDSS.47 ? 0. and government decision makers who must determine the feasibility of the agronomic use of PR. where % CCE = 8.84). More research is needed to explore these PR reactions and crop responses to the composting of PR in the ﬁeld. Lim and Gilkes (2001) attributed the increased solubility and agronomic effectiveness of the processed PR to the dominant amorphous materials formed during mechano-milling. compared to that of WSP fertilizers. 2009). is primarily responsible for PR dissolution rather than soil acidity as in the conventional farming. more work will be needed to model a residual RAE of PR for a given residual crop over a given period of time.2).iaea. it is essential to integrate all important factors affecting the agronomic effectiveness of PR into a comprehensive system to better understand these processes. The relationship between the calcium carbonate equivalent percentage (CCE) of PR and the percentage of dissolved P followed a quadratic model. (2004) reported that pH of a composting pile dropped from initial 6–5 in the mesophilic phase only for a few days. and soon after the pH began to increase and stayed constant around pH 7–8 in the thermophilic. in the cases of composting organic materials with PR. IFDC has developed and published its own PRDSS model for PR sources varying in reactivity for different crop species (Smalberger et al. 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. respectively. The results from this long-term ﬁeld study show that the continuous use of medium. the surface area of PR was reduced. to help choose between WSP fertilizers and PR. 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. and ﬁnally to maturing phase of the composting. Because it is designed to be practical. this process is similar to the calcination of francolite containing apatite-bound CO3 to ﬂuorapatite (Chien and Hammond 1991).17 at a 20–30-cm depth for North Carolina PR and from 0. especially in countries endowed with indigenous PR deposits. Kuo et al. (2005) found that soil D pH (pH of PR-treated soil—pH of control soil) values ranged from 0. Lim et al. extension workers.28 at a 0–5-cm depth to 0. the more P dissolved from PR. In a long-term (16 years) ﬁeld study with a pastoral soil treated with two PR sources at a P rate of 30 kg P/ha/year.org/dapr/srv/en/home). similar to the mechanism of the dissolution of apatite by neutral citrate solution. However. More work is needed to understand the inconsistent effects of mechanical milling on the physical and chemical reactions and agronomic effectiveness of PR. Therefore. 123 . For example. Loganathan et al. 2006). Thus.Nutr Cycl Agroecosyst (2011) 89:229–255 237 acidic soil environment (Chien et al.to high-reactivity PR sources can signiﬁcantly reduce the rate of acidiﬁcation in pastoral soils. For example.iswam. 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.
Mixing PR with WSP can sometimes be agronomically and economically effective under these conditions.3%). high soil pH. either by partial acidulation or by compaction of PR with WSP. degree of acidulation. which consists of un-acidulated PR and acidulated WSP. the effect of soil properties. such as pH and P-ﬁxing capacity. which contains low amounts of (Fe2O3 ? Al2O3) impurities (2. The spread (±10%) along the one-to-one line (dashed line) is shown by dotted lines (Chien et al. 2003b) 123 . resulting in better plant root development. or short-term crop growth. This method was effective because the WSP was able to provide available P to the plants initially (starter effect). the agronomic use of PR may not be as feasible as that of WSP. 3 Dry-matter yield of maize grown with TSP and modiﬁed PR products made from (a) Huila PR and (b) Capinota PR (Chien et al. and the initial and residual P effects (Chien 2003b). such as low PR reactivity. Many studies have provided valuable information on the factors affecting the agronomic effectiveness of mixtures of PR and WSP. In one study. the crop species grown. Fig. (2004) showed that P uptake from Patos PR in the presence of WSP was higher than that from Patos PR alone. 2009) A Under certain conditions.8%). Figure 3 shows PAPR and compacted (PR ? TSP) products that performed equally well using Huila PR (Colombia). Partial acidulation of low-reactive PR (PAPR). 2 Comparison of observed and predicted relative agronomic effectiveness (RAE) for (a) initial and (b) residual applications of PR and WSP.238 Nutr Cycl Agroecosyst (2011) 89:229–255 A B PR had been applied alone. The compacted product (PR ? TSP) was more effective than PAPR made with Capinota PR (Bolivia). which in turn allowed the plants to utilize the PR more effectively later in their development than if the B Fig. Prochnow et al. 2004). Another way is to mix PR with WSP by dry granulation (compaction). is one way to achieve this goal. which contains a signiﬁcant amount of (Fe2O3 ? Al2O3) impurities (8. 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. the starter effect of water-soluble P on PR effectiveness. indicating the beneﬁcial starter effect of watersoluble P on the effectiveness of Patos PR. These factors include the reactivity. and degree of Fe and Al impurities of the PR source.
respectively. b. This reaction of H3PO4 with unacidulated PR not only reduces the P ﬁxation of the WSP component in PAPR by reactions with Fe–Alminerals but also allows additional P to be released into the WSP pool. and 100% as effective as TSP. (1999). in increasing the grain yield of upland rice. part of the H3PO4 produced by MCP hydrolysis will be neutralized by the unacidulated PR. Babana and Antoun (2006). (2000). This study suggests that there is agronomic 123 . the citrate solubility of these two PR sources increased signiﬁcantly from almost none to a maximum of 90 and 51% of total P. 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 Ca–Fe-Al–P. Sokoto and Singh (2008). (7) Timemsi PR (Mali) by Babana and Antoun (2005). (2009).5 and thus can dissolve Fe and Al minerals. (10) Sokoto PR (Nigeria) by Agbenin (2004). Mendoza et al. which are not suitable for acidulation because of their high Fe–Al content. the IFDC (2003). (2008) characterized and conducted agronomic evaluations of two non-apatite PR sources (Sapucaia and Juquia) from Brazil. Several books on these subjects have also been published since 1998 by the IAEA (2002a. (2007). Without calcination. (15) Minjingu PR (Tanzania) by Mutuo et al. Somado et al. (2003). respectively. (11) North Carolina PAPR by McLay et al. For ﬂooded rice. and compacted (PR ? WSP) products have been reported in the literature since 1998. (9) Ogun PR (Nigeria) by Akintokun et al. The released H3PO4 can lower soil pH to as low as 1. These studies raise doubts about the ability of the AOAC procedure to accurately extract plant-available P compounds (Chien et al. 2003b) Figure 4 shows that the RAE of PAPR increases with the soil’s P-ﬁxing capacity and that PAPR can be more effective than SSP in soils with very high P-ﬁxing capacities. (2008). After calcination at 500°C for 4 h. (17) Gafsa PR (Tunisia) and Arad (Israel) by Gatiboni et al. (2006). In a recent study. and (18) Riecito PR (Venezuela) by Casanova et al. (13) Phalanowa PR (South Africa) by Loganathan et al. The results indicate that some of the citrate-insoluble P of certain P fertilizers might also be available to plants. Begum et al. The chemistry of soil reactions as explained by Chien (2003b) is as follows. dissolves in the soil solution. (4) China PAPR by Aye et al. (2) Kaiyang PR (China) and Gafsa PR by Satter et al. PAPR. 4 Relationship between soil P-ﬁxing 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. 89. (2003). (16) Hahotoe PR (Togo) and PAPR by Agyin-Birikorang et al. Francisco et al. With PAPR. (2003). (2004). When MCP. which contains both WSP and PR. and 0% for the Gafsa PR. For the reader’s information. (2009). (2006) (8) Ben Guerir PR (Morocco) by Rivaie et al. (5) Trinidad de Guedes PR (Cuba) and PAPR by Rodriguez and Herrera (2002). which is the P component in SSP or TSP. (2002). The two calcined P sources and the highly reactive Gafsa PR were 83. (2002). and the FAO (2004). 2009). which in turn react with WSP to form water-insoluble Fe–Al–P. (6) compacted Jamakotra PR (India) with MAP by Nair et al. we list some additional reports categorized by the alphabetical order of country’ name: (1) Djebel Onk PR (Algeria) by Nemeth et al. it is hydrolyzed to DCPD and H3PO4 in the meta-stable triple-point solution (Lindsay 1979). These soil reactions decrease the P availability from SSP or TSP because of the P sorption effect of the Fe–Al minerals. (1999). X-ray diffraction showed that the crystalline crandallite mineral was transformed to an amorphous form after calcination.Nutr Cycl Agroecosyst (2011) 89:229–255 239 Fig.4). (3) Jinxiang PR (China) by Xiong et al. (14) Eppawala PR (Sri Lanka) by Zoysa et al. (2002). (12) North Carolina PR by Rajan (2002). the corresponding values were 72 and 68% for the two calcined P sources. 2006). respectively. both PR sources were totally ineffective for upland rice grown on an acidic soil (pH 5. (2004). Many studies on the agronomic use of apatitic PR.
5 19. ranged from 44 to 87% in drymatter yield. The concept takes into account the ‘‘equivalent water solubility’’ of the water-insoluble P residues. 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 20.9 59 1.5 94 US2 21. which is calculated from the RE of the water-insoluble residue.1%. 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. 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).8 19. even when the soil was limed (pH 7.6).1 46 2. For example.3 19.1% = 19. the total P of the water-insoluble P residues of the US1 product was 3. However. These results support previous studies showing recovered magnesium phosphates to be effective in acidic soils. as shown in Table 1. respectively). the equivalent available P in the water-insoluble P residues was 3.9 82 5. the total effective watersoluble P was 17.4 97 UK1 20.0 17. 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. which can be recovered from municipal. and the effective water-soluble P as a percentage of total P was (19.5%) was smaller than that of the UK products (90. b.7 17.4% = 3.4–95.4 19.3%). Thus.8%) was lower than that of the UK products (average 92.8%). (2009) found that recovered struvite and dittmarite were as effective as TSP for wheat grown in a neutral soil (pH 6. In short.5 98 a RE = Relative effectiveness with respect to TSP Total effective water-soluble P (%) Effective water-soluble P as % of total P 123 . The relative effectiveness (RE) of these water-insoluble P residues with respect to MCP. More research is needed to determine whether recovered Mg phosphates could become useful alternative P fertilizer sources in conventional and organic farming operations.4 ? 2. c. as shown in Table 4.5/20.9 18. The US and UK products exhibited similar ranges of effective water-soluble P as a percentage of total P (94–97 and 94–98%.5%. 2003a.6 94 UK2 19. Johnston and Richards (2003a) also advocated a new concept of calculating the ‘‘effective’’ availability of water-insoluble P residues compared to WSP. Because its RE based on dry-matter yield was 63% of that of WSP (MCP).3% 9 0. Massey et al. This threshold value was ofﬁcially adopted by the EC in 2004. they do have certain agronomic values compared to WSP compounds (Prochnow et al. Prochnow et al.2%). as calculated by the substitution-rate method. and agricultural wastewaters.7 20. 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. as shown in Table 1. which was grown on 13 soils with widely varying properties.63 = 2. and they provide evidence that recovered phosphates are also effective in slightly alkaline soils (Johnston and Richards 2003b). industrial.5).4 63 4.7 17. 2008). the range of actual water solubility values for the US products (84.0–85.3% (20. Table 4 shows the calculated effective P as a percentage of total P in the four TSP products. Interest is growing in the use of magnesium phosphates as P sources for crops in the form of struvite (MgNH4PO4Á6H2O) and dittmarite (MgNH4 PO4ÁH2O).240 Nutr Cycl Agroecosyst (2011) 89:229–255 potential in calcined non-apatite PR sources that cannot otherwise be used for direct application or chemical acidulation. Both are water-insoluble but citrate-soluble P compounds.7) 9 100 = 94%. but the calculated actual water solubility of the US products (average 84.
Cd uptake is greater in leafy vegetables than in maize or wheat (Morvedt 2005). but less Cd will be present than Cd in TSP because no PR is used. TSP uses only 24–30% of PR-P and 70–76% of H3PO4–P (Davister 1998). application rate. the dissolution of both Cd–P and Ca–P increases with decreasing soil pH. the Cd content associated with P in apatite minerals can vary widely (Table 5). Heavy metal uptake by plants is one possible avenue of entry into the human food chain through direct or indirect consumption.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. soil type. 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. Grant et al. Ammoniation of Cd-containing H3PO4 will produce DAP and MAP products that also contain Cd. 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. fully—acidulated P fertilizers (Morvedt 2005). the resulting TSP may contain 40–50% of the TSP-Cd from the PR-Cd and the remaining Cd from H3PO4–Cd. gradual accumulation of Cd usually occurs in soils only after long-term application of Cd-containing P fertilizers. The chemical forms of Cd in acidulated P fertilizers are Cd(H2PO4)2 and CdHPO4.Nutr Cycl Agroecosyst (2011) 89:229–255 241 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. In the production of H3PO4-based P fertilizers. Cd in PR originates from the substitution of Cd for Ca in the apatite structure (Iretskaya and Chien 1999). Morvedt 2005). (1999) noted that the Cd concentration of P fertilizers. especially cadmium (Cd). and crops grown are important factors when considering the relationship between added Cd and plant uptake. long-term experiments may be the most 123 . 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. Grant et al. which are Cd analogs of the Ca and NH4 compounds found in commercial. for crop production. Grant et al. all of the Cd will remain in SSP produced by acidulation of the PR with H2SO4. If a PR source contains a signiﬁcant amount of Cd. H3PO4 is ﬁrst produced by acidulation of PR with H2SO4 followed by separation of H3PO4 and precipitation of phosphogypsum. Thus. Thus if H3PO4 is used to acidulate the same PR. (1999) stated that Cd availability may be greater with MAP use than with DAP use because MAP is initially acidic whereas DAP is alkaline. Therefore. There have also been numerous review articles on the issue of Cd impacts from the use of P fertilizers (Alloway and Steinnes 1999. Unlike SSP which uses 100% PR-P as P source. 1999. It has been suggested that the soil factors affecting Cd availability may be similar to those affecting the P availability of Ca–P. For example. The plant availability of Cd in P fertilizers also depends on soil texture and plant species. Depending on the sources of PR. Because the Cd rate applied depends on the P rate used. The source of Cd in P fertilizers is PR. Numerous greenhouse and ﬁeld 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. As much as 30–50% of the Cd in PR is transferred to phosphogypsum and the remaining Cd stays in the H3PO4 during the process (Wakeﬁeld 1980). Cd uptake by crops is higher in acidic soils than in alkaline soils (Iretskaya and Chien 1999).
particularly in developing countries (Grant et al.0 2.0 1. 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. The Association of American Plant Food Control Ofﬁcials (AAPFCO).8 g Cd/ha at a fertilizer application rate of 20 kg P/ha. suggested in 2005 that the standard Cd limit in P fertilizers should be 4. which is higher than the 0. Bolan et al.9 g/ha in Japan.4 mg Cd/kg per percent of P content (Morvedt 2005). Numerous studies have shown little or no effect of liming on crop Cd uptake under ﬁeld conditions. several countries have imposed limits on the total Cd concentration that may be present in fertilizer materials.0 2. As noted above. comprising the fertilizer regulatory ofﬁcials in each state.9 1. 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. 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. Soil organic matter can reduce the toxic effects of Cd in contaminated soils under acidic conditions. Nevertheless. (1999) pointed out that the efﬁcacy of liming under ﬁeld conditions is less consistent and of a smaller magnitude than that noted in container-growth studies. (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.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. higher Cd concentrations were measured for soil samples 123 . Grant et al. The interaction between pH and organic matter in their effects on Cd in soils may explain these differences.0 1.7–4.9 kg Cd/ha per 365day period (US EPA 2007). However. 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.0 4.0 6. there is no standard limit of maximum allowable Cd in P fertilizers for the whole country. Cadmium inputs in P fertilizers containing the maximum allowable Cd limits range from 0. Morvedt (2005) summarized the results of long-term ﬁeld experiments with TSP made from Florida PR and applied at an annual P rate of 15–30 kg/ha after [50 years.0-g Cd/ha range in maximum allowable Cd inputs imposed by Western European regulations (Table 6). the rate of Cd accumulation appears to be slow. 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. Grant et al. (2005) calculated that at an annual application rate of 20 kg P/ha. 1999). Because fertilizer regulations in the United States are enacted on a state-by-state basis. at a normal annual rate of fertilizer input (20 kg P/ha).242 Nutr Cycl Agroecosyst (2011) 89:229–255 meaningful to assess the environmental effects of Cd in P fertilizers.4 4. 1999). However. global reserves of PR containing low levels of Cd are relatively limited. Table 6 shows the proposed limits of Cd in P fertilizers in various countries. it would take from 214 years (with Gafsa PR containing 70 mg Cd/kg) to 2. This recommendation is based primarily on greenhouse and growth-chamber studies. Removing Cd from PR during processing may not be economically viable at current fertilizer prices. Efforts to establish allowable limits of Cd in P fertilizers in the United States began in the mid-1990s. This is equivalent to a Cd input to soil of 8. at pH 6–8. In contrast. despite the technologies that may be available.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.0 0. This could have important implications for food production. The selection of PR sources that are low in Cd should reduce the concentration of Cd in ﬁnished P products after the manufacturing process.7 g/ha in The Netherlands to 6. These authors concluded that although P fertilizer addition represents the major source of Cd input to soils.
TSP. but Cd uptake was lower from the directly applied PR (Table 8).0 6.44B A NC = North Carolina. fully acidulated P fertilizers (SSP. Just as the total P content of P fertilizer is irrelevant to crop P uptake.8 19.0 24.5 vs.8 0.135A 0.7 1.68B 3.2 H2O-P (%) 0 5.5 2. whereas the two P sources produced the same rice grain yield (Table 8). PAPR = PR acidulated at 50% with H2SO4.5 DTPA-Cd (mg kg-1) 0. For example.066B 0.0 1.5 79.6 A Uptake of Cd by grainb (lg pot-1) 1. especially long-term experiments under ﬁeld conditions. agro-climatic conditions. 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. 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. it is expected that acidulation of PR will release soluble P simultaneously with soluble Cd. which had signiﬁcant Cd content (Table 8).114A NC-PR NC-SSP Togo-PAPR Togo-SSP a b 27.7 6. Because Cd and P are present in the same apatite structure.7 Citrate-P (%) 2.8 0.2 18.3 16.5 25.3 9.6A A 1. This discrepancy is a serious issue that lawmakers and environmental regulators may need to reconsider.88 A Concentration of Cd in grainb (lg pot-1) 0.25 2.3 6. 1999). the total Cd added was only slightly less from NC-PR than NC-SSP (70.0 57.8 8. A study by Iretskaya et al. The results showed that the Cd concentration in upland rice grains was 0.8 0 4. more research is needed. and just as crop uptake of P is determined by the available P content of a fertilizer (Chien 2004a). 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 (%) 13.051 mg/kg Cd with 50% acidulation with H2SO4 compared to 0. not available Cd. (1999) showed that Cd uptake by upland rice was increased by raising the degree of acidulation of Togo PR.05 123 .3 2.7 31. 79.0 12.5 (H2O ? Citrate)-P (%) 2.6 9.Nutr Cycl Agroecosyst (2011) 89:229–255 243 with higher organic matter content because of the complexation of Cd by soluble organic matter (Grant et al. MAP. SSP = 100% acidulation of PR with H2SO4 Means followed by the same letter within columns are not signiﬁcantly different at P \ 0.3A 24. Most published research reports and reviews on Cd contamination associated with the use of P fertilizers focus exclusively on commercial. 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. and DAP).114 mg/kg Cd with 100% acidulation.7 54.6) (Iretskaya and Chien 1999) P sourcea Cd rate added (lg g-1) 70.3 Grain yieldb (g pot-1) 25.8 69. laws that regulate the maximum permissible Cd content of fertilizers are based on total Cd.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. However. crop Cd uptake is related to the available Cd content of the P fertilizer and not to the total Cd content (Chien 2004b) However. and crop species.2 Total Cd (mg kg-1) 47.8 6.0 35.051B 0. to unravel these conﬂicting reports on the effects of liming on Cd uptake as inﬂuenced by soil properties. The results showed that Cd uptake by rice was more related to DTPA-extractable Cd than to the total amount of Cd added.0 mg Cd/kg).
(2003b) in a preliminary greenhouse study.99B 0. mainly as a result of human activities. There are many reports in the literature on the use of P fertilizers 123 . 3. stem. The bulk-blending of Cd-containing P fertilizers with KCl can thus reduce Cd uptake by crops compared equivalent granulated PK fertilizers. In this study.06C 0.68–3. 2009). as shown in Table 7.34A 0. the former may contribute less to Cd uptake by crops than WSP sources.68 vs. straw and roots (Chien et al. If this assumption holds true. 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. These complexes would be less likely to form when KCl and Cd-containing P granules are physically separated in soil-applied bulkblended PK fertilizers. all sources of P and K.2 vs.8A 0.25 lg Cd/pot). this process has become popular worldwide. The results showed that the agronomic effectiveness in increasing crop yield was equal for Cd-containing SSP and reagent-grade MCP (0% Cd). Although PK fertilizers. 2007).26C Seed yield of control plants (no P and K) = 1. The above hypothesis was tested and conﬁrmed by Chien et al.66A 0. Due to the simplicity of bulk blending and its relatively low investment and operating costs. 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. (1997) reported that increased chloride (Cl) content in irrigated waters imposes a high risk of producing crops with high Cd concentrations.35 B Strawc (mg kg-1) 1. thereby increasing the possibility of forming CdCl0 2 and CdCl1? complexes.2). The Cd uptake data reﬂected the much lower content of DTPA-Cd in NC-PR than in NC-SSP (0.36 mm in diameter). 2003b) PK source Seed yielda. Chien et al. whether produced by granulation or bulk-blending. and pod samples from NC-SSP (1. and these reactions result in 2 enhanced Cd uptake. were used in the study. (2003b) hypothesized that if a WSP fertilizer has a high Cd content. 8. The results also suggest that if PR and PAPR are as agronomically effective as fully acidulated P sources. McLaughlin et al. not NPK fertilizers. 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.5 A b Cd concentrationsb Seeds (mg kg-1) 0. In all plant tissue samples. Upland rice and soybean were grown to maturity and Brachiaria grass was cut 4 times in an acidic soil (pH 5. It is believed that Cl ions form relatively strong complexes with Cd2? in the form of CdCl1? and CdCl0 in solution. the superiority of bulk blending compared to granulation in decreasing Cd uptake would also apply to NPK compound fertilizers. Based on these observations. In granulated PK fertilizers. A soil is generally considered contaminated with Pb when its total concentration exceeds 400 mg Pb/kg.27C Granulated (SSP ? KCl) Bulk-Blended (SSP) ? (KCl) Bulk-Blended (MCP) ? (KCl) a b c 23. Concentrations of Cd in plant tissue samples of all crops were much lower for MCP than for SSP. and remediation is required at this level (Yoon et al.4 g/pot Means followed by the same letter within columns are not signiﬁcantly different at P \ 0. it was expected that the inclusion of N would not affect the results (Chien et al. One example using a soybean crop is shown in Table 9. (g pot-1) 27.7 mg Cd/kg). Cd concentrations obtained with granulated PK fertilizer (SSP ? KCl) were signiﬁcantly higher than those obtained with bulk-blended PK (SSP ? KCl) fertilizers. had the same granule size (1. granulation of this WSP fertilizer with KCl may result in greater Cd uptake by crops compared to an equivalent bulkblended PK fertilizer.1A 29.244 Nutr Cycl Agroecosyst (2011) 89:229–255 Table 9 Seed yield of soybean and Cd concentrations in soybean seeds. KCl and Cd-containing P fertilizers are present within the same granule and are thus in close contact.05 Combined leaf.54A 0. whether granulated or bulk-blended with KCl.88 B Root (mg kg-1) 1.
2003. stimulating aquatic plant life. 2001. the presence of P in eroded sediments (Baker and Laﬂen 1983. Similarly. Preedy et al. Among plant nutrients. P runoff from pastures in Britain was reported to be higher with WSP than with manure (Preedy et al. Chen et al. it became clear that changes were occurring in many lakes and reservoirs. dissolved P loss. Bosso et al. However. 2008. The following additional references have been reported since 1998: Ma and Rao 1999. and methods of P application (Bundy et al. industry. The results indicated that P export was less when P fertilizers were incorporated instead of broadcast. Daverede et al. 2002. Iowa that compared P runoff losses from ammonium polyphosphate fertilizer to those from liquid swine manure with and without soil incorporation. 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. and leaching of P into the groundwater in sandy soils (Maguire and Sims 2002). 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. Tabbara (2003) observed higher concentrations and losses of all P forms with the fertilizer treatment. 2001). Lin et al. 2003.Nutr Cycl Agroecosyst (2011) 89:229–255 245 to immobilize Pb by converting less stable Pb compounds. In a study near Ames. The resulting anaerobic condition in marine systems caused by this depletion of oxygen is known as hypoxia. In the late 1960s. The higher losses that occurred with the 123 . can biologically ﬁx atmospheric N2. These increased nutrient levels promoted undesirable algal growth. P is essential for biological N ﬁxation and the support of algal growth. recreation. 2005). 1998. 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. and that P export was greater when P fertilizers were used than when livestock manures were used. 1992. the effectiveness of PR in immobilizing soil Pb depends strongly on the reactivity or solubility of the PR used. WSP fertilizers (e. Miretzky and Fernandez 2009. 1999). Withers et al. 2003). 2001. Data on P export in terms of total P loss. Phosphorus enrichment of surface waters can result in intensiﬁed cultural eutrophication problems and overall degradation of water quality. 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.g. 2009). especially in industrialized countries. 2004). such as cerrusite (PbCO3). such as chloropyromorphite [Pb5(PO4)3Cl] (Lindsay 1979). Foy 2005). 2003. Torbert et al. Chen et al. Sharpley et al. Loss of P from agricultural practices has been identiﬁed as a major cause of impaired surface-water quality (US EPA 2009). In general. Cao et al. Effects of P fertilizer application on P runoff and eutrophication Many recent experiments investigating P losses have focused on overland ﬂow pathways. 2008). 2005. and ﬂow-weighted total P reﬂect the amount of available P for the promotion of eutrophication. resulting from increasing nutrient loads. comparisons between P fertilizers and other P amendments (especially livestock manures and slurries). P is perhaps more critical than N for algal growth because some species of algae. It should be emphasized that. Some recent examples of P losses in overland ﬂows following the land application of P fertilizers and livestock manures are shown in Table 10. as for the agronomic use of PR in conventional or organic farming (Chien et al. These contributions occur mainly through surface runoff of P in dissolved water (Heathwaite et al. that P export increased with increasing P fertilizer application rate. The use of WSP fertilizers is one of the potential agricultural practices contributing to the eutrophication of water bodies (Alexander et al. 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 Pb–P compounds. Such waterquality degradation may impair water use for ﬁsheries. that there was more P runoff from irrigated pasture (Australia). to more stable Pb compounds with very low solubility and bioavailability. Bolan et al. such as bluegreen algae (Cyanobacteria). 2003.. However.
This difference in the orchards and paddy rice ﬁeld was closely related to the amounts of soil and water lost (Huang et al.2 35.200 12. Phosphorus loss signiﬁcantly increased during the fallow period and was intensiﬁed by heavy rain-induced runoff events (Udawatta et al.210 1.70 23. 1999). Soil P accumulation increases the loss of particulate P when soil particles are detached and transported in runoff. On sloping lands in Yunnan Province.6 0 22 17. topography. 2007).1 1.88 3.76 15. 2005).4 4. 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.4 0. Harrod and Theurer 2002). Slurry = cow manure.010 10. Studies indicate that fertilizers left on the soil surface are most prone to loss.210 1. 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.9 26.630 60 1. such as soil erodibility.60 0.5 14.6 11.980 2. especially if applied to grassland soils. 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.3 32 45 1. APP = liquid ammonium polyphosphate. 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.4 5.680 – 90 90 90 90 0.7 68.100 13.2 57. and in many high rainfall areas (Torbert et al. 2004).6 7.4 13. 2007) and paddy rice ﬁelds (Jiao et al. (mg L-1 P) P loss (% of TP applied) – \0. or wet soils. Manure = poultry manure TP = total P FWTP = ﬂow-weighted total P fertilizer were attributed to the greater water solubility of P in the fertilizer. and cultivation practices (Sharpley et al.9 48 48 48 7.246 Nutr Cycl Agroecosyst (2011) 89:229–255 Table 10 Recent examples of P losses in overland ﬂow following application of P fertilizers as compared to livestock manures (Withers et al.12 3. 2004). sloping lands.332 24. B = broadcast.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.863 1.0 5. Orchards cultivated on sloping lands lost far more P through runoff than did paddy rice ﬁelds.680 – 6.7 – 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 5.0 0.300 22 40 86 11 11 36 74 45 1. 1999). China. (2003. 2004) 123 .6 7. Nash et al.2 6.2 – 6.980 2.9 1. if applied just before a storm or irrigation event. land cover. 2000. The amounts of P lost through runoff are also dependent on factors related to soil erosion risk.0 35. Fertilizer P sources and management The sources of acidulated P fertilizers may also affect the export of P to water resources. P losses were greatest from farmlands with slopes of 68–128 and gradually decreased beyond this slope range (Duan et al.804 1.600 10.2 18.
2003.35 0.6 22. Little information is available on the use of non-conventional P fertilizers. Soil P adsorption of non-granular SSP may be faster than that of granular DAP. Such soil inﬁltration may help minimize the environmental impact of P during the winter months while maintaining available P for plants in the following growing season. 0. where they may be less subject to loss through runoff or erosion. 0. This process would be especially important for polyphosphates. such as reactive PR Cumulative dissolved reactive P (DRP) loss (kg ha-1) Alvira Berks Watson Averagea 0. In a paddy ﬁeld. This result indicates that an overdose of P fertilizer will impose a high risk of P runoff from paddy ﬁelds to watercourses during rainy seasons or in water drainage practices that are adopted in paddy rice production for controlling overgrown rice tillers.45B -1 32. and 240 kg P/ha resulted in losses of 0.43 0.74B a Average DRP and total P loss values in the same row followed by the same letter are not signiﬁcantly different at P \ 0.50. (2003. 2006. polyphosphates may present less runoff risk than orthophosphates when applied to the surface. TSP.2 20. whereas commercial-grade DAP is always in a granular form. application of 0. as a result of the hydrolysis of water-soluble MCP in SSP (Lindsay 1979). More research is needed to investigate the effects of different acidulated P fertilizers (SSP. resulting in less P export from SSP. data from Hart et al. Shigaki et al. 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. If this were the case.5–9. MAP. More work.30 0. 2004. 120.52 0. 2008). and DAP) that vary in solubility.5 19. respectively (Xia et al. 2004). but to the greater water solubility of DAP. Table 11 shows that both cumulative total and dissolved reactive P losses from surface runoff from the three soils were signiﬁcantly lower with reactive North Carolina PR than with TSP. Kovar (2006) suggested that ﬂuid P sources applied to the soil surface would move into the soil proﬁle. 3. 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 ﬂow.23 0.39 0. which are thought to be less subject to soil adsorption. is needed to validate this conclusion.2 14. granular form.68 0. 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. Most research and review reports on the use of P fertilizers in relation to eutrophication are exclusively concerned with conventional fully acidulated P fertilizers. non-granular form. Large P losses (5. Therefore. to sustain crop productivity and their inﬂuence on P runoff. such as CaHPO4. 2007). 60.18 0. which are related to bioavailable P for algal growth and eutrophication (Sharpley et al.83 Berks Watson Averagea 0. 25.Nutr Cycl Agroecosyst (2011) 89:229–255 247 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. which also contains MCP.31 0.97 kg P/ha to runoff water.23C 0.9A 33. and particle size on P runoff risks. 1992).7A Cumulative total P loss (kg ha ) Alvira 0. 2008). The greater P export from TSP than from SSP was likely due to the greater water solubility of TSP. indicating that reactive PR may pose a lower eutrophication risk (Shigaki et al. (2004) showed that both dissolved reactive P and particulate P.13. Many SSP fertilizers are produced in an irregular. 2007).5 16. were higher from TSP than from SSP at the same rate of P application (35 kg P/ha). Xia et al.2 15. 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. Cao and Zhang 2004.94. the greater P export from DAP was likely due not to the formation of waterinsoluble P from SSP. including ﬁeld studies.28 0.32C 0. Another possible factor may be the effect of fertilizer particle size on P runoff. should exhibit P export results similar to those of SSP. However.05 or PAPR. as explained by Nash et al.72 0.0 kg P/ha) in overland ﬂow from pasture soils in Australia were observed when P 123 . TSP. Thus.02 and 5.
The period of greatest risk for P losses from paddy ﬁelds was within 1–2 months after P application (Zhang et al. Although generally small in relation to the P fertilizer added.248 Nutr Cycl Agroecosyst (2011) 89:229–255 fertilizer was applied prior to irrigation. however. (2001) studied the inﬂuence of tillage and P placement on P losses in runoff water from a somewhat poorly drained soil (Woodson silt loam. 2008). Zhu et al. Mixing WSP fertilizers into the soil signiﬁcantly decreased P losses relative to surface P application such that DRP losses from amended. Broadcast P applications increased P losses from ridge-till to no-till systems. 2007).6 kg P/ha). and ‘‘intensiﬁed’’ from mulberry ﬁelds. 2004). Thus.1 kg/ha in 4 months). for 5 years. including mulberry. (2008) reported that P runoff losses inﬂuenced by vegetation followed an order of turf grass [ secondary forest [ sloping land [ bamboo. Effects of cropping systems on P runoff losses Phosphorus runoff losses vary greatly among cropping systems. Cao et al. decreased with time after P fertilizer application. requiring a minimum of three to 4 days without rain or irrigation to avoid excessive P losses (Bush and Austin 2001. 1998. 2005). which was two times higher than that lost from the rice–wheat rotation system (Zhang et al. Wu et al. soil P incorporation via soil mixing is not applicable to no-till cropping systems. Phosphorus lost through runoff from vegetable ﬁelds was 0. Howard et al. crop growth rates generally slowed while irrigation quotas increased. 1. ‘‘open’’ from vegetable ﬁelds. These losses are characterized by very high P concentrations. P losses in runoff often surpass P losses in farmlands. however. followed by wheat and paddy rice (0. On sloping lands in southwestern China. while summer irrigation induced little P loss. They found signiﬁcant interactions between tillage and P placement for soluble P losses. In fall. In fertilized grasslands or forests. Phosphorus loss was mostly ‘‘incidental’’ from paddy ﬁelds. Nash et al.5% slope) in a grain sorghum–soybean rotation. 2005). The order observed in this region was farmland [ artiﬁcial forest [ grassland with bushes [ secondary forest (Song et al. The greatest N and P losses occurred in the winter dry season due to irrigation in the paddy rice-rape rotation. it was found that the amount of P lost increased with P fertilizer rate. mixed soils were not signiﬁcantly different from those of un-amended soil (Kleinman et al. These losses are most commonly observed when rain events occur soon after P fertilizer is applied to the land surface. namely overland ﬂow and drain ﬂow. The rate and magnitude of soil P release to runoff and soil leachates are determined by the soil’s P sorption properties and the depth and time of soil– water contact.17 mg/l in drainage water across the growing season (Zeng et al. the inﬂuence of tillage system was inconsistent. however. vegetables. 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. It has been suggested that the time interval between P application and irrigation is crucial. 1998. 2003). and wheat-rice rotation. 2002). Phosphorus losses were greatest in mulberry ﬁelds (1. In irrigated areas in semiarid northwestern China. (2005) studied P losses from different cropping systems. 2008). In a study investigating the export of P from farmlands to the Tai Lake region of China. This minor P loss in summer was attributed to ﬂourishing crops that removed available P from soils and to the small irrigation quota imposed in the summer. Kimmell et al. incidental losses occur in rapid ﬂow pathways. and was smaller in soil with better water inﬁltration than in soil with poor inﬁltration. In the rice–wheat rotation system. 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. P losses in runoff from farmlands were much higher than from nonfarmlands that did not receive fertilizers. 2004). However. (2007) reported that P losses varied greatly with P rates and cropping systems in the Tai Lake region.0–1. where most of the soil-rainfall interaction occurs (Haygarth et al. Turtola and Yli-halla 1999). 123 . fall irrigation caused considerable P losses to drainage water. Hart et al. However. mostly in the form of dissolved P (Withers et al. 2005).27% of applied P. raising P concentrations up to 0. 1999. The lack of soil inversion in grasslands and no-till ﬁelds causes preferential accumulation of P at the surface.84 kg P/ha) and vegetables (0. A number of experiments have shown that incorporating fertilizers into the soil minimizes P loss (Withers et al. The lowest P losses occurred in the rice–wheat or rice-green manure rotation.
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 ﬁelds. oxalate. (2001) reported that in no-till corn. which correlates well with actual P uptake or crop yield. Fang et al. Pote et al. (2005) have noted. Mehlich-3. However. Some of these agronomic STP methods are also used for environmental P risk assessment because of the link between P fertilizer application. However. Daverede et al. in general. Table 12 shows some examples of the agronomic and environmental STP threshold values recommended by several of these states. (2009) afﬁrms the importance of critical source areas and hydrology in a practical P-Index when estimating risks of soil P runoff losses. The STP threshold guidelines and P recommendations vary widely among states. and P losses from agricultural lands. 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.edu/SERA_17_Publications. An environmental P workgroup (SERA-17) has been established in the United States with a stated mission to minimize P losses from agriculture. Westermann et al. Some well-known STP methods include Bray-1. publishes summaries of recent advances in research.htm. 123 . 2005). 2005). STP. That study underscores the need to better understand chronic diffuse P transport. Consequently. (1996) showed that a wide range of P tests were similarly related to P concentrations in runoff. as Maguire et al. Many states in the United States have established environmental STP threshold guidelines. Many STP methods have been developed for speciﬁc soils with a particular range of soil properties and for different cropping systems. The main advantage of using the environmental STP threshold approach over other more complex P loss assessment tools.vt. NaOH.Nutr Cycl Agroecosyst (2011) 89:229–255 249 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. which is the P fraction that contributes most directly to eutrophication in freshwater bodies affected by agricultural nonpoint-source pollution.ext. 2001). is that it is quick and inexpensive and the agronomic STP data may already be available (Maguire et al. Fixen and Grove 1990). The workgroup meets annually. and FeO strip methods to estimate soil algal-bioavailable P. Olsen. chemical. (2005) compared Bray-1. A recent report by Buda et al. (2000) reported that runoff P concentrations increased considerably when soils were more than 25–35% P saturated. They explained that this increase was related to the change from highenergy to low-energy P binding sites. and yield. Hooda et al. many researchers have reported results using this new technique (Hooda et al. Further information can be found in the website http://www. Mehlich-2. (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. most STP methods attempt to measure the socalled available soil P. Mehlich-3. 2005). A non-conventional P test using paper impregnated with iron oxide (FeO strip) to estimate bioavailable P in agricultural runoff was ﬁrst reported by Sharpley (1993). there are numerous disadvantages in using a simple STP threshold to represent complex and interactive hydrologic. 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. though few paddy soils in this area reached these values. and advises federal and state service and regulatory agencies. The peak point for P pollution risk in paddy rice ﬁelds in the Tai Lake region of China ranged from 25 to 30 mg P/kg of soil available Olsen P (Cao et al. the FeO strip method approximated algalbioavailable P most accurately. P uptake. In general. sera17. Bray-1 P soil extraction values and sediment concentrations in runoff were signiﬁcantly related to the concentrations and amounts of algal-available P and total P. particularly for calcareous soils. Mehlich-1. 2000. Among these methods. No signiﬁcant differences were observed between tillage systems for total P and algal-available P in runoff. It should be noted that. such as the P site index. Since then. develops position papers. Bundy et al. Bray-2. The most current procedure using the FeO strip to estimate bioavailable P in runoff is described by Meyers and Pierzynski (2009). and resin (Beegle 2005. 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.
[150 mg P/kg: apply no P until soil test is \150 mg P/kg [75 mg P/kg: use P Index. Adetunji MT. Smith R. By managing P applications so that they remain near the agronomic optimum. References Fig. Bolan NS (2009) Effect of organic and inorganic phosphate the critical agronomic STP value for crop yield is well below the critical environmental STP ‘‘threshold’’ for P loss (Fig. Singh BR (eds) Cadmium in soils and plants. Abekoe MK.250 Nutr Cycl Agroecosyst (2011) 89:229–255 Table 12 Soil test phosphorus (STP) threshold values and P management recommendations in several states of the US (Maguire et al. The selection of appropriate sources of P fertilizer and rates. Hedeley MJ. Dordrecht. Nolan J. 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. Together. Akintokun PO (2003) Phosphorus availability to soybean from an indigenous phosphate rock sample in soils from southern Nigeria. Arlington Aye TM. timing. Kluwer Academic Publishers. Brakebill J (2008) Differences in phosphorous and nitrogen delivery to the Gulf of Mexico from the Mississippi River Basin. Loganathan P. Steinnes E (1999) Anthropogenic additions of cadmium to soils. 5). Eur J Soil Sci 55:55–61 Agyin-Birikorang S. 2005). One is linked to agronomic considerations. Conclusions As Withers et al. In: McLaughlin MJ. these two principles provide the foundation for sustainable fertilizer use. Association of Ofﬁcial Analytical Chemists. Boyer E. Oladeji OO (2007) Enhancing the agronomic effectiveness of natural phosphate rock with poultry manure: a way forward to sustainable crop production. (2005) have pointed out two underlying principles govern the optimum use of P fertilizers. it may be possible to maintain optimum crop growth while also protecting surface water quality (Maguire et al. 2005) Agbenin JO (2004) Free energy and kinetics of dissolution of Sokoto rock phosphate and the implication for replenishing phosphorus in the savanna soil of Nigeria. Nutr Cycl Agroecosyst 79:113–123 Akintokun OO. vol I. Environ Sci Technol 42(3):822–830 Alloway BJ. 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. pp 97–123 AOAC (1999) Ofﬁcial methods of analysis. and placement of application should be carefully considered. The best practices of integrated nutrient management should be 123 . Lefroy RDB. 16th edn. such as toxic Cd accumulation in soils and eutrophication of water bodies. 5th revision. Nutr Cycl Agroecosyst 65:35–41 Alexander RB. Schwarz G. The goal of P fertilizer management is to optimize crop production while minimizing the risks of environmental impacts. while the other is linked to environmental concerns. 5 Inﬂuence of soil test phosphate (STP) on crop yield and P loss in runoff (Maguire et al.
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