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a Department of Soil Sciences, Swedish University of Agricultural Sciences, P.O. Box 7014, SE-750 07 Uppsala, Sweden
b Dipartimento di Valorizzazione e Protezione delle Risorse Agroforestali, University of Turin, Via Leonardo da Vinci 44, I-10095 Grugliasco (TO), Italy
* Corresponding author (Katarina.Borling{at}mv.slu.se).
Received for publication February 12, 2003.
| ABSTRACT |
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0.79). The CaCl2TP was also linearly related to ratios between Olsen P or P-AL and a single-point phosphorus sorption index (PSI; r2
0.86). These ratios, which are easily determined and gave good correlations with CaCl2TP, seemed to be the most useful estimates of potential P release for risk assessment systems.
Abbreviations: Alox, Feox, and Pox, ammonium oxalateextractable aluminum, iron, and phosphorus, respectively CaCl2RP, CaCl2extractable reactive phosphorus CaCl2TP, CaCl2extractable total phosphorus CaCl2UP, CaCl2extractable unreactive phosphorus DPS, degree of phosphorus saturation EPC, equilibrium phosphorus concentration Olsen P, NaHCO3extractable phosphorus P-AL, ammonium lactateextractable phosphorus PSC, phosphorus sorption capacity PSCmax, maximum phosphorus sorption capacity PSCox, phosphorus sorption capacity calculated using the equation of Börling et al. (2001) PSI, phosphorus sorption index STP, soil test phosphorus
| INTRODUCTION |
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Agronomic soil tests for P, such as Olsen P or Mehlich-3 P, are often used as an estimate of P source in risk assessment as large amounts of data are available for these methods (Sims et al., 2000). Significant correlations between STP values and P release to drainage water have been reported for individual soils (e.g., Heckrath et al., 1995; Hesketh and Brookes, 2000). However, critical STP values above which P release increases significantly can differ between soils (Hesketh and Brookes, 2000).
The soil PSC, which also influences P release, can be used in addition to STP to predict P release from soil to solution (van der Zee et al., 1990; Sharpley, 1995). The ratio of sorbed P to PSC of the soil can be estimated. If the parameters are expressed in the same units, it is possible to estimate the DPS in the soil:
![]() | [1] |
Degree of P saturation estimates how close the soil is to saturation (Sharpley, 1995) and provides possibilities to compare soils with varying P sorption capacities. It can thus be useful as an estimate of P source in risk assessment systems (van der Zee et al., 1990; De Smet et al., 1996).
Sorbed P is usually estimated using P extracted with acid ammonium oxalate solution (van der Zee and van Riemsdijk, 1988), anion exchange resin P (Sibbesen, 1978), iron-impregnated strips (van der Zee et al., 1987), or different STP methods (Sharpley, 1995; Kuo et al., 1988; Kleinman et al., 2000). The PSC can be determined from P sorption isotherms and calculations based on the Langmuir or Freundlich equations. However, some indirect methods, which are less laborious, can also be used to estimate PSC. One is based on extraction of iron (Fe) and aluminium (Al) in acid ammonium oxalate solution (Schwertmann, 1964). Another is based on a single point addition of P (Bache and Williams, 1971) from which a PSI is calculated. The PSI has been shown to be a good estimate of PSC in Swedish soils (Börling et al., 2001). Different methods of estimating sorbed P and PSC can be combined to determine DPS. In the Netherlands and several other countries, P extracted with ammonium oxalate has been used to estimate sorbed P, while Fe and Al in the same extract are used to estimate PSC. Sharpley (1995) used Melich-3 P or iron-impregnated-strip P to estimate sorbed P and sorption isotherms to estimate PSC.
The method to be used to estimate sorbed P and PSC for determination of DPS in a region or a country needs to be tested on representative soil types. Furthermore, it needs to be well correlated with measures of P concentration in the soil solution or in runoff or drainage waters (an intensity factor). Some authors measure P concentration in tile drains or runoff (e.g., Heckrath et al., 1995; Sharpley, 1995) or in lysimeter experiments (e.g., Hesketh and Brookes, 2000) while others estimate P concentration by extracting P in water to simulate runoff (e.g., McDowell and Sharpley, 2001a, 2001b) or in CaCl2 to simulate P in soil solution (e.g., Hesketh and Brookes, 2000; McDowell and Sharpley, 2001a).
The objective of this study was to identify soil variables suitable for prediction of potential P release from soil to solution to be used as a tool in a risk assessment for P leaching losses. Two soil tests for P were studied, Olsen P and P-AL, which is the most common agronomic method used in Sweden. Since few studies have been conducted on P saturation in Swedish soils, DPS or the ratio of sorbed P and an index of PSC were calculated and evaluated by combining several different methods of estimating sorbed P and PSC. In this study, P extractable in CaCl2 was used as an estimate of P release from soil to solution.
| MATERIALS AND METHODS |
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Soil Analysis
Texture was determined by the pipette sedimentation procedure as described by Ljung (1987). Soil pH was measured in water at a soil to water ratio of 1:5. Organic carbon (C) was determined by dry combustion in an E-12 CNS 2000 carbon analyzer (LECO, St. Joseph, MI). Olsen P was determined according to Olsen and Sommers (1982). The P-AL buffered solution (pH = 3.75) was determined as described by Egnér et al. (1960). The P-AL was also determined in soils sampled before the start of field experiments (initial samples) (Carlgren and Mattsson, 2001).
The ammonium oxalateextractable iron, aluminium, and phosphorus (Feox, Alox, and Pox, respectively; pH = 3) were determined according to Schwertmann (1964). Iron and aluminium in the oxalate extract were analyzed by atomic absorption spectroscopy. Phosphorus was measured colorimetrically according to Wolf and Baker (1990). Phosphorus sorption isotherms were derived from sorption data of at least nine KH2PO4 additions per soil. Two grams of air-dried soil (
2 mm) were equilibrated with 20 mL 0.01 M CaCl2 containing different amounts of P. Two drops of toluene were added to inhibit microbial activity. The tubes were shaken for 20 h at 21°C. Following centrifugation at 3000 rpm for 10 min, the equilibrium P concentration in the solution (C) was analyzed colorimetrically according to Murphy and Riley (1962). The amount of P sorbed by the soil (X), in mmol kg1 soil, was calculated by subtracting the amount of P in the equilibrium solution from the amount added. Phosphorus sorption at a single-point addition of 19.4 mmol P kg1 soil was also determined following the same procedure (Börling et al., 2001).
Soil samples were equilibrated with 0.01 M CaCl2 (1:3 w/v) at 23°C for 1 h (Schofield, 1955). Following centrifugation at 1500 rpm for 10 min, extracts were filtered through Millipore (Billerica, MA) filter paper (<0.45 µm) and P was subsequently fractionated. The CaCl2RP in the filtered solution was determined according to the green malachite method (Ohno and Zibilske, 1991). The CaCl2TP was determined after digestion in sulfuricperchloric acid (Martin et al., 1999). In brief, a 4-mL portion of the filtrate was evaporated and dried at 105°C and 1 mL H2SO4 (18 M) and 0.5 mL HClO4 (12 M) were added to the dried matter. The samples were then digested at 200°C, cooled, and diluted to 10 mL with deionized water. Phosphorus in the digestate was determined according to the malachite green method. The CaCl2extractable unreactive phosphorus (CaCl2UP) was calculated as the difference between CaCl2TP and CaCl2RP.
Sorption Isotherms and Saturation Index
The values for Pox, Feox, and Alox were used for calculating DPS according to Eq. [2]:
![]() | [2] |
= 0.5 as suggested by van der Zee et al. (1990).
The maximum phosphorus sorption capacity (PSCmax) was calculated from P sorption isotherms using the Langmuir equation in soil sampled from Level A, as these soils were not influenced by P excess (Börling et al., 2001). Also, equilibrium phosphorus concentration (EPC) was calculated for soils in Level A, using the lowest part of the sorption isotherm at P concentrations of 0 to 0.10 mg L1, where the isotherm is usually linear (Hartikainen, 1991). The EPC was defined as the P concentration in the solution at which no net sorption or desorption occurred and it was calculated as the P concentration in the equilibrium solution when P sorbed equaled zero (Hartikainen, 1991). Phosphorus sorption capacity was also calculated using the equation suggested for Swedish soils by Börling et al. (2001):
![]() | [3] |
Four different estimates of DPS (DPS-2 to DPS-5) were calculated by combining Olsen P or P-AL (recalculated in mmol P kg1 soil) with the above-mentioned methods of estimating PSC (Table 4).
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Statistical Analyses
Unless specified, all analyses were performed in triplicate. Soils were sampled from one replication in the field, which limits the ability to do statistical analysis on the differences between treatments at each site (which is not the main purpose of this study). However, differences between treatments in all soils were calculated with the nine sites as replicates and were separated by t test at 95% probability. The statistical analyses were performed using SAS (SAS Institute, 1999).
| RESULTS AND DISCUSSION |
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r2
0.99) for all soils in Level A. Values of EPC obtained were equal to or less than 0.025 mg L1. These values are low compared with those obtained by Hartikainen (1991) for five cultivated Finnish soils that did not receive any P application for seven years (EPC
0.043 mg L1). This indicates that in Level A, very small amounts of P were sorbed to the soil surfaces in agreement with the low Olsen P values and the decreases in P-AL compared with the initial samples. Hence, soils from Level A were considered depleted in P.
Total P released by CaCl2 increased with increasing STP for all soils, but the increases differed markedly between soils (Fig. 2a, 2b)
. Several authors have used this kind of relationship to calculate a change point in STP, above which P release increases more per unit STP than below (e.g., Heckrath et al., 1995). However, as this long-term field experiment only consisted of four different P levels for each soil, it was not possible to accurately calculate the change point. According to McDowell et al. (2001) at least eight points were needed to determine the change point with sufficient accuracy. Nevertheless, a visual estimate indicates that the change point was probably not reached in the four soils with greatest PSCmax (Högåsa, Ekebo, Kungsängen, and Orup) while the others had probably exceeded the change point in Levels C or D (Fig. 2a, 2b). The logarithm of CaCl2TP was linearly correlated with Olsen P (r2
0.77) and P-AL (r2
0.74) for each soil. Soils with low PSC released more P into CaCl2 solution than soils with high PSC at the same STP level (Fig. 3a, 3b)
. The CaCl2RP was related to Olsen P and P-AL in an analogous way to CaCl2TP (i.e., soils having the lowest P sorption capacities had the largest increase in CaCl2RP as soil P status increased). The results obtained in this work were similar to those obtained by Sharpley (1995). The CaCl2RP fraction represents mainly inorganic orthophosphate, though it may also contain small amounts of P hydrolyzed from organic substances or colloids (Sinaj et al., 1998; McDowell and Sharpley, 2001b). In the soils studied, reactive P was by far the main P form released at high CaCl2TP, while CaCl2UP, which represents organic P and inorganic polyphosphates (Ron Vaz et al., 1993) or colloids (Sinaj et al., 1998), was the dominant form in soils with low P status. The CaCl2UP ranged from 1.7 to 96% of CaCl2TP (Fig. 4)
. A similar decrease in relative content of unreactive P in response to increasing total P was found by McDowell and Sharpley (2001b) and Ron Vaz et al. (1993). In contrast to CaCl2RP and CaCl2TP, CaCl2UP was more or less constant from Levels A to D and was not correlated to STP. However, unreactive P measured after extraction of dried soil can partly consist of P released from lysis of microbial cells since microbes can be killed by osmotic shock after rapid rewetting (Turner and Haygarth, 2001). Thus, microbial P in the soil could be a more important factor for CaCl2UP than STP. Hence, there are good relationships between STP and CaCl2TP and CaCl2RP, but these relationships are dependent on soil P sorption properties and are therefore site specific.
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The DPS-2 and DPS-3 estimates were determined according to Eq. [1] using either Olsen P or P-AL (recalculated in mmol kg1) to estimate sorbed P while PSCmax (in mmol kg1) represented PSC (Table 4). Since PSCmax can be influenced by P fertilization (Bache and Williams, 1971), it was determined using soils from Level A, which had not received P fertilization since the start of the field experiment, and PSCmax was considered to represent maximum PSC in the soils. Like ammonium oxalate, the acid ammonium lactate solution can extract some Ca-bound phosphate. However, the complexes formed by the lactate and the acetate ions in the ammonium lactate solution are much weaker than the ones formed by the oxalic ions. The P-AL was approximately twice the amount of Olsen P. The result was that DPS values calculated with P-AL were approximately double those calculated with Olsen P. It should be kept in mind that comparison with the critical value of 25% that is usually used for DPS-1 (Breeuwsma and Silva, 1992) is not relevant, since the methods of analyses are not comparable. The CaCl2TP was exponentially correlated to DPS-2 and DPS-3 (r2
0.83; Table 4). For DPS-4 and DPS-5, PSC was determined according to Eq. [3]. Correlations with CaCl2TP gave similar results as for DPS-2 and DPS-3 with r2
0.79 (Table 4). This means that by considering PSC in addition to STP, soils with varying soil properties, such as clay content, pH, and PSC, can be compared regarding P release. The exponential relationship indicates that the strength of P bonding decreases as soils become more saturated with P (Barrow, 1978).
The ratios of Olsen P or P-AL (recalculated in mmol kg1) to PSI (mmol kg1) were also calculated. The PSI was determined in all P levels of the soils. As Levels B, C, and D were fertilized with P, sorbed P cannot be considered negligible compared with P sorption measured in Level A, and can thus affect PSI (Bache and Williams, 1971). As expected PSI decreased from Levels A to D but differences were not statistically significant (Table 3). Linear correlations were obtained when CaCl2TP was plotted against the ratios of Olsen P to PSI and P-AL to PSI for all soils (r2
0.86, significant at the 0.001 probability level; Fig. 5a, 5b)
. Since CaCl2RP constitutes the main part of TP at high soil P levels, ratios of Olsen P to PSI and P-AL to PSI were also related to CaCl2RP (Fig. 5c, 5d) and similar linear correlations were obtained (r2
0.90, significant at the 0.001 probability level).
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Both linear (Sharpley, 1995; Lookman et al., 1996) and nonlinear relationships (Kleinman et al., 2000) have been found between sorption saturation and P released in previous studies. When PSCmax or Feox and Alox were used to estimate PSC in this study, exponential relationships were obtained with CaCl2TP, while linear relationships were obtained when PSI was used to estimate PSC. Values of PSCmax or Feox and Alox were not influenced by P fertilization and gave more or less constant denominators for each site resulting in exponential relationships, while PSI gave a slightly decreasing denominator with increasing soil P level, even if differences were not statistically significant, and resulted in linear relationships.
The DPS-2 and DPS-3 estimates are valuable for understanding the relationship between DPS and P release. However, PSCmax is laborious to obtain through sorption isotherms and normally, depleted soil samples such as those from Level A are not available for PSCmax analysis, so DPS-2 and DPS-3 are not suitable in risk assessment systems. Therefore, two estimates of PSC, PSCox and PSI, which are both well related to PSCmax as shown by Börling et al. (2001), were tested. The DPS-4 and DPS-5 estimates and the ratios of Olsen P to PSI and P-AL to PSI were well correlated to CaCl2TP (r2
0.79 and r2
0.86, respectively). So, if values of Feox and Alox are available for soils, DPS-4 and DPS-5 could be a useful tool for predicting potential P release in risk assessment systems. However, since PSI is relatively easy to determine, and due to the high correlations both with CaCl2TP and CaCl2RP, the ratios Olsen P to PSI and P-AL to PSI seemed to be the most useful variables for predicting potential P release in risk assessment systems for Swedish noncalcareous soils.
| CONCLUSIONS |
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In young soils, such as those used in this study, extraction with ammonium oxalate can dissolve apatite (Uusitalo and Tuhkanen, 2000) and may thus overestimate sorbed P. Therefore, DPS based on extraction with ammonium oxalate does not seem to be a good method for the soils in this study. The DPS-2 and DPS-3 estimates were well correlated (r2
0.83) to CaCl2TP. However, since PSCmax is laborious to estimate and unfertilized plots are rarely available, the two methods did not prove to be suitable for risk assessment systems. Since DPS-4 and DPS-5 were well correlated to CaCl2TP (r2
0.79) they could be useful tools for predicting potential P release in risk assessment systems, if values of Feox and Alox are available for soils. The ratios of Olsen P to PSI and P-AL to PSI resulted in good correlations with both CaCl2TP and CaCl2RP (r2
0.86, significant at the 0.001 probability level). As those ratios are easily determined and well correlated with potential P release, their use in risk assessment systems for soils could be viable.
| ACKNOWLEDGMENTS |
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| REFERENCES |
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