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a Crop and Soil Science Dep., 512 Plant and Soil Science Bldg, Michigan State Univ., East Lansing MI 48824
b Soil and Water Science Dep., P.O. Box 110510, Univ. of Florida, Gainesville, FL 32611-0510
* Corresponding author (ooladeji{at}msu.edu).
Received for publication March 30, 2007.
| ABSTRACT |
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Abbreviations: Alox, oxalate-extractable aluminum Al-WTR, aluminum water treatment residual APSC, amendment phosphorus storage capacity DM, dry matter DPS, degree of phosphorus saturation Feox, oxalate-extractable iron PAN, plant-available nitrogen Pox, oxalate-extractable phosphorus PSR, phosphorus saturation ratio SPSC, soil phosphorus storage capacity STP, soil test phosphorus TSP, triple superphosphate WEP, water-extractable phosphorus WTR, water treatment residuals
| INTRODUCTION |
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Applications of WTR are often based on an arbitrary dry weight amendments/soil ratio, with little account taken of the chemical composition of the materials used to determine the WTR rates (Peters and Basta, 1996; Basta and Storm, 1997; Gallimore et al., 1999; Ippolito et al., 1999; Brown and Sartain, 2000; Haustein et al., 2000; Codling et al., 2002; Dayton et al., 2003; Novak and Watts, 2004). Application rates of WTR solely based on dry weight percentages (fixed soil/amendment ratio) can result in excessive or inadequate immobilization of soil soluble P depending on the amount and reactivity of Al and or Fe added in the WTRs. Determining the appropriate application rate of WTR is complicated due to the variations in chemical properties of the residuals as influenced by the source of water, treatment chemicals, and processing chemicals used by treatment plants (O'Connor et al., 2004). Properties that affect the P sorption capacity of WTR include Al, Fe, and P concentrations and metal oxide forms (amorphous and crystalline). Makris (2004) showed that WTRs had Al concentrations that ranged between 37 and 103 g kg–1 for Al-WTRs and between 1.5 and 9.8 g kg–1 for Fe-WTRs, along with varying P and Fe concentrations. Twenty-one Al-WTRs used in a study by Dayton et al. (2003) varied widely in total Al (14.7–177 g kg–1), Fe (5.02–49.9 g kg–1), and P (0.20–4.04 g kg–1) concentrations.
In a batch equilibration study that examined components of WTR that contribute to P sorption properties, oxalate extractable Al (Alox) correlated with the linearized Langmuir Pmax values (Dayton et al., 2003). Similarly, sorption capacities of various WTRs were shown by O'Connor et al. (2002) to depend on the oxalate-extractable Al, Fe, and P concentrations of the WTRs. Haustein et al. (2000) compared two Al-rich materials and their potentials to reduce runoff P from excessively P-affected fields. Material with a greater Al concentration (46.7 g kg–1), applied at 9 and 18 Mg ha–1, decreased runoff P amounts to below those of control plots throughout the 4-mo experimental period. However, at the same WTR application rates, the material with the lowest Al concentration (15.9 g kg–1) decreased the runoff P for only 1 mo. Paulter and Sims (2000) reported a relationship (r = 0.61; p = 0.01) between P sorption and amorphous Al and Fe concentrations of soils. Elliott et al. (2002) suggested that the P saturation index (which is the same as P saturation ratio [PSR]) of WTR, determined from 0.2 M oxalate extractable P, Al, and Fe concentrations (Pox, Alox, and Feox, respectively), was useful for determining WTR application rates. However, soils and P-sources that can be co-applied with WTR can also vary in Pox, Alox, and Feox. Thus, the compositional variability of soils, P-sources (if co-applied with WTR), and WTRs needs to be accounted for in determining the amount of WTR to be applied to a soil.
Potential indices of environmental P losses are the degree of phosphorus saturation (DPS) and PSR. Both DPS and PSR are calculated as ratios of Pox to the sum of Alox and Feox of the soil or amendment, but with an
-value (which depends on soil characteristics) included in the denominator for DPS calculation (van der Zee et al., 1987; Breeuwsma and Silva, 1992; Nair et al., 2004).
A recent study by Nair and Harris (2004) recommended determining the soil P storage capacity (SPSC) values rather than DPS as an index to predict the amount of additional P a soil can sorb before exceeding a threshold soil equilibrium concentration. The SPSC values can indicate the risk arising from P loadings and the inherent P sorption capacity of the soil. The SPSC values range from negative values (for highly P-affected soils) to positive values (for less P-affected soils). Zero SPSC values represent the value at which the soil PSR is at the 0.15 threshold value and above which the P concentration in soil solution increases rapidly (Nair and Harris, 2004).
A growing consensus among researchers is that if soils can be managed to maintain the soil test P (STP) at levels that optimize crop yields, the risk of offsite P transport will be minimized (Higgs et al., 2000; O'Connor and Elliott, 2006). However, this agronomic optimal needs to be determined, and its suitability as a basis for WTR application rate needs to be evaluated. Application of WTR, if based on the agronomic SPSC threshold, targets only the excess P that poses environmental threats and is not expected to negatively affect the P pools needed to meet plant P requirement.
Our objective was to identify the agro-environmental SPSC threshold value, which could serve as basis for applying WTR.
| Materials and Methods |
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5.5 g kg–1), whereas the Pompano biosolids have a moderate (
1.2 g kg–1) WEP content. One WTR (aluminum-based, obtained from Manatee Co. Water Treatment Plant, Bradenton, FL) was used in the study. The soil and the amendments (P-sources and WTR) were analyzed as reported in Oladeji et al. (2007).
Glasshouse Pot Experiments
The 5-mo glasshouse study was a three-factorial experiment arranged in a randomized complete block design with three replicates per treatment. An extra pot per block was left untreated as the control. Two application rates of the P-sources were used to attain P-based and N-based nutrient management. The application rates of P-sources equivalent to 44 kg total P ha–1 (P-based) and 179 kg plant available nitrogen (PAN) ha–1 (N-based) (Kidder et al., 2002) were calculated from the total P and N contents of the P-sources. Mineralization rates of 40% of total N in biosolids and 60% of total N in manure were assumed in the calculation, based on previous experience in similar studies (O'Connor et al., 2004). The P applied at the N-based rate varied (Table 1
) because of differences in the P/N ratios of the P-sources. The equivalent TSP fertilizer N-based rate used was 88 kg P ha–1, which was smaller than the rate of P applied when biosolids or manure are applied at an N-based rate but twice the applied P at a P-based rate. Ammonium nitrate was applied to the P-based treatments of the biosolids and manure treatments to equalize the N supplied by the amendments that differ in total N levels (Table 1). No ammonium nitrate was applied to the N-based treatments except for the TSP. Three rates of WTR application (0, 10, and 25 g kg–1 oven-dry basis) were used for the study, based on previous work (O'Connor et al., 2002). Potassium-magnesium sulfate (22% S, 18% K, and 11% Mg), equivalent to 444 kg ha–1, was added to each treatment to provide adequate and uniform S, K, and Mg. Each treatment combination was thoroughly mixed with soil (8.5 kg), wetted to the maximum water-holding capacity of the soil, and allowed to equilibrate for 1 wk before planting. The P supplied at the P-based rates was fixed, and the only variables affecting the SPSC of the P-based treatments were the Al and Fe loads of the P-source applied and the WTR rate. The P, Al, and Fe supplied at the N-based rates varied with P-sources. Hence, SPSC values of the N-based rates were affected by the P, Al, and Fe loads of the P-source applied and by the WTR rate. The wide range of soil P, Al, and Fe loads at P-based and N-based rates, with and without WTR, ensured the variability in SPSC values needed for the regression studies. All 25 treatments (including control) received the same amount of N (179 kg PAN ha–1).
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50 g) were taken with an auger of 5 cm diameter from each pot for analysis.
Phosphorus concentrations in the plant samples were determined colorimetrically (Murphy and Riley, 1962) after ashing, and digestion with 6 M HCl was performed as detailed in Jones and Case (1990). Soil samples taken were analyzed for 0.2 M oxalate-extractable P (Pox), Al (Alox), and Fe (Feox) by inductively coupled plasma atomic emission spectroscopy (Plasma 3200; PerkinElmer, Wellesley, MA) after extraction at a 1:60 soil/solution ratio (Schoumans, 2000). The SPSC values were calculated from the soil oxalate extractable P, Fe, and Al concentrations as:
![]() | [1] |
Water-extractable phosphorus was determined in the soil samples by shaking the samples with deionized water at a 1:10 soil/solution ratio for 1 h (Kuo, 1996). The P concentration in the filtered (<0.45 µm) extract was determined colorimetrically using the Murphy and Riley (1962) method.
Field Experiment
The field experiment had similar treatments as the glasshouse experiment, and the data obtained were used to validate the glasshouse experiments. The field site consisted of 51 plots (20.7 x 95 m) arranged in three blocks of 17 plots. The experimental setup, P-sources and application rates, and WTR type were identical to those used in the glasshouse study. However, unlike the glasshouse experiment where three rates of WTR applications were used, the field experiment used two application rates (0 and 10 g kg–1). The P-sources and WTR were surface applied in May 2003. Ammonium nitrate was applied to the plots that received P-based rates of the organic sources and TSP plots to equal the N supplied in treatments at N-based rates of the organic sources. The N fertilizer (22.7 kg per plot) was split applied twice (at the start of the experiment and after the first harvest 2 mo later). The amendments were applied once during the study (May 2003), but the study extended through December 2004. Soil samples from the A (0–5 cm), E, and Bh horizons of each plot were taken in June 2003 (1 mo), January 2004 (8 mo), and December 2004 (19 mo) after treatments were surface applied. The samples were analyzed for WEP, Pox, Alox, and Feox, and the SPSC was calculated for each soil sample as described for the glasshouse study. The test plant (established bahiagrass) was harvested twice (July and October) in 2003 and four times (July, August, October, and November) in 2004 from each plot, and the DM yields and tissue P concentrations were determined for each harvest. Grass cuttings were obtained by laying out a 1 by 1 m frame on each plot and cutting all the grass within the frame with hand shears to a height of 5 cm above the ground surface. Bahiagrass cuttings were placed in pre-weighed bags and dried for several days to constant weight at 65°C. Phosphorus concentrations were measured in samples of each plant harvest as described in the glasshouse study, and P uptake was calculated as the product of the P concentration and plants yield. Weighted P concentrations was determined for 2003 and 2004 harvests as total P uptake divided by total DM yield for each year.
Statistical Analysis
Analysis of variance (ANOVA) was performed on SPSC values calculated for the two sets of soil samples collected during the glasshouse experiment and three samples from the field experiment. Differences among treatments were analyzed as a three-way factorial experiment with a randomized complete block design, using the PROC GLM procedure of the SAS software (SAS Institute, 1999). Means of the various treatments were separated using contrast or Tukey test at a significance (
) level of 0.05. Regression between soil WEP and SPSC values was used to determine the environmental thresholds and between plant P concentrations and SPSC to determine the agronomic threshold. The critical plant P concentrations and SPSC values (change point) were identified using the Cate-Nelson method (Cate and Nelson, 1971).
| Results and Discussion |
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7.6 (Table 3
), whereas the WTR had a pH of 5.6. The WTR total Al concentration was 157 g kg–1, >90% (145 g kg–1) of which was amorphous (0.2 M ammonium oxalate extractable) (McKeague et al., 1971). Total P was greatest for Boca Raton biosolids (47.3 g kg–1), representing the upper limit of P concentrations typically found in biosolids produced nationally (USEPA, 1995). The poultry manure had the least total P but had a moderately high WEP and a greater percentage of WEP than in either biosolid. The WEP values of the organic sources were greatest in the Boca Raton biosolids (5.52 g kg–1), followed by poultry manure (4.57 g kg–1) and Pompano biosolids (1.16 g kg–1). A greater portion of total P in manure is water soluble, as indicated by greatest percentage of WEP in manure (18%), followed by Boca Raton biosolids (11%) and Pompano biosolids (4%). Total and oxalate Al and Fe concentrations were smaller in manure than in the two biosolids, but manure total Ca concentration was greater than in the biosolids. The greater Ca in manure likely results from Ca-rich additives in the animal feeds, the greater part of which is excreted in the manure (Nair et al., 1998). The greater Pox and smaller Feox and Alox values of Boca Raton biosolids resulted in a greater PSR (1.44) value than for Pompano biosolids (0.7) (Table 3). A PSR >1.25 was identified as a critical value for biosolids P loss in a leaching study by Elliott et al. (2002) and is consistent with the greater water-soluble P measured in Boca Raton biosolids. The greater PSR of the Boca Raton biosolids suggests greater P lability than in Pompano biosolids. Phosphorus sources with larger PSR values are expected to have lower SPSC (or negative values) when applied at equal P rates than those with smaller PSR values. The amendment P storage capacity (APSC; equivalent to SPSC in soil) of the Al-WTR is positive due to a large Al concentration (Table 3). Total P and N concentrations, the basis for the application rates, were greatest in Boca Raton biosolids and least in poultry manure. These differences affected the P, Fe, and Al loads and resulted in different SPSC values of the soils amended with different P-sources at P- or N-based rates. The SPSC values of the surface soils (0–5 cm) from the field and the samples taken during the glasshouse study were affected by the WTR, P-source, and P-source rate at p = 0.05 (ANOVA; data not shown).
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The addition of WTR increased P storage capacity for all P-source treatments applied at P- or N-based rates. However, SPSC values were greater at the P-based than at the N-based rates when an equal amount of WTR was applied with each P-source. Varying amounts of WTR are needed depending on the source PSR to achieve equal SPSC values for soils treated with various P-sources. The variations in SPSC values could be adjusted by applying WTR based on the desired SPSC value.
Values of SPSC at time zero increased with WTR addition in all samples taken during the study (Fig. 1) due to reduction in soil P:Al+Fe ratio (PSR) of the soil. The SPSC values at the P-based rate (without WTR) were close to 0 mg P kg–1, confirming the rate (P-based) as environmentally friendly. Negative SPSC values (an indication of P in excess of soil P sorption capacity) were observed at the N-based rates (without WTR) and at 10 g kg–1 WTR time final samples, except for the TSP treatment. Negative SPSC values at the N-based rates of P-sources indicated the soils received excess P and is consistent with other studies reporting that N-based rates of residuals load soils with excess P that could cause negative environmental impact (Reddy et al., 1980; Pierzynski, 1994; Peterson et al., 1994; Maguire et al., 2000). The SPSC values were increased by the addition of 25 g WTR kg–1 to the N-based rate of all P-sources and by 10 g WTR kg–1 in some treatments (Fig. 1).
The SPSC values of field samples taken in June 2003, January 2004, and December 2004 from the soil A-horizons during the field study are shown in Fig. 2
. The soil chemistry of subsurface horizons was unaffected by the surface-applied treatments, and E and Bh horizons had similar SPSC values in all treatments (data not shown). The SPSC values of the E-horizon soil samples were similar, negative, and approximately zero and indicate saturation with P and an inability to hold added P. The SPSC values of the Bh horizon soils were positive and similar (
147 mg kg–1) for all treatments. Positive SPSC values were expected for the Al-rich Bh horizon. Other researchers have noted high P-retention capacity in the spodic Bh horizon in Spodosols compared with surface A and E horizons (Mansell et al., 1991; Nair et al., 1998; Nair et al., 2004).
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Soil P Storage Capacity, Soluble P, and Plant Growth
Plant yields and tissue P concentrations varied with P-sources, P-source application rates, and the amounts of WTR added (data not shown). For most of the P-sources and at either application rate, plant yields and tissue P concentrations values were greatest in the absence of WTR and least with the 25 g WTR kg–1 soil treatment.
Soil soluble P, as indicated by the WEP values, increased as soil SPSC values decreased in the glasshouse study (Fig. 3a ). However, the rate of change in the WEP values with SPSC (slope) was greater for soils with negative SPSC values than for soils with positive SPSC values and suggests a change point at zero SPSC value (Fig. 3). Similar trends were obtained with the field data (Fig. 3b). Thus, applications of the P-sources and/or WTR to achieve zero or positive SPSC values were accompanied by minimal soil soluble P and could be considered environmentally friendly.
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Zero SPSC values have been suggested (Nair and Harris, 2004) as a conservative environmental threshold and could be recommended because the agro-environmental threshold based on the rationale that agronomic threshold is below the environmental threshold. No negative agronomic impact is expected at the environmental threshold, which is typically 3 to 4 times greater than agronomic threshold (O'Connor and Elliott, 2006). Thus, STP can be maintained at levels that optimize crop yields while minimizing the risk of offsite P transport (Higgs et al., 2000). This can be achieved through WTR application based on the agronomic threshold.
The range of bahiagrass P concentrations (1.5–6 g kg–1) encompasses the critical P concentration value of
2.0 g kg–1 identified by a Cate-Nelson type of approximation (Fig. 4
) (Cate-Nelson, 1971). The critical (agronomic threshold) P concentration can be defined as the concentration above which there is no plant yield response to increased P concentration. Below a P concentration of 2.0 g kg–1, the bahiagrass DM yield was reduced, and little or no response in the plant DM yield to increasing P concentrations was observed above a P concentration of 2.0 g kg–1. Kincheloe et al. (1987) indicated that tissue P concentrations of 2 to 4 g kg–1 are within a range sufficient for grass production, but the 1.6 to 1.7 g kg–1 P concentrations observed in pastures (which include bahiagrass) by Adjei et al. (2000) were considered limiting values.
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The glasshouse data suggest that by applying a P-source, WTR, or both to attain a zero SPSC value, sufficient P concentrations in the plant for growth are ensured without causing negative environmental impacts. Similarly, a zero SPSC value ensured plant P concentrations of 2 g kg–1 in the field study (Fig. 4c). A SPSC value of zero could serve as an agronomic threshold and a basis for determining the rates of WTR to be applied. Thus, P-sources can be applied at any rate without negative environmental impact if sufficient WTR is applied to achieve an amended soil SPSC value of zero. Applying WTR to attain a SPSC soil value of zero maintains soil soluble P values below the environmental change point but above the optimum plant P concentration. Application rates of WTR based on desired soil SPSC values ensure applying the amount needed for optimum plant growth with no risk of excessive P immobilization.
The SPSC and APSC values can be used to determine the amount of WTR needed to be applied to a P-affected soil or to be co-applied with the P-sources. The SPSC-based rate can account for the P, Al, and Fe concentrations in the residuals and the soil and the (environmental) threshold soil P value. Thus, the WTR rate required to attain a desired SPSC value can be calculated to ensure a soil P concentration below the environmental threshold as well as sufficient plant available P. Similar to the SPSC, the APSC of the P-sources (APSCsource) and WTR (APSCWTR) can be calculated as in Eq. [2].
![]() | [2] |
![]() | [3] |
The SPSC values expected and observed in time zero soil samples of each treatment at the three rates of WTR in the glasshouse study are shown in Table 4 , along with estimated amounts of WTR needed to achieve SPSC value of 0 mg kg–1 at the two rates of the four P-sources. At the P-based rate, applying at least 10 g kg–1 WTR gave measured and observed SPSC values greater than zero for all the P-sources, which indicates that more WTR was applied than necessary. However, N-based rates <25 g kg–1 but >10 g kg–1 WTR were indicated by the measured SPSC values as needed by manure, Pompano, and TSP treatments. The measured SPSC also suggested that >25 g kg–1 WTR is needed by Boca Raton biosolids to achieve a SPSC value of 0 mg kg–1. Estimated SPSC values (expected) differed from the observed values and suggested that <10 g kg–1 is needed in all the treatments except at N-based rate of Boca Raton biosolids. For this treatment, >10 g kg–1 but <25 g kg–1 WTR is expected to give a zero SPSC value. Further study may be needed to explain the differences between the observed and the expected SPSC values. However, among the reasons that could explain the differences is the inability to achieve thorough mixing of amendments with soil despite daily mixing during the 1-wk incubation period (before time zero sampling). For example, pellets of undissolved TSP were observed in the time zero samples during the analysis. Also, reaction of the oxalate extractant with Ca in Ca-rich amendments such as manure and TSP can reduce the measured Pox, Alox, and Feox (Loeppert and Inskeep, 1996) and can contribute to the differences in expected and observed SPSC values. Nevertheless, the SPSC values estimated using Eq. [3] related well with the observed SPSC values at time zero (r2 = 0.8; p < 0.05) and support the use of SPSC as a basis for WTR rate determination.
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| Summary and Conclusions |
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The application rate of WTRs required to minimize negative agronomic and/or environmental impacts depends on the soil; WTR; and P-sources Al, P, and Fe composition. A WTR with greater oxalate Al and Fe concentrations results in greater SPSC values and, hence, lower soil soluble P concentrations than WTRs with lower Al concentrations. Application rates of WTR based on a desired soil SPSC value ensure applying the amount of amendment needed to control P loss without the risk of excessive plant-available P immobilization. The zero soil SPSC value was identified as the critical point above which the plant P concentrations can be sufficiently reduced to decrease plant yields and below which the soil soluble P (and hence potential P loss) may increase. Amendment P storage capacity, an equivalent term of SPSC for the P-sources, needed for the calculation of WTR rate was also suggested. Glasshouse and field data show that applying P-sources and WTR to attain zero SPSC values optimizes agronomic and environmental benefits of the residuals.
| ACKNOWLEDGMENTS |
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| NOTES |
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| REFERENCES |
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