Relative movement and soil fixation of soluble organic and inorganic phosphorus

There is considerable concern about pollution of surface waters with P. Although most of the research has focused on inorganic P in surface runoff, it has recently become possible to easily follow the fate of soluble organic P forms in soils and waters. Two experiments were performed to compare the relative mobility and soil fixation affinity of orthophosphate monoesters, orthophosphate diesters, and soluble inorganic P. We used three P substrates, 4-methylumbelliferyl phosphate (MUP), deoxyribonucleic acid (DNA), and KH(2)PO(4) in (i) a soil column experiment and (ii) a soil P adsorption test tube experiment. Shortly after columns were prepared, approximately two pore volumes of 0.005 M CaCl(2) were passed through 25 cm length columns containing 10 cm of loamy sand amended with approximately 10 mg P as MUP, DNA, or KH(2)PO(4) above 15 cm of nonamended loamy sand. The total net quantity of 757.8 microg P 2L(-1) of orthophosphate diesters in the leachate from the DNA columns exceeded the net quantity of orthophosphate monoesters in leachate from the MUP columns (4.6 microg P 2L(-1)) and soluble inorganic P from the KH(2)PO(4) columns (34.0 microg P 2L(-1)). Adsorption of soluble organic and inorganic P in the test tube experiment yielded similar results: DNA, containing orthophosphate diesters, had a relatively low affinity for soils. In both experiments, high concentrations of other P compounds were identified in samples treated with organic P substrates, suggesting enzymatic hydrolysis by native soil phosphatase enzymes. These findings indicate that repeated application of organic forms of P could lead to significant leaching of P to ground water.     

Sequestration of phosphorus by acid mine drainage floc

Solubilization and transport of phosphorus (P) to the water environment is a critical environmental issue. Flocs resulting from neutralizing acid mine drainage (AMD) were tested as a possible low-cost amendment to reduce the loss of soluble P from agricultural fields and animal wastewater. Flocs were prepared by neutralizing natural and synthetic solutions of AMD with limestone, lime, ammonium hydroxide, and sodium hydroxide. Phosphorus sequestration was tested in three distinct environments: water, soil, and manure storage basins. In water, flocs prepared from AMD adsorbed 10 to 20 g P kg(-1) dry floc in equilibrium with 1 mg L(-1) soluble P. Similar results were observed for both Fe-based and Al-based synthetic flocs. A local soil sample adsorbed about 0.1 g P kg(-1), about two orders of magnitude less. The AMD-derived flocs were mixed with a high-P soil at 5 to 80 g floc kg(-1) soil, followed by water and acid (Mehlich-1) extractions. All flocs performed similarly. About 70% of the water-extractable P was sequestered by the floc when applied at a rate of 20 g floc kg(-1) soil, whereas plant-available P only decreased by about 30%. Under anaerobic conditions simulating manure storage basins, all AMD flocs reduced soluble P by greater than 95% at a rate of 0.2 g floc g(-1) rainbow trout (Oncorhynchus mykiss) manure. These findings indicate that AMD flocs could be an effective agent for preventing soluble P losses from soil and manure to the water environment, while at the same time decreasing the costs associated with AMD treatment.     

XANES spectroscopic analysis of phosphorus speciation in alum-amended poultry litter

Aluminum sulfate (alum; Al(2)(SO(4))(3).14H(2)O) is used as a chemical treatment of poultry litter to reduce the solubility and release of phosphate, thereby minimizing the impacts on adjacent aquatic ecosystems when poultry litter is land applied as a crop fertilizer. The objective of this study was to determine, through the use of X-ray absorption near edge structure (XANES) spectroscopy and sequential extraction, how alum amendments alter P distribution and solid-state speciation within the poultry litter system. Our results indicate that traditional sequential fractionation procedures may not account for variability in P speciation in heterogeneous animal manures. Analysis shows that NaOH-extracted P in alum amended litters is predominantly organic ( approximately 80%), whereas in the control samples, >60% of NaOH-extracted P was inorganic P. Linear least squares fitting (LLSF) analysis of spectra collected of sequentially extracted litters showed that the P is present in inorganic (P sorbed on Al oxides, calcium phosphates) and organic forms (phytic acid, polyphosphates, and monoesters) in alum- and non-alum-amended poultry litter. When determining land application rates of poultry litter, all of these compounds must be considered, especially organic P. Results of the sequential extractions in conjunction with LLSF suggest that no P species is completely removed by a single extractant. Rather, there is a continuum of removal as extractant strength increases. Overall, alum-amended litters exhibited higher proportions of Al-bound P species and phytic acid, whereas untreated samples contained Ca-P minerals and organic P compounds. This study provides in situ information about P speciation in the poultry litter solid and about P availability in alum- and non-alum-treated poultry litter that will dictate P losses to ground and surface water systems.     

Phosphorus composition of manure from swine fed low-phytate grains: evidence for hydrolysis in the animal

Including low-phytic-acid grains in swine diets can reduce P concentrations in manure, but the influence on manure P composition is relatively unknown. To address this we analyzed manure from swine fed one of four barley (Hordeum vulgare L.) varieties. The barley types consisted of wild-type barley (CDC bold, normal barley diet) and three low-phytic-acid mutant barleys that contained similar amounts of total P but less phytic acid. The phytic acid concentrations in the mutant barleys were reduced by 32% (M422), 59% (M635), and 97% (M955) compared with that in the wild-type barley, respectively. Phosphorus concentrations were approximately one-third less in manures from animals fed low-phytic-acid barleys compared with those fed the wild-type variety. Phytic acid constituted up to 55% of the P in feed, but only trace concentrations were detected in NaOH-EDTA extracts of all manures by solution (31)P nuclear magnetic resonance (NMR) spectroscopy. Phosphate was the major P fraction in the manures (86-94% extracted P), with small concentrations of pyrophosphate and simple phosphate monoesters also present. The latter originated mainly from the hydrolysis of phospholipids during extraction and analysis. These results suggest that phytic acid is hydrolyzed in swine, possibly in the hind gut by intestinal microflora before being excreted in feces, even though the animals have little phytase activity in the gut and derive little nutritional benefit from phytate P. We conclude that feeding low-phytic-acid grains reduces total manure P concentrations and the manure P is no more soluble than P generated from normal barley diets.     

Phosphorus movement and speciation in a sandy soil profile after long-term animal manure applications

Long-term application of phosphorus (P) with animal manure in amounts exceeding removal with crops leads to buildup of P in soil and to increasing risk of P loss to surface water and eutrophication. In most manures, the majority of P is held within inorganic forms, but in soil leachates organic P forms often dominate. We investigated the mobility of both inorganic and organic P in profile samples from a noncalcareous sandy soil treated for 11 yr with excessive amounts of pig slurry, poultry manure, or poultry manure mixed with litter. Solution 31P nuclear magnetic resonance spectroscopy was used to characterize NaOH-EDTA-extractable forms of P, corresponding to 64 to 93% of the total P concentration in soil. Orthophosphate and orthophosphate monoesters were the main P forms detected in the NaOH-EDTA extracts. A strong accumulation of orthophosphate monoesters was found in the upper layers of the manure-treated soils. For orthophosphate, however, increased concentrations were found down to the 40- to 50-cm soil layers, indicating a strong downward movement of this P form. This was ascribed to the strong retention of orthophosphate monoesters by the solid phase of the soil, preventing orthophosphate sorption and facilitating downward movement of orthophosphate. Alternatively, mineralization of organic P in the upper layers of the manure-treated soils may have generated orthophosphate, which could have contributed to the downward movement of the latter. Leaching of inorganic P should thus be considered for the assessment and the future management of the long-term risk of P loss from soils receiving large amounts of manure.     

Variation in some chemical parameters and organic matter in soils regenerated by the addition of municipal solid waste

The organic fraction of a municipal solid waste was added in different doses to an eroded soil formed of loam and with no vegetal cover. After three years, the changes in macronutrient content and the chemical-structural composition of its organic matter were studied. The addition of the organic fraction from a municipal solid waste had a positive effect on soil regeneration, the treated soils being covered with spontaneous vegetation from 1 yr onwards. An increase in electrical conductivity and a fall in pH were noted in the treated soils as were increases in macronutrients, particularly N and available P and the different carbon fractions. Optical density measurements of the organic matter extracted with sodium pyrophosphate showed that the treated soils contained an organic matter with less condensed compounds and with a greater tendency to evolve than the control. A pyrolysis-gas chromatography study of the organic matter extracted with pyrophosphate showed large quantities of benzene both in the treated soils and control; pyrrole was also relatively abundant, although this fragment decreased as the dose rose. Xylenes and pyridine were present in greater quantities in the control and furfural in the treated soils. Three years after addition to the soil, the organic matter had a higher proportion of fragments derived from aromatic compounds and a smaller proportion derived from hydrocarbons. Similarity indices showed that, although the added and newly formed organic matter 3 yr after addition continued to differ from that of the original soil and to be more mineralizable, the transformations it has undergone made it more similar to the original organic matter of the soil than it was at the moment of being added.     

Soil biogeochemical characteristics influenced by alum application in a municipal wastewater treatment wetland

Constructed treatment wetlands are a relatively low-cost alternative used for tertiary treatment of wastewater. Phosphorus (P) removal capacity of these wetlands may decline, however, as P is released from the accrued organic soils. Little research has been done on methods to restore the treatment capacity of aging constructed wetlands. One possibility is the seasonal addition of alum during periods of low productivity and nutrient removal. Our 3-mo mesocosm study investigated the effectiveness of alum in immobilizing P during periods of reduced treatment efficiency, as well as the effects on soil biogeochemistry. Eighteen mesocosms were established, triplicate experimental and control units for Typha sp., Schoenoplectus californicus, and submerged aquatic vegetation (SAV) (Najas guadalupensis dominated). Alum was slowly dripped to the water column of the experimental units at a rate of 0.91 g Al m(-2) d(-1) and water quality parameters were monitored. Soil cores were collected at experiment initiation and completion and sectioned into 0- to 5- and 5- to 10-cm intervals for characterization. The alum floc remained in the 0- to 5-cm surface soil, however, soil pH and microbial parameters were impacted throughout the upper 10 cm with the lowest pH found in the Typha treatment. Plant type did not impact most biogeochemical parameters; however, data were more variable in the SAV mesocosms. Amorphous Al was greater in the surface soil of alum-treated mesocosms, inversely correlated with soil pH and microbial biomass P in both soil layers. Microbial activity was also suppressed in the surface soil of alum-treated mesocosms. This research suggests alum may significantly affect the biogeochemistry of treatment wetlands and needs further investigation.     

Chemical immobilization of lead, zinc, and cadmium in smelter-contaminated soils using biosolids and rock phosphate

Chemical immobilization, an in situ remediation method where inexpensive chemicals are used to reduce contaminant solubility in contaminated soil, has gained attention. We investigated the effectiveness of lime-stabilized biosolid (LSB), N-Viro Soil (NV), rock phosphate (RP), and anaerobic biosolid (AB) to reduce extractability and plant and gastrointestinal (GI) bioavailability in three Cd-, Pb-, and Zn-contaminated soils from smelter sites. Treated (100 g kg(-1) soil) and control soils were incubated at 27 degrees C and -0.033 MPa (0.33 bar) water content for 90 d. The effect of soil treatment on metal extractability was evaluated by sequential extraction, on phytoavailability by a lettuce bioassay (Lactuca sativa L.), on human GI availability of Pb from soil ingestion by the Physiologically Based Extraction Test. The largest reductions in metal extractability and phytoavailability were from alkaline organic treatments (LSB and NV). Phytotoxic Zn [1188 mg Zn kg(-1) extracted with 0.5 M Ca(NO3)2] in Blackwell soil (disturbed soil) was reduced by LSB, NV, and RP to 166, 25, and 784 mg Zn kg(-1), respectively. Rock phosphate was the only treatment that reduced GI-available Pb in both gastric and intestinal solutions, 23 and 92%, respectively. Alkaline organic treatments (LSB, NV) decreases Cd transmission through the food chain pathway, whereas rock phosphate decreases risk from exposure to Pb via the soil ingestion pathway. Alkaline organic treatments can reduce human exposure to Cd and Pb by reducing Zn phytotoxicity and revegetation of contaminated sites.     

Phosphorus losses in furrow irrigation runoff

Phosphorus (P) often limits the eutrophication of streams, rivers, and lakes receiving surface runoff. We evaluated the relationships among selected soil P availability indices and runoff P fractions where manure, whey, or commercial fertilizer applications had previously established a range of soil P availabilities on a Portneuf silt loam (coarse-silty, mixed, superactive, mesic Durinodic Xeric Haplocalcid) surface-irrigated with Snake River water. Water-soluble P, Olsen P (inorganic and organic P), and iron-oxide impregnated paper-extractable P (FeO-Ps) were determined on a 0.03-m soil sample taken from the bottom of each furrow before each irrigation in fall 1998 and spring 1999. Dissolved reactive phosphorus (DRP) in a 0.45-microm filtered runoff sample, and iron-oxide impregnated paper-extractable P (FeO-Pw), total P, and sediment in an unfiltered runoff sample were determined at selected intervals during a 4-h irrigation on 18.3-m field plots. The 1998 and 1999 data sets were combined because there were no significant differences. Flow-weighted average runoff DRP and FeO-Pw concentrations increased linearly as all three soil P test concentrations increased. The average runoff total P concentration was not related to any soil P test but was linearly related to sediment concentration. Stepwise regression selected the independent variables of sediment, soil lime concentration, and soil organic P extracted by the Olsen method as related to average runoff total P concentration. The average runoff total P concentration was 1.08 mg L(-1) at a soil Olsen P concentration of 10 mg kg(-1). Soil erosion control will be necessary to reduce P losses in surface irrigation runoff.     

Comparison of phosphorus forms in wet and dried animal manures by solution phosphorus-31 nuclear magnetic resonance spectroscopy and enzymatic hydrolysis

Both enzymatic hydrolysis and solution (31)P nuclear magnetic resonance (NMR) spectroscopy have been used to characterize P compounds in animal manures. In this study, we comparatively investigated P forms in 0.25 M NaOH/0.05 M EDTA extracts of dairy and poultry manures by the two methods. For the dairy manure, enzymatic hydrolysis revealed that the majority of extracted P was inorganic P (56%), with 10% phytate-like P, 9% simple monoester P, 6% polynucleotide-like P, and 18% non-hydrolyzable P. Similar results were obtained by NMR spectroscopy, which showed that inorganic P was the major P fraction (64-73%), followed by 6% phytic acid, 14 to 22% other monoesters, and 7% phosphodiesters. In the poultry manure, enzymatic hydrolysis showed that inorganic P was the largest fraction (71%), followed by 15% phytate-like P and 1% other monoesters, and 3% polynucleotide-like P. NMR spectroscopy revealed that orthophosphate was 51 to 63% of extracted P, phytic acid 24 to 33%, other phosphomonoesters 6 to 12%, and phospholipids and DNA 2% each. Drying process increased orthophosphate (8.4% of total P) in dairy manure, but decreased orthophosphate (13.3% of total P) in poultry manure, suggesting that drying treatment caused the hydrolysis of some organic P to orthophosphate in dairy manure, but less recovery of orthophosphate in poultry manure. Comparison of these data indicates that the distribution patterns of major P forms in animal manure determined by the two methods were similar. Researchers can utilize the method that best fits their specific research goals or use both methods to obtain a full spectrum of manure P characterization.     

Phosphorus concentrations in soil and subsurface water: a field study among cropland and riparian buffers

Riparian buffers can be effective at removing phosphorus (P) in overland flow, but their influence on subsurface P loading is not well known. Phosphorus concentrations in the soil, soil solution, and shallow ground water of 16 paired cropland-buffer plots were characterized during 2004 and 2005. The sites were located at two private dairy farms in Central New York on silt and gravelly silt loams (Aeric Endoaqualfs, Fluvaquentic Endoaquepts, Fluvaquentic Eutrudepts, Glossaquic Hapludalfs, and Glossic Hapludalfs). It was hypothesized that P availability (sodium acetate extractable-P) and soil-landscape variability would affect P release to the soil solution and shallow ground water. Results showed that P availability tended to be greater in crop fields relative to paired buffer plots. Soil P was a good indicator of soil solution dissolved (<0.45 microm) molybdate-reactive P (DRP) concentrations among plots, but was not independently effective at predicting ground water DRP concentrations. Mean ground water DRP in corn fields ranged from < or =20 to 80 microg L(-1), with lower concentrations in hay and buffer plots. More imperfectly drained crop fields and buffers tended to have greater average DRP, particulate (> or =0.45 microm) reactive P (PRP), and dissolved unreactive P (DUP) concentrations in ground water. Soil organic matter and 50-cm depth soil solution DRP in buffers jointly explained 75% of the average buffer ground water DRP variability. Results suggest that buffers were relatively effective at reducing soil solution and shallow ground water DRP concentrations, but their impact on particulate and organic P in ground water was less clear.     

Phosphorus flux from wetland soils affected by long-term nutrient loading

Wetland soils play a key role in the cycling of nutrients within an ecosystem. Since soils are potentially a source or a sink for inorganic nutrients, it is important to quantify their influence on overlying water quality in order to understand their importance in overall ecosystem nutrient budgets. Laboratory and field studies were performed in the northern Everglades (WCA-2A) to determine the magnitude of phosphorus (P) flux between the soil and the overlying water column, under various redox conditions. The P flux was estimated using three techniques: intact soil cores, in situ benthic chambers, and porewater equilibrators. There was reasonable agreement between the P flux estimated using intact soil cores and benthic chambers; however, P flux estimates using the porewater equilibrators were considerably lower than the other two techniques. Models of solute flux, based solely on soil physico-chemical characteristics, may substantially underestimate soil-water nutrient exchange processes. Phosphorus flux measured with the intact soil cores varied from 6.5 mg m(-2) d(-1) near nutrient inflow areas to undetectable flux 4 km away from the inflow. Oxygen consumption varied from 4 mg m(-2) d(-1) near the inflow to a constant 1 to 2 mg m(-2) d(-1) at a distance of 4 km from the inflow. Rate of consumption of NO3- -N and SO4(2-) showed no significant trend with respect to distance from inflow. Nitrate N and SO4 consumption rates averaged 120 and 130 mg m(-1) d(-1), respectively. Consumption of O2 was correlated with P flux, whereas NO3- -N and SO4(2-) consumption were not.     

Phosphorus speciation in manure-amended alkaline soils

Two common manure storage practices are stockpiles and lagoons. The manure from stockpiles is applied to soils in solid form, while lagoon manure is applied as a liquid. Soil amendment with manure in any form introduces a significant amount of phosphorus (P) that exists in both organic and inorganic forms. However, little is known about P speciation in manure stored under different conditions, or the subsequent forms when applied to soils. We used solution (31)P nuclear magnetic resonance (NMR) spectroscopy and conventional P fractionation and speciation methods to investigate P forms in dairy manure and liquid lagoon manure, and to study how long-term amendment with these manures influenced surface and subsurface soil P speciation. Our results show that the P forms in solid and lagoon manure are similar. About 30% of the total P was organic, mostly as orthophosphate monoesters. On a dry weight basis, total P was much higher in the solid manure. In the manure-amended soils the total P concentrations of the surface soils were similar, regardless of manure type. Total P in the subsurface soil was greater in the lagoon-manure-amended soil than the solid-manure-amended subsurface soil. However, the fraction of organic P was greater in the subsurface of the solid-manure-amended soil. The NMR results indicate that the majority of organic P in the soils is phytic acid, which is enriched in the surface soils compared with the subsurface soils. These results provide insight into P speciation and dynamics in manure-amended soils that will further increase our understanding on how best to manage manure disposal on soils.     

Effects of soil phosphorus status on environmental risk assessment of glyphosate and glufosinate-ammonium

The increased use of herbicides poses a risk to the aquatic environment. Easy and economical methods are needed to identify the fields where specific environment protection measures are needed. Phosphorus (P) and organophosphorus herbicides compete for the same adsorption sites in soil. In this study the relationship between P obtained in routine Finnish agronomic tests (acid ammonium acetate [P(AC)]) and adsorption of glyphosate and glufosinate-ammonium was investigated to determine whether P(AC) values could be used in the risk assessment. The adsorption of glyphosate ((N-(phosphonomethyl)glycine) and glufosinate-ammonium (2-amino-4-(hydroxymethylphosphinyl)butanoic acid) was studied in a clay and a sandy loam soil enriched with increasing amounts of P added as potassium dihydrogen phosphate. Desorption was also determined for some P-enriched soil samples. The adsorption of both herbicides diminished with increasing P(AC) value. The correlations between Freundlich adsorption coefficients obtained in the adsorption tests and P(AC) were nonlinear but significant (r > 0.98) in both soils. The exponential models of the relationship between soil P(AC) values and glyphosate adsorption were found to fit well to an independent Finnish soil data set (P < 0.1 for glyphosate and P < 0.01 for glufosinate-ammonium). The desorption results showed that glufosinate-ammonium sorption is not inversely related to soil P status, and the high correlation coefficients obtained in the test of the model were thus artifacts caused by an abnormal concentration of exchangeable potassium in soil. The solved equations are a useful tool in assessing the leaching risks of glyphosate, but their use for glufosinate-ammonium is questionable.     

Biosolids decomposition after surface applications in west Texas

In a semiarid environment, climate is a critical factor in the decomposition of surface-applied biosolids. This study examined the effect of 2- to 7-yr exposure times on the composition of single applications of New York, NY biosolids in western Texas. Exposure time effects on organic matter, N, P, S, Cu, Cr, Pb, Hg, and Zn were studied near Sierra Blanca, TX. Due to organic matter decomposition, total organic C decreased from 340 g kg(-1) in fresh biosolids to 180 g kg(-1) in biosolids after 82 mo of exposure, whereas the inorganic ash content of the biosolids increased from 339 to 600 g kg(-1). Total N decreased from 50 to 10 g N kg(-1) and total S decreased from 12 to 6 g S kg(-1). Bicarbonate-available P in the biosolids decreased from 0.9 to 0.2 g kg(-1). Successive H2O extractions yielded soluble P concentrations consistent with dicalcium phosphate (dical) for fresh biosolids and tricalcium phosphate (trical) for biosolids exposed for 59 months or more. Sparingly soluble phosphates, such as dical and trical, potentially yield > 0.5 mg P L(-1) in runoff waters for extended periods after biosolids applications, especially after multiple applications. Selective dissolution of the biosolids indicated that as much as 66 to 78% of P exists as iron phosphates, 16 to 21% as Fe oxides, and 5 to 12% as insoluble Ca phosphates. Chemical analyses of ash samples suggest that Cu and Zn have been lost from biosolids through leaching or runoff and no losses of Pb, Cr, or Hg have occurred since application.     

Phosphorus exchangeability and leaching losses from two grassland soils

Although phosphate phosphorus (P) is strongly sorbed in many soils, it may be quickly transported through the soil by preferential flow. Under flood irrigation, preferential flow is especially pronounced and associated solute losses may be important. Phosphorus losses induced by flood irrigation were investigated in a lysimeter study. Detailed soil chemical analyses revealed that P was very mobile in the topsoil, but the higher P-fixing capacity of the subsoil appeared to restrict P mobility. Application of a dye tracer enabled preferential flow pathways to be identified. Soil sampling according to dye staining patterns revealed that exchangeable P was significantly greater in preferential flow areas as compared with the unstained soil matrix. This could be partly attributed to the accumulation of organic carbon and P, together with enhanced leaching of Al- and Fe-oxides in the preferential flow areas, which resulted in reduced P sorption. The irrigation water caused a rapid hydrologic response by displacement of resident water from the subsoil. Despite the occurrence of preferential flow, most of the outflowing water was resident soil water and very low in P. In these soils the occurrence of preferential flow per se is not sufficient to cause large P losses even if the topsoil is rich in P. It appears that the P was retained in lower parts of the soil profile characterized by a very high P-fixing capacity. This study demonstrates the risks associated with assessing potential P losses on the basis of P mobility in the topsoil alone.     

Wet chemical and phosphorus-31 nuclear magnetic resonance analysis of phosphorus speciation in a sandy soil receiving long-term fertilizer or animal manure applications

In areas under intensive livestock farming and with high application rates of animal manure, inorganic and organic phosphorus (P) may be leached from soils. Since the contribution of these P compounds to P leaching may differ, it is important to determine the speciation of P in these soils. We determined the effect of various fertilization regimes on the P speciation in NaOH-Na2EDTA (ethylenediaminetetraacetic acid) and water extracts of acidic sandy soil samples from the top 5 cm of grassland with wet chemical analysis and 31P nuclear magnetic resonance (NMR) spectroscopy. These soils had been treated for a period of 11 years with no fertilizer (control), N (no P application), N-P-K, or different animal manures. Inorganic P was highly elevated in the NaOH-Na2EDTA extracts of the soils amended with N-P-K or animal manures, while organic P increased only in the soil treated with pig slurry. Water-extractable P showed a similar trend. As indicated by 31P NMR, orthophosphate monoesters were the main organic P compounds in all soils. Our results suggest that long-term applications of large amounts of P fertilizer and animal manures caused an accumulation of inorganic P, resulting in an increase of the potential risk related to mobilization of inorganic P in the top 5 cm of these soils.     

Sorption dynamics of organic and inorganic phosphorus compounds in soil

Phosphorus retention in soils is influenced by the form of P added. The potential impact of one P compound on the sorption of other P compounds in soils has not been widely reported. Sorption isotherms were utilized to quantify P retention by benchmark soils from Indiana, Missouri, and North Carolina when P was added as inorganic P (Pi) or organic P (beta-D-glucose-6-phosphate, G6P; adenosine 5'-triphosphate, ATP; and myoinositol hexaphosphate, IP6) and to determine whether soil P sorption by these organic P compounds and Pi was competitive. Isotherm supernatants were analyzed for pH and total P using standard protocols, while Pi and organic P compounds were assayed using ion chromatography. Under the controlled conditions of this study, the affinity of all soils for P sources followed the order IP6 > G6P > ATP > Pi. Each organic P source had a different potential to desorb Pi from soils, and the order of greatest to least Pi desorption was G6P > ATP > IP6. Glucose-6-phosphate and ATP competed more directly with Pi for sorption sites than IP6 at greater rates of P addition, but at the lesser rates of P addition, IP6 actually desorbed more Pi. Inositol hexaphosphate was strongly sorbed by all three soils and was relatively unaffected by the presence of other P sources. Decreased total P sorption due to desorption of Pi can be caused by relatively small additions of organic P, which may help explain vertical P movement in manured soils. Sorption isotherms performed using Pi alone did not accurately predict total P sorption in soils.     

Phosphorus leaching in relation to soil type and soil phosphorus content

Phosphorus losses from arable soils contribute to eutrophication of freshwater systems. In addition to losses through surface runoff, leaching has lately gained increased attention as an important P transport pathway. Increased P levels in arable soils have highlighted the necessity of establishing a relationship between actual P leaching and soil P levels. In this study, we measured leaching of total phosphorus (TP) and dissolved reactive phosphorus (DRP) during three years in undisturbed soil columns of five soils. The soils were collected at sites, established between 1957 and 1966, included in a long-term Swedish fertility experiment with four P fertilization levels at each site. Total P losses varied between 0.03 and 1.09 kg ha(-1) yr(-1), but no general correlation could be found between P concentrations and soil test P (Olsen P and phosphorus content in ammonium lactate extract [P-AL]) or P sorption indices (single-point phosphorus sorption index [PSI] and P sorption saturation) of the topsoil. Instead, water transport mechanism through the soil and subsoil properties seemed to be more important for P leaching than soil test P value in the topsoil. In one soil, where preferential flow was the dominant water transport pathway, water and P bypassed the high sorption capacity of the subsoil, resulting in high losses. On the other hand, P leaching from some soils was low in spite of high P applications due to high P sorption capacity in the subsoil. Therefore, site-specific factors may serve as indicators for P leaching losses, but a single, general indicator for all soil types was not found in this study.     

Effect of manure application timing, crop, and soil type on phosphorus leaching

Phosphorus (P) leaching losses from manure applications may be of concern when artificial drainage systems allow for hydrologic short-cuts to surface waters. This study quantified P leaching losses from liquid manure applications on two soil textural extremes, a clay loam and loamy sand soil, as affected by cropping system and timing of application. For each soil type, manure was applied at an annual rate of 93 800 L ha(-1) on replicated drained plots under maize (Zea mays L.) in early fall, late fall, early spring, and as a split application in early and late spring. Manure was applied on orchardgrass (Dactylis glomerata L.) in split applications in early fall and late spring, and early and late spring. Drain water was sampled at least weekly when lines were flowing, and outflow rate and total P content were determined. High P leaching losses were measured in the clay loam as soon as drain lines initiated flow after manure application. Flow-weighted mean P leaching losses on clay loam plots averaged 39 times higher (0.504 mg L(-1)) than those on loamy sand plots (0.013 mg L(-1)), and were above the USEPA level of concern of 0.1 mg L(-1). Phosphorus losses varied among application seasons on the clay loam soil, with highest losses generally measured for early fall applications. Phosphorus leaching patterns in clay loam showed short-term spikes and high losses were associated with high drain outflow rates, suggesting preferential flow as the main transport mechanism. Phosphorus leaching from manure applications on loamy sand soils does not pose environmental concerns as long as soil P levels remain below the saturation level.