Phosphorus fractions and speciation in an alkaline, manured soil amended with alum, gypsum, and Epsom salt.

Snowmelt runoff is a dominant pathway of phosphorus (P) losses from agricultural lands in cold climatic regions. Soil amendments effectively reduce P losses from soils by converting P to less soluble forms; however, changes in P speciation in cold climatic regions with fall-applied amendments have not been investigated. This study evaluated P composition in soils from a manured field with fall-amended alum (Al2(SO4)3·18H2O), gypsum (CaSO4·2H2O), or Epsom salt (MgSO4·7H2O) using three complementary methods: sequential P fractionation, scanning electron microscopy with energy-dispersive X-rays (SEM-EDX) spectroscopy, and P K-edge X-ray absorption near-edge structure spectroscopy (XANES). Plots were established in an annual crop field in southern Manitoba, Canada, with unamended and amended (2.5 Mg ha-1) treatments having four replicates in 2020 fall. Soil samples (0-10 cm) taken from each plot soon after spring snowmelt in 2021 were subjected to P fractionation. A composite soil sample for each treatment was analyzed using SEM-EDX and XANES. Alum- and Epsom salt-treated soils had significantly greater residual P fraction with a higher proportion of apatite-like P and a correspondingly lower proportion of P sorbed to calcite (CaCO3) than unamended and gypsum-amended soils. Backscattered electron imaging of SEM-EDX revealed that alum- and Epsom salt-amended treatments had P-enriched microsites frequently associated with aluminum (Al), iron (Fe), magnesium (Mg), and calcium (Ca), which was not observed in other treatments. Induced precipitation of apatite-like species may have been responsible for reduced P loss to snowmelt previously reported with fall application of amendments.

Alum reduced phosphorus release from flooded soils under cold spring weather conditions.

The effectiveness of amendments such as alum [Al2 (SO4 )3 ·18H2 O] in reducing phosphorus (P) loss to floodwater has been reported under summer conditions and laboratory-controlled environments, but not under actual spring weather conditions in cold climate regions with high diurnal temperature variations when potential for P losses is high. The effectiveness of alum in reducing P release under Manitoba spring weather conditions was evaluated in a 42-day experiment using 15-cm soil monoliths from eight agricultural soils, which were unamended or alum-amended (5 Mg ha-1 ) and flooded to a 10-cm head. Dissolved reactive P (DRP) concentrations and pH of porewater and floodwater were determined on flooding day and every 7 days after flooding (DAF). Porewater and floodwater DRP concentrations in unamended soils increased 1.4- to 4.5-fold, and 1.8- to 15.3-fold, respectively, from 7 to 42 DAF. In alum-amended soils, DRP concentrations averaged across soils was 43%-73% (1.0-2.0 mg L-1 ) lower in porewater, and 27%-64% (0.1-1.2 mg L-1 ) lower in floodwater than unamended soils during the flooding period. The reduction of DRP by alum was more pronounced under high fluctuating diurnal spring air temperature than with controlled air temperature (4°C) in a previous similar study. Acidic pH in porewater and floodwater due to alum did not persist over 7 days. This study showed that alum application is a viable option in reducing P released to floodwater in agricultural soils of cold regions where flooding-induced P loss is prevalent in the spring.

Phosphorus Release and Speciation in Manganese(IV) Oxide and Zeolite-Amended Flooded Soils.

Phosphorus (P) losses from flooded soils and subsequent transport to waterways contribute to eutrophication of surface waters. This study evaluated the effectiveness of MnO2 and a zeolite Y amendment in reducing P release from flooded soils and explored the underlying mechanisms controlling P release. Unamended and amended (MnO2 or zeolite, surface-amended at 5 Mg ha-1) soil monoliths from four clayey-alkaline soils were flooded at 22 ± 2 °C for 56 days. Soil redox potential and dissolved reactive P (DRP), pH, and concentrations of major cations and anions in porewater and floodwater were analyzed periodically. Soil P speciation was simulated using Visual MINTEQ at 1, 28, and 56 days after flooding (DAF) and P K-edge X-ray absorption near-edge structure spectroscopy and sequential fractionation at 56 DAF. Porewater DRP increased with DAF and correlated negatively with pe+pH and positively with dissolved Fe. Reductive dissolution of Fe-associated P was the dominant mechanism of flooding-induced P release. The MnO2 amendment reduced porewater DRP by 30%-50% by favoring calcium phosphates (Ca-P) precipitation and delaying the reductive dissolution reactions. In three soils, the zeolite amendment at some DAF increased porewater and/or floodwater DRP through dissolution of Ca-P and thus was not effective in reducing P release from flooded soils.

Flooding-induced inorganic phosphorus transformations in two soils, with and without gypsum amendment.

Anaerobic conditions developed during flooding can increase phosphorus (P) losses from soils to waterways. Soil amendment with gypsum (CaSO4 ·2H2 O) can effectively reduce flooding-induced P release, but its effectiveness is soil dependent, and the reasons are poorly understood. The objectives of this study were to reveal the possible inorganic P transformations during flooding of two soils (acidic-Neuenberg sandy loam [NBG-SL] and alkaline-Fyala clay [FYL-Cl]), with and without gypsum amendment prior to flooding. Porewater samples collected at 0, 35, and 70 d after flooding (DAF) from soils incubated in vessels were analyzed for dissolved reactive P (DRP); pH; and concentrations of calcium (Ca), magnesium, iron (Fe), manganese, chloride, nitrate, sulfate, and fluoride. Thermodynamic modeling using Visual MINTEQ software and chemical fractionation of soil P were used to infer P transformations. Soil redox potential (Eh) decreased with flooding and favored reductive dissolution of Fe-associated P increasing porewater DRP concentrations. Greater solubility of Ca-P under acidic pH maintained a higher DRP concentration in NBG-SL during early stages of flooding. A subsequent increase in pH with flooding and higher Ca concentration with added gypsum enhanced the stability of Ca-P (ß-tricalcium phosphate and octacalcium phosphate), reducing the DRP concentration in gypsum-amended NBG-SL. Stability of Ca-P was less affected with flooding and gypsum amendment in FYL-Cl soil because it had an alkaline pH and inherently higher Ca concentration. The FYL-Cl, with a more rapid decrease in Eh than NBG-SL, became severely reduced, releasing more P and Fe by 70 DAF. These conditions favored vivianite formation in FYL-Cl but not in NBG-SL.

Phosphorus mobilization in unamended and magnesium sulfate-amended soil monoliths under simulated snowmelt flooding.

Enhanced release of phosphorus (P) from soils with snowmelt flooding poses a threat of eutrophication to waterbodies in cold climatic regions. Reductions in P losses with various soil amendments has been reported, however effectiveness of MgSO4 has not been studied under snowmelt flooding. This study examined (a) the P release enhancement with flooding in relation to initial soil P status and (b) the effectiveness of MgSO4 at two rates in reducing P release to floodwater under simulated snowmelt flooding. Intact soil monoliths were collected from eight agricultural fields from Southern Manitoba, Canada. Unamended and MgSO4 surface-amended monoliths (2.5 and 5.0 Mg ha-1) in triplicates were pre-incubated for 7 days, then flooded and incubated (4 °C) for 56 days. Pore water and floodwater samples collected at 7-day intervals were analyzed for dissolved reactive P (DRP), pH, Ca, Mg, Fe and Mn. Redox potential (Eh) was measured on each day of sampling. Representative soil samples collected from each field were analyzed for Olsen and Mehlich 3-P. Simulated snowmelt flooding enhanced the mobility of soil P with approximately 1.2-1.6 -fold increase in pore water DRP concentration from 0 to 21 days after flooding. Mehlich-3 P content showed a strong relationship with the pore water DRP concentrations suggesting its potential as a predictor of P loss risk during prolonged flooding. Surface application of MgSO4 reduced the P release to pore water and floodwater. The 2.5 Mg ha-1 rate was more effective than the higher rate with a 21-75% reduction in average pore water DRP, across soils. Soil monoliths amended with MgSO4 maintained a higher Eh, and had greater pore water Ca and Mg concentrations, which may have reduced redox-induced P release and favored re-precipitation of P with Ca and Mg, thus decreasing DRP concentrations in pore water and floodwater.

Phosphorus release from intact soil monoliths of manure-amended fields under simulated snowmelt flooding.

Anaerobic conditions developed in soils with flooding can enhance the release of soil P to overlying water, but little information is available for soils with a long history of manure application. We examined the P release from manure-amended soils under simulated snowmelt flooding. Intact monoliths from manured (solid swine manure [SSM] or liquid swine manure [LSM]) and unamended (control) field plots were collected from Carman, Manitoba. Monoliths were frozen for 7 d, thawed, flooded, and incubated at 4 ± 1 °C. Redox potential, pH, and concentrations of dissolved reactive P (DRP), Ca, Mg, Fe, and Mn in pore water and floodwater were determined weekly up to 56 d after flooding (DAF) and at 84 DAF. Redox potential decreased with DAF with a greater and more rapid decrease in SSM (from ∼300 to <0 mV by 84 DAF) compared with LSM and control (∼100 mV by 84 DAF). Pore water and floodwater DRP concentrations were significantly greater in manured treatments than in the control at all DAFs and in SSM than in LSM for most DAF. Whereas floodwater DRP concentrations remained relatively stable in the control treatment, concentrations in manured treatments increased substantially from the onset of flooding to 35-42 DAF (threefold to fourfold increase) and remained relatively stable thereafter. Significantly greater P release from SSM- than from LSM-treated monoliths was due to greater input of P and the higher organic matter content in SSM-treated soils. These favored the rapid development of anaerobic conditions that further induced P release.

Phosphorus mobilization from intact soil monoliths flooded under simulated summer versus spring snowmelt with intermittent freeze-thaw conditions.

Enhanced phosphorus (P) release from flooded, anaerobic soils has been extensively studied under summer temperatures but not under cold temperatures with intermittent freeze-thaw events. We investigated the temperature and freeze-thaw effects during flooding on the release of P to floodwater from soil monoliths (15-cm depth) collected from eight agricultural fields in Manitoba. Soil monoliths were flooded with reverse osmosis water and incubated for 56 d under simulated summer flooding (SSF; 22 ± 1 °C) or snowmelt flooding with intermittent freeze-thaw (IFT; 4 ± 1 °C with intermittent freezing) in triplicates. Redox potential (Eh), pore water and floodwater dissolved reactive P (DRP) concentrations, pH, and concentrations of Ca, Mg, Fe, and Mn were determined weekly. In seven soils, Eh decreased rapidly with days after flooding (DAF) under SSF to values <200 mV but not under IFT. Both pore water and floodwater DRP concentrations significantly increased with DAF in all soils under SSF and in seven soils under IFT. Although DRP concentrations were consistently greater under SSF than IFT in four soils, other soils had similar concentrations at certain DAF. Significant relationships between ion concentrations and redox status that fitted both IFT and SSF data in most soils suggest that similar redox-driven mechanisms are responsible for the P release; however, less P was released under IFT than under SSF because soils were not severely reduced under IFT. Substantial P release in a few soils under IFT appeared to be unrelated to redox status, suggesting other P release mechanisms that are not redox driven.

Temperature and freezing effects on phosphorus release from soils to overlying floodwater under flooded-anaerobic conditions.

Increased phosphorus (P) availability under flooded, anaerobic conditions may accelerate P loss from soils to water bodies. Existing knowledge on P release to floodwater from flooded soils is limited to summer conditions and/or room temperatures. Spring snowmelt runoff, which occurs under cold temperatures with frequent freeze-thaw events, is the dominant mode of P loss from agricultural lands to water bodies in the Canadian Prairies. This research examined the effects of temperature on P dynamics under flooded conditions in a laboratory study using five agricultural soils from Manitoba, Canada. The treatments were (a) freezing for 1 wk at -20 °C, thawing and flooding at 4 ± 1 °C (frozen, cold); (b) flooding unfrozen soil at 4 ± 1 °C (unfrozen, cold); and (c) flooding unfrozen soil at 20 ± 2 °C (warm). Pore water and surface water were collected weekly over 8 wk and analyzed for dissolved reactive phosphorus (DRP), pH, calcium, magnesium, iron (Fe), and manganese (Mn). Soils under warm flooding showed enhanced P release with significantly higher DRP concentrations in pore and surface floodwater compared with cold flooding of frozen and unfrozen soils. The development of anaerobic conditions was slow under cold flooding with only a slight decrease in Eh, whereas under warm flooding Eh declined sharply, favoring reductive dissolution reactions releasing P, Fe, and Mn. Pore water and floodwater DRP concentrations were similar between frozen and unfrozen soil under cold flooding, suggesting that one freeze-thaw event prior to flooding had minimal effect on P release under simulated snowmelt conditions.

Predicting Phosphorus Release from Anaerobic, Alkaline, Flooded Soils.

Anaerobic conditions induced by prolonged flooding often lead to an enhanced release of phosphorus (P) to floodwater; however, this effect is not consistent across soils. This study aimed to develop an index to predict P release potential from alkaline soils under simulated flooded conditions. Twelve unamended or manure-amended surface soils from Manitoba were analyzed for basic soil properties, Olsen P (Ols-P), Mehlich-3 extractable total P (M3P), Mehlich-3 extractable molybdate-reactive P (M3P), water extractable P (WEP), soil P fractions, single-point P sorption capacity (P), and Mehlich-3 extractable Ca (M3Ca), and Mg (M3Mg). Degree of P saturation (DPS) was calculated using Ols-P, M3P or M3P as the intensity factor, and an estimated adsorption maximum based on either P or M3Ca + M3Mg as the capacity factor. To develop the model, we used the previously reported floodwater dissolved reactive P (DRP) concentration changes during 8 wk of flooding for the same unamended and manured soils. Relative changes in floodwater DRP concentration (DRP), calculated as the ratio of maximum to initial DRP concentration, ranged from 2 to 15 across ten of the soils, but were ≤1.5 in the two soils with the greatest clay content. Partial least squares analysis indicated that DPS3 calculated using M3P as the intensity factor and (2 × P) + M3P as the capacity factor with clay percentage can effectively predict DRP ( = 0.74). Results suggest that P release from a soil to floodwater may be predicted using simple and easily measurable soil properties measured before flooding, but validation with more soils is needed.