Sorption of phosphorus in field-moist and air-dried samples from four weakly developed cultivated soil profiles

Sorption of phosphorus (P) in complete soil profiles in northern Europe is not adequately documented. I measured the sorption in genetic horizons of four cultivated soils (Inceptisols, Spodosol) in Finland using both field‐moist and air‐dried soil samples, fitted modified Freundlich equations (Q = a × I^b ? q) to the data, and presented the results in quantity/intensity (Q/I) graphs. Least‐squares‐estimates for the parameters of the modified Freundlich equation (a, b, q) were found to be imprecise measures of sorption. Values derived from the fitted equations (the amount of P sorbed at the P concentration of 2 mg litre^?1 and P buffering capacity at the same concentration) were more precise. Both were correlated with concentrations of oxalate‐extractable iron and aluminium. In all soils, there was a distinct difference in sorption between the fertilized Ap horizons and the subsurface horizons, which retained P strongly. Most of the sorption capacity was located in the B horizons at depths between 0.3 and 0.7 m. The results demonstrate the effects of soil‐forming processes and human impact on the sorption of P in the soils. Drying the samples prior to the sorption experiments altered the shape of the Q/I graphs. It increased dissolution of P at small P concentrations, sorption at large P concentrations, and the estimates for P buffering capacity. The effects of drying soil samples on the results and the imprecision of the parameters estimated with the modified Freundlich equation should be taken into account when interpreting results of Q/I experiments.     

Interacting effects of cation saturation and drying, freezing, or aging on the extractability of nonylphenol and phenanthrene from a sandy soil

Purpose

The structure and properties of the soil organic matter and its interactions with solutes may be altered by changes in soil chemistry and by the aging of soil. The main objective of this study was to investigate the effect of long-term aging and cation saturation of soil on the extractability and degradability of two hydrophobic xenobiotics in soil. In addition, it was tested if drying or freezing of soils can accelerate the relevant aging processes.

Materials and methods

The sandy topsoil was treated by either 0.1?M NaCl, CaCl₂, AlCl₃ solutions or water and samples were sterilized by ??-radiation and spiked with ¹⁴C-labeled nonylphenol (NP) or phenanthrene (Phe) at 10???g?g^?1 of soil. Samples were then used in four parallel experimental setups: (1) 9?months of aging under sterile conditions, (2) inoculation by native original soil with further 7?months of aging (bioaging), (3) drying and wetting or (4) freezing and thawing of soils. After different time intervals, the extractability of xenobiotics with water, cyclodextrin, and ethanol was investigated.

Results and discussion

During 9?months of aging under sterile conditions a continuous decrease of NP and Phe extractability and an increase of the non-extractable fraction occurred. During the 7?months of biologically active aging, the mineralization of NP was lower than of Phe while more NP remained extractable than Phe. In comparison to the sterile aging, the bioaging led to a less formation of non-extractable residues of NP and Phe. The long-term sterile aging effects on NP-extractability were also achieved by short-term freezing and thawing of the soils, while aging of Phe was better mimicked by drying?Cwetting cycles. The effects of cation saturation of soils on xenobiotics extractability were less pronounced.

Conclusions

Sterile aging, bioaging, freezing, and thawing facilitate the formation of the non-extractable fraction of NP and Phe in the soils. Different cation treatments alter soil properties, but the effects on aging of NP and Phe in soils were negligible.     

Effects of soil organic matter on pH-dependent phosphate sorption by soils

Effects of soil organic matter (80M) on P sorption of soils still remain to be clarified because contradictory results have been reported in the literature. In the present study, pH-dependent P sorption on an allophanic Andisol and an alluvial soil was compared with that on hydrogen peroxide (H₂0₂)-treated, acid-oxalate (OX)-treated, and dithionite-citrate- bicarbonate (DCB)-treated soils. Removal of 80M increased or decreased P sorption depending on the equilibrium pH values and soil types. In the H₂O₂ OX-, and DCB-treated soils, P sorption was pH-dependent, but this trend was not conspicuous in the untreated soils. It is likely that 80M affects P sorption of soils through three factors, competitive sorption, inhibition of polymerization and crystallization of metals such as AI and Fe, and flexible structure of metal-80M complexes. As a result, the number of available sites for P sorption would remain relatively constant in the wide range of equilibrium pH values in the presence of 80M. The P sorption characteristics were analyzed at constant equilibrium pH values (4.0 to 7.0) using the Langmuir equation as a local isotherm. The maximum number of available sites for P sorption (Q _max) was pH-dependent in the H₂0₂-, OX-, and DCBtreated soils, while this trend was not conspicuous in the untreated soils. Affinity constants related to binding strength (K) were less affected by the equilibrium pH values, soil types, and soil treatments, and were almost constant (log K ≈ 4.5). These findings support the hypothesis that 80M plays a role in keeping the number of available sites for P sorption relatively constant but does not affect the P sorption affinity. By estimating the Q _max and K values as a function of equilibrium pH values, pH-dependent P sorption was well simulated with four or two adjustable parameters. This empirical model could be useful and convenient for a rough estimation of the pH-dependent P sorption of soils.     

Effect of the storage conditions of soil samples on carbon and nitrogen extractability

Concentrations of carbon and nitrogen extractable by 0.05 M K₂SO₄ (C_ext and N_ext, respectively) in 14 soils of different ecosystems vary from 16 to 205 and from 4 to 53 mg/kg, respectively. The portion of C_ext in soil organic matter is 0.06 to 0.38% of total carbon, and the portion of N_ext is 0.12–1.05% of total nitrogen. The storage of samples and their preparation to analysis differently affect the extractability of elements. The concentration of C_ext is less variable than the concentration of N_ext. An increase in C extractability (by 1.4–6.7 times) is a common feature of all soils under drying; at the following incubation of dried soils, the extractability of C decreases by 28–56%. The extractability of N increases not only under drying (by 1.5–7.1 times) and the following incubation of samples (by 25–60% to 2–3 times), but also under freezing of most soils and at the incubation of fresh and defrozen samples. A close direct correlation is observed between the initial water content of soil and the relative increase in C extractability under drying and N extractability under freezing and drying.     

Effects of air-drying on the adsorption and desorption of phosphate and levels of extractable phosphate in a group of acid soils,New Zealand

The effects of air-drying field-moist soils on the adsorption and desorption of added phosphate and on the levels of extractable native soil phosphate were examined using the A and B horizons of a group of four acid soils.Air-drying increased the capacity of all the soil samples to adsorb phosphate. At an equilibrium solution concentration of 0.5 μg P ml^?1, the increase in the quantity of phosphate adsorbed following drying ranged from 23% to 70% of that adsorbed by the moist samples. Considerable hysteresis in phosphate adsorption—desorption isotherms was observed for both moist and dried soil samples indicating that the additional phosphate adsorbed by the dried samples was held with the same strength as that held by the moist samples.Air-drying the soil samples caused a small decrease in soil pH of approximately 0.1 pH unit and a general increase in levels of EDTA-extractable Fe, Al and organic matter. Quantities of native soil phosphate extractable with EDTA, resin and NaHCO₃ were also increased. Concentrations of oxalate- and pyrophosphate-extractable Fe and Al and exchangeable Al were, however, unaffected by drying.It was also shown that when the phosphate content of NaHCO₃ extracts is measured using the conventional molybdenum blue method, orthophosphate plus a differing amount of acid-hydrolysable organic P present in the extract is measured.     

Phosphorus exchange properties of European soils and sediments derived from them

The sorption and desorption of phosphorus (P) from eroding soil particles in land runoff are important processes contributing to agriculturally‐driven eutrophication. We investigated the P‐exchange properties and related chemical characteristics of contrasting European agricultural soils and sediment material eroded from them under indoor (small‐scale) and outdoor (larger‐scale) rainfall simulations. Quantity‐intensity (Q/I) relationships revealed large variation in equilibrium P concentrations at zero net P sorption (EPC₀) (0–10.3 mg l⁻¹) and instantly labile P (−Q₀, the amount of P to be desorbed to obtain a P equilibrium concentration of 0 mg l⁻¹) (2–75 mg kg⁻¹), both correlating closely with Al‐bound P and the P saturation degree of Al oxides (DPS_Alox). Maximum P sorption (Q_max) (43–515 mg kg⁻¹) also correlated most closely with Al_ox. The indoor and outdoor rainfall simulations produced sediments with different P sorption properties: in the indoor simulation (less kinetic energy, constant slope), the sediments had larger EPC₀ values, and usually larger −Q₀ values, than the sediments in the outdoor simulation (greater kinetic energy, variable slopes). Furthermore, the P exchange properties of the sediments differed from those of the bulk soil depending on the enrichment of soil P‐sorption components (Fe/Al oxides, clay). The outdoor simulation indicated that sites with gentle slopes produced sediments that were more enriched with Al_ox, Fe_ox, Mn_ox and organic C than those with steeper slopes. In this study, when the bulk soil had an initial EPC₀ greater than 1.3 mg l⁻¹, the outdoor rainfall simulation produced sediment with smaller EPC₀ and vice versa, indicating that, depending on the P status of the bulk soil, the sediment material was acting as source or sink for P during transport. However, on the basis of their EPC₀ values, most eroding sediments might be expected to desorb, rather than adsorb, P when entering surface water.     

INORGANIC SOIL PHOSPHORUS

Sixteen soils and 4 soil preparations were cropped exhaustively with ryegrass in the glasshouse and monocalcium phosphate potentials (½pCa+pH₂PO₄=1) were measured after each of 6 consecutive harvests. The amounts of phosphorus (Q) removed from the soils by ryegrass accounted for 95·1–96·6 per cent of the variance in 1 for 3 soils and 2 soil preparations (P < 0·001), for 88·4–93·7 Per cent of the variance for 6 soils and 2 soil preparations (0·001 < P < 0·01), for 71·6–82·6 per cent of the variance for 3 soils (0·01 < P < 0·05) and for insignificant amounts of the variance for 4 soils. Values of ΔI/ΔQ ranged from 7 × 10^–4 to 431 × 10^–4½pCa+pH₂PO₄/ppm P removed from soil. ΔI/ΔQ tended to decrease (i.e. the soils were more buffered) with increasing clay contents and with increasing amounts of NaHCO₃-soluble P and to increase (i.e. the soils were less buffered) with increasing amounts of CaCO₃. Variations in organic C did not significantly affect ΔI/ΔQ. The following equation accounts for 81 per cent of the variance in ΔI/ΔQ for all soils except those in equilibrium with octacalcium phosphate: ΔI/ΔQ× (10⁴) = 225·9–4·17(% clay)+8·01(% CaCO₃)–1·38(ppm NaHCO₃-soluble P).     

Relationship between mineralization and immobilization of nitrogen influenced by various conditions of submerged soils

The relationship between mineralization of soil nitrogen and immobilization of added nitrogen in submerged soils were studied under various soil conditions in a laboratory experiment. Selected factors which constituted soil conditions were content of soil organic nitrogen, quantity of nitrogen addition, temperature, soil drying, puddling, and period of incubation. Each factor contained some treatments in it.

The ratio of mineralization to immobilization, M/I, was relatively constant under various soil conditions. The values of M/I were around 2 except the soil drying treatments, indicating that the amount equivalent to about half of mineralized nitrogen is immobilized simultaneously under nitrogen added condition. Even so, if considered in detail, treatments that stimulate the microbial activities were observed to have increasing effect on M/I.

The ratio of additional mineralization caused by nitrogen addition to immobilization, ΔM/I, is considered to be an index to know the influence of nitrogen addition on the quantitative change of soil nitrogen level. This value was around 1 in the soil without any application of organic matters, and around 0.6 in the soil receiving straw compost for 10 years. Factors that have close relations with the value of ΔM/I were soil organic nitrogen level, temperature, soil drying, and period of incubation.     

Low-molecular weight organic acids improve plant availability of phosphorus in different textured calcareous soils

Understanding the role of organic acids on phosphorus (P) sorption capacity of soils is very important for its economic and friendly management. Combining P application with low-molecular weight organic acids could result in its higher plant availability for prolonged time. Therefore, citric and oxalic acid (at the rate of 1.0 mM kg^?1 soil) were evaluated for their effect on P sorption capacity and its plant availability in two different textured calcareous soils. Organic acids decreased P sorption capacity and organic carbon partition coefficient (K_oc) whereas increased Gibbs free energy (ΔG) of P. Organic-acid-treated soils required lesser quantity of P fertilizer to produce soil solution P concentration optimum for plant growth (external P requirement [EPR_0.2]), that is, 0.2 mg L^?1. Citric acid was efficient than oxalic acid in the above effects. P sorption parameters of Freundlich model were negatively correlated with lime potential and ΔG whereas had positive correlation (P < 0.05) with EPR_0.2 and K_oc. Incubation with oxalic acid increased available P in loamy sand and loam soil by 20% and 30%, respectively. Thus, organic acids could help reduce application rate of P fertilizer through lowering its adsorption in highly P-fixing soils without compromise on yield.     

Effect of the soil dehydration temperature on the vapor-phase sorption of <Emphasis Type="Italic">p</Emphasis>-xylene

The effect of two methods for the preparation of soil samples for sorption experiments—hard (dehydration at 105°C) and mild (drying over P₂O₅ at 20°C in vacuum) drying—on the values of the vaporphase sorption of p-xylene was studied depending on the content of organic matter in the soil. It was shown with dark gray forest and chernozemic soils as examples that the hard drying of soil samples taken from the upper layer of the humus profile with a high content (>4%) of organic carbon decreased their sorption capacity in the range of 0–5% by 7–81%. Therefore, the method is unsuitable for these soils. It was also found that the mild method of soil preparation had obvious analytical advantages.     

Physical treatment and reinoculation of soil: Effects on microorganisms and enzyme activities

Three soils, sandy loam, clay loam, and muck were subjected to different physical treatments, reinoculated with fresh soil and the effect of these treatments on the numbers of microorganisms and soil enzyme activities was studied. Soils were subjected to air-drying, freeze-drying, freezing, dry ice-freezing, autoclaving and oven drying. The results indicated that the microbial populations increased with some of the physical treatments after 2 or 7 days incubation, while, some of the treatments decreased the populations. Air-drying the clay loam inhibited urease and phosphatase activities. None of the treatments inhibited dehydrogenase activity in either the clay loam or the muck. However, a stimulatory effect after 4 days was evident in the muck with heat treatments. Heat treatments inhibited phosphatase activity in all soils and urease activity throughout the experiment in loams, whereas after 14 days, there was a rapid recovery of urease activity in the muck soil. Autoclaving resulted in a pronounced increase in C₂H₂ reduction in the three types of soils. Heating appears to have an effect in an organic soil where the formation of 2,3,5-triphenyltetrazolium formazan (formazan) and C₂H₄ were significantly increased.     

长期不同施肥红壤磷素特征和流失风险研究

为探索长期施肥对红壤磷素吸附固持的影响,分析不同施肥土壤磷流失风险及影响因素。在南方丘陵区红壤上开展了持续25年的长期定位试验,处理包括:不施肥(CK)、施氮肥(N)、施磷肥(P)、施钾肥(K)、施氮磷钾肥(NPK1)、施2倍量氮磷钾肥(NPK2)、单施有机肥(OM)和氮磷钾配施有机肥(MNPK)。研究了不同施肥下土壤全磷、Olsen-P、Mehlich1-P、CaCl2-P含量及磷吸持指数(PSI)、磷饱和度(DPS)的变化,探讨不同施肥处理土壤对磷的吸附和解吸特征,并分析了土壤磷指标与土壤有机碳、pH、CEC之间的关系。结果表明:长期施用化学磷肥有利于补充土壤磷素,特别是土壤全磷,并使Olesn-P和Mehlich 1-P有增加趋势,而对CaCl2-P影响不显著;施用化肥对DPS影响不显著,单施磷会降低PSI,低量氮磷钾提高了PSI,高量氮磷钾处理与对照差异不显著;长期施用有机肥(猪粪)土壤全磷增加,而Olsen-P、Mehlich 1-P和CaCl2-P则大幅累积, PSI显著降低, DPS显著增加。长期施用化肥处理土壤对新添加磷的吸附较强,长期施用有机肥降低了土壤对新添加磷的吸附;土壤全磷、Olsen-P、Mehlich1-P、CaCl2-P、PSI、DPS及最大吸附容量(Qm)与土壤pH、CEC、土壤总有机碳(TSOC)、土壤水溶性有机碳[冷水提取水溶性有机碳(CWSOC)和热水提取水溶性有机碳(HWSOC)]间相关性较高;土壤磷指标和土壤有机碳、pH、CEC指标之间存在典型相关关系,第1对和第2对典型变量的典型相关系数分别为0.997和0.951,达显著水平。研究表明,施用有机肥是调节土壤磷的供给和保持的重要措施,土壤水溶性有机碳和pH可能是反映红壤磷素供应和流失的关键指标。     

Sorption of isotopically exchangeable and non-exchangeable phosphate by some soils of Colombia and Brazil, and comparisons with soils of southern Nigeria

Fourteen soils from Colombia and Brazil provided a wide range of sorption characteristics. Curves of sorbed phosphate that was exchangeable to ³²P were described by Freundlich's equation, and of non-exchangeable phosphate by Temkin's equation. Exchangeable phosphate was associated with aluminium in poorly-crystalline oxides and in organic complexes. Non-exchangeable phosphate was related to aluminium in organic complexes, and especially to the ratio of AI/C in them. In Nigerian soils similar mechanisms controlled sorption of phosphate but oxides and organic complexes of iron were important. The concentration of phosphate in solution when affinities of soil for exchangeable and non-exchangeable phosphate are equal, and the importance of organic matter, are discussed in relation to soil management and to responses of crops to fertilizer phosphate. The results indicate that sorption curves should not be split into sections.     

Factors affecting the soil sorption of iodine

Iodine-129 is an important radionuclide released from nuclear facilities because of its long radioactive half-life and its environmental mobility. Its retention in surface soils has been linked to pH, organic matter, and Fe and Al oxides. Its inorganic solution chemistry indicates I will most likely exist as an anion. Three investigations were carried out to provide information on the role of the inorganic and organic chemistry during sorption of I by soil. Anion competition using Cl^? showed that anion exchange plays a role in I sorption in both mineral and organic soils. The presence of Cl decreased the loss of I^? from solution by 30 and 50% for an organic and a carbonated sandy soil respectively. The I remaining in solution was associated primarily with dissolved organic carbon (DOC). The loss rate from solution appears to depend on two reactions of I with the soil solids (both mineral and organic) creating both a release to and a loss from solution, and the reaction of I with the DOC (from very low to high molecular weight). Composition analyses of the pore water and the geochemical modelling indicate that I sorption affects the double-charged anion species in solution the most, particularly SO₄ ^?. Iodide introduced to natural bog groundwater at three concentrations (10^?3, 10^?1 and 10 meq L^?1) remained as I^? and was not lost from solution quickly, indicating that the association of I with DOC is slow and does not depend on the DOC or I concentration. If sorption of I to soil solids or DOC is not sensitive to concentration, then stable I studies, which by necessity must be carried out at high environmental concentrations, can be linearly extrapolated to radioactive I at much lower molar concentrations.     

Effects of Soil Drying on Soil pH and Nutrient Extractability

A sample set from a field experiment conducted at two sites, a commercial organic potato farm and a conventionally managed experiment station farm, was used to compare the extractability of nutrients in field-moist and air-dried soils. Standard soil characterization methods of the Maine Soil Testing Service were used to determine soil pH and extractable nutrient content. The data were analyzed with Systat using paired t-tests. Air drying decreased soil pH and increased extractability of calcium, micronutrients, and metals. Many of the observed changes were probably a result of increasing surface acidity with drying. Drying increased the extractability of inorganic phosphorus, probably because of disruption of aluminophosphate complexes, particularly in conventionally managed soils, which had received high amounts of inorganic phosphorus fertilizer. Drying also increased the extractability of complexed phosphorus, probably both organically and inorganically complexed phosphorus, and decreased the extractability of potassium, probably by enhancing potassium fixation in clay interlayers.     

不同有机物料对黑土及其复合胶体比表面积和电荷性质的影响

通过盆栽试验研究了施用动物粪便、动物残体、草本残体、木本残体4种不同有机物料对黑土胶体及黑土阳离子交换量(CEC)的影响。结果表明:不同来源有机物料对黑土胶体及黑土CEC的影响存在差异。与CK相比,动物粪便处理下黑土胶体比表面降低7.33%,而动物残体处理下提高了59.58%,木本残体提高了57.46%,草本残体提高了100.18%。pH<6时,各处理土壤胶体表面可变电荷量(Q表面)的曲线大致相似;在pH>6时,各有机处理土壤胶体样的表面电荷(Q样)均高于CK,并且动物粪便与木本残体的Q表面曲线相似且数值较高,CK与动物残体Q表面的曲线大致相同且数值较低。在pH为8～10时,各处理Q样由大到小依次为:动物粪便>木本残体>动物残体>草本残体>CK,动物粪便土壤胶体参比的表面电荷(Q参)与动物残体Q参的曲线大致相同并且数值较高,CK与草本残体Q参曲线相似且数值较低。不同来源有机物料对黑土CEC的影响也有所不同,动物粪便、动物残体、木本残体显著提高黑土CEC,而草本残体作用不明显。     

Phosphorus sorption and availability indices as affected by properties of calcareous soils

Abstract

The Olsen solution is usually considered the best extractant for estimating P availability in calcareous soils, but predictability of the response to P fertilizers is often low under field conditions. In this study, soil characteristics influencing P sorption and extractability were evaluated. Forty‐one soils varying in CaCO₃, pH, and clay content were selected from pastures to minimize the effect of recent P additions. A P sorption index (PSI) determined from a single addition of 150 mg P/100 g soil was related to soil Ca and CaCO₃, but the correlation coefficients were rather low (r = 0.46 and 0.38, respectively). A P availability index (PAI), determined from the increase in extractable soil P after adding 50 mg P/kg to a suspension and allowing it to dry, was correlated quite well with cation exchange capacity and clay content (r = ‐0.61 for each) in soils with pH < 8.8. The PAI also had a positive relationship with the density of the processed soil sample (r = 0.60). The relationship between PAI and soil Ca (r = ‐0.51) was also better than that between PSI and soil Ca. Inclusion of initial soil P and organic carbon along with CEC increased the predictability of PAI from 37% to 59%. In soils with pH > 8.8, soil pH was the dominant factor controlling the PAI (r = 0.92).     

Potassium dynamics of a forest soil developed on a weathered schist regolith

Soils of the humid tropics are poor in available potassium due to intensive weathering and leaching of nutrients. A study was conducted to investigate the mineralogy and potassium supplying capacity of a forest soil developed on a weathered schist regolith. The quantity–intensity (Q/I) approach was used in thisstudy. The schist regolith showed deep weathering and intense leaching throughout the profile, resulting in low cation exchange capacity (CEC) and available K in soil and saprolite layers. The mineralogy of the regolith was dominanted by kaolinite, gibbsite and goethite. Feldspar, mica and mica–smectite minerals were observed in the lower saprolite layers. The Q/I parameters showed that the soils and saprolites were low in K supply power. This observation was attributed to weathering and intense leaching. The free energy values of K replacement (ΔG _r°) also suggest that soils and saprolites of the schist regolith were deficient in K. The Q/I parameters significantly correlated with organic carbon and clay content, CEC, pH and exchangeable K.     

Predicting environmental soil phosphorus limits for dissolved reactive phosphorus loss

The dependence of runoff dissolved reactive phosphorus (DRP) loss on soil test P or rapid estimations of degree of P saturation (DPS) often varies with soil types. It is not clear whether the soil‐specific nature of runoff DRP versus DPS is due to the different sorption characteristics of individual soils or the inability of these rapid DPS estimates to accurately reflect the actual soil P saturation status. This study aimed to assess environmental measures of soil P that could serve as reliable predictors of runoff DRP concentration by using soils collected from Ontario, Canada, that cover a range of chemical and physical properties. A P sorption study was conducted using the Langmuir equation  to describe amount of P sorbed or desorbed by the soil (Q_s, mg/kg) versus equilibrium P concentration (C, mg/L) in solution, where Q_max is P sorption maximum (mg/kg), k represents P sorption strength (L/mg), and Q₀ (mg/kg) is the P sorbed to soil prior to analysis. Runoff DRP concentration increased linearly with increasing DPS_sorp (i.e. the ratio of (Q₀ + Q_D)/Q_max) following a common slope value amongst soil types, while the P buffering capacity (PBC₀) at C = C₀ yielded a common change point, below which runoff DRP concentration decreased greatly with increasing PBC₀ compared to that above the change point, where C₀ and Q_D represent the equilibrium P concentration and amount of P desorbed, respectively. Both DPS_sorp and PBC₀ showed great promises as indicators of runoff DRP concentration.