Phosphorus speciation in cultivated organic soils revealed by P K‐edge XANES spectroscopy

Cultivated organic soils make a significant contribution to phosphorus (P) leaching losses from agricultural land, despite occupying a small proportion of cultivated area. However, less is known about P mobilisation processes and the P forms present in peat soils compared with mineral soils. In this study, P forms and their distribution with depth were investigated in two cultivated Histosol profiles, using a combination of wet chemical extraction and P K‐edge X‐ray absorption near‐edge structure (XANES) spectroscopy. Both profiles had elevated P content in the topsoil, amounting to around 40 mmol kg^?1, and P speciation in both profiles was strongly dominated by organic P. Topsoils were particularly rich in organic P (P‐org), with relative proportions of up to 80%. Inorganic P in the profiles was almost exclusively adsorbed to surface reactive aluminium (Al) and iron (Fe) minerals. In one of the pro‐files, small contributions of Ca‐phosphates were detected. A commonly used P saturation index (PSI) based on ammonium‐oxalate extraction indicated a low to moderate risk of P leaching from both profiles. However, the capacity of soil Al and Fe to retain P in organic soils could be reduced by high competition from organic compounds for sorption sites. This is not directly accounted for in PSI and similar indices. Accumulation of P‐org in the topsoil may be attributable by microbial peat decomposition and transformation of mineral fertiliser P by both microbiota and crops. Moreover, high carbon–phosphorus ratio in the surface peat material in both profiles suggests reduced net mineralisation of P‐org in the two soils. However, advancing microbial peat decomposition will eventually lead to complete loss of peat horizons and to mineralisation of P‐org. Hence, P‐org in both profiles represents a huge potentially mobilised P pool.     

长期日光温室试验条件下不同施肥处理对土壤团聚体稳定性和铁铝氧化物含量的影响

Soil in greenhouses is likely to suffer a gradual decline in aggregate stability. Determination of the effects of different fertiliser practices on soil aggregate stability is important for taking advantage of solar greenhouses. Soil aggregate stability and iron(Fe) and aluminium(Al) oxide contents were investigated in a 26-year long-term fertilisation experiment in greenhouse in Shenyang, China,under eight fertiliser treatments: manure(M), fertiliser N(FN), fertiliser N with manure(MN), fertiliser P(FP), fertiliser P with manure(MP), fertiliser NP(FNP), fertiliser NP with manure(MNP), and control without any fertiliser(CK). A wet sieving method was used to determine aggregate size distribution and water-stable aggregates(WSA), mean weight diameter and geometric mean diameter as the indices of soil aggregate stability. Different fertiliser treatments had a statistically significant influence on aggregate stability and Fe and Al oxide contents. Long-term application of inorganic fertilisers had no obvious effects on the mass proportion of aggregates. By contrast, manure application significantly increased the mass proportion of macroaggregates at the expense of microaggregates. All treatments, with the exception of FNP, significantly increased the stability of macroaggregates but decreased that of microaggregates when compared with CK. Aggregation under MP and MN was better than that under M and MNP; however,no significant differences were found among inorganic fertiliser treatments(i.e., FN, FP, and FNP). A positive relation was found between pyrophosphate-extractable Fe and WSA(r = 0.269), but no significant relations were observed between other Fe and Al oxides and aggregate stability.     

巢湖低丘山区典型植被覆盖类型土壤磷形态分异特征

以巢湖低丘山区为研究对象,分析了该地区5种典型植被覆盖类型表层土壤磷素含量与形态特征及其影响因素.结果表明:次生马尾松林有机碳、总氮、速效氮、总磷与速效磷均高于其他样地,尾矿裸地养分含量为最低,但酸度最大.5种样地0～5、5～10与10～20 cm 3个土层弱吸附态磷(Ex-P)和钙结合态磷(Ca-P)含量均较低,灌木林与次生马尾松林土壤活性态磷[铝结合态磷(Al-P)与铁结合态磷(Fe-P)]含量显著高于其他样地,而惰性态磷[闭蓄态磷(O-P)、钙结合态磷(Ca-P)与残余磷(Res-P)]则以地上群落结构较稳定的草地和次生马尾松林最高,其中5～10 cm土层残余磷(Res-P)含量则以人工恢复林最高.3个土层尾矿裸地各形态磷含量均显示较低水平,但其Fe-P、Al-P含量在总磷中所占比例高于其他样地,所以流失危害大.土层间Ex-P、Al-P、O-P、Ca-P与TP含量均随土层的加深而降低,但Fe-P与Res-P含量在土层间规律不明显.相关分析表明土壤Res-P与其他形态磷间具有显著的正相关关系,“活化磷”,即Ex-P、Fe-P、Al-P三者间也存在显著正相关关系.土壤养分与磷的各种形态显示了良好的正相关关系,但速效磷与O-P、Res-P呈显著负相关关系.     

Forms and pedogenetic distribution of extractable iron and aluminum in selected soils of Nigeria

The content of various forms of Fe and Al in six well-drained soil profiles sampled from different parts of Nigeria was determined by selective extraction methods. Dithionite-Fe (total free Fe oxides) content increases with the increase of depth. The oxalate-extractable Fe (amorphous Fe oxides) constitutes less than 10% of the total free Fe oxides throughout the profiles. The active Fe ratio decreases with the increase of profile depth, suggesting that larger proportions of Fe oxides are present as crystalline forms in the lower horizons of these well-drained profiles. Little or no relationships were found in the case of Al.The constant clay/dithionite-Fe ratio within the four profiles from the wetter southern part of Nigeria indicates the co-migration of clay and Fe oxides from the A horizon into the B horizon (lessivage). However, this relationship was not observed in the two soil profiles sampled from the drier northern part of the country.The need for expansion or alteration of the present U.S.D.A. system of soil classification is emphasized.     

向海湿地土壤中无机磷酸盐的存在形态研究

对由向海湿地采集的土壤样品进行了无机磷酸盐形态 (吸附态磷、铝磷、铁磷、闭蓄态磷、钙磷 )分析 ,结果表明 ,钙磷是无机磷酸盐的主要组成部分 ,在各土壤发生层中含量最高 ;除吸附态磷外 ,其它各形态的磷含量总体上有随土壤深度增加而逐渐减少的趋势。铝磷、铁磷、闭蓄态磷受 p H值的影响显著 ,与 p H值呈显著负相关 ,而吸附态磷与钙磷含量则受 p H值的影响甚微。     

Transformation of added phosphorus to acid upland soils with different soil properties in Indonesia

Abstract

The transformation of added phosphorus (P) to soil and the effect of soil properties on P transformations were investigated for 15 acid upland soils with different physicochemical properties from Indonesia. Based on oxide-related factor scores (aluminum (Al) plus 1/2 iron (Fe) (by ammonium oxalate), crystalline Al and Fe oxides, cation exchange capacity, and clay content) obtained from previous principal component analyses, soils were divided into two groups, namely Group 1 for soils with positive factor scores and Group 2 for those with negative factor scores. The amounts of soil P in different fractions were determined by: (i) resin strip in bicarbonate form in 30 mL distilled water followed by extraction with 0.5 mol L^?1 HCl (resin-P inorganic (P_i) that is readily available to plant), (ii) 0.5 mol L^?1 NaHCO₃ extracting P_{i and} P organic (P_o) (P which is strongly related to P uptake by plants and microbes and bound to mineral surface or precipitated Ca-P and Mg forms), (iii) 0.1 mol L^?1 NaOH extracting P_i and P_o (P which is more strongly held by chemisorption to Fe and Al components of soil surface) and (iv) 1 mol L^?1 HCl extracting P_i (Ca-P of low solubility). The transformation of added P (300 mg P kg^?1) into other fractions was studied by the recovery of P fractions after 1, 7, 30, and 90 d incubation. After 90 d incubation, most of the added P was transformed into NaOH-P_i fraction for soils of Group 1, while for soils of Group 2, it was transformed into resin-P_i, NaHCO₃-P_i and NaOH-P_i fractions in comparable amounts. The equilibrium of added P transformation was reached in 30 d incubation for soils of Group 1, while for soils of Group 2 it needed a longer time. Oxide-related factor scores were positively correlated with the rate constant (k) of P transformation and the recovery of NaOH-P_i. Additionally, not only the amount of but also the type (kaolinitic) of clay were positively correlated with the k value and P accumulation into NaOH-P_i. Soils developed from andesite and volcanic ash exhibited significantly higher NaOH-P_i than soils developed from granite, volcanic sediments and sedimentary rocks. Soil properties summarized as oxides-related factor, parent material, and clay mineralogy were concluded very important in assessing P transformation and P accumulation in acid upland soils in Indonesia.     

Mechanisms controlling the mobility of dissolved organic matter, aluminium and iron in podzol B horizons

The processes governing the (im)mobilization of Al, Fe and dissolved organic matter (DOM) in podzols are still subject to debate. In this study we investigated the mechanisms of (im)mobilization of Al, Fe and organic matter in the upper and lower B horizons of two podzols from the Netherlands that are in different stages of development. We equilibrated batches of soil material from each horizon with DOM solutions obtained from the Oh horizon of the corresponding soil profiles. We determined the amount of (im)mobilized Al, Fe and DOM after addition of Al and Fe at pH 4.0 and 4.5 and initial dissolved organic carbon (DOC) concentrations of 10 mg C litre^?1 or 30 mg C litre^?1, respectively. At the combination of pH and DOC concentrations most realistic for the field situation, organic matter was retained in all horizons, the most being retained in the lower B horizon of the well‐developed soil and the least in the upper B horizon of the younger profile. Organic matter solubility seemed to be controlled mainly by precipitation as organo‐metal complexes and/or by adsorption on freshly precipitated solid Al‐ and Fe‐phases. In the lower B horizons, at pH 4.5, solubility of Al and Fe appeared to be controlled mainly by the equilibrium with secondary solid Al‐ and Fe‐phases. In the upper B horizons, the solubility of Al was controlled by adsorption processes, while Fe still precipitated as inorganic complexes as well as organic complexes in spite of the prevailing more acidic pH. Combined with a previous study of eluvial horizons from the same profiles, the results confirm the important role of organic matter in the transport of Al and Fe to create illuvial B horizons initially and subsequently deepening and differentiating them into Bh and Bs horizons.     

Neutral Ammonium Citrate Extraction of Biosolids Phosphorus

Abstract

Matching biosolids application rates to crop phosphorus (P) needs requires quantifying the P fertilizer replacement value of biosolids. Neutral ammonium citrate (NAC) extraction of P, used for assessing available P in mineral fertilizers, was evaluated for 35 different biosolids. Biosolids NAC‐P was not statistically different (p=0.05) from total P using strong acid digestion (EPA 3051‐P). High P recovery by NAC was attributed to dissolution of P‐containing iron (Fe)/aluminum (Al) oxides under the aggressive extracting conditions (0.88 M citrate at 65°C). Citrate effectively dissolves P‐binding Fe/Al hydrous oxides, the very components that reduce phytoavailability when biosolids are land applied. Greenhouse studies with pasture grass (Paspalum notatum Flugge) grown in P‐deficient soils amended with biosolids revealed P phytoavailability was not correlated (r²=0.10) with biosolids NAC‐P. Phytoavailability was inversely correlated (r²=0.66) with biosolids total Al+Fe content. The NAC extraction, designed for commercial fertilizers, is inappropriate for quantifying biosolids phytoavailable P.     

长期施肥条件下设施栽培土壤无机磷组分及其剖面分布特点

采用张守敬和Jackson(1957年)提出的土壤无机磷分组测定方法,对施肥17年的蔬菜保护地土壤无机磷的形态及其剖面分布规律进行了研究。结果表明,土壤无机磷组分及其剖面分布受施入的有机肥影响较大。施有机肥组(A组),土壤中O-P含量占无机磷总量百分数最高,平均为35%～47%;不施有机肥组(B组),土壤中Ca-P含量占无机磷总量百分数最高,平均为29%～39%。长期施用有机肥能够增加20cm以下土层中无机磷含量;施有机肥组(A)和不施有机肥组(B)各处理土壤不同形态无机磷含量均随土层加深而逐渐降低,但在0～60cm土层内,有机肥组不同形态无机磷含量均高于不施有机肥组。长期施用磷肥会增加土壤中无机磷的积累量,而且有效性较高的Ca-P、Al-P积累程度高于较稳定的O-P、Fe-P积累程度。     

Phosphorus Availability and Transformation as Affected by Repeated Phosphorus Additions in an Ultisol

Phosphorus (P) solubility and transformation in soils determine its availability to plants and loss potential to the environment, and soil P dynamics is impacted by fertilization and soil properties. A Ultisol sample was interacted with 20 mg L^?1 P solution from one to ten times. The P-reacted soils were then analyzed for water-soluble P (0.01 M calcium chloride (CaCl₂)–extractable P); plant-available P (Olsen P); ammonium chloride P, aluminum P, iron P (NH₄Cl-P, Al-P, Fe-P, respectively); and occluded P (Oc-P). The degree of P saturation (DPS) was calculated from ammonium oxalate–extractable Al, Fe, and P. The amount of P sorbed by the soil was highly correlated with the frequency of P addition with high percentage of P adsorbed initially and gradually decreased as the P addition continued. The relative abundance of the five P fractions in the P-reacted soil was in the order of Fe-P (36.5 percent) > Al-P (35.6 percent) > Oc-P (22.8 percent) > Ca-P (2.7 percent) > NH₄Cl-P (2.3 percent). Both Olsen P and CaCl₂-P were significantly increased by the repeated P addition process and highly correlated in an exponential function. The DPS was increased above the so-called critical point of 25 percent after the first P saturation process and kept increasing as the P addition continued. The P availability and adsorption in the soil were controlled by soil free and amorphous Al and Fe. The results suggest that repeated P application will build soil P to an excessive level, and consequently result in poor P-use efficiency and high P-loss potential to surface and groundwater.     

模拟淋溶条件下沼液对菜田土壤磷素淋洗及其形态的影响

以不同磷水平菜田土壤为研究对象,通过土柱淋溶模拟试验,探讨施用沼液对土壤磷素形态及其移动性的影响。结果表明:与单施去离子水的对照相比,施用沼液通过减少淋洗溶液体积降低淋洗液中总磷含量722.3μg·柱~(-1),中、高磷土壤淋洗液总无机磷(TIP)分别减少507.2μg·柱~(-1)和1 319μg·柱~(-1)。低、中磷土壤淋洗液中水溶性无机磷(DIP)减少158.1μg·柱~(-1)和474.3μg·柱~(-1)。在低磷土壤中,施用沼液对剖面土壤全磷、有机磷和速效磷含量影响显著,上层(0~7 cm)土壤增加的比例分别为34.8%、37.7%和148%,土壤p H值显著降低0.39个单位,下层(7~14 cm)土壤增加的比例分别为18.5%、29.3%和32.9%,土壤p H值显著降低0.28个单位。在中磷土壤中,施用沼液对上层土壤全磷含量影响未达到显著水平,速效磷增加比例20.1%,下层土壤p H值降低0.33个单位。在高磷土壤中,施用沼液对剖面土壤全磷、有机磷和速效磷含量影响未达到显著水平,下层土壤p H值降低0.34个单位。因此,施用沼液降低土壤磷素淋洗,增加低磷土壤磷素有效性含量,但对中磷和高磷水平土壤的磷素影响未达到显著水平。     

耕作方式对黄绵土无机磷形态的影响

以设置在陇中黄土高原并已经进行了5年的田间定位试验为基础,采用蒋-顾石灰性土壤无机磷分级法,研究了不同耕作方式对黄绵土无机磷形态的影响。结果表明,供试土壤中78.6%的磷以无机磷形式存在,且以Ca-P占绝大多数。无机磷各形态含量排列顺序为:Ca10-P Ca8-P O-PAl-P Fe-PCa2-P。与传统耕作不覆盖(T)相比,免耕秸秆覆盖(NTS)、免耕不覆盖(NT)、传统耕作结合秸秆还田(TS)均可降低土壤中的Ca8-P、O-P和0—5 cm土层中的Ca10-P含量,其中NTS最为明显;NTS处理可提高土壤中的Al-P、Fe-P含量。不同处理中,Ca2-P、Ca8-P、Al-P、Fe-P均以0—5 cm土层中含量最高,且随着土层的增加呈下降趋势;但是Ca10-P 以5—10 cm土层含量最高;各处理O-P在土壤剖面中的变化没有显著差异。     

Soil organic matter stabilization in acidic forest soils is preferential and soil type-specific

Minerals with large specific surface areas promote the stabilization of soil organic matter (SOM). We analysed three acidic soils (dystric, skeletic Leptic Cambisol; dystric, laxic Leptic Cambisol; skeletic Leptic Entic Podzol) under Norway spruce (Picea abies) forest with different mineral compositions to determine the effects of soil type on carbon (C) stabilization in soil. The relationship between the amount and chemical composition of soil organic matter (SOM), clay content, oxalate‐extractable Fe and Al (Fe_o; Al_o), and dithionite‐extractable Fe (Fe_d) before and after treatment with 10% hydrofluoric acid (HF) in topsoil and subsoil horizons was analysed. Radiocarbon age, ¹³C CPMAS NMR spectra, lignin phenol content and neutral sugar content in the soils before and after HF‐treatment were determined and compared for bulk soil samples and particle size separates. Changes in the chemical composition of SOM after HF‐treatment were small for the A‐horizons. In contrast, for B‐horizons, HF‐soluble (mineral‐associated) and HF‐resistant (non‐mineral‐associated) SOM showed systematic differences in functional C groups. The non‐mineral associated SOM in the B‐horizons was significantly depleted in microbially‐derived sugars, and the contribution of O/N‐alkyl C to total organic C was less after HF‐treatment. The radiocarbon age of the mineral‐associated SOM was younger than that of the HF‐resistant SOM in subsoil horizons with small amounts of oxalate‐extractable Al and Fe. However, in horizons with large amounts of oxalate‐extractable Al and Fe the HF‐soluble SOM was considerably older than the HF‐resistant SOM. In acid subsoils a specific fraction of the organic C pool (O/N‐alkyl C; microbially‐derived sugars) is preferentially stabilized by association with Fe and Al minerals. Stabilization of SOM with the mineral matrix in soils with large amounts of oxalate‐extractable Al_o and Fe_o results in a particularly stable and relatively old C pool, which is potentially stable for thousands of years.     

Phosphate sorption by Egyptian,Ethiopian and German soils and P uptake by rye (Secale cereale L.) seedlings

Phosphate sorption was studied in samples (0 - 20 cm depth) of five soils from Egypt (pH 7.4 - 8.7), four soils from Ethiopia (pH 3.9 - 5.3) and six soils from Germany (pH 3.3 - 7.2). Sorption parameters were calculated according to Pagel and Van Huay (1976) and according to Langmuir (Syers et al., 1973). Phosphate sorption parameters and oxalate extractable Fe and Al (Fe_ox, Al_ox) were related to the phosphate uptake by young rye plants in Neubauer pot experiments. P sorption parameter after Pagel and Van Huay (A) correlated significantly positively with the Fe_ox and Al_ox content in acid (r = 0.73) as well as in calcareous soils (r = 0.89) if the whole equilibrium concentration range (0 - 14 mg P/L) was considered. The relations calculated after Langmuir (B) were similar. P uptake by rye in acid soils was negatively correlated with the affinity constant n (r = ?0.76, (A)). In calcareous soils, a negative correlation between P uptake and affinity constant was calculated in the lower P equilibrium range (0 - 2.8 mg P/L) only for (B). Thus, P uptake decreased with increasing strength of P bonding to soil. From these results it is concluded that phosphate sorbed to Fe/Al oxides is an important P source for plants in acid and calcareous soils.     

Podzol development with time in sandy beach deposits in southern Norway

The coastal areas of SE Norway provide suitable conditions for studying soil development with time, because unweathered land surfaces have continuously been raised above sea level by glacio‐isostatic uplift since the termination of the last ice age. We investigated Podzol development in a chronosequence of six soils on sandy beach deposits with ages ranging from 2,300 to 9,650 y at the W coast of the Oslofjord. The climate in this area is rather mild with a mean annual temperature of 6°C and an annual precipitation of 975 mm (Sandefjord). The youngest soil showed no evidence of podzolization, while slight lightening of the A horizon of the second soil (3,800 years) indicated initial leaching of organic matter (OM). In the 4,300 y–old soil also Fe and humus accumulation in the B horizon were perceptible, but only the 6,600 y–old and older soils exhibited spodic horizons. Accumulation of OM in the A horizons reached a steady state in <2,300 y, while in the B horizons OM accumulated at increasing rates. pH dropped from 6.6 (H₂O)/5.9 (KCl) in the recent beach sand to 4.5 (H₂O)/3.8 (KCl) within approx. 4,500 y (pH_H2O)/2,500 y (pH_KCl) and stayed constant thereafter, which was attributed to sesquioxide buffering. Base saturation showed an exponential decrease with time. Progressive weathering was reflected by increasing Fe_d and Al_d contents, and proceeding podzolization by increasing amounts of pyrophophate‐ and oxalate‐soluble Fe and Al with soil age. These increases could be best described for most Fe and Al fractions by exponential models. Only the increasing amounts of Fe_p could be better described by a power function and those of Fe_o by a linear model.     

山东石灰性潮土、褐土无机磷的形态、转化和有效性

应用蒋柏藩、顾益初提出的“石灰性土壤无机磷分级方法”研究了山东省石灰性潮土、褐土、砂姜黑土的无机磷组成、转化和对作物的有效性。结果表明,石灰性土壤无机磷中以Ca10-P占绝对优势,约占无机磷总量的54.52％,其次为O-P,占21.55％,Al-P、Fe-P,Ca8-P分别占5～10％,Ca2-P只有1.08％;在土壤剖面中各级无机磷皆随剖面深度增加而减少;水溶性磷肥施入土壤后,在作物一个生长季节内主要转化成Ca8-P,占全部转化量的50～70％,其次是Ca2-P,占10～30％,Al-P占11～13％,Fe-P很少,占5％左右;在各级无机磷中对作物有效性顺序是Ca2-P>Al-P、Fe-P>Ca8-P>O-P、Ca10-P。     

Predicting phosphorus sorption isotherm parameters in soil using data of routine laboratory tests

Knowledge of phosphorus(P) sorption dynamics across different soil types could direct agronomic and environmental management of P. The objective of this study was to predict P isotherm parameters for a national soil population using data of routine laboratory tests. Langmuir and Freundlich sorption parameters were calculated from two different ranges(0–25 and 0–50 mg P L~(-1)) using an archive of representative agricultural soil types from Ireland.Multiple linear regression(MLR) identified labile forms of aluminium(Al) and iron(Fe), organic matter(OM), cation exchange capacity(CEC), and clay as significant drivers. Langmuir and Freundlich sorption capacities, Freundlich affinity constant, and Langmuir buffer capacity were predicted reliably, with R~2 of independent validation 0.9. Sorption isotherm parameters were predicted from P sorbed at a single concentration of 50 mg P L~(-1)(S_(50)). An MLR prediction of P sorption maximum in the 0–50 mg P L~(-1) range was achieved, to an accurate standard, using S_(50), OM, and Mehlich-3 Fe(R~2 of independent calibration and validation being 0.91 and 0.95, respectively). Using Giles' four shapes of isotherms(C, L, H, and S), L non-strict-and C-shaped isotherm curves accounted for 64% and 27% of the soils, respectively. Hierarchical clustering identified a separation of isotherm curves influenced by two ranges of Mehlich-3 Al. Soils with a low range of Mehlich-3 Al(2.5–698 mg kg~(-1)) had no incidence of rapid sorption(C shape). Single point indices, Al, or available soil data make the regression approach a feasible way of predicting Langmuir parameters that could be included with standard agronomic soil P testing.     

Short-term phosphorus sorption and desorption in contrasting cropped Vertisols

Vertisols are important cropping soils in tropical and subtropical areas, but in many regions, decades of cropping has substantially reduced concentrations of plant-available phosphorus (P), especially in the subsoil layers. Phosphorus behaviour in P-depleted Vertisols has received comparatively little attention, and the availability of P following the addition of inorganic P fertilisers at different concentrations is poorly understood. In this study, we evaluated short-term P sorption and desorption behaviour in cropped Vertisols in relation to specific soil physical and chemical properties. We collected the surface and subsurface of 15 Australian soils with a broad range of physical and chemical properties, comprising nine Vertisols, three Ferralsols, two Lixisols and one Calcisol. For each soil, we generated sorption and desorption curves (fitted with a Freundlich equation), determined soil physical and chemical properties likely to influence P sorption and evaluated the relationships between the measured soil properties and the Freundlich equation sorption coefficients. The P sorption curves differed drastically between soils, with the sorption equation coefficients (a_S × b) significantly correlated with the P buffering index (PBI) and clay content. Clay content itself was correlated with citrate-extractable Fe and Al oxides and BET surface area. Vertisols formed on basaltic parent materials had greater Fe and Al oxide concentrations, resulting in an overall greater P sorption capacity. Sorption and desorption hysteresis were mostly small. The reacting materials in these soils probably had limited ability to continue to react with P. The Vertisols differed in their capacity to replenish P in the soil solution by desorbing different proportions of previously sorbed P, although the proportion of desorbable P generally increased with greater concentrations of sorbed P. These results suggest that for fertiliser management in these soils, smaller volumes of P enrichment combined with higher P concentrations may result in a greater P recovery by the crop.     

Labile, recalcitrant, and inert organic matter in Mediterranean forest soils

The biochemical quality of soil organic matter (SOM) was studied in various profiles under Quercus rotundifolia Lam. stands on calcareous parent material. Special attention was paid to the question of how biochemical quality is affected by position within the soil profile (upper versus lower horizons). The following global SOM characteristics were investigated: (a) overall recalcitrance, using hydrolysis with either hydrochloric or sulphuric acid; (b) hydrolyzable carbohydrates and polyphenolics; (c) extractability by hot water and quality of the extract; and (d) abundance of inert forms of SOM: charcoal and soot-graphite. The recalcitrance of soil organic carbon (OC) decreases with depth, following the order: H horizons>A horizons>B horizons. In contrast, the recalcitrance of nitrogen is roughly maintained with depth. The ratio carbohydrate C to total OC increases from H to B horizons, due to the increasing importance of cellulosic polysaccharides in B horizons, whereas other carbohydrates are maintained throughout the soil profile at a relatively constant level, 12-15% of the total OC in the horizon. Whereas the quality of the hydrolyzable carbon (measured by the carbohydrate to polyphenolic C ratio) decreases with depth from H to B horizons, the quality of the hot-water extractable organic matter is much higher in B horizons than in A or H horizons. The relative importance of both charcoal and soot-graphitic C and N tends to increase with depth. The ratio black/total is usually higher for N than for C, a result that suggests that inert SOM may represent a relevant compartment in the nitrogen cycle. Overall, our data suggest that in Mediterranean forest soils the organic matter in B horizons could be less stable than often thought.     

Phosphate Speciation and Citrate-Induced Mobilization of P in an Acric Oxisol

Billions of dollars are spent annually in Brazil on imported phosphorus (P) fertilizers for agricultural crops produced on Oxisols. Phosphate fixation by Oxisols is a main limitation to crop productivity because these highly weathered soils have a high phosphate adsorption capacity. The objective was to determine whether reaction of an Acric Oxisol with citrate increases P availability. Columns of P-amended subsoil material were leached with 1 mM citrate solution, and effluent was monitored. Solid-phase speciation was measured for different stages of leaching using X-ray absorption near edge structure (XANES) spectroscopy at the P K-edge. When soil columns were leached with up to 56 column pore volumes of 1 mM citrate solutions, no P was detected in column effluent samples, whereas aluminum (Al) and iron (Fe) increased up to 30 and 1.4 µmol L^?1, respectively. The XANES analysis suggested that with increased leaching, a minor proportion of phosphate adsorbed on Fe-oxides increased as phosphate adsorbed on Al-oxides decreased. The results indicated that citrate tends to induce minor species redistribution of phosphate between Al- and Fe-oxide bound forms, but P mobilization was trivial compared with complexometric mobilization of Fe and Al.