Speciation of Aluminum in Solution of an Acidic Sandy Soil Amended with Organic Composts

The effects of organic amendments (10 and 50 g/kg soil of yard waste, yard + municipal waste, GreenEdge, and synthetic humic acid) on soil chemical properties related to aluminum (Al) phytotoxicity and nutrient availability were evaluated. Compost amendment increased Mehlich 3–extractable calcium (Ca), magnesium (Mg), phosphorus (P), and potassium (K) in the soil by 3.5–260 times. No significant effect of composts on total Al in solution was observed. Organic amendments increased solution pH and decreased the activities of phytotoxic Al species to less than the critical levels, as a result of the formation of aluminate and humic acid–Al complexes. Low‐molecular‐weight organic acids were not effective in forming complexes with Al. Application of composts increased the concentrations of most nutrients in soil solution, suggesting a potential for ameliorating subsoil, but care must be taken to avoid nitrogen (N) and P leaching. Amending composts to acidic soils appears a useful strategy for diminishing Al phytotoxicity potential and improving soil fertility.     

Assessment of potentially reactive pools of aluminum in Andisols using a five-step sequential extraction procedure

A five-step sequential extraction procedure was developed for the partitioning of soil aluminum (Al) into five fractions: exchangeable, weakly organic bound, strongly organic bound, inorganic non-crystalline and crystalline. The results obtained by the sequential extraction method for Al were compared with those estimated from single extractions using identical operating conditions applied in each individual sequential fraction. The Al content in the extracts was measured by inductively coupled plasma optical emission spectrometry. The results indicated that the first four steps [potassium chloride (KCl), copper chloride (CuCl₂), sodium pyrophosphate (Na₄P₂O₇), acid ammonium oxalate ((NH₄)₂C₂O₄)] in the sequential procedure could be as effective as single extraction methods at estimating exchangeable Al, weakly organic bound Al, strongly organic bound Al, and non-crystalline Al. However, the crystalline Al content by sequential procedure was not in agreement with single extraction procedures. Further, the sequential extractions resulted in more consistent estimates of the aluminum/silicon (Al/Si) molar ratio and allophane and crystalline Al contents than single extractions method. Results of X-ray diffraction on the soil samples confirm the presence of appreciable amounts of at least three types of crystalline minerals, including gibbsite, vermiculite or halloysite. Our result implies that the sequential method can be more reliable in estimating the various Al forms in Andisols.     

Aluminum Forms in Solid Phase of Soils Developed over Schists as a Function of Land Use

ABSTRACT

Land use may modify certain soil properties while soil physicochemical characteristics can influence metal partitioning in soils. Therefore, the total content and various forms of aluminum (Al) in solid phase of schist-developed topsoils (0–20 cm) in NW Spain under different land uses (i.e., forest, pasture, and cultivation) were evaluated to identify the Al-bearing phases. Aluminum fractionation was performed, using a six-step sequential extraction procedure with ammonium acetate, hydroxylamine hydrochloride, ammonium oxalate in darkness, hydrogen peroxide, ammonium oxalate under ultraviolet radiation, and acid digestion. Mean concentrations of total Al were similar in the soils under three land uses. Mean percentage of the various Al forms in all soils were in the following order: residual fraction > amorphous compounds > crystalline compounds > water-soluble/exchangeable/specifically adsorbed > bound to oxidizable organic matter > manganese oxides. The forest soils contained considerably higher contribution of amorphous compounds (16.3%) to total Al concentration compared with the soils under other two uses (mean about 9%). Maximum mean concentration of exchangeable Al was also observed in forest soils (mean 8.8% of total Al vs. about 4% in pasture soils and cultivated soils); this is attributed to lower pH and higher organic matter content of the forest soils. Thus, this study revealed the impact of land use on the Al-bearing phases and, hence, in its bioavailability to plants.     

EFFECT OF SOIL pH AND ORGANIC MATTER ON LABILE ALUMINIUM IN SOILS UNDER PERMANENT GRASS

The rates of extraction of Na, K, Mg, Ca, and Al with 1M NH₄ NO₃ from the mineral-and organic-rich layers of some Park Grass (Rothamsted) soils were measured at the pH of the soil. Below pH 3.7 exchangeable Al, derived from the kinetics curve, increases with decreasing soil pH and is less in the organic-rich layer. The sum of the basic exchangeable cations, ∑(Na + K + Mg + Ca), increases with increasing soil pH and is more in the organic-rich layer. The extraction of exchangeable Al obeys first order kinetics, the rate constant being similar for all the soils (mean value 36 ± 7 × 10^?6|s^?1), which implies that exchangeable Al is released from surfaces with similar properties for the adsorption of Al, and that the rate is not affected by soil pH and organic matter. The rate of extraction of non-exchangeable Al is the same in the mineral-and organic-rich layers of each soil, and is maximal at about pH 3.7, decreasing sharply at more and less acid pH values.     

Evaluation of two coal-derived organic products in ameliorating surface and subsurface soil acidity

Acidity in the soil surface and subsurface is of major concern in horticulture, cropping and pasture production systems in southern Australia. Broadcast applications of lime to the surface have proved to be ineffective in ameliorating subsurface acidity in the short term. Two calcium-saturated coal-derived organic products, an ‘oxi-product’ (OXPR) and an ‘oxi-fulvate’ (OXFU), were evaluated for use as liming materials with specific consideration given to amelioration of subsurface acidity. The effects of these two organic products and of lime on the chemical composition of the A₁ and A₂ horizons of an acid red podzol were investigated in leaching columns, 20 cm long. OXPR and OXFU supplying 80 or 160 g Ca m^?2 were compared to 160 g Ca m^?2 applied as CaCO₃ and a control receiving no amendments. The effects of CaCO₃ on exchangeable Al and pH were limited to the surface 2 cm. In contrast, the two organic amendments were effective in decreasing exchangeable Al and increasing pH and exchangeable Ca to depth, the extent being a function of amendment and rate applied. The formation of inorganic and organic complexes were assumed to be responsible for the movement of Al out of the column in the leachate, although significant quantities of Al were precipitated in the column. Significant linear regressions were observed between the ionic strength and Al in the leachate. Significant quantities of Mg and K were displaced by Ca and leached from the column; consequently, this loss must be considered against the benefits of decreased exchangeable Al when assessing fertility for plant production.     

外源铜和镍在土壤中的化学形态及其老化研究

采用连续提取法测定了外源铜和镍进入田间土壤后的化学形态分布,比较研究了这2种重金属在3种不同类型土壤(红壤,水稻土和潮土)中随老化时间的形态转化和分布.结果表明,外源铜以残留态(40%～60%)和EDTA可提取态(40%)为主;随老化时间,EDTA可提取态、易还原锰结合态及铁铝氧化态向残留态转化;外源镍在酸性红壤中以可交换态(40%)和残留态(30%～50%)为主,在中性水稻土中以EDTA可提取态(30%)和残留态(30%～50%)为主,在碱性潮土中以铁铝氧化态(20%)和残留态(40%)为主.随老化时间,水溶态、可交换态、EDTA可提取态等向残留态转化.土壤pH较低时水溶态和可交换态含量较高,但是同时随老化时间的降低量也明显;pH较高时有利于易还原锰结合态和有机质结合态的转化.     

Long-term amendment of four different compost types on a loamy silt Cambisol: impact on soil organic matter,nutrients and yields

This study investigated the long-term effects of different composts (urban organic waste compost (OWC), green waste compost (GWC), cattle manure compost (MC) and sewage sludge compost (SSC)) compared to mineral fertilisation on a loamy silt Cambisol, after a 7-year start-up period. The compost application rate was 175 kg N ha^?1, with 80 kg mineral N ha^?1 and without. Soil characteristics (soil organic carbon (SOC), carbon-to-nitrogen (C/N) ratio and soil pH), nutrients (nitrogen (N), phosphorous (P) and potassium (K)) and crop yields were investigated between 1998 and 2012. SOC concentrations were increased by compost applications, being highest in the SSC treatments, as for soil pH. N contents were significantly higher with compost amendments compared to mineral fertilisation. The highest calcium-acetate-lactate (CAL)-extractable P concentrations were measured in the SSC treatments, and the highest CAL-extractable K concentrations in the MC treatments. Yields after compost amendment for winter barley and spring wheat were similar to 40 kg mineral N ha^?1 alone, whereas maize had comparable yields to 80 kg mineral N ha^?1 alone. We conclude that compost amendment improves soil quality, but that the overall carbon (C) and N cycling merits more detailed investigation.     

Evaluation of Coconut Wastes as an Amendment to Acidic Soils in Low-Input Agricultural System

The effectiveness of plantation wastes along with locally available organic materials in ameliorating acidic soil was studied by conducting an experiment with coconut husk, poultry manure, vermicompost, and compared with limestone. Application of organic amendments significantly increased the soil pH, and it was greatest in poultry manure–amended soils followed by vermicompost and coconut husk + poultry manure treatments. The relative liming efficiency was greatest for poultry manure through out the observation period of 180 days. The coconut husk alone showed the least liming effect and its liming efficiency had increased when applied in combination with poultry manure and or vermicompost. This increase in soil pH was mirrored by significant reductions in exchange acidity, exchangeable aluminum (Al³⁺), diethylenetriaminepentaacetic acid (DTPA)–extractable iron (Fe²⁺), and manganese (Mn²⁺) and increases in cation exchange capacity, exchangeable bases, especially calcium (Ca), and Olsen-extractable phosphorus (P) by addition of organic amendments and lime. This study indicated the potential of using coconut husk along with poultry manure for managing acidic soils in low-input agricultural systems, especially in tropical islands.     

Distribution of Aluminum Fractionation in the Acidic Rhizosphere Soils of Masson Pine (Pinus massoniana Lamb)

The modified Tessier’s sequential extraction procedure and rhizobox cultivation were employed to investigate the distribution of aluminum (Al) fractions in the acidic rhizosphere soil of Masson pine (Pinus massoniana lamb) seedlings. The results showed that the Al in soils was fractionated into five operationally defined fractions. Three sets of soil samples used in the rhizoboxes were collected from the three forest sites in the southeast of China: Sichuan, Zhejian, and Jiangsu. At the end of 100-day cultivation, the rhizosphere Al fractions for the original or bulk soils were in the order of residual > iron-manganese (Fe-Mn) oxides > organic > carbonate > exchangeable. However, in rhizosphere soil, the Al fraction follows the order of residual > organic > Fe-Mn oxides > carbonate > exchangeable. On average, the rhizosphere experienced significant increase in organically bound Al and slight decrease in exchangeable Al contents, but had decreases in contents for the other three Al fractions compared to the nonrhizosphere. The correlation analysis indicated that the Al contents accumulated in roots were significantly and positively correlated with exchangeable Al contents in the rhizosphere, and also characterized by the major portion of organically bound Al, which exhibited a bioavailable transformation of Al fractions. Results indicated that decreases in both redox potential and soil pH, as well as increase in dissolved organic carbon (DOC), were observed in the rhizosphere. Exchangeable Al and organic Al fractions were dependent mainly on soil pH (hydrogen ion concentration) and DOC, accordingly. Decreasing rhizosphere pH from 5.93 to 3.42 accelerated the secretion of organic carbon. These data are helpful for understanding the mobility and bioavailability of Al fractions in the acidic rhizosphere soils of Masson pine.     

碱渣与菜籽饼共施对茶园土壤酸度调控的研究

Rapeseed cake (RC), the residue of rapeseed oil extraction, is effective for improving tea (Camellia sinensis) quality, especially taste and aroma, but it has limited ability to ameliorate strongly acidic soil. In order to improve the liming potential of RC, alkaline slag (AS), the by-product of recovery of sodium carbonate, was incorporated. Combined effects of different levels of RC and AS on ameliorating acidic soil from a tea garden were investigated. Laboratory incubations showed that combined use of AS and RC was an effective method to reduce soil exchangeable acidity and Al saturation and increase base saturation, but not necessarily for soil pH adjustment. The release of alkalinity from the combined amendments and the mineralization of organic nitrogen increased soil pH initially, but then soil pH decreased due to nitrifications. Various degrees of nitrification were correlated with the interaction of different Ca levels, pH and N contents. When RC was applied at low levels, high Ca levels from AS repressed soil nitrification, resulting in smaller pH fluctuations. In contrast, high AS stimulated soil nitrification, when RC was applied at high levels, and resulted in a large pH decrease. Based on the optimum pH for tea production and quality, high ratios of AS to RC were indicated for soil acidity amelioration, and 8.0 g kg-1 and less than 2.5 g kg-1 were indicated for AS and RC, respectively. Further, field studies are needed to investigate the variables of combined amendments.     

Composts Vary in Their Effect on Soil P Pools and P Uptake by Wheat

With diminishing world reserves of phosphorus (P) deposits and rising fertilizer prices, it is important to find alternate sources of P for crops. The aim of this research was to evaluate the effect of four different composts C1 (animal manure and straw), C2 (garden waste), C3 (wood chips and bark), and C4 (kitchen waste) on soil P pools and P uptake by wheat on 14, 28, and 72 days after compost application. The composts were applied as a 2.5 cm thick layer on the soil surface. During sampling, only the soil underlying compost was sampled. Soil pH and total organic carbon were not affected by the amendments. Soil respiration was significantly higher in compost-amended soils compared with the unamended soil except with C4 on day 72. Addition of composts increased plant growth, and P uptake being highest on day 72 with C1 and C4. With little effect on available P concentration on day 14, there was a conversion of organic P into inorganic P in the compost treatments suggesting net mineralization of organic P on day 28. On day 72, the concentrations of the less labile P forms were higher in the compost treatments compared with the unamended suggesting precipitation and fixation as well as synthesis of organic P. This study showed that mulching with composts having high available and total P concentrations can provide plants with P and also increase soil P concentrations which could reduce the fertilizer requirement for the following crop.     

Influence of Long‐Term Sodic‐Water Irrigation,Gypsum, and Organic Amendments on Soil Properties and Nitrogen Mineralization Kinetics under Rice–Wheat System

Abstract

Influence of long‐term sodic‐water (SW) irrigation with or without gypsum and organic amendments [green manure (GM), farmyard manure (FYM), and rice straw (RS)] on soil properties and nitrogen (N) mineralization kinetics was studied after 12 years of rice–wheat cropping in a sandy loam soil in northwest India. Long‐term SW irrigation increased soil pH, exchangeable sodium percentage (ESP), and sodium adsorption ratio (SAR) and decreased organic carbon (OC) and total N content. On the other hand, application of gypsum and organic amendments resulted in significant improvement in all these soil properties. Mineralization of soil N ranged from 54 to 111 mg N kg^?1 soil in different treatments. Irrigation with SW depressed N mineralization. In SW‐irrigated plots, two flushes of N mineralization were observed; the first during 0 to 7 d and the second after 28 d. Amending SW irrigated plots with GM and FYM enhanced mineralization of soil N. Gypsum application along with SW irrigation reduced cumulative N mineralization at 56 days in RS‐amended plots but increased it under GM‐treated, FYM‐treated, or unamended plots. Nitrogen mineralization potential (N_o) ranged from 62 to 543 mg N kg^?1 soil. In the first‐order zero‐order model (FOZO), the easily decomposable fraction ranged from 5.4 to 42 mg N kg^?1 soil. Compared to the first‐order single compartment model, the FOZO model could better explain the variations in N mineralization in different treatments. Variations in N_o were influenced more by changes in pH, SAR, and ESP induced by long‐term SW irrigations and amendments rather than by soil OC.     

Increases in pH and soluble salts influence the effect that additions of organic residues have on concentrations of exchangeable and soil solution aluminium

It has been suggested that additions of organic residues to acid soils can ameliorate Al toxicity. For this reason the effects of additions of four organic residues to an acid soil on pH and exchangeable and soil solution Al were investigated. The residues were grass, household compost, filter cake (a waste product from sugar mills) and poultry manure, and they were added at rates equivalent to 10 and 20 t ha^?1. Additions of residues increased soil pH measured in KCl (pH_(KCl)) and decreased exchangeable Al³⁺ in the order poultry manure > filter cake > household compost > grass. The mechanism responsible for the increase in pH differed for the different residues. Poultry manure treatment resulted in lower soil pH measured in water (pH_(water)) and larger concentrations of total (Al_T) and monomeric (Al_mono) Al in soil solution than did filter cake. This was attributed to a soluble salt effect, originating from the large cation content of poultry manure, displacing exchangeable Al³⁺ and H⁺ back into soil solution. The considerably larger concentrations of soluble C in soil solution originating from the poultry manure may also have maintained greater concentrations of Al in soluble complexed form. There was a significant negative correlation (r = ?0.94) between pH_(KCl) and exchangeable Al. Concentrations of Al_T and Al_mono in soil solution were not closely related with pH or exchangeable Al. The results suggest that although additions of organic residues can increase soil pH and decrease Al solubility, increases in soluble salt and soluble C concentrations in soil solution can substantially modify these effects.     

ALLEVIATING THE INFERTILITY OF AN ACID SULPHATE SOIL BY USING GROUND BASALT WITH OR WITHOUT LIME AND ORGANIC FERTILIZER UNDER SUBMERGED CONDITIONS

A study was conducted into the alleviation of the infertility of an acid sulphate by using ground basalt with or without ground magnesium limestone (GML) and organic fertilizer. Fresh soils were treated with the amendments and subjected to two cycles of submergence and drying. The soil was dominated by kaolinite, mica and smectite. The untreated soil pH was <3·5 and solution Al was high. GML application at 4 t ha⁻¹ was able to increase pH and subsequently reduced Al toxicity sufficiently to allow for rice growth. After 4 months of submergence, the pH of the sample treated with 4 t ground basalt ha⁻¹ had increased from 3·61 to 3·94, with concomitant decrease of Al. In the same cycle, the soil pH increase was much higher (reaching 5·22). Ground basalt is thus comparable with GML as an acid soil ameliorant. Within the experimental period, the ground basalt had mostly disintegrated and dissolved. The solution pH had further increased (to 5·94) in the second cycle because of dissolution of more ground basalt. This means that it takes time for ground basalt to completely dissolve and consequently supply Ca, Mg, K and P to the growing crop in the field. Applying 0·25 t organic fertilizer ha⁻¹ into the soil had no significant effect on either pH or Al. This form of organic matter (compost) contains essential nutrients. It is recommended that 4 t ground basalt should be applied in combination with 0·25 t organic fertilizer ha⁻¹ a few months ahead of the growing season for maximal benefit. This study showed that ground basalt can be effectively used to ameliorate highly acidic soils. Copyright © 2011 John Wiley & Sons, Ltd.     

Importance of Noncrystalline Hydroxide Phases in Sequential Extractions to Fractionate Antimony in Acid Soils

Abstract

Sequential extraction techniques have been used to make inferences about speciation of phosphorus (P) and to a lesser extent arsenic (As) in soils. However, sequential extraction studies on the less‐abundant group V element, antimony (Sb), are limited. In this work, a widely used P sequential extraction scheme was modified and used to extract P, As, and Sb from two acidic soils from the Macleay River floodplain, NSW, that were enriched with Sb (26.9 and 23.0 mg kg^?1). An ammonium oxalate–oxalic acid step was included in the extraction sequence to dissolve the noncrystalline iron (Fe) and aluminium (Al) hydroxide phase. It extracted 30 to 47% of Sb, indicating the importance of this fraction, which may be mobilized in the floodplain by acid sulfate soil processes and periodic waterlogging. The original method overestimated P, As, and Sb in the residual fraction (30–71%). Relative efficiency values of extracts for P, As, and Sb were compared, and inferences about phase distributions were made. The results suggest some potential in using extractions to assess bioavailability of Sb in soil.     

Fractionation of Cd and Zn in Cd-contaminated soils amended by sugarcane waste products from an ethanol production plant

Purpose

Sugarcane waste products (boiler ash, filter cake, and vinasse) from an ethanol production plant were used as soil amendments by adding 3 % (w/w) in single and/or in combination, with a research focus towards stabilization of cadmium (Cd) and zinc (Zn) in contaminated soils. The objective of this laboratory study was to evaluate the effects of adding these sugarcane waste products on bioavailability of Cd and Zn over time (aging) in Cd- and Zn-contaminated agricultural soils of Thailand.

Materials and methods

Two agricultural contaminated soils of low (<3 mg kg^?1) and high (10–15 mg kg^?1) Cd concentrations were collected from Tak Province, Northwest Thailand. Fourteen treatments were sampled at 2-week intervals for 84 days for metal bioavailability using BCR extraction procedures (proposed by The Standards, Measurements and Testing Programme of the European Union, SM&T) that determined exchangeable (BCR1), reducible (BCR2), oxidizable (BCR3), and residual (BCR4) fractions, and total concentration was determined using aqua regia digestion and microwave digestion.

Results and discussion

Cd was potentially bioavailable, predominantly in exchangeable (BCR1) and reducible (BCR2) fractions, while the higher contribution of Zn was more prevalent in refractory fractions (BCR2 and BCR4). Aging had an influence on fractionation of Cd and Zn, most notably in the first two fractions (BCR1 and BCR2) of BCR sequential extraction, which resulted in reduction of exchangeable Cd during the first few weeks of incubation (T?=?0 to 28 days). At the end of pot experiment, the exchangeable Cd fraction in the low Cd (LCdS) soil was reduced from 2.3 to 4.7 % and 9.4 to 39.9 % in low and high Cd (HCdS)-contaminated soils, respectively, as compared to nonamended soils.

Conclusions

The observed reduction in exchangeable Cd (BCR1) in the amended soils at the 3 % (w/w) application rate, the low total metal concentrations, and the significant amount of essential plant nutrients (N, P, and K) within these waste products highlight the benefits of amending metal-rich soils with them.     

不同改良剂对酸性土壤的修复效应

为明确不同改良剂对酸性植烟土壤的修复效应,采用盆栽试验,分析了施用丰收延酸性土壤改良剂、金叶酸性土壤改良剂及石灰后土壤pH、水解性酸、潜性酸及土壤交换性能的动态变化。结果表明:施用改良剂可提高土壤pH 3.01%~24.11%,降低土壤水解性酸16.08%~50.46%、交换性Al 3+51.80%~64.27%、交换性H+含量84.12%~93.56%,提高土壤交换性盐基总量45.18%~46.16%、阳离子交换量0.33%~20.10%、盐基饱和度21.35%~49.78%。施用土壤改良剂后,土壤pH先升高后下降,至移栽60天后趋于稳定;土壤水解性酸在烤烟移栽后30~90天差异较小,至移栽后120天略有增加。施用石灰的土壤交换性氢、交换性铝一直下降,但施用丰收延、金叶酸性土壤改良剂的土壤交换性铝下降至烟苗移栽后120天略有增加,土壤交换性氢上升至烟苗移栽后120天大幅度下降。施用土壤改良剂后,土壤交换性盐基总量、阳离子交换量、盐基饱和度一直提高,但变化幅度较小。不同土壤改良剂的材料来源及组成成分不同,其对酸性土壤的恢复效果也不同,以施用石灰的效果最好。     

红壤中铝的形态

以改进的连续分级提取方法,用１ｍｏｌ／Ｌ,ＫＣｌ,０．２ｍｏｌ／Ｌ,ＨＣｌ,０．１ｍｏｌ／Ｌ Ｎａ４Ｐ２Ｏ７（ｐＨ８．５）,ＤＣＢ溶液,０．３３ｍｏｌ／Ｌ,柠檬酸钠和０．５ｍｏｌ／Ｌ ＮａＯＨ为提取剂,把红壤中可提取的非晶态铝区分为交换态铝,肿附态无机羟基铝,有机配合态铝,氧化铁结合态铝,层间铝和非晶态铝硅酸盐。     

Development of Analytical Procedure for the Determination of Exchangeable Cr(VI) in Soils by Anion-exchange Fast Protein Liquid Chromatography with Electrothermal Atomic Absorption Spectrometry Detection

Analytical procedure for the determination of exchangeable Cr(VI) was developed. In order to optimise the extraction procedure, the efficiency of extraction of exchangeable Cr(VI) in soil samples was investigated in KH₂PO₄–K₂HPO₄ buffer solutions (0.015 up to 0.2 mol l^?1), adjusted to the pH of the soil. Phosphate buffer was used to efficiently desorb Cr(VI) from soil particles. The extraction time (mechanical shaking) ranged from 1 up to 72 h. Cr(VI) in soil extracts was determined by anion-exchange fast protein liquid chromatography with electrothermal atomic absorption detection (FPLC-ETAAS). The study was performed on soil samples from the field treated with the tannery waste for seventeen years. Samples were analysed in the 16 year after the last waste application. It was experimentally proven that the optimal phosphate buffer concentration was 0.1 mol l^?1 and extraction time 16 h. An additional experiment was done to confirm that during the extraction, soluble Cr(III) was not oxidised to Cr(VI) by Mn(IV) oxides present in soil samples. For this purpose soil with the same characteristics, but not treated with tannery waste, was spiked with Cr(III) and the analytical procedure performed. No measurable Cr(VI) concentrations were detected. The repeatability of measurement was 2.5%, while the reproducibility of measurement was 6.9%. The accuracy of the analytical procedure was tested by spiking of soil samples with Cr(VI). The recoveries were better than 95%. The analytical procedure with limit of detection (LOD) 15 ng g^?1 of Cr(VI) was sensitive enough for the determination of exchangeable Cr(VI) in soils. In field soil samples analysed the concentrations of exchangeable Cr(VI) were found to be about 200 ng g^?1.     

Isolating the influence of pH on the amounts and forms of soil organic phosphorus

Soil pH influences the chemistry, dynamics and biological availability of phosphorus (P), but few studies have isolated the effect of pH from other soil properties. We studied phosphorus chemistry in soils along the Hoosfield acid strip (Rothamsted, UK), where a pH gradient from 3.7 to 7.8 occurs in a single soil with little variation in total phosphorus (mean ± standard deviation 399 ± 27 mg P kg^?1). Soil organic phosphorus represented a consistent proportion of the total soil phosphorus (36 ± 2%) irrespective of soil pH. However, organic phosphorus concentrations increased by about 20% in the most acidic soils (pH < 4.0), through an accumulation of inositol hexakisphosphate, DNA and phosphonates. The increase in organic phosphorus in the most acidic soils was not related to organic carbon, because organic carbon concentrations declined at pH < 4.0. Thus, the organic carbon to organic phosphorus ratio declined from about 70 in neutral soils to about 50 in strongly acidic soils. In contrast to organic phosphorus, inorganic phosphorus was affected strongly by soil pH, because readily‐exchangeable phosphate extracted with anion‐exchange membranes and a more stable inorganic phosphorus pool extracted in NaOH–EDTA both increased markedly as soil pH declined. Inorganic orthophosphate concentrations were correlated negatively with amorphous manganese and positively with amorphous aluminium oxides, suggesting that soil pH influences orthophosphate stabilization via metal oxides. We conclude that pH has a relatively minor influence on the amount of organic phosphorus in soil, although some forms of organic phosphorus accumulate preferentially under strongly acidic conditions.