The forms of occurrence of manganese in some acidic soils

The forms of occurrence of Mn were examined in some acidic surface and sub-soils from areas of permanent grassland using chemical extractants. Despite high total contents of Mn in some of the soils and low pH, only minor proportions occurred as exchangeable Mn²⁺. Much larger proportions were present as reducible hydrous oxides, e.g. up to 38% and 54% of the total contents in surface and subsoils, respectively, were present as hydroquinone extractable, or easily reducible, Mn. Reducible forms of Mn were poorly correlated with other more mobile forms. Large proportions of the total Mn contents were accounted for when estimates of different fractions were calculated from differences in amounts extracted by different individual extractants, i.e. M NH₄OAc, 0.2% hydroquinone, 0.1 M pyrophosphate, and ammonium oxalate. The distribution of Mn amongst the different fractions as determined by a sequential fractionation scheme differed markedly from the distribution calculated by differences. In particular, there was a marked change in form after extraction with pyrophosphate.     

Forms of aluminium in some acid permanent grassland soils

The more labile forms of aluminium in a range of soils from areas of permanent grassland were determined with a number of selective extractants. The amounts of exchangeable A1 extracted with molar KCl were dependent upon pH, while the amounts exchangeable with 0.3 M LaCl³, although much greater, were not well correlated with pH. There were good correlations between soil organic C content and A1 extracted by (i) 0.5 M EDTA and (ii) 0.1 M potassium pyrophosphate. Pyrophosphate extracted greater amounts than any of the other extractants (sodium citrate/dithionite, ammonium oxalate (dark), acid oxalate (UV radiation), as well as those already mentioned). It was concluded that much of the extractable A1 in soils was associated with organic matter. Addition of lime to one of the soils reduced the amount of A1 extracted by all reagents except dithionite and acid oxalate solutions. There were considerable differences between soils in their release of A1 to continuous leaching with 0.01 M CaCl². Despite these differences between the soils in organically bound extractable Al, the differences in the amounts and patterns of release of A1 with CaCl² did not appear to be related to organic matter contents, nor to the other determined properties.     

Evidence of dissolved trivalent manganese in acidic forest soils

Background

Evidence of trivalent manganese (Mn³⁺) in the aqueous phase of soils is unknown so far although this strong oxidant has large environmental implications.

Aims

We aimed to modify a spectrophotometric protocol (porphyrin method) and to discriminate between Mn²⁺ and Mn³⁺ in the aqueous phase of forest soils based on kinetic modeling.

Methods

We investigated manganese speciation in 12 forest floor solutions and 41 soil solutions from an acidic forest site by adjusting pH and correcting for absorbance.

Results

The solutions showed broad ranges in pH (3.4−6.3), dissolved organic carbon (DOC, 1.78−77.1 mg C L⁻¹), and total Mn (Mn_T, 23.9−908 µg L⁻¹). For acidic solutions, a pH-buffer was added to increase the pH of the solutions to 7.5−8.0, and background absorption was corrected for colored solutions, that is, solutions high in DOC. This was done to accelerate the reaction kinetics and avoid overestimation of Mn_T concentrations. After the pH and color adjustments, the comparison of Mn_T concentrations between the porphyrin method and optical emission spectrometry showed good agreement. Trivalent Mn, which is stabilized by organic ligands, constitutes significant proportions in both forest floor solutions (10−87%) and soil solutions (0.5−74%).

Conclusions

The dissolved Mn³⁺ is present in acidic forest soils. Thus, we revise the paradigm that this species is not stable and encourage to apply the revised method to other soils.     

The control of aluminium solubility in some acidic Australian soils

The variation in the solubility of aluminium in some acid soils of south-eastern Australia has been investigated. The hypothesis was that leaching of silicic acid influenced the extent of clay decomposition, and hence aluminium solubility, in accord with Le Chatelier's principle. In lower rainfall areas (< 800 mm) control of Al solubility was consistent with a poorly crystalline kaolinite as the source phase, while at higher rainfall (> 1200 mm) it was consistent with gibbsite control. However, soluble silica concentrations were too high for gibbsite and kaolinite to be thermodynamically stable phases. The hypothesis was modified to take account of a quasi-equilibrium in the open soil system, in which clay dissolution and A1 solubility appear to depend on the relative rates of H⁺ input and of silica leaching. These may result in a supersaturated, or possibly even undersaturated system, at any point in time. The relative sizes of the organic sink and mineral Al source determine the influence of organic matter on Al solubility.     

Predicting the lime requirement of soils under permanent grassland and arable crops

Abstract. Graphs of soil pH against time were plotted for the Park Grass Experiment at Rothamsted Experimental Station, begun in 1856, and the Long-term Liming Experiments at Rothamsted and Woburn farms, begun in 1962. These showed that the magnitude and duration of the effect of lime applications varied with soil type, initial pH, fertilizer nitrogen application, and the crop grown. Simple equations for each situation were linked to form an empirical model which, with appropriate input data for soil type, crop, and initial and target pH, predicted the lime needed to reach that pH. Model predictions compared well with estimates from a Woodruff-type buffer method. The model forms a sound basis for a more comprehensive lime requirement model covering the whole of the United Kingdom.     

The forms of cobalt in some Scottish soils as determined by extraction and isotopic exchange

The results of fractionation and correlation studies provided evidence that cobalt in soils is associated predominantly with the soil oxide fraction, particularly the manganese oxides. Only a small proportion of the total cobalt present in soils was extracted by acetic acid, EDTA, pyrophosphate or hydroxylamine. Cobalt extracted with these reagents was considered to be derived principally from easily reducible manganese oxides, although the origin of the cobalt extracted by acetic acid in particular was not well defined. The bulk of the cobalt present in soils appeared to be occluded by more highly crystalline oxide materials or was present in the structures of primary and secondary minerals. Labile cobalt in soil was assessed by extraction with acetic acid and EDTA and by determination of isotopically exchangeable cobalt. The amounts of cobalt extracted by both EDTA and acetic acid were highly dependent on the length of extraction period and on the temperature of extraction. Neither of these reagents appeared likely to give good estimates of the quantity or intensity factors of soil cobalt supply to plants as defined by the isotopic exchange determinations.     

Boron adsorption characteristics of some acidic alluvial soils in relation to soil properties

Abstract

We investigated boron (B) adsorption characteristics for 16 acid alluvial soils as a function of equilibrium B concentration (0–80 μg/mL) and the effect of soil properties on such adsorption. The adsorption data for the soils could be described by Freundlich, Temkin, and BET isotherm equations over the entire concentration ranges studied, and by Langmuir and Eadie‐Hofstee equations only over a limited range. In general, the B adsorption capacity and the energy of retention of the soils calculated from different equations are low, the average Langmuir adsorption maxima and bonding energy constant being 21.47 μg/g and 0.113 mL/μg, respectively, making B susceptible to leaching losses. Simple and multiple regression analysis show that the adsorption capacities are significantly influenced by organic carbon (C), cation exchange capacity (CEC), and different forms of aluminium (Al) content in soils. The energy related constants are also influenced by the forms of Al in soils. Existence of significant correlations between constants obtained from different equations confirmed the adsorption characteristics of the soils.     

The reduction mechanism of manganese in paddy soils

Hydroquinone method manganese (soluble in pH 7.0, 1 N-ammonium acetate solution containing 0.2 percent hydroquinone) and microbially active manganese (soluble in pH 7.0, 1 M-magnesium sulfate solution after flooding soils with or without Chinese milk vetch for 12 or 20 days respectively at 30°C) of 22 paddy soils were determined. The amounts of manganese reduced with sodium oxalate under acid conditions (oxalate method manganese (a) and (b), the former was determined under more rigorous conditions than the latter) were also determined and compared with hydroquinone method manganese and microbially active manganese.

Their levels of many soil samples representing soil groups were also determined to examine the dlfferences In amounts of active manganese among soil groups. The results obtained are as follows.

The relationship between microbially and chemically active manganese. 1) The amounts of microbially active manganese in soils were 48 to 68 mg Mn per 100 g oven-dried soil and these were increased by the addition of Chinese milk vetch. 2) The amounts of hydroquinone method manganese were less than microbially active manganese, and the amounts of oxalate method manganese (b) were larger than microbially active manganese. The amounts of oxalate method manganese (a) were the largest of all the types of manganese. 3) There were high correlations between the amounts of various types of active manganese described in 2). The levels of microbially and chemically active manganese. 1) The amounts of microbially active manganese lay between the amounts of chemically active manganese determined by the hydroqulnone method and by the oxalate method (b) In all soil samples representing soil groups. High correlations were found between these types of active manganese. 2) The hydroquinone method was considered to be unsuitable for quantitatively determining the amounts of chemicallY active manganese in soils of high organic matter content. 3) In both cases of microbially active manganese and chemically active manganese, tha widest range and the largest amount determined were both observed in strongly gley soila. The averages of theae types of active manganese were high in strongly gley soils, pea, and muck soils, and black soils. The differences among soil groups were smalle1 than the differences among soil samples, and little tendency was observed in the differences among soil groups.

From these findings described above it is suggested that the oxalate methoo (b) is more appropriate than the hydroqulnone method for determining chemically active manganese as an index of microbially active manganese.     

Aluminum,manganese, and iron tolerance improves performance of wheat genotypes in waterlogged acidic soils

Waterlogging results in high shoot concentrations of iron (Fe), aluminum (Al), and manganese (Mn) in wheat grown in acidic soil. The verification of this observation in several acidic soils, development of screening techniques, and identification of genotypes differing in tolerance made it possible to test whether tolerance of ion toxicities improves performance of wheat in waterlogged acid soils. Six wheat varieties selected for tolerance/intolerance of Al, Mn, and Fe were grown in three acidic soils (pH_CaCl2 4.1–4.3) with or without waterlogging for 40 d. In terms of relative shoot dry weight, Al‐, Mn‐, and Fe‐tolerant genotypes tolerated waterlogging better, outperforming intolerant genotypes by 35%, 53%, and 32%, respectively, across the soils. The Al‐tolerant genotype had up to 1.8‐fold better root growth than the intolerant genotype under waterlogging. Waterlogging increased DTPA‐extractable soil Mn (71%) and Fe (89%), and increased shoot Fe (up to 7.6‐fold) and Al (up to 5.9‐fold) for different genotypes and soils. The Al‐tolerant genotype maintained lower tissue concentrations of Al as compared to intolerant genotypes during waterlogging. Waterlogging delayed crop development but distinctly less so in the tolerant than in the intolerant genotypes, thus jeopardizing the capacity of intolerant genotypes to produce yield in Mediterranean climates with dry finish of the season. Pyramiding multiple ion tolerances into current wheat varieties with desirable agronomic and quality characteristics to enhance their performance under waterlogged acid soils should be considered.     

The process of manganese depositton in paddy soils

Abstract

The changes in quality and quantity of phenolic substances in the decaying process of rice straw in a soil were compared under moist and flooded conditions for 200 days. The amounts of phenolic substances divided into fractions of humic acid and fulvic acid, ether- and butanol-extractable and organic solvent-unextractable fractions, then the amounts of individual phenolic acids were determined. The following results were obtained.

1) Alkali-extractable total phenolics as well as individual phenolic acids decreased more rapidly under moist, than under flooded, conditions as rice straw decayed in the soil. The phenolics present were mainly attributable to the straw, not to the soil.

2) The decrease in the level of total phenolics in the early stage of the decaying process was mainly due to the decrease in ether-extractable phenolic compounds in the fulvic acid fraction, and in the later stage, was mainly due to the decrease in butanol-extractable phenolics in the humic acid fraction.

3) The amounts of butanol-extractable phenolics and organic solvent-unextractable phenolics were larger in humic acid than in fulvic acid. On the other hand, a larger amount of organic solvent-extractable phenolics, especially ether-extractable phenolics, was present in fulvic acid.

4) The degradation patterns and pathways of individual phenolic acids in the decaying process of rice straw in soil were found to be the lame as those of decaying straw without soil which were reported previously.

5) The level of phenolic substances in the humic acid was not greatly changed during the decaying process, but the phenolic substances in fulvic acid rapidly increased for 30 days and then rapidly decreased to a constant level.     

Sources of nitrite in a permanent grassland soil

The objective of this study was to separate the observed nitrite (NO₂^–) concentration in a permanent grassland soil into process‐specific subpools. A laboratory experiment was carried out where either the nitrate and/or ammonium pool was labelled with ¹⁵N at 60 atom % excess. The main N transformations that occurred in this experiment were analysed with a ¹⁵N tracing model extended with a NO₂^– submodel. Techniques that have been used to date have been only able to identify NO₂^– subpools related to nitrification (NO₂^–_nit) and denitrification (NO₂^–_den). With the analysis presented here, we were able to quantify the size of an additional NO₂^– pool in the soil related to organic N turnover (NO₂^–_org). All transformations related to NO₂^– turnover of the three subpools occurred simultaneously. After non‐linear parameter optimization the model predicted that on average NO₂^–_den, NO₂^–_nit and NO₂^–_org pools contributed 57, 33 and 10% to the total soil NO₂^– concentration. The finding that heterotrophic processes can contribute to the NO₂^– dynamics in permanent grassland soils might also have important implications for the understanding of gaseous N production that are tightly linked to NO₂^– turnover. Further work is needed to find out how important the conversion of organic N to NO₂^– is in other soil‐based ecosystems and to identify the microbial groups responsible for this process.     

Behavior of manganese in some acid soils in Western Germany in relation to pH and air-drying

The relationships of pH to Mn concentrations in equilibrium soil solutions of strongly acid soils (pH < 4.5) were studied. The values of Mn concentrations did not conform to the solubility relationships of MnO₂, Mn₂O₃ or Mn(OH)₃. On the othr hand, a significant relationship between pMn and exchangeable Mn (r = 0.636^**, N =43) was observed. This suggest that the levels of Mn in solution are primarily controlled by exchangeable Mn in response to pH changes.

Mineral soil samples when air-dried showed a 1.5 to more than 8-fold increase in amounts of NH₄Cl-extractable Mn. This increase was not observed in soil samples rich in organic matter (> 5% organic carbon), thus excluding the possibility of release of Mn from the organic fraction of the soil. The increase is considered a consequence of increased solubility of Mn-oxides.     

印度酸性耕作土中总锰、铁以及可提取态锰、铁的水平、分布及其与土壤性质的关系研究

A total of 400 surface soil(0–15 cm) samples were collected from cultivated soils representing four soil series,namely,Hariharapur,Debatoli,Rajpora and Neeleswaram in Orissa,Jharkhand,Himachal Pradesh and Kerala states of India,respectively,and were analyzed to measure the contents of total and extractable Mn and Fe,to establish the relationship among total and extractable Mn and Fe and soil properties,and to characterize the spatial distribution pattern of Mn and Fe in some cultivated acid soils of India. The contents of total as well as extractable Mn and Fe varied widely with extractants and soil series. However,the amounts of Mn or Fe extracted by diethylene triamine penta-acetic acid(DTPA),Mehlich 1,Mehlich 3,0.1 mol L-1 HCl and ammonium bicarbonate DTPA(ABDTPA) were significantly correlated with each other(P 0.01). Based on the DTPA-extractable contents and the critical limits(2 mg Mn kg-1soil and 4.5 mg Fe kg-1 soil) published in the literature,Mn and Fe deficiencies were observed in 7%–23% and 1%–3% of the soil samples,respectively. The content of soil organic carbon(SOC) had greater influence on total and DTPA-extractable Fe than did soil pH. Geostatistical analysis revealed that total and DTPA-extractable Mn and Fe contents in the acid soils were influenced by soil pH,SOC content,and exchangeable cations like potassium,calcium and magnesium. Spatial distribution maps of total and DTPA-extractable Mn and Fe in soil indicated different distribution patterns.     

The effect of sulphur dioxide on extractable manganese in soils

Abstract

The treatment of soil with SO₂ caused rapid increases in concentrations of water soluble plus exchangeable (extractable) Mn. The extractable Mn increased with increasing pressure of SO₂ and time of exposure, and increased with increasing water contents up to field capacity but decreased beyond this point. The addition of peat to a sandy loam increased the effect of SO₂ on extractable Mn while the addition of lime decreased the effect. Reactive Mn oxides in soils may contribute significantly to SO₂ sorption by soils.     

The effect of cobalt stress on growth and physiological traits and its association with cobalt accumulation in barley genotypes differing in cobalt tolerance

Cobalt (Co) is beneficial for legume plants and not an essential element for most plants. There is no sufficient information about the effect of Co stress on barley growth. The current experiment was carried out to investigate the effects of different Co levels (25, 50, 75, and 100 µM) on growth and physiological traits of three barley genotypes (B325, J36, and B340) differing in Co tolerance. The results showed that Co stress inhibited plant growth, decreased chlorophyll content and photosynthetic rate, and enhanced oxidative stress. However, the effects differed among genotypes, with B325 and B340 being the most and the least affected, respectively. Co stress caused decrease and increase of manganese (Mn) and phosphorus (P) concentrations in both roots and shoots, respectively; iron (Fe) concentration had little change in shoots and a significant decrease in roots. The current results showed a close association of Co tolerance and its accumulation in plant tissues.     

Estimation of plant available manganese in acidic subsoil horizons

Abstract

General agreement does not exist as to the most appropriate method to estimate plant available Mn in soils. In the current investigation soil and soil solution Mn were measured in limed and unlimed treatments of 11 acidic subsoil horizons and related to plant Mn concentrations, Mn uptake and growth of subterranean clover (Trifolium subterraneum L. cv. Mt. Barker) and switchgrass (Panicum virgatum cv. Cave‐in‐Rock). Manganese measurements were taken at planting and harvest and included: Mn extracted by 1M NH₄OAc (pH 7), 0.01M CaCl₂, 0.05M CaCl₂, 0.033M H₃PO₄, 0.005M DTPA, 0.2% hydroquinone in 1M NH₄OAc (pH 7), 0.01M NH₂ OH.HCl 4 2 in 0.01M HNO₃, total soil solution Mn and concentrations and 2+ activities of Mn²⁺ calculated from the GEOCHEM program. Measured and calculated values of soil solution Mn generally gave the best correlations with subterranean clover and switchgrass Mn concentrations and Mn uptake. Root Mn concentrations were highly correlated with soil solution Mn measurements taken at harvest with r=0.97 and r=0.95 (p<0.01) for subterranean clover and switchgrass respectively. The Mn extracted by 0.01M CaCl was also significantly correlated (p<0.01) with plant Mn concentrations and Mn uptake and proved to be better than the other extractants in estimating plant available Mn. Although Mn concentrations as high as 1769 mg/kg (shoots) and 8489 rag/kg (roots) were found in subterranean clover, Mn did not appear to be the major factor limiting growth. Measures of soil and soil solution Mn were not strongly correlated with yield. Both Al toxicities and Ca deficiencies seemed to be more important than Mn toxicities in limiting growth of subterranean clover and switchgrass in these horizons.     

Microbial and enzyme activity in soils amended with a natural source of easily available carbon

The addition of sugar beet to soils as a source of C led to an increase in the availability of easily utilizable C (glucose), which in turn markedly increased numbers of soil bacteria and of the yeast Williopsis californica. Nitrification, P solubilization, urea hydrolysis (and the subsequent nitrification of liberated NH _inf4 ^sup+ ) were stimulated by this amendment. The stimulation of nitrification may have been a result of increased heterotrophic nitrification. In contrast, the concentration of sulphate in S^o-amended soils declined following amendment, presumably as the result of enhanced S immobilization. Activity of the enzymes amylase, aryl sulphatase, invertase, phosphatase, dehydrogenase, and urease were all stimulated by the sugar beet amendment. These results suggest that sugar beet amendment could be used to increase the rate of release of plant-available ions from fertilizers such as insoluble phosphates. Problems may arise, however, from a subsequent increase in nitrification and reduced sulphate availability.     

Release of interlayer potassium in Norwegian grassland soils

Potassium (K) release from sources that are not initially exchangeable is attributed to depletion of interlayer K of micas and clay minerals or weathering of feldspars. The aim of the present study was to estimate the K release from interlayer K. Soil samples from 17 field experiments in ley on a range of mineral soils in Norway were used in the study. The change in K‐fixation capacity was used as an estimate of depletion of interlayer K. It was assumed that the increase in K‐fixation capacity during 3 yr of cropping was equivalent to the amount of K depleted from the interlayer positions. Mean K fixation increased in the majority of the soils during 3 yr of grass cropping both with and without K application. The increase in K fixation indicated that without K application, the K uptake from interlayer K amounted to 43%, 28%, and 26% of the K yield for clay soils, high‐K sandy soils, and low‐K sandy soils, respectively. Including K uptake from exchangeable K in the topsoil and from subsoil, the explained K uptake amounted to 79%, 69%, and 81% for the three groups of soil, respectively. Simple linear‐regression analyses showed that the change in K fixation during 3 yr of grass cropping was best explained by the percentage of clay in the soil.     

Spatial variability of earthworm populations in a permanent polder grassland

Summary We studied the earthworm distribution in a permanent polder grassland by making two detailed surveys in 1983 and in 1990. Geostatistical procedures were used to investigate the changes in species composition and to determine the dispersal rate. Attention was focused on two soil survey variables closely related to earth-worm distribution, the thickness of the A_h horizon and the number of burrows. The dispersal rate between the two survey dates was 13 m year^–1 compared with 10 m year^–1 before 1983. The difference was attributed either to the development of new population centres due to dispersal by cow's feet or tractor wheels, this altering the spatial dynamics, or to a lag phase in population development in the years following inoculation.     

Progress in studies of nitrate leaching from grassland soils

Abstract. The large input of research effort on aspects of nitrate leaching over the last two decades has produced many innovative scientific and practical results. The MAFF Nitrate Programme has enabled considerable progress to be made in unravelling much of the complexity of the grassland nitrogen (N) cycle, and identifying gaps as essential first stages in providing improved managements for N in grassland systems. From a practical standpoint, there have been key outputs which have allowed the identification of options for policy, and which should allow grassland farmers to increase the efficiency of N use throughout their farming system and thereby improve the sustainability of their enterprises. As well as quantifying N transformations, transfers and losses, other important outcomes have been the development of user-friendly models of N cycling (NCYCLE and variants) and an easy to use field kit to determine mineral N in pasture soils. The use of modelling to produce fertilizer recommendations with a Decision Support System and of new approaches developed within the Programme, in particular system synthesis desk studies, and 'farmlet' investigations to determine the consequences of modifying N flows and losses, have allowed us to produce solutions to satisfy the dual aims of meeting environmental and economic production targets.