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1.
Al chemistry was studied in two acidic watersheds, one with a podzol, the other with an acid brown soil, in the Vosges mountains (N.E. France), by analysing both leaching and centrifugation soil solutions and spring waters over 3 yr. In the podzol, Al was mobilized in the eluvial horizons under the predominant influence of organic acidity, then leached down the profile as organic and F-bound Al. Strong undersaturation with respect to proto-imogolite and imogolite showed that the proto-imogolite theory of podzolization could not apply. Al was transferred from the soil to spring water mostly as Al3+ and Al-F. Al3+, as well as additional minor species (AlOH2+, AlSO4 +), originated from the redissolution of the top of the spodic horizons under the influence of both soil solution acidity and the occurrence of mobile anions derived from atmospheric deposition. Conversely, in the acid brown soil, Al mobilization was regulated by nitrate and occurred mainly as Al3+. Most of Al was retained in the deep soil and only traces of monomeric Al reached spring water. In the podzol eluvial horizons, soil solutions were undersaturated with respect to all relevant mineral phases and their chemical composition agree with the concept of a mobilization of Al from the solid soil organic Al and a control of Al3+ activity by complexation reaction with the solid and soluble soil organic matter and F. In the acid brown soil, soil solutions were found to be in equilibrium with natural alunite, and the formation of this mineral, if confirmed, would account for the occurrence of 'open' vermiculites instead of the expected hydroxy-Al interlayered vermiculites. Al solubility control in surface water of both watersheds remains unclear. The Al-F species in both watersheds and the likely control of Al solubility by alunite in the acid brown soil emphasize the influence of acid deposition on Al chemistry in acid watersheds.  相似文献   

2.
This paper presents aluminium (Al)-solubility data for two acid forest soils (Inceptisol and Spodosol), obtained in connection with lysimeter measurements (tension-cup and zero-tension lysimeters) and batch equilibrium experiments. The solubility of Al obtained in the batch experiments was used as a reference to test whether Al3+in soil solutions collected by the lysimeters was in equilibrium with secondary forms of solid-phase Al (Al(OH)3or organically bound Al). The relation between pH and Al3+activity found for the zero-tension lysimeter solutions collected from the Inceptisol agreed well with that obtained in the batch experiment. This suggests that Al3+in the lysimeter solutions were in, or close to, equilibrium with the solid phase, whether this was organically bound Al (A horizon) or an Al(OH)3phase (B horizon). For the tension-cup lysimeters, solutions obtained from the Inceptisol B and Spodosol Bs1 horizons were generally close to equilibrium with respect to secondary solid-phase Al (apparently Al(OH)3; average ion activity product was 109.3and 108.8, respectively), whereas the Inceptisol A and Spodosol Bh solutions were not. The Al solubility in Inceptisol A and Spodosol Bh horizons was consistently higher than that obtained in the batch equilibrium experiment, indicating that the sampled solution partly originated from the underlying horizons. Thus, tension-cup lysimeters should be used with care in soils (or in parts of soil profiles) having steep solute concentration gradients because the soil volume from which the sample is drawn with this lysimeter type seems to be poorly defined.  相似文献   

3.
The Al species in the soid and liquid phases were studied in eight soils developed from slates in a watershed subjected to acid deposition. From soil solution data the mechanisms possibly controlling Al solubility are also discussed. The soils are acidic, organic matter rich and with an exchange complex saturated with Al. In the solid phase, more than 75% of non-crystalline Al was organo-Al complexes, mostly highly stable. In the soil solutions, monomeric inorganic. Al forms were predominant and fluoro-Al complexes were the most abundant species, except in soil solutions of pH<4.8 and Al L/F ratio >3, in which Al3+ predominated and sulphato-Al complexes were relatively abundant. The most stable phases were kaolinite, gibbsite and non-crystalline Al hydroxides. In most samples, Al solubility was controlled by Al-hydroxides. Only in a few cases (solutions of pH 4-5, Al3+ activity >40 µmol L-1 and SO4 content >200 µmol L-1), Al-sulphates such as jurbanite also could exert some control over Al solubility. In adition to these minerals, a possible role of organo-Al complexes or the influence of adsorption reactions of sulphate is considered, especially for samples with very low Al3+ content (<0.5 µmol L-1).  相似文献   

4.
Abstract

Al toxicity in plants is related to the activity of Al3+ and Al‐hydroxy monomers in the soil solution, whereas Al complexed with ligands such as fluoride (F), sulphate (SO4 2‐), and oxalate is not toxic. Estimation of toxic Al relies on measurement of “labile”; Al after short contact times with colorimetric reagents or cation‐exchange resins. However, shifts in equilibrium may result in non‐toxic forms of Al reacting with the complexing agent or resin.

A series of laboratory experiments tested the degree to which labile Al is related to Al3+ in simplified media and compared methods of estimating labile Al in the presence of organic ligands and in soils. Cation‐exchange resins extracted more than the theoretical concentration of Al3+ from solutions containing a range of concentrations of OH and SO4 2‐. More Al was extracted in 15 s by 8‐hydroxy‐quinoline than by Chelex‐100 from solutions of Al‐humate at pH 4. In sands which had been spiked with Al and organic matter, the estimation of labile Al varied with both the method of measurement and type of extract. The cations present in commonly used soil‐extracting chloride solutions can decrease the proportion of organically complexed Al.  相似文献   

5.
Abstract

Hydroponic studies with soybean (Glycine max [L.] Merr.) have shown that µmol L?1 additions of Mg2+ were as effective in ameliorating Al rhizotoxicity as additions of Ca2+in the mmol L?1 concentration range. The objectives of this study were to assess the ameliorative effects of Mg on soybean root growth in acidic subsoils and to relate the soil solution ionic compositions to soybean root growth. Roots of soybean cultivar Plant Introduction 416937 extending from a limed surface soil compartment grew for 28 days into a subsurface compartment containing acid subsoils from the Cecil (oxidic and kaolinitic), Creedmoor (montmorillonitic) and Norfolk (kaolinitic) series. The three Mg treatments consisted of native equilibrium soil solution concentrations in each soil (50 or 100 µmol L?1) and MgCl2 additions to achieve 150 and 300 µmol L?1 Mg (Mg150 and Mg300, respectively) in the soil solutions. Root elongations into Mg-treated subsoils were compared with a CaCO3 treatment limed to achieve a soil pH value of 6. Subsoil root growth responses to the Mg treatments were less than for the lime treatments. Root length relative to the limed treatments for all subsoils (RRL) was poorly related to the activity of the soil solution Al species (Al3+ and Al-hydroxyl species) and Mg2+. However, the RRL values were more closely related to the parameters associated with soil solution Ca activity, including (Ca2+), (Al3+)/(Ca2+) and (Al3+)/([Ca2+] + [Mg2+]), suggesting that Ca could be a primary factor ameliorating Al and H+ rhizotoxicity in these subsoils. Increased tolerance to Al rhizotoxicity of soybean by micromolar Mg additions to hydroponic solutions, inducing citrate secretion from roots to externally complex toxic Al, may be less important in acid subsoils with low native Ca levels.  相似文献   

6.
Complexation with organic matter controls the activity of dissolved Al3+ in many soils. The buffering intensity of these soils is largely dependent on the H+/Al3+ exchange ratio, i.e. the number of protons consumed by the solid phase when one Al3+ is released. Here, the H+/Al3+ exchange ratio was determined from batch titrations using solutions of fulvic acid (FA) as a model for soil organic matter. Aluminium was added, from 1.04 to 6.29 mmol Al per g FA, which is within the range of humus‐bound Al found in the upper B horizon of podzolized soils. Furthermore, pH was varied with NaOH to give values between 3.5 and 5.0. The H+/Al3+ exchange ratio ranged between 1.49 and 2.23 with a mean of 1.94. It correlated positively with pH and the total concentration of Al present. Theoretically, this can be explained with a partial hydrolysis of bound Al. The slope of logAl (log10 of Al3+ activity) against pH generally underestimated the actual exchange ratio, which can partly be attributed to the systems being diluted (100 mg FA l?1). However, where 4 mmol Al or more had been added per g FA, the logAl slope gradually approached ?3 between pH 4.5 and 5.0. This might be the result of a shift from Al3+ activity control by humus complexation to control by Al(OH)3(s).  相似文献   

7.
The molar ratio of base nutrient cations to total dissolved aluminum (BC : Altot) in the soil solution was measured at six forest sites in Switzerland in acid mineral soils to determine whether the ratio measured in the field was lower than the critical value of 1, as predicted by the mapping of exceedances of critical loads of acidity. The soil chemistry was then related to the soil solution composition to characterize the typical effective base saturation (BS) and BC : Al ratio in soil leading to critical BC : Altot in the soil solution. The median BC : Altot ratio in the soil solution never reached the critical value in the root zone at any sites for the whole observation period (1999–2002), suggesting that the BC : Altot ratios measured in the field might be higher than those modeled for the determination of critical loads of acidity. The gibbsite model usually applied for the calculation of critical loads was a poor predictor of the Al3+ activity at the study sites. A curvilinear pH‐pAl3+ relationship was found over the whole range of pH (3.8–6.5). Above a pH of 5.5, the slope of the pH‐pAl3+ relation was close to 3, suggesting equilibrium with Al(OH)3. It decreased to values smaller than 1.3 below a pH of 5.5, indicating complexation reactions with soil organic matter. The BS and the BC : Al ratios in the soils were significantly correlated to the BC : Altot ratios in the soil solution. The soil solutions with the lowest BC : Altot ratios (≤ 2) were typically found in mineral soils with a BS below 10 % and a BC : Al ratio in the soil lower than 0.2. In acid pseudogleyed horizons overlying a calcareous substrate, the soil solution chemistry was strongly influenced by the composition of the underlying soil layers. The soil solutions at 80 cm had pH values and BC : Altot ratios much higher than expected. This situation should be taken into account for the calculations of critical loads of acidity.  相似文献   

8.
Alum sludge derived from a municipal wastewater plant was used as a soil amendment in a greenhouse study with barley (Hordeum vulgare) as the test crop. Treatment variables included the soil pH (4.5, 5.1 and 6.5), the amount of Al in the sludge (control = 30 mg AlT/g; alum sludges = 38 and 52 mg AlT/g), and the sludge application rate (100 and 270 kg NT/ha). Soil amendment with the two alum sludges reduced soil pH, increased Al3+ activity in the soil solution, and reduced barley growth over the 6-week experiment. Barley growth decreased as the Al3+ activity in the sludged soil solution increased, but for a given Al3+ the phytotoxicity of Al was markedly pH dependent. For example, at a pH of 5.0 ± 0.1 an Al3+ activity of 0.5 μM was sufficient to inhibit plant growth by about 50% this IC50 value increased five-fold to about 2.5 μM when the soil pH was 4.5 ± 0.1. This decrease in the toxicity of Al50 with acidification was explained in terms of a competitive interaction between the H+-ion and Al3+ at the root surface. Stepwise multiple regression allowed the prediction of aerial leaf biomass from soil pH and sludge application rate.  相似文献   

9.
Two sequential extractions with unbuffered 0.1 m BaCl2 were done to study the release of salt-exchangeable H+ and Al from mineral horizons of five Podzols and a Cambisol. Released Al was found to have a charge close to 3+ in all horizons and in both extractions. This finding was supported by the near-equality of the titrated exchangeable acidity (EAT) and the sum of exchangeable acids (EA = He + 3Ale, calculated from the pH and Al concentration of the extract). The ratio between EA of the second and the first extraction was over 0.50 in the Bs2 and C horizons and smaller in the other horizons. H+ was assumed to be in equilibrium with weak acid groups, and the modified Henderson–Hasselbach equation, pKHH = pH ? n log (α/(1 ? α)), was used to explain pH of the extract. The degree of dissociation (α) was calculated as the ratio between effective and potential cation exchange capacity. Value of the empirical constant n was found to be near unity in most horizons. When the monoprotic acid dissociation was assumed in all horizons, pKHH had the same value in both extractions. For Al3+, two equilibrium models were evaluated, describing (i) complexation reactions of Al3+ with soil organic matter, and (ii) equilibrium with Al(OH)3. Apparent equilibrium constants were written as (i) pKo = xpH ? pAl3+, and (ii) log Qgibbs= log Al3+ ? 3log H+. The two extractions gave an average reaction stoichiometry x close to 2 in all horizons. Results suggest that an equilibrium with organic Al complexes can be used to express dissolved Al3+, aluminium being apparently bound to bidentate sites. The value of log Qgibbs was below the solubility of gibbsite (log Kgibbs = 8.04) in many horizons. In addition, log Qgibbs of the second extraction was greater than that of the first extraction in all horizons except the C horizon. This indicates that equilibrium with Al(OH)3 cannot explain dissolved Al3+ in the soils. We propose that the models of pKHH and pKo can be used to simulate exchangeable H+ and Al3+ in soil acidification models.  相似文献   

10.
Colorimetric and ion exchange methods are commonly used to distinguish and measure Al species in natural waters. Unfortunately they also include weakly complexed Al species in their ‘reactive' or ‘labile' Al fractions and thus are of limited value for the estimation of free Al3+. Capillary electrophoresis (CE) has the potential for direct measurement of Al3+, and its performance has been verified experimentally. The method also detected the stable and positively charged AlOx+ complex formed with oxalic acid. It was compared with a colorimetric and an ion exchange method by analysing artificial solutions containing low molecular weight organic acids as well as soil extracts and seepage waters and was found to be the only method closely matching the theoretically calculated values of free Al3+. In samples from the upper soil horizons of an acid forest soil less than 14% of total Al was present as free Al3+, whereas the colorimetric method found more than 65%, and the ion exchange method more than 80% of total Al in a ‘reactive' or ‘labile' form. The latter methods thus would seriously overestimate Al toxicity, whereas using CE Al toxicity is likely to be only slightly underestimated.  相似文献   

11.
Exchangeable and soluble soil aluminum (Al) is limiting plant growth in many soils worldwide. This study evaluated the effects of increasing rates of dolomite and magnesium carbonate (MgCO3) on Al3+, pH, dissolved organic carbon, cations, anions, and Al speciation on oil palm Deli dura × AVROS pisifera root growth. Dolomite and MgCO3 additions significantly raised linearly soil solution pH, magnesium (Mg2+), nitrate (NO3 ?) and chlorine (Cl?) concentrations; exponentially decreased the activity of phytotoxic Al species [aluminum (Al3+), aluminum sulfate (Al2SO4), and aluminum fluoride (AlF3)]; and reduced manganese (Mn) concentration and activity. High activity of those species exponentially reduced root dry weight. Optimum oil palm growth was achieved at: <50 μM monomeric Al, < 30 μM Mn, and <0.20 unit of the ratio Al+Mn to calcium (Ca)+Mg. High activity of Al species and Mn in acidic soil solution cause significant reduction of the root growth. Soil acidity alleviation either with dolomite or MgCO3 mitigates the toxic effect of Al and Mn.  相似文献   

12.
Exchange reactions between 0.0in AlCl3 solutions of different pH and Ca-saturated montmorillonite, vermiculite, illite, and soils from the Park Grass Experiment at Rothamsted and the Deerpark Experiment, Wexford, Ireland, showed that Al3+ and Al(OH)2+ were adsorbed from solutions of pH > 4.0 and Al3+ and H+ from solutions of pH < 3.0. When Al was adsorbed, the cation exchange capacity of Ca-saturated soils and clays increased. Conventional Ca: Al exchange isotherms showed that Al3+ was strongly preferred to Ca2+ on all soils and clays. The equilibrium constant for Ca: Al exchange, K, was identical for soils before and after oxidizing their organic matter and did not vary, for any exchanger, with Al-saturation or the initial pH of the AlCl3 solution. This proved the validity of the procedure used for calculating exchangeable Al3+. K values for Ca:Al exchange favoured Al3+ in the order: vermiculite > Park Grass soil > Deerpark soil > illite > montmorillonite. The influence of surface-charge densities of the clay minerals on this order is discussed and a method proposed and tested for calculating the K value of a soil from its mineralogical composition.  相似文献   

13.
《Soil biology & biochemistry》2012,44(12):2427-2431
Arbuscular mycorrhizal spores and glomalin-related soil protein (GRSP) isolated from acid soils were analyzed using confocal laser scanning microscopy (CLSM) for Al detection. Mycorrhizal structures of Glomus intraradices produced under in vitro conditions as well as spores and GRSP from neutral and Cu-polluted soils were used as contrasting criteria. Spores and GRSP from soils with 7 and 70% Al saturation showed autofluorescence which increased especially at the highest soil Al level and when Al3+ solution was added. G. intraradices spores showed fluorescence only when exogenous Al3+ was added. On the contrary, spores and GRSP from neutral and Cu-polluted soils showed little or no significant fluorescence. This fluorescence shown by fungal structures and GRSP when subjected to high Al (of endogenous or exogenous origin) suggest a high capacity for Al immobilization, which could be an effective way to reduce Al activity and phytotoxicity in acid soils.  相似文献   

14.
Labile Al in the soil solution measured by 8-hydroxyquinoline (AlHQ) was a better predictor of plant growth than trivalent Al (AlIC3+) measured by ion chromatography (IC). HQ reacted with some organic Al complexes which did not separate during chromatography. In the presence of oxalic acid, AlHQ was greater than AlIC3+, which was the same as the greater than Al3+ (Al3+Calc), whereas in the presence of citric acid, AlHQ was greater than AlIC3+, and both were greater than Al+3Calc, In extracts of soils that had been acidified, Al3+IC was less than AlHQ, which was similar to Al3+Calc, when it was assumed that the only complexing ligands were OH? and F?. The proportion of Al3+IC in the soil solutions decreased more than AlHQ as the pH increased. Organic ligands appeared to form complexes with Al at the expense of AIF complexes. Forms of Al detected by IC differed in CaCl2 extracts and soil solutions. AlHQ in the CaCl2 extracts and soil solution were closely correlated, although the proportion of AlHQ was higher in the CaCl2 extracts. And soil solutions. AlHQ in the CaCl2 extracts and soil solution were closely correlated, although the proportion of AlHQ was higher in the CaCl2 extracts.  相似文献   

15.
Arbuscular mycorrhizal spores and glomalin-related soil protein (GRSP) isolated from acid soils were analyzed using confocal laser scanning microscopy (CLSM) for Al detection. Mycorrhizal structures of Glomus intraradices produced under in vitro conditions as well as spores and GRSP from neutral and Cu-polluted soils were used as contrasting criteria. Spores and GRSP from soils with 7 and 70% Al saturation showed autofluorescence which increased especially at the highest soil Al level and when Al3+ solution was added. G.intraradices spores showed fluorescence only when exogenous Al3+ was added. On the contrary, spores and GRSP from neutral and Cu-polluted soils showed little or no significant fluorescence. This fluorescence shown by fungal structures and GRSP when subjected to high Al (of endogenous or exogenous origin) suggest a high capacity for Al immobilization, which could be an effective way to reduce Al activity and phytotoxicity in acid soils.  相似文献   

16.
This paper describes the effect of treating a nutrient-poor forest soil in monolith lysimeters with H2SO 4, pH 3.0, for 4.75 yr. The lysimeters were instrumented with porous cup probes to distinguish processes occurring in each soil horizon. In the A horizon base cation exchange and sulphate absorption were the principal proton- consuming processes whereas lower down the profile Al3+ dissolution from hydrous oxides dominated. Acid treatment thus reduced the amount of amorphous Al in the lower horizons, but exchangeable Al was unaffected. Sulphate absorbtion was positively correlated with the distribution of Al hydrous oxides. High rates of nitrification reduced the differences between acid and control monoliths, but acid treatment significantly reduced soil pH down to 75 cm and reduced the levels of exchangeable base cations in the litter and A horizons. Acid treatment increased the leaching rates of base cations and Al. Consideration of the total base cation content shows that acid treatment increased the rate of weathering by 0.7–1.4 k eq ha?1 yr?1. The results should be useful in modelling more realistic rates of acid input to similar soils.  相似文献   

17.
From acidic tea soils of Kagoshima Prefecture in Japan, some soil properties were determined and 38 strains of acid tolerant microorganisms were isolated. Different Al3+ concentrations were applied to YG media to estimate Al resistance. Selected microbial strains could grow strongly in the liquid media in the presence of 100 mM Al3+ and survive even in 300 mM Al3+ at pH 3.0. Their base sequences of 28S rDNA-D1/D2 were determined and sequence data were searched using the Basic Local Alignment Search Tool (BLAST) system. The results of sequencing revealed that the isolates belong to two different species, Cryptococcus sp. and Candida palmioleophila. When cultivated with various Al3+ concentrations, the yeast growth was inhibited at a concentration of 200 mM. Pre-cultivation of these strains with 0–30 mM Al3+ did not promote the growth response caused by Al3+. Inductively-Coupled Plasma-Mass Spectrometry (ICP-MS) was used to assess the elimination of Al. The amount of Al remaining in culture media was decreased considerably after cultivation. Due to a capacity for resistance to significant Al concentrations as well as high Al elimination, these acid tolerant and Al resistant yeasts may have potential applications in the bio- and phyto-remediation of Al and acid-contaminated soils.  相似文献   

18.
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 (AlT) and monomeric (Almono) 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 AlT and Almono 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.  相似文献   

19.
有机肥缓解小麦铝毒效果的研究   总被引:13,自引:0,他引:13  
以交换性Al为1.83[1/3Al3+]cmol/kg的淋溶型水田砂质土(低Al毒)和交换性Al为6.05[1/3Al3+]cmol/kg的黄筋泥(红壤,高Al毒)为供试土壤,研究了有机肥对缓解小麦铝毒的效果。盆栽试验(均有充足N、P、K基肥)结果表明,小麦(扬表5号)在这两种土壤上均发生Al毒。在前一种土壤上生育不良,减产约一半左右,后一种土壤上几近绝收。施用生产中常量猪厩肥(约22.5/hm2),与施用石灰比较,在低Al毒土壤上,产量接近施石灰处理(90%~100%),能基本消除Al毒;在高Al毒土壤上,同样表现出一定的解Al毒效果,但还不够明显,产量只为石灰处理的1/4。土壤测定表明,施用猪厩肥使交换性Al下降18.1%~38.7%。植株分析也表明,吸收的Al相应减少。土壤Al毒明显抑制小麦对K、Ca、Mg的吸收;对S则有促进吸收的趋势;对N、P、Fe、Zn的吸收影响不大。在Al毒土壤上施用猪厩肥,不仅降低Al的吸入,并可减缓Al对小麦Ca、Mg、K吸收的抑制作用,有利于体内营养元素间的平衡。  相似文献   

20.
It is shown that Al-humate and fulvate precipitates in Bs horizons of pH > 4.6 can be the source of the soluble aluminium which is rapidly released in equilibrium studies to give log10{Al3+} + 3pH values near 9.4 at 8°C, so that it is not necessary to postulate an anomalously reactive but sparingly soluble Al(OH)3 phase. These Al-organic precipitates will have reached equilibrium in the natural soil environment with the more slowly reacting hydroxy-aluminium precipitates present, including proto-imogolite allophane, but can release Al3+ much more rapidly than the inorganic precipitates in laboratory equilibrations and soil leaching episodes that yield lysimeter waters. Equilibrium concentrations of Al reported in a range of Bs horizons indicate that the allophanes present are less soluble than proto-imogolite sols prepared in the laboratory and matured for up to 2 years.  相似文献   

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