Modelling pH buffering and aluminium solubility in European forest soils

The pH buffering and aluminium solubility characteristics of acid soil are important in determining the soil's response to changes in precipitation acidity. The chemistry of soil organic matter (humic substances) plays a key role in both processes, yet is complex and still poorly understood. Nevertheless, models of humic substance chemistry have been developed, one of which is WHAM–S, which contains a model (Model V) of proton and metal binding at discrete sites on humic substances and considers electrostatic effects on the binding strength. Here we have tested the ability of WHAM–S to model solution pH and Al using batch titration studies on organic and mineral soil horizons from forested sites in Norway, Germany and Spain, with ambient pH values from 3.73 to 5.73. We optimized the model predictions by adjusting the amounts of soil aluminium and humic substances within defined limits, taking the contents of copper chloride‐extractable Al and the base‐extractable organic matter as starting values. The model simulated both pH and dissolved Al well with optimized amounts of aluminium and humic substances within the defined limits (root mean squared error for pH from 0.01 to 0.22, for p[Al]_aq (total dissolved Al) from 0.03 to 0.49, five data points). Control of dissolved Al by dissolved organic matter was important particularly at above‐ambient pH. In two mineral horizons we improved the fits by assuming that Al could precipitate as Al(OH)₃. The optimized model also gave reasonable predictions of pH and dissolved Al in supernatants obtained by repeated leaching of the soil horizons. The results show that humic substances dominate the control of pH and dissolved Al in most of the horizons studied. Control by Al(OH)₃ occurs but is the exception.     

Rapid,Wet Oxidation Procedure for the Estimation of Silicon in Plant Tissue

Abstract

The quantification of silicon (Si) in plant samples is being requested more frequently, especially in agricultural laboratories associated with the determination of nutritional requirements of sugarcane (Saccharum officinarum L.) and rice (Oryza sativa L.). The analysis of plant material for Si can be protracted, especially if laboratories do not have access to X‐ray flourescence (XRF) instrumentation and large numbers of samples are involved. A simplified procedure using equipment considered standard in most agricultural laboratories is reported. Dry, ground plant material is subjected to nitric acid/peroxide oxidation in a low‐pressure laboratory microwave digestion system. The hydrated silica liberated from the organic matrix is dissolved in a small volume of sodium hydroxide solution also using the microwave digestion system. Silicon is measured by inductively coupled plasma atomic emission spectrometry (ICP‐AES). This method gives results that are linearly correlated with the much slower conventional techniques and avoids using hazardous chemicals (hydrofluoric acid) sometimes employed in other microwave methods.     

Orthophosphate and organic phosphate in the soil solution of four sandy soils in relation to pH‐evidence for humic‐FE‐(AL‐) phosphate complexes

Abstract

Soil from the Ap‐horizon of four acid sandy soils differing mainly in Corg content was adjusted to pH values between 3 and 7.5 with NaOH and HCl respectively and incubated for two weeks. Afterwards, displaced soil solution was obtained and analyzed.

The concentrations of Fe, Al, and P showed a broad minimum in the pH range from 4 to 6. The concentration of these elements strongly increased with the increase of pH to 7.5. Acidification below pH values of 4 led to a slight increase.

Separation of dissolved organic carbon by ultrafiltration before the photometric orthophosphate determination decreased measured concentrations in comparison to direct determination in two of the four soils. This decrease was more pronounced for soil solutions with higher concentrations of organic carbon. The effect of acid hydrolysis of organic phosphorus during orthophosphate determination can be explained by existence of humic‐Fe‐(Al phosphate complexes in the soil solution. These complexes can account for more than 50% of the total organic P in solution.     

Complexometric gel permeation chromatography of soluble humic substances using Sephadex G-25

Sephadex G-25 was used with 0.01 m sodium acetate containing a concentration of 3×10^?5m Cu(II) as eluent to establish the molecular-size distribution (MSD) and the Cu complexation of molecular-weight fractions of organic solutes. The appropriateness of this modified gel permeation method for complexometric measurements on soluble humic Substances was investigated employing various types of soil solutions. The presence of Cu in the eluent had an effect on the MSD obtained by elimination of electrostatic repulsion between gel and solutes. No evidence was found that the presence of Cu in the chromatographic system induced aggregation of the organic substances. The Cu-binding capacity of the samples as obtained with this gel permeation method was found to increase linearly over a wide sample concentration range varying from 40–2000 mg C dm^?3. No interference was observed between the Cu-complexation by exclusion and inclusion peaks in the chromatograms. The analyses revealed that the fraction apparently low in molecular weight makes a large contribution to the complexation potential of forest soil solutions.     

Phosphite determination in fertilizers after online sequential sample preparation in a flow injection system

A flow injection spectrophotometric system is proposed for phosphite determination in fertilizers by the molybdenum blue method after the processing of each sample two times on-line without and with an oxidizing step. The flow system was designed to add sulfuric acid or permanganate solutions alternately into the system by simply displacing the injector-commutator from one resting position to another, allowing the determination of phosphate and total phosphate, respectively. The concentration of phosphite is obtained then by difference between the two measurents. The influence of flow rates, sample volume, and dimension of flow line connecting the injector-commutator to the main analytical channel was evaluated. The proposed method was applied to phosphite determination in commercial liquid fertilizers. Results obtained with the proposed FIA system were not statistically different from those obtained by titrimetry at the 95% confidence level. In addition, recoveries within 94 and 100% of spiked fertilizers were found. The relative standard deviation (n = 12) related to the phosphite-converted-phosphate peak alone was 相似文献   

Purification of cyclopiazonic acid by liquid chromatography

A purification procedure for cyclopiazonic acid has been developed, using sequential preparative and semi-preparative liquid chromatography. Crude cyclopiazonic acid (324 mg) was extracted from a 1 L fermentation medium with chloroform-methanol (80 + 20), dried, dissolved in chloroform, and chromatographed on an oxalic acid/silica preparative column with chloroform-methanol (99 + 1) as the eluant. A semi-preparative oxalic acid/silica column and chloroform-methanol (99.5 + 0.5) were then used for rechromatography of the partially purified cyclopiazonic acid. This second chromatographic treatment yielded fractions from which cyclopiazonic acid was readily crystallized (106.7 mg; 33% recovery). Analytical chromatography was developed using an amino column in an ion-exchange mode, with a methanol-phosphate buffer eluant. Response was linear from 10 to 800 micrograms/injection of standard solutions. Cyclopiazonic acid chemically binds sodium from soda-lime vials.     

DISSOLUTION KINETICS OF SILICATE MINERALS IN AQUEOUS CATECHOL SOLUTIONS

Fine particle samples of silicate minerals and of gibbsite were shaken with solutions of pyrocatechol, 4-nitro-pyrocatechol or 3,4-dihydroxybenzoic acid at pH 9·3–9·7 and 25°C. In 63 days, from 1·4 per cent (illite) to 17·9 per cent (nepheline) of the silica present was dissolved. Except for kaolinite in solutions of the two substituted catechols, the aluminosilicates dissolved incongruently, leaving residues enriched with aluminium. When accumulated amounts of elements (Si, Al, Na, K) dissolved from nepheline were plotted against time on log-log paper straight lines were obtained. For quartz, kaolinite, and in some cases gibbsite similar plots could be approximated by two straight-line segments. The plots for microcline and oligoclase may be described by a combination of three-line segments. Several possible reaction mechanisms are discussed but a mechanism which explains the similar rate profiles has not yet been formulated.     

水稻土中水溶性有机碳对铁还原过程的贡献

【目的】 淹水稻田中Fe (Ⅲ) 还原过程与有机质的厌氧分解和氮、磷、硫等营养元素的有效性密切相关。通过探讨水溶性有机碳 (DOC) 对Fe (Ⅲ) 还原过程的贡献,以期为深入理解淹水稻田中铁循环耦联的碳、氮、磷、硫循环提供理论基础。 【方法】 采集我国不同植稻区的20个典型水稻土,通过有机碳分析仪及三维荧光光谱扫描比较分析不同水稻土DOC的含量及荧光特性;并模拟稻田淹水过程对水稻土进行厌氧淹水培养,采用微生物生长模型对不同水稻土厌氧培养过程中Fe (Ⅲ) 还原特征进行表征;依据相关分析和冗余分析,明确水稻土DOC与Fe (Ⅲ) 还原过程的关系。 【结果】 不同水稻土DOC含量为0.250～1.082 g/kg,仅占土壤有机碳的2.06%～6.86%。三维荧光光谱扫描鉴定得到不同水稻土DOC中4个共有的类腐殖酸荧光组分,其中陆源的UVC类腐殖酸和UVC+UVA类腐殖酸组分在不同水稻土中具有较高荧光强度,分别为0.799～4.570和0.830～5.273。水源的可见光区类腐殖酸和UVA腐殖酸的含量相对较低。各类腐殖酸来源以外源输入为主,内源输入为辅。不同水稻土铁还原潜势a、最大Fe (Ⅲ) 还原速率 (V_max) 及达到最大Fe (Ⅲ) 还原速率对应的时间 (T_Vmax) 间均差异显著,淹水5 d时水稻土中易被还原的非晶态氧化铁已基本被还原。DOC的腐殖化系数与Fe (Ⅲ) 还原特征参数存在显著相关性。其中以陆源的大分子量UVC类腐殖酸对a和V_max的贡献最高,陆源的UVC+UVA类腐殖酸和水源的UVA腐殖酸与a和V_max的相关关系也达到显著或极显著水平,而DOC含量的贡献最小。 【结论】 水稻土DOC的腐殖化程度及其中陆源腐殖酸类组分的荧光强度与Fe (Ⅲ) 还原潜势和Fe (Ⅲ) 还原反应速率呈正相关。水稻土DOC除了作为Fe (Ⅲ) 还原过程的电子供体外,其还以电子穿梭体的形式在Fe (Ⅲ) 还原过程中起重要作用。      

Cation binding by acid-washed peat, interpreted with Humic Ion-Binding Model VI-FD

A sample of ombrotrophic peat from Moor House in northern England was extensively extracted with dilute nitric acid (pH 1) to free it of bound cations. Suspensions of the acid‐washed peat (5–30 g l^?1), prepared with different concentrations of background electrolyte (NaCl and KCl), were used to conduct batch acid–base titrations. A strong dependence of proton release on ionic strength (I) was observed, the apparent acid dissociation constant (pK_app) being found to decrease by approximately 1.0 for each tenfold increase in I. This behaviour could not be explained satisfactorily with Humic Ion‐Binding Model VI, a discrete‐site/electrostatic model of cation binding by humic substances, parameterized with data from laboratory studies on isolated samples. More success was obtained by abandoning the impermeable‐sphere electrostatic submodel used in Model VI, and instead assuming the peat to consist of aggregates with fixed internal volume, and with counterion accumulation described by the Donnan model, as proposed by Marinsky and colleagues. The fixed‐volume Donnan model (Model VI‐FD) could also approximately explain other reported results from acid–base titrations of peat, including the effects on the titrations of complexing cations (Al, Ca, Cu). Copper titrations of the Moor House sample were performed using an ion‐selective electrode, with peat suspensions in the acid pH range, at two ionic strengths, and in the presence of Al and Ca. The measured concentrations of Cu²⁺ were in the range 10^?13?10^?5 m . Model VI‐FD provided reasonable fits of the experimental data, after optimization of the intrinsic binding constant for Cu, the optimized value being close to the default value derived previously from data referring to isolated humic substances. The optimized constants for Al and Ca, derived from their competition effects, were also close to their default values. Additional experiments were performed in which the centrifugation‐depletion method was used to measure the binding of a cocktail of metals (Al, Ni, Cu, Zn, Cd, Eu, Pb) at a single pH. The model correctly predicted strong binding of Al, Cu, Eu and Pb, and weaker binding of Ni, Zn and Cd. For the strongly binding metals, the dissolved forms were calculated to be mainly due to complexes with dissolved humic matter, whereas the free ions (Ni²⁺, Zn²⁺, Cd²⁺) dominated for the weakly binding metals. Acid‐washed soil appears to provide a valuable intermediate between isolated humic substances and untreated soil for the investigation of cation binding by natural organic matter in the natural environment.     

An automatic procedure for determination of available iron in Indian soils

Abstract

An on‐line automatic procedure for the flow injection analysis (FIA) determination of iron (Fe) in a variety of soil extracts with common laboratory reagents, i.e., thiocyanate, thiocyanate +1,10‐phenanthroline/bipyridine has been tested. The apparent molar absorptivity of the complexes lies in the range of (5.5–7.0)x10³ L mole^‐1 cm^‐1 at an absorption maximum between 470–495 nm. The detection limit of the method is 15 ppb Fe. The sample output is 100 samples/hr. Almost all ions associated with Fe in the soil extract do not interfere in this method. Optimization of FIA variables, composition of the complex, and effect of other ions on the determination of Fe are discussed. The method has been used for determination of Fe status in a variety of agricultural soils in east Madhya Pradesh, India.     

Efficiency of diethylaminoethyl cellulose in the isolation of dissolved organic matter from forest soil solutions

Abstract

Diethylaminoethyl cellulose (DEAE cellulose), a weak anion exchange resin, has been used to isolate dissolved organic matter (DOM) from soil solutions collected from three different soil types, to investigate the amount of DOM isolated from soil solutions of various origin, and the extent to which inorganic ions are isolated together with DOM. The concentration of DOM in the various soil solutions ranged from 2.5 to 32.8 mg#lbL^‐1 DOC. More than 80% of dissolved organic carbon (DOC) was usually isolated with DEAE cellulose. High concentrations of aluminum (Al) and sulfate (SO₄ ^2‐) in the soil solutions have reduced DOC recovery. More than 90% of potassium (K⁺), calcium (Ca²⁺), and magnesium (Mg²⁺), were removed during the isolation procedure, but 10 to 20% of Al and 30 to 40% of iron (Fe) were isolated together with the DOC, probably due to strong complexation to DOM. The advantages of using DEAE cellulose were that the use of strong acids and bases was limited and that pH adjustments of the sample, leading to chemical modification of DOM, was not required.     

Effect of dissolved organic matter on the precipitation and mobility of the lead compound chloropyromorphite in solution

Chloropyromorphite, CPM, Pb₅(PO₄)₃Cl, is one of the most insoluble lead minerals. Inducing the formation of CPM by application of phosphate to soil has been suggested for immobilizing Pb at contaminated sites. We have examined the effect of organic matter on the completeness and the rate of CPM precipitation and on the particle size and the mobility of CPM crystals. We did experiments at pH 3–7 and with varying content of dissolved organic C, 0–72 mg C l^?1, mixing Pb(NO₃)₂ (0.5 mmol l^?1) and phosphate (2 mmol l^?1) solutions. The organic matter was extracted from samples of a forest floor. The precipitates were identified by X‐ray diffraction, and their size and shape were analysed by scanning electron microscopy and by photon correlation spectroscopy. The presence of organic matter in the solutions did not affect the mass of CPM that precipitated within 30 minutes at pH 5, 6 and 7. At pH 3 and 4, however, organic matter strongly inhibited the precipitation. The particles were markedly smaller in solutions containing organic matter than without at all pHs and passed through water‐saturated columns filled with calcareous sand, whereas the precipitates from the carbon‐free solutions did not. We suggest that the organic matter blocked the surfaces of crystal seeds and impaired crystal growth. At high pH, organic matter may additionally decrease the crystal size of the individual crystals by increasing the number of crystal seeds. We conclude that organic matter in the solution might limit the potential of phosphate to immobilize Pb in soil because it favours the formation of mobile colloids.     

Phosphorus retention and release of anions and organic carbon by two Andisols

Andisols can absorb large amounts of phosphorus rapidly, and then release it slowly, yet the mechanisms by which they retain P and release it for plant growth are poorly understood. Ligand exchange of organic compounds from Al–humic complexes by P and/or Si release – due to breakdown of allophanic microstructure to provide sorption sites – might account for the retention of P, but its extent is not known. We applied a soil column flow-through technique to quantify the release of anions and organic carbon (C) associated with P sorption by two andic soils, and we related the anion release to possible mechanisms for the retention of P. Phosphate (H₂PO₄^–, HPO₄^2–) sorption and concurrent anion desorption were obtained by passing a 1-g P 1^–1 (32 mmol KH₂PO₄ in 1 mm CaCl₂) solution through the soil columns (25 cm³). Total dissolved P, Fe, Al, S, Ca, Mg, K, Mn, organic C and pH were determined in the eluent. Changes in eluent pH and the patterns of the retention of P and corresponding concentrations of Al, Si and organic C in the eluent were similar for the two Andisols. The general pattern and changes in pH of the eluent coincided with changes in the patterns of release of organic C and Si and the rate of P retention. Release of silica accounted for < 6% of the P sorbed and had only a minor role in P retention in these two Andisols. Release of organic C, however, accounted on a molar basis for 40% and 83%, respectively, of the P sorbed. Direct measurements of the pH of the eluent and release of anions and organic C concurrent to P retention contribute to rapid assessment of the controlling mechanisms of P retention. The results indirectly confirm the hypothesis of ligand exchange of solution P with organic complexes held on allophanic surfaces. The organic C release, however, is not specifically related to either the fast or the slow P retention phase. The shift in the controlling P retention reaction associated with a change from the fast to the slow P retention phase is clearly indicated by an abrupt change of the pH of the eluent. This shift, in previous studies identified graphically by a change in slope of the P sorption isotherm, can be identified directly by measuring the pH of the matrix.     

Partitioning of polycyclic aromatic hydrocarbons (PAH) to water-soluble soil organic matter

The mobility of polycyclic aromatic hydrocarbons (PAH) in soils can be influenced by the presence of dissolved organic matter. Partition coefficients of selected polycyclic aromatic hydrocarbons, ranging from 3-ring to 6-ring compounds, to water-soluble soil organic matter (WSSOM) were determined. Partition coefficients were determined for WSSOM obtained from two soils under agricultural use and forest and for commercially available humic acid (Aldrich), taking advantage of a reversed phase (C₁₈) separation method. The WSSOM was characterised with regard to charge and hydrophilic/hydrophobic properties with a dissolved organic matter (DOM) fractionation method. No sorption to WSSOM was found for the tri- and tetracyclic PAH, whereas the penta- and hexacyclic PAH showed a significant binding to both types of WSSOM and to Aldrich humic acid. The affinity of penta- and hexacyclic PAH to WSSOM was considerably lower compared to the affinity to Aldrich humic acid. This is suggested to be due to the lower amount of hydrophobic fractions, c. 30%, in the natural WSSOM as compared to Aldrich humic acid. Effective partition coefficients (Koc_eff) for the sorption of PAH to bulk soil calculated from K_DOC and DOM in the naturally occurring concentration range were only 60–70% of the K_oc values in pure water. The impact of DOM on pollutant transport is further influenced by non-equilibrium behaviour of PAH in soils and by sorption of DOM to the solid-soil matrix. Several scenarios are described in which the effect of DOM on pollutant transport may become important.     

Preparation and characterization of model humic polymers containing organic phosphorus

The nature of organic P in soil organic matter was studied by evaluating the incorporation of serine, phosphoserine, ethanolamine, phosphoethanolamine and glycerophosphate into model humic polymers prepared by chemical oxidation of polyphenols. Elemental and functional group analysis indicated that the composition of model humic polymers ranged as follows: organic C, 50.6–56.8%; total acidity, 7.86–11.87m-equiv g^?1; carboxyl, 1.42–2.00 m-equiv g^?1; total hydroxyl, 6.79-10.0 m-equiv g^?1; ash, 6.4–13.9%; E₄/E₆ ratio, 5.34–6.19; organic N, 0.70–1.65% and organic P, 0.254–0.942%. These values are within the ranges reported for soil humic substances. The only non-phenolic compounds incorporated into model humic polymers were those containing free amino groups. The P content of model polymers was not increased by the presence of KH₂PO₄, glycerophosphate, serine or ethanolamine whereas phosphoserine and phosphoethanolamine resulted in model polymers containing 0.254 and 0.942% P, respectively. Further characterization studies of the model polymer containing phosphoethanolamine (HA-PE) showed that most of the C (83.2%), N (79.8%) and P (75.3%) was in the humic acid fraction. Gel filtration of HA-PE showed that 0.5% of the polymer was present in high molecular weight (mol. wt) components (mol. wt > 100,000) and 74.8% of the polymer was in two components of mol. wt 10,000–50,000. The majority of the organic P in HA-PE was associated with the medium molecular weight fractions (79.2%) while 16.8% of the P was associated with materials possessing mol. wt < 10,000. Attempts to demonstrate the presence of organic P functional groups contained in HA-PE by infrared spectroscopy was limited by the relatively small amounts of organic P incorporated into the model humic polymers. The results obtained show that a portion of the unidentified organic P in soil humic substances may arise from the incorporation of organic compounds containing both amino and phosphate ester functional groups during oxidative polymerization of polyphenols.     

Rapid, Micro-Methods to Estimate Plant Silicon Content by Dilute Hydrofluoric Acid Extraction and Spectrometric Molybdenum Method

By treating 0.5 g DW of a plant sample directly with 10 ml of a dilute hydrofluoric acid solution (HF solution, 1.5 M HF—0.6 M HCl), all the silica in plant (as much as 150 mg SiO₂) was dissolved within 1 h. After dilution of the extract with 40 mL of distilled water, the silica in the extract was measured by the spectrometric molybdenum yellow method. The molybdenum yellow method, in which silica in 0.1 mL of the diluted extract can be determined in 8 min, is well suited to rapid, micro-estimations of the silica content in plants. In the micro-modification, the size of the plant sample was reduced to 100 mg DW. The analytical procedure was simple, and the analytical time was less than 2 h. The method can save much labor and time, compared with the gravimetric analysis. The dissolution with HF solution and the molybdenum yellow method were also applied to the measurement of the content of silica separated by acid digestion of rice plants. Excellent agreement in the silica measurement of rice plants was confirmed among the direct extraction method, the gravimetric method and the digestion-separation-dissolution method. In the molybdenum yellow method, the addition of boric acid enabled to mask the interference of hydrofluoric acid, and the least amount of citric acid required for the elimination of phosphorus interference was proposed. In conclusion in this report, recommended methods for the rapid estimation of the silica content in rice plants were presented.     

Evaluation of the possibilities of using humic acids obtained from lignite in the production of commercial fertilizers

Purpose

Technological progress and high market demand contributed to a significant interest in the production of fertilizers based on humic acids. The aim of this study was to evaluate the possibilities of using humic acids obtained from lignite in the production of new commercial products. For this purpose, it is necessary to determine the quality standard requirements for such material. Properties of humic acids depend on source of origin as well as method of its extraction.

Materials and methods

The humic acids were extracted from polish deposit of lignite–Sieniawa Lubuska by alkaline extraction using for this purpose six kinds of extractants: 0.1 M NaOH and 0.25 M NaOH, 0.1 M KOH and 0.25 M KOH, and 0.1 M Na₄P₂O₇ and 0.25 M Na₄P₂O₇. The humic samples were used in solid powder form and characterized by UV-Vis spectroscopy, ¹³C NMR spectroscopy, fluorescence spectroscopy, and thermal analysis.

Results and discussion

The determining factor influencing a degree of humic acids extraction from lignite and their structure is type of extractant. The largest efficiency of extraction (about 50%) was obtained with the use of NaOH solutions. All examined humic acids were generally characterized by simple and heterogeneous molecularly structure with low molecular weight and low aromatic polycondensation. Therefore, it can be concluded that humic acids extracted with NaOH and KOH solutions are less condensed than those extracted with Na₄P₂O₇ solutions. It can suggest that humic acids obtained from lignite using solutions of Na₄P₂O₇ are characterized by a low transformation degree and greater amount of carboxyl groups.

Conclusions

Low rank coal can be successfully used in agriculture as a rich source of humic acids. Reagent used in their extraction, apart from high efficiency should have a neutral impact on their structure. Studies on the physicochemical properties of humic acids can be helpful in predicting behaviors of such fertilizer components in the environment and in inventing new products taking the principles of sustainable development into consideration.

     

Absorption spectra of humic acids

For the purpose of explaining the forming process of soil humic acids, the author determined the absorption spectra of various humic acids. From soils and peats which were pretreated with 5% HCl at 70°C for 30 minutes or from those which were not, humic acids were extracted by treating with 0.5% NaOH at boiling temperature for 30 minutes. In these humic acids, the one which is extracted after acid pretreatment is provisionally designated as SrL humic acid and the other as L humic acid. The supernatant alkaline solutions obtained by centrifuging the above mentioned extracts were acidified with hydrochloric acid, and precipitated humic acids were filtered and washed with water until Cl' free. Humic acids were dissolved in 0.1% NaOH and ultrafiltered using collodion membrane. The filtrates were acidified with hydrochloric acid and humic acids were collected by centrifuging, transferred on the filter paper, washed with dilute hydrochloric acid and water successively, then air-dried and pulverized.     

Etude de la nutrition potassique du sorgho III‐relations entee les teneurs en cations et la composition en acides organiques des feuilles

Abstract

Extracts that are coloured, owing to dissolved organic matter, give rise to an interference when boron is determined by the colorimetric Azomethine‐H method. A scheme is presented in which boron is removed from coloured extracts by dialysis. In this way the interference can be removed automatically. The suggested scheme allows hydroponic solutions and extracts of soils, peat‐based composts and plant materials to be analysed without further treatment at a rate of 20 hr^‐1. The limit of detection is 0.05ppm B in solution. Recoveries of boron added to extracts from all types of sample were excellent. The effects of some interferences were investigated and found not to be significant under normal working.     

Dissolution of aluminum and iron phosphate by humic acids

Abstract

An investigation was conducted to study the effect of humic (HA) and fulvic acid (FA) on the dissolution of aluminum phosphate (AlPO₄) and iron phosphate (FePO₄), to analyze the dissolution products, and assess their availability to plants. The rate of dissolution was determined by shaking 10 mg of Al‐ or FePO₄ with 0 to 800 mg L^‐1 of HA or FA solutions at pH 7.0 for 0 to 192 hours. The phosphorus (P) concentration was measured in the extracts by spectrophotometry, whereas the nature of P‐humic acid complexes was determined by ³¹P NMR analysis. Availability of dissolution products was studied by growing corn plants in aerated hydroponic solutions receiving treatments of 50 mg Al‐ or FePO₄ and 0 to 800 mg L^‐1 of HA or FA at pH 5.0. The results indicated that the amount of P released by HA or FA increased with time. Humic acid was more effective than FA in dissolving the metal phosphates. The ³¹P NMR analysis showed that the dissolution products contained free orthophosphates and minor amounts of P‐humic acid complexes. This confirms the role of HA as a powerful chelator of Al and Fe, liberating in this way the orthophosphate anions. Corn plants grown in hydroponics, with AlPO₄ or FePO₄ as the source of P, exhibited better growth performance when HA or FA are present.