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.     

Effects of liming on organic matter decomposition and phosphorus extractability in an acid humic Ranker soil from northwest Spain

Summary A laboratory incubation experiment was carried out over 17 weeks to determine the effect of liming on soil organic matter. The amount of lime as calcium hydroxide [Ca(OH)₂] required to completely neutralise exchangeable Al was found to be five times the standard lime requirement. This large amount of lime had a limited overall effect on the short-term stability of soil organic matter, causing the release of 1300 g g^-1 of C (1.7% total soil C) above the control during the incubation. Liming may have altered the potential availability of soil organic matter and organic P, as shown by a marked reduction in the extractability of soil organic P with sodium bicarbonate and sodium hydroxide. The latter was unlikely to be due to the formation of calclium-P artefacts, and may be attributed to the combined chemical effects of added calcium hydroxide and precipitation of exchangeable Al on the nature and solubility of soil organic constituents and organomineral complexes. The addition of lime increased the degradation of added oak leaf litter by 50%, from 3.2 to 4.7 mg g^-1, as determined by CO₂ evolution. The enhanced litter degradation indicated increased microbial activity in limed soil, but this improvement had only minor effects on the stability of native organic matter. This study highlights the need for further research into the relationships between the chemical nature of organic P in soil and the physical, chemical, temporal, and agronomic factors that control its turnover and availability.     

Studies on the effect of humic acid on availability of phosphorus

It is believed that some organic compounds form complexes with iron and aluminum and prevent the fixation of phosphate applied to soils.     

Tolerance of eastern gamagrass to excess aluminum in acid soil and nutrient solution

Eastern gamagrass, Tripsacum dactyloides L., has been reported to tolerate a wide variety of soil conditions, including drought, flooding, and acidity, but its specific tolerance to aluminum (Al) has not been tested. One strain of this species, PMK Select Lot 94 SFG‐1, was tested for its tolerance to excess Al in an acid, Al‐toxic Tatum subsoil (clayey, mixed, thermic, Typic Hapludult) and in nutrient solutions containing Al. Roots were able to penetrate unfertilized Tatum subsoil at pH levels as low as 4.1–4.2 (1:1 soil‐water), at Al saturations of 64 to 77% of CEC, and to tolerate Al concentrations in nutrient solution that would be lethal for many crop plants. For example, with 4 mg Al L^‐1 and a final solution pH of 4.67, shoot and root dry weights were 75 and 76%, respectively, of those with no Al. Even with 24 mg Al L^‐1 and a final solution pH of 4.13, shoot and root dry weights were 45 and 46%, respectively, of those for the no Al check treatment. Hence, this strain of gamagrass shows promise for use on soils having acidic, Al‐toxic subsoil layers that act as root barriers and predispose plants to injury by drought. Roots of gamagrass are also reported to penetrate hard clay pans and to create root channels for subsequent crops that lack this ability. Current studies indicate that the strain tested was susceptible to a chlorosis resembling iron (Fe) deficiency when grown in a Jiffy Mix potting mixture or with excess Al in nutrient solutions. Hence, gamagrass is tentatively being classified as a calcifuge [Al tolerant‐Fe‐inefficient]. In the current experiment, considerable plant to plant variability was noted regarding susceptibility to this chlorosis factor and to a purpling symptom resembling phosphorus (P) deficiency. Results indicate that an exhaustive screening of gamagrass populations could identify strains that are more suitable for specific soil situations.     

The origin of oxygen in soil humic substances

The ¹⁸O/¹⁶O ratios of a number of soil humic and fulvic acids were measured and compared with those of lignin and cellulose samples originating from the same area. The average enrichments above ground water were: cellulose 32%₀ humic and fulvic acid 29%₀ and lignin 14%₀, suggesting that the oxygen in humic and fulvic acid originates pricipally from cellulose or other plant carbohydrates and not lignin as has been suggested.     

Carbon,iron, and aluminum responses to controlled water table fluctuations in sandy soil material

Purpose

Seasonal fluctuating water tables are common in sandy coastal plain soils, but their role in soil organic carbon dynamics is uncertain. Seasonal saturation influences biogeochemical processes that affect fate of organic matter and metals. A column study was conducted to test hypotheses that shallow water table (SWT) fluctuations reduce CO₂ loss (H1), increase leaching of dissolved organic C (DOC) and metals (Al and Fe) (H2), and result in greater net soil C storage (H3).

Materials and methods

The A- and E-horizon material of moderately well-drained sandy soils from five sites was collected for the study. Ten columns (two per site) of 90-cm height were packed to a thickness of 60 cm with E-horizon material, above which was packed 15 cm of A-horizon material from the same soil. Five columns were subjected to SWT treatments and five to deep water table (DWT) treatments. Upward CO₂ flux was measured using a NaOH (1 M) trap. Metal and DOC-C concentrations in leachates and in water sampled at the surface of columns were measured. Soil samples from the columns were collected by depth at 5–6-cm increments and tested for total and organic C, metals, and <50-μm material distribution by WT treatment.

Results and discussion

Upward flux of CO₂ was significantly less for SWT treatment. Higher DOC (for all events) and Fe concentrations (for first 18 days) were measured in SWT leachates as compared to DWT. Metal- and C concentrations were correlated (P?<?0.0001) for surface pore water samples of SWT but not for DWT. Net loss of C was significantly less under SWT condition. Results indicate significant water-table effects on magnitude and direction of C flux (solution or gaseous) and <50-μm particle distribution for sandy coastal plain soils materials.

Conclusions

Changes in water table depth can potentially alter not only net soil C storage but also the proportion of C converted to CO₂ versus DOC. Differences in the proportion would have consequences for C dynamics in ecosystems dominated by soils with fluctuating water tables such as occur extensively in the coastal plain of the SE USA and elsewhere.

     

Use of phosphorus vectors to monitor changes in soil phosphorus

Abstract

A study was conducted to evaluate the use of P vectors to predict the amount of P required on a yearly basis to maintain a constant solution‐solid phase P relationship in an irrigated calcareous and a dryland acid soil. Irrigated potato‐spring barley and dryland spring pea spring‐barley crop rotations established at the two locations. Mono‐calcium phosphate (0–45–0) was applied annually at five levels, ranging from 0–4 times estimated crop removal. Phosphorus vectors were determined on soil samples by equilibration with standard P solutions. Yields tended to increase with added P on the calcareous soil; however, significant responses were not recorded at either location. Consequently, critical P vectors were not established. A constant solution‐solid phase P relationship was maintained by addition of P equal to that removed by the crop on the calcareous soil. A constant solution‐solid phase P relationship was not maintained on the acid soil.     

The sodium-amalgam reduction of soil and fungal humic substances

Two soil humic acids and a “humic acid” synthesized in the laboratory by Stachybotrys chartarum were reduced with Na-amalgam. The reduction products were methylated, separated by preparative gas chromatography and identified by matching their mass and micro-infrared spectra with those of authentic specimsens.Yields of reduction products identified ranged from 2.7 to 4.2% of the initial weights of the humic materials. Major products identified were N-methyl-benzylsulfonamide, methylated phenolic acids, aromatic aldehydes and C₆C₂ - and C₆C₃ - compounds with 0 in the side chains. Since the Na-amalgam reduction of both soil and fungal humic materials produces the same or similar compounds, the method provides little information on the origin of these compounds, that is, whether they are lignin- or flavonoid-derived or synthesized by microorganisms. Compared with oxidative degradation methods, Na-amalgam reduction appears to be inefficient and tells little about the chemical structure of humic acid polymers.     

黑土长期定位试验原状土搬迁对土壤胡敏酸荧光性质的影响

在黑土长期定位试验地原状土搬迁的基础上,采用荧光光谱学方法分析了土壤中胡敏酸在搬迁前后不同年度间的荧光结构,旨在揭示黑土搬迁过程中胡敏酸结构的变化规律,为长期定位试验地原土搬迁提供可行性的依据。土壤胡敏酸的荧光光谱显示,胡敏酸在搬迁后第一年总体特征峰波长有不同程度的红移现象,即有了轻微的老化现象,分子芳构化及缩合度程度增加,在搬迁后第二年有所缓解,这种短期的老化现象在M、 MNPK处理中更为明显,在两个不同土层中的变化没有明显不同。胡敏酸分子中的五环芳烃化合物及其它结构简单的芳烃化合物没有受到土壤搬迁的扰动。     

Determination of DTNB-reactive sulphhydryl groups in soil humic acids: their enrichment in humic acids from volcanic acid soils

Thirteen acid soils were collected from typical volcanic regions in Japan (S content: 0.9–4.1, mean = 2.2g kg^?1; pH (H₂O): 2.81–3.93, mean = 3.33), as well as nine reference soils (S: 0.6–1.7, mean= 1.1 gkg^?1; pH(H₂O): 4.10–4.74, mean = 4.47). Humic acids were extracted from the soils separately with 0.1 M NaOH and precipitated by acidification (pH = 2, HCl). After purification, the humic acids were subjected to colorimetric analysis using a DTNB reagent [5,5′-dithiobis(2–nitrobenzoic acid] for the active -SH group. Since humic acids have significant absorption at 4I2 nm, the coloured compound (5–mercapto-2–nitrobenzoic acid) was separated from the humic acids by ultrafiltration or solvent extraction prior to the colorimetric measurement. Humic acids also caused discoloration of the coloured compound when they coexisted in the reaction solutions. Thus, the reproducible determination of -SH was accomplished by employing a standard addition technique (-SH standard: cysteine). Although -SH contents obtained by the ultrafiltration method were considerably higher than those by the solvent-extraction method, probably due to the denaturation of humic acids by the higher buffer concentration used in the ultrafiltration method, they correlated well with each other. The humic acids from acid soils contained apparently higher concentrations of -SH (120–510, mean = 270mg S kg^?1 by the ultrafiltration method; 8–110, mean = 38mg S kg^?1 by the solvent-extraction method) compared to those from reference soils [20–260, mean = 90mg S kg^?1 by the former; not detectable (<5)-34, mean = 11 mg S kg^?1 by the latter]. This -SH enrichment in the humic acids from acid soils may result from the degradation and subsequent humification of S-rich debris of plants and micro-organisms and/or direct incorporation of volcanic acid gas (H₂S) into the humic acids.     

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

Abstract

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

Humic substances in acid organic soils: modelling their release to the soil solution in terms of humic charge

Batch titration experiments were carried out with organic soil samples in order to investigate the release to the solution phase of humic substances (HS). Measurements were made of pH, dissolved organic carbon (DOC) concentration, and the concentration of mono-meric (inorganic + organic) aluminium, as functions of added acid or base. DOC was taken to be entirely due to HS. The results can be interpreted in terms of a model in which the soil is considered to contain two types of HS–mobile or potentially mobile (HSM), and immobile (HSI). The binding of inorganic ions by the HS is calculated using humic ion-binding model IV, previously developed in this laboratory. Model IV allows the charges on the HS (Z_HSM, Z_HST) to be calculated; these are determined mainly by the binding of H+ and A13+. Concentrations of HS in solution, [HS_aq], are given by the equation: where |Z_HSM| is the modulus of Z_HSM, n_HSM is the carboxyl group content of HSM, c_HSM is the soil content of HSM, β is a fitting parameter, and square brackets, [ ], indicate concentrations. For most of the soils a value for β of 3 gives acceptable agreements between measured and calculated values of [HS_aq], indicating a major influence of charge on release. The optimized value of c_HSM differs considerably among soils, whereas c_HIS varies by only a factor of about two. Total humic contents (c_HSM+ c_HSI estimated by model optimization are in approximate agreement with values estimated by extraction of the soils with NaOH.     

Dilute acid-soluble phosphorus in fresh air-borne tephras and fixation with an increase in active aluminum and iron

Fresh rhyolite-to-andesite tephras ground to less than 0.15 mm particles contained dilute acid-soluble phosphorus (P) as in the case of cultivated upland soils in Japan. The amount of P determined by Truog extraction (Truog P) ranged between 119 and 784 mg P₂O₅ kg^-1 in 12 rhyolite-to-andesite tephras, and that determined by a modified Bray P₂ extraction method (modified Bray P₂) ranged between 133 and 812 mg P₂O₅ kg^-1. In contrast, the Truog P-content in fresh basaltic andesite-to-basalt tephras was only 3.4–23 mg P₂O₅ kg^-1, and the modified Bray P₂-content was in the range of 41–185 mg P₂O₅ kg^-1, although the total P-content of the two tephra groups was in almost the same range.

Among 12 rhyolite-to-andesite tephras, those from Mt. Usu that erupted in 1977 and from Mt. Pinatubo that erupted in 1991 were selected for detailed studies. Fine particle size fractions of these tephras showed higher Truog P values than the coarse ones. The Truog P values further increased in the heavy fraction with a particle density of 2.8 or greater. In this heavy fraction, apatite was detected by energy dispersive X-ray (EDX) analysis, indicating the contribution of the mineral to the high Truog P. Dilute sulfuric acid treatment of the tephras at 80°C for 15 d followed by neutralization increased the amount of active Al and Fe and decreased the Truog P values of these tephras. These results suggested that the amount of apatite rapidly decreased with weathering in volcanic ash soils.     

Aluminum and iron(III) species in the soil solution including organic complexes with citrate and humic substances

The solubility of Al and Fe in soil is of relevance for their toxicity and availability, respectively, to plant roots. Humic substances as the main part of stable soil organic matter and citrate which is often excreted by P deficient plants are strong complexants of Al and Fe(III). Therefore, equations were developed to calculate the Al and Fe(III) species distribution in the soil solution in the presence of humic substances and citrate as organic ligands. Calculations in the pH range 4.0–7.0 showed that at higher pH humic-Al complexes were the most important species whereas AlOH-citrate^? dominated between pH 4.0 and 5.4. Free monomeric Al and AlSO₄⁺ were of minor relevance. Iron(III) species calculations showed that humic-Fe complexes were the main species in the pH range 4.0–7.0. But if mugineic acid, a Fe complexing phytosiderophore released into the rhizosphere by graminaceous plant species, was present in the soil solution (10^?6 M), Fe-mugineic acid complexes accounted for most of the Fe in solution. Fe-citrate^? was relevant at lower pH but contributed little to Fe(III) species at pH > 6.0. The results demonstrate the strong importance of the considered organic ligands for Fe and Al in the soil solution.     

On the components of soil humic acids (Part iv) on the absorption spectra of the components of B-type humic acid

Introduction

Concerning the A-type humic acid found in different kinds of soil the writers fractionated each of its components and measured its lightabsorbing power and compared the characteristics of those components.     

The effect of humic acids on the availability of phosphorus fertilizers in alkaline soils

Abstract. The effect of humic acids on transformation of phosphorus fertilizer was studied in an alkaline soil. Soil P was fractionated following 4 and 15 days incubation after humic acids were applied with phosphorus fertilizer to the soil. The availability of phosphate in the soil and total phosphorus in plants were determined at earing stage and at maturity in a pot experiment, and wheat yield was examined in a field trial. Addition of humic acids to soil with P fertilizer significantly increased the amount of water soluble phosphate, strongly retarded the formation of occluded phosphate and increased P uptake and yield by 25%.     

Insights into sorption and leaching behavior of sulfadiazine in soil as affected by humic acid

Journal of Soils and Sediments - Sulfonamides with high mobility in the soil pose a significant threat to environmental ecology and human health. Organic matter is known to affect the sorption and...     

Cobalt,copper, and manganese adsorption by aluminium and iron oxides and humic acid

Abstract

Adsorption of cobalt (Co), copper (Cu), and manganese (Mn) by synthetic aluminium oxide, ferrihydrite, goethite, extracted humic acid, and a sandy soil sample were determined as a function of metals concentration (0–1.2 mM) and pH (3.8–8.2). For each pH and adsorbent, the Langmuir adsorption maximum (adsorption capacity) was calculated. The position of the adsorption curves for Co, Cu, and Mn as a function of pH has been shown to be related to the first hydrolysis constant of the cations in solution (pK₁). The sequence of preference of the three metals to the studied adsorbents decreased in order Cu >> Co > Mn. The results obtained from this study showed that the Co, Cu, and Mn adsorption characteristics of soils are probably controlled to large extent by their organic matter and oxides contents.