Unlocking fixed soil phosphorus upon waterlogging can be promoted by increasing soil cation exchange capacity

Phosphorus (P) adsorbed by iron (Fe) oxyhydroxides in soil can be released when the Fe(III) minerals are reductively dissolved after soil flooding. However, this release is limited in tropical soils with large Fe contents and previous studies have suggested that P sorbs or precipitates with newly formed Fe(II) minerals. This hypothesis is tested here by scavenging Fe²⁺ in flooded soils by increasing the cation exchange capacity (CEC) of soil through resin application (30 cmol_c kg^?1; Na‐form). Three soils from rice paddies with contrasting properties were incubated in aerobic and anaerobic conditions with or without resin and with or without addition of organic matter (OM) to stimulate redox reactions. Dissolved Fe was 0.1–1.1 mm in unamended anaerobic soils and decreased to less than 0.07 mm with resin addition. Anaerobic soils without resin and aerobic soils with or without resin had marginal available P concentrations (<2 mg P kg^?1; anion‐exchange membrane P). In contrast, available P increased 3‐ to 14‐fold in anaerobic soils treated with resins, reaching 16 mg P kg^?1 in combination with extra OM. Application of Ca‐forms of resin did not stimulate P availability and dissolved Ca concentrations were larger than in unamended soils. Resin addition can increase P availability, probably by a combination of reducing solution Fe²⁺ (thereby limiting the formation of Fe(II) minerals) and increasing the OM solubility and availability through reducing dissolved Ca²⁺. The soil CEC is a factor controlling the net P release in submerged soils.     

Influence of pH on the redox chemistry of metal (hydr)oxides and organic matter in paddy soils

Purpose

The primary purpose of this study was to determine how flooding and draining cycles affect the redox chemistry of metal (hydr)oxides and organic matter in paddy soils and how the pH influences these processes. Our secondary purpose was to determine to what extent a geochemical thermodynamic equilibrium model can be used to predict the solubility of Mn and Fe during flooding and draining cycles in paddy soils.

Material and methods

We performed a carefully designed column experiment with two paddy soils with similar soil properties but contrasting pH. We monitored the redox potential (Eh) continuously and took soil solution samples regularly at four depths along the soil profile during two successive flooding and drainage cycles. To determine dominant mineral phases of Mn and Fe under equilibrium conditions, stability diagrams of Mn and Fe were constructed as a function of Eh and pH. Geochemical equilibrium model calculations were performed to identify Mn and Fe solubility-controlling minerals and to compare predicted total dissolved concentrations with their measured values.

Results and discussion

Flooding led to strong Eh gradients in the columns of both soils. In the acidic soil, pH increased with decreasing Eh and vice versa, whereas pH in the alkaline soil was buffered by CaCO₃. In the acidic soil, Mn and Fe solubility increased during flooding due to reductive dissolution of their (hydr)oxides and decreased during drainage because of re-oxidation. In the alkaline soil, Mn and Fe solubility did not increase during flooding due to Mn(II) and Fe(II) precipitation as MnCO₃, FeCO₃, and FeS. The predicted levels of soluble Mn and Fe in the acidic soil were much higher than their measured values, but predictions and measurements were rather similar in the alkaline soil. This difference is likely due to kinetically limited reductive dissolution of Mn and Fe (hydr)oxides in the acidic soil. During flooding, the solubility of dissolved organic matter increased in both soils, probably because of reductive dissolution of Fe (hydr)oxides and the observed increase in pH.

Conclusions

Under alternating flooding and draining conditions, the pH greatly affected Mn and Fe solubility via influencing either reductive dissolution or carbonate formation. Comparison between measurements and geochemical equilibrium model predictions revealed that reductive dissolution of Mn and Fe (hydr)oxides was kinetically limited in the acidic soil. Therefore, when applying such models to systems with changing redox conditions, such rate-limiting reactions should be parameterized and implemented to enable more accurate predictions of Mn and Fe solubility.     

Speciation and Solubility Control of Aluminium in Soils Developed from Slates of the River Sor Watershed (Galicia,NW Spain)

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).     

Arsenic Chemistry in Soils: An Overview of Thermodynamic Predictions and Field Observations

Published information, both theoretical and experimental, on As chemical behavior in soils is reviewed. Because of many emission sources, As is ubiquitous. Thermodynamic calculations revealed that As(V) species (HAsO ₄ ^2- >H₂AsO ₄ ^- at pH 7) are more abundant in soil solutions that are oxidized more than pe+pH>9. Arsenic is expected to be in As(III) form (HAsO ₂ ⁰ =H₃AsO ₃ ⁰ >AsO ₂ ^- =H₂AsO ₃ ^- at pH 7) in relatively anoxic soil solutions with pe+pH<7. Adsorption on soil colloids is an important As scavenging mechanism. The adsorption capacity and behavior of these colloids (clay, oxides or hydroxides surfaces of Al, Fe and Mn, calcium carbonates, and/or organic matter) are dependent on ever-changing factors, such as hydration, soil pH, specific adsorption, changes in cation coordination, isomorphous replacement, crystallinity, etc. Because of the altering tendencies of soil colloids properties, adsorption of As has become a complex, empirical, ambiguous, and often a self contradicting process in soils. In general, Fe oxides/hydroxides are the most commonly involved in the adsorption of As in both acidic and alkaline soils. The surfaces of Al oxides/hydroxides and clay may play a role in As adsorption, but only in acidic soils. The carbonate minerals are expected to adsorb As in calcareous soils. The role of Mn oxides and biogenic particles in the As adsorption in soils appears to be limited to acidic soils. Kinetically, As adsorption may reach over 90% completion in terms of hours. Precipitation of a solid phase is another mechanism of As removal from soil solutions. Thermodynamic calculations showed that in the acidic oxic and suboxic soils, Fe-arsenate (Fe₃(AsO₄)₄)₂) may control As solubility, whereas in the anoxic soils, sulfides of As(III) may control the concentrations of the dissolved As in soil solutions. In alkaline acidic oxic and suboxic soils, precipitation of both Fe- and Ca-arsenate may limit As concentrations in soil solutions. Field observations suggest that direct precipitation of discrete As solid phases may not occur, except in contaminated soils. Chemisorption of As oxyanions on soil colloid surfaces, especially those of Fe oxide/hydroxides and carbonates, is believed to a common mechanisms for As solid phase formation in soils. It is suggested that As oxyanions gradually concentrate on colloid surfaces to a level high enough to precipitate a discrete or mixed As solid phase. Arsenic volatilization is another As scavenging mechanism operating in soils. Many soil organisms are capable of converting arsenate and arsenite to several reduced forms, largely methylated arsines which are volatile. These organisms may generate different or similar biochemical products. Methylation and volatilization of As can be affected by several biotic (such as type of organisms, ability of organism for methylation, etc.) and abiotic factors (soil pH, temperature, redox conditions, methyl donor, presence of other ions, etc.) factors. Information on the rate of As biotransformations in soils is limited. In comparison to the biologically assisted volatilization, the chemical volatilization of As in soils is negligible.     

Assessment of phosphate solubility in forest and highly fertilized Andisols and Andic soils

Abstract

Phosphate solubility in Andisols and Andic soils (forest and fertilized) has been studied in soil solutions at two soil:solution ratios (1:2.5 and 1:25). Forest soils approached the variscite solubility (pIAP=30.4±0.3) while fertilized soils were closer to the amosphous analog of variscite (pIAP= 29.8±0.2). In some samples, phosphorus (P) activities were consistent with simultaneous equilibrium between aluminum (Al) and iron (Fe) phosphates. The dilution ratio, DR=10(P)_1:25/(P)_l:25, was 10.0±0.4 for all samples. This suggests a dissolution of phosphate minerals attaining apparent saturation in 24 h. However, the high content of dissolved organic carbon and Al in aqueous extracts also pointed to the existence of soluble ternary complexes of P with Al(Fe)‐humus complexes. These results could be consistent with simultaneous control between the dissolution of variscite‐like minerals and humus‐Al(Fe)‐P associations. Nevertheless, DR seems a valuable criterion to assess soil P status, especially in fertilized soils with high active Al and Fe contents.     

The influence of vegetation and soil type on the speciation of iron in soil water

Soluble organic matter derived from exotic Pinus species has been shown to form stronger complexes with iron (Fe) than that derived from most native Australian species. It has also been proposed that the establishment of exotic Pinus plantations in coastal southeast Queensland may have enhanced the solubility of Fe in soils by increasing the amount of organically complexed Fe, but this remains inconclusive. In this study we test whether the concentration and speciation of Fe in soil water from Pinus plantations differs significantly from soil water from native vegetation areas. Both Fe redox speciation and the interaction between Fe and dissolved organic matter (DOM) were considered; Fe – DOM interaction was assessed using the Stockholm Humic Model. Iron concentrations (mainly Fe²⁺) were greatest in the soil waters with the greatest DOM content collected from sandy podosols (Podzols), where they are largely controlled by redox potential. Iron concentrations were small in soil waters from clay and iron oxide‐rich soils, in spite of similar redox potentials. This condition is related to stronger sorption on to the reactive clay and iron oxide mineral surfaces in these soils, which reduces the amount of DOM available for electron shuttling and microbial metabolism, restricting reductive dissolution of Fe. Vegetation type had no significant influence on the concentration and speciation of iron in soil waters, although DOM from Pinus sites had greater acidic functional group site densities than DOM from native vegetation sites. This is because Fe is mainly in the ferrous form, even in samples from the relatively well‐drained podosols. However, modelling suggests that Pinus DOM can significantly increase the amount of truly dissolved ferric iron remaining in solution in oxic conditions. Therefore, the input of ferrous iron together with Pinus DOM to surface waters may reduce precipitation of hydrous ferric oxides (ferrihydrite) and increase the flux of dissolved Fe out of the catchment. Such inputs of iron are most probably derived from podosols planted with Pinus.     

Review on iron availability in soil: interaction of Fe minerals,plants, and microbes

Purpose

The rationale of this paper is to review the state of the art regarding the biotic and abiotic reactions that can influence Fe availability in soils. In soil, the management-induced change from oxic to anoxic environment results in temporal and spatial variations of redox reactions, which, in turn, affect the Fe dynamics and Fe mineral constituents. Measuring the Fe forms in organic complexes and the interaction between bacteria and Fe is a major challenge in getting a better quantitative understanding of the dynamics of Fe in complex soil ecosystems.

Materials and methods

We review the existing literature on chemical and biochemical processes in soils related with the availability of Fe that influences plant nutrition. We describe Fe acquisition by plant and bacteria, and the different Fe–organic complexes in order to understand their relationships and the role of Fe in the soil carbon cycle.

Results and discussion

Although total Fe is generally high in soil, the magnitude of its available fraction is generally very low and is governed by very low solubility of Fe oxides. Plants and microorganisms can have different strategies in order to improve Fe uptake including the release of organic molecules and metabolites able to form complexes with Fe^III. Microorganisms appear to be highly competitive for Fe compared with plant roots. Crystalline Fe and poorly crystalline (hydro)oxides are also able to influence the carbon storage in soil.

Conclusion

The solubility of crystalline Fe minerals in soil is usually very low; however, the interaction with plant, microbes, and organic substance can improve the formation of soluble Fe^III complexes and increase the availability of Fe for plant growth. Microbes release siderophores and plant exudates (e.g., phytosiderophores, organic acids, and flavonoids), which can bind and solubilize the Fe present in minerals. The improved understanding of this topic can enable the identification of effective solutions for remedying Fe deficiency or, alternatively, restricting the onset of its symptoms and yield’s limitations in crops. Therefore, development and testing of new analytical techniques and an integrated approach between soil biology and soil chemistry are important prerequisites.     

Early detection of the effects of compaction in forested soils: evidence from selective extraction techniques

Purpose

Soil compaction resulting from mechanisation of forest operations reduces air permeability and hydraulic conductivity of soil and can result in the development of hydromorphic and/or anoxic conditions. These hydromorphic conditions can affect physico-chemical properties of the soils. However, early detection of these effects on mineralogical portion of soils is methodologically difficult.

Materials and methods

To analyse the effects of soil compaction on iron minerals in loamy Luvisol, three compacted and three non-compacted soil profiles up to the depth of 50 cm were collected from an artificially deforested and compacted soils after 2 years of treatment. Soil was compacted with the help of 25 Mg wheeler’s load to increase the dry bulk density of soil from 1.21?±?0.05 to 1.45?±?0.1 g cm^?3. Soil samples were analysed by X-ray diffraction (XRD) and were treated by citrate bicarbonate (CB) and dithionite citrate bicarbonate (DCB) under controlled conditions. Major and minor elements (Fe, Al, Mg, Si and Mn) were analysed by ICP-AES in the CB and DCB extracts.

Results and discussion

It was found that X-ray diffraction is not an enough sensitive method to detect the quick mineralogical changes due to soil compaction. Results obtained from CB-DCB extractions showed that soil compaction resulted in larger CB and smaller DCB extractable elements as compared to non-compacted soil. Labile Fe was found 30 % of total Fe oxides in compacted soil against 10–14 % in non-compacted soils. Compaction thus resulted in Fe transfer from non-labile to labile oxides (s.l.). Results showed that soil compaction leads to the reduction of Fe³⁺ to Fe²⁺. The effects of hydromorphic conditions due to soil compaction were observed up to the depth of 35 cm in forest soil profile. Furthermore, a close association of Al with Fe oxides was observed in the soil samples, while Mn and Si were mainly released from other sources, Mg showing an intermediate behaviour.

Conclusions

Hydromorphic conditions owing to soil compaction affect the mobility and crystallisation process of iron mineral. CB-DCB selective extraction technique, in contrast to XRD technique, can be effectively used to examine the possible effects of soil compaction on iron minerals.

     

Effect of iron oxide on phosphate sorption by calcite and calcareous soils

Pure calcite (AR grade CaCO₃) was treated with ferrous perchlorate solution to give a surface coating of iron (Fe) oxide. Maximum sorption (x_m) of phosphate (P) by the calcite increased from 18.2 to 160 mg P kg^?1 as the amount of coating increased from 0.00 to 16.0 g Fe₂O₃, kg^?1 CaCO₃. Evidence for Fe oxide coatings on carbonate minerals in two Sudanese soils was obtained by optical microscopy and electron-probe microanalysis. The relative contributions of carbonate and Fe oxide minerals, and Fe oxide coatings to P sorption in these soils were calculated, based on an assumed model of oxide distribution. Separate-phase Fe oxide was the major contributor (30–40%) to P sorption in the soils; the Fe oxide coatings on carbonate minerals were only minor contributors (< 6%), and the contribution of uncoated carbonate minerals was found to be negligible (<1 %). These results suggest a very minor role for carbonate minerals, even when coated with Fe oxide, in the sorption of P by these calcareous, Sudanese soils.     

Activity measurements of Ni2+ in soils

Nickel activities were measured in 11 alkaline and slightly acidic soils using the chelate method. The measured activities ranged from 10^?6.82 to 10^?8.78 M and were inversely related to the pH of the soils. The measured Ni²⁺ activities in the 11 soils could be predicted using the following expression: (Ni²⁺) = 10^6.95 (H⁺)². The solubility of Ni was plotted on a log (Ni²⁺) vs. pH solubility diagram for various Ni solid phase compounds. It is most likely that NiFe₂O₄ (trevorite) is the solid phase controlling Ni solubility in these soils. Identification of the presence of this mineral needs further investigation.     

Effect of redox conditions on phosphate exchangeability and iron forms in a soil amended with ferrous iron

Application of iron (Fe) -rich amendments to soils has been proposed as a means of decreasing phosphorus (P) losses from soils. However, anoxic conditions following soil saturation are known to increase Fe and P solubility in soils, thus cancelling out the potential benefits. Our aim was to evaluate the effects of continuous oxic, continuous anoxic and alternating anoxic/oxic conditions on P exchangeability and Fe forms in soil amended with Ca(OH)₂ and FeSO₄. We incubated amended and unamended soils under these conditions for 8 weeks and measured Fe forms and P exchangeability. Under oxic conditions, addition of Ca(OH)₂ and FeSO₄ resulted in a strong decrease in P exchangeability and an increase in oxalate-extractable Fe. Mössbauer analyses suggested that an unidentified Fe oxide (D1oxide) with a strong sorbing capacity for P was precipitated. Under continuously anoxic conditions, P exchangeability and oxalate-extractable Fe increased with or without the amendments. Mössbauer analyses suggested that there was a partial dissolution of the D1oxide phase, precipitation of another unidentified Fe oxide (S3) and a reduction of structural Fe³⁺ in phyllosilicate, thereby increasing soil negative charge. These transformations resulted in a strong increase in rapidly exchangeable P. Alternating anoxic and oxic periods induced the dissolution and precipitation of iron oxides and the increase and decrease in P exchangeability. Implications of the results for limiting P losses from grassland soils are discussed.     

Silicon,aluminum, and oxalic acid interactions in two California forest soils

Abstract

The release of solid‐phase soil aluminum (Al) from two soils was studied under acidic conditions and also in the presence of monosilicic acid. The soils support mixed‐conifer forests in the mid‐elevation Western Sierra Nevada in northern California, but differ in their state of development and mineralogy as shown by Al, iron (Fe), and silicon (Si) concentrations. The pyrophosphate‐extractable Al (Al_p) pool, which was a main source of released Al, decreased after a two‐month leaching with nitric (HNO₃) or oxalic (HO₂C‐CO₂H) acids. Addition of monosilicic acid (SiO₂.XH₂O) to the acid extractants resulted in a further decrease of Al. Solution monosilicic acid was removed from solution by sorption on Fe oxides/hydroxides in the soil with the higher dithionite‐extractable Fe pool. In the less developed soil with lower pedogenic Fe, the formation of short‐range‐ordered aluminosilicates, even in the presence of a strong Al chelator, was responsible for the removal of a portion of the monosilicic acid from solution. Pedogenic Fe inhibited the formation of short‐range‐ordered aluminosilicates more than the presence of a strong Al chelator. Both the solution phase and surface reactions are important in the pedogenic formation of alumino‐silicate minerals.     

Soils in the semi-arid area of the El Melah Lagoon (NE Tunisia) — Variability associated with a closing evolution

Soils of the semi-arid area of the El Melah coastal lagoon (NE Tunisia), with a closing evolution dynamic, were studied aiming: (1) the chemical and mineralogical characterization of surface and subsurface layers of soil profiles from locations previously submerged and of soils developed on dunes; (2) to evaluate the dependence on the environment conditions of the geochemical patterns of the soils; and (3) to determine chemical and mineralogical variations with the emersion of the sediments resulting from the decrease in the extent of the area permanently covered by water in the lagoon. The compositional results obtained showed significant differences depending on the environment (littoral plain, old dunes and sandy spit), but soils of the different environmental zones studied do not appear to be significantly polluted as far as trace elements are concerned. Among the elements studied, high element/Sc ratios and variations were found for As, Sb and Zn. Antimony is more concentrated in coarser samples suggesting its adsorption in Fe or Mn oxides coating quartz grain surfaces. Arsenic and zinc may be incorporated into the carbonates structure, as well as adsorbed on, or coprecipitated with, iron oxides. Zinc may also be significantly incorporated in clay minerals. Iron was found to be more oxidized in the cultivated soil from the old dune strand; and more reduced in the sandy spit where ankerite occurs suggesting the reduction of Fe³⁺ in oxide/hydroxides by microorganisms and incorporation of Fe²⁺ in carbonates. REE patterns, particularly the HREE/LREE are correlated with carbonates, indicating preferential incorporation of the HREE in carbonates, and of the LREE in clay minerals/iron oxides. High Ga contents were found in soils and sediments rich in clay minerals/Al, suggesting its incorporation in clay minerals structure. Therefore, Ga may be used as an indicator of the clay minerals proportion in sediments and soils. Carbonates, sulphates, besides Fe and/or Mn oxides and clay minerals, appear to play an important role on the trace elements distribution.     

Factors Affecting the Formation,Nature, and Properties of Iron Precipitation Products at the Soil–Root Interface

Abstract

A number of iron oxides (hematite, goethite, lepidocrocite, maghemite, and magnetite) or short‐range ordered precipitates (ferrihydrite) may be found in soil environments, but in the rhizosphere the presence of organic ligands released by plants (exudates) or microorganisms promote the formation of ferrihydrite. Iron ions are liberated into soil solution by acidic weathering of minerals and then precipitated either locally or after translocation in soil environments. Humic and fulvic acids as well as organic substances produced by plants and microorganisms are involved in the weathering of primary minerals. Organic compounds play a very important role in the hydrolytic reactions of iron and on the formation, nature, surface properties, reactivity, and transformation of Fe oxides. Organic substances present in the rhizosphere interact with Fe promoting the formation of ferrihydrite and organo‐mineral complexes. The solubility of Fe precipitation products is usually low. However, the formation of soluble complexes of Fe(II) or Fe(III) with organic ligands, usually present in the rhizosphere increases the solubility of Fe‐oxides. Mobilization of Fe from Fe oxides by siderophores is of great importance in natural systems. They can form stable Fe(III) complexes (pK up to 32) and thus mobilize Fe from Fe(III) compounds. These higher Fe concentrations are important for the supply of Fe to plant roots which excrete organic acids at the soil–root interface. Iron oxides adsorb a wide variety of organic and inorganic anions and cations, which include natural organics, nutrients, and xenobiotics. There is competition between anions and cations for the surfaces of Fe‐oxides. Root exudates suppress phosphate or sulfate adsorption on Fe‐oxides. This is a mechanism by which plant roots mobilize adsorbed phosphate and improve their phosphate supply. Anions adsorption on iron oxides modify their dispersion/flocculation behavior and thus their mobility in the soil system. That can increase or decrease the possibility of contact between Fe‐oxides and organics or organisms able to dissolve them.     

Evaluation of arsenite sorption in Spanish soils

Abstract

Arsenite sorption was studied at different temperatures (30,40, and 50°C) to investigate processes that remove arsenite from soil solution (adsorption or precipitation), and if adsorption was taking place, how many sites were involved in this process, and their nature. Adsorption was the only reaction reducing levels of soluble arsenite in the two alkaline soils used in this experiment, Jijona and Agost; however, arsenite precipitation occurred in an acidic substrate (pH 4.0), Galicia soil. Iron (Fe) oxides and clay minerals were the soil components controlling arsenite sorption in the Jijona soil (pH 7.9 and high levels of Fe oxides). Calcite and clay minerals were the inorganic constituents involved in arsenite sorption in the Agost soil (pH 8.0 and high levels of CaCO₃). Arsenite sorption was an endothermic and non‐spontaneous process. The fact that the higher the temperature, the higher the arsenite sorption, however, was likely due to an increase in the diffusion rate.     

Short‐Term Effect of Lime,Phosphorus, and Iron Amendments on Water‐Extractable Lead and Arsenic in Orchard Soils

Abstract

Lead arsenate was extensively used to control insects in apple and plum orchards in the 1900s. Continuous use of lead arsenate resulted in elevated soil levels of lead (Pb) and arsenic (As). There are concerns that As and Pb will become solubilized upon a change in land use. In situ chemical stabilization practices, such as the use of phosphate‐phosphorus (P), have been investigated as a possible method for reducing the solubility, mobility, and potential toxicity of Pb and As in these soils. The objective of this study was to determine the effectiveness of calcium carbonate (lime), P, and iron (Fe) amendments in reducing the solubility of As and Pb in lead‐arsenate‐treated soils over time. Under controlled conditions, two orchard soils, Thurmont loam (Hapludults) and Burch loam (Haploxerolls), were amended with reagent‐grade calcium carbonate (CaCO₃), iron hydroxide [Fe(OH)₃], and potassium phosphate (KH₂PO₄) and incubated for 16 weeks at 26°C. The experimental results suggested that the inorganic P increased competitive sorption between H₂PO₄ ^? and dihydrogen arsenate (H₂AsO₄ ^?), resulting in greater desorption of As in both Thurmont and Burch soils. Therefore, addition of lime, potassium phosphate, and Fe to lead‐arsenate‐contaminated soils could increase the risk of loss of soluble As and Pb from surface soil and potentially increase these metal species in runoff and movement to groundwater.     

Cyanide in paper de‐inking sludge used as a soil amendment

Paper de‐inking sludge is processed during the recycling of paper, and is sometimes used as a soil amendment. In this study the effect of a compost application on the cyanide (CN) status in soils of a public park was investigated. The compost was a mixture of chipped limbs and paper de‐inking sludge. Furthermore, the cyanide solubility was studied by conducting batch experiments with different pH levels. Total cyanide in the amended soils ranged from 540 to 740 mg CN kg^—1, and water soluble cyanide from 170 to 370 μg CN l^—1 as determined by means of an aqueous extract. Easily‐liberatable cyanides, which include the toxic free cyanide (HCN and CN^—) and weak metal‐cyanide complexes, were not present in the soil. From this result and the fact that iron blue pigments are used during paper printing, it can be inferred that cyanides occurring here were exclusively stable iron‐cyanide complexes [Fe(CN)₆]. With increasing pH the solubility of cyanide increased. In contrast to soils of coking plants, in which cyanide occur as Berlin blue, Fe₄[Fe(CN)₆]₃, the cyanide solubility in the paper de‐inking sludge amended soils was substantially lower, especially in the neutral and alkaline range. Thus, cyanides in paper de‐inking sludge could be present as sparingly soluble metal‐cyanide compounds with the general formula A₂B[Fe^II(CN)₆] with A = K⁺, Na⁺ and B = Ca²⁺ or divalent transition metals and B₂[Fe^II(CN)₆] with B = divalent transition metals. Pollution exposure by the pathways soil → human, and soil → air → human can be neglected. However, since leaching of iron‐cyanide complexes into the ground water cannot be excluded, and since they are decomposed to HCN when exposed to day light, environmental hazards by the pathway soil → ground water → surface water are possible. This is the risk arising from paper de‐inking sludge applications to soils.     

Stability in solution and reactivity with soils and soil components of iron and zinc complexes

Naturally derived complexes with the ability to complex (unidentate) or chelate (polydentate) metals are a cheaper alternative to synthetic chelates to correct micronutrient deficiencies, but despite their widespread use there is a lack of knowledge on their agronomic performance. The aim of this paper was to evaluate the stability of iron (Fe) and zinc (Zn) lignosulfonate, gluconate, amino acid, and humate complexes in solution over time and at different pH values. Also, their stability in a concentrated nutrient solution and their reactivity with soils and soil components was evaluated. In our experimental conditions, all the complexes (except Fe amino acid) remained stable in solution for an extended period of time. All Zn complexes and the Fe lignosulfonate were stable in solution up to pH 7.0–7.5, while Fe gluconate only maintained 20%–40% of the iron in solution in the pH range 5–11 and Fe amino acid and humate complexes barely maintained small concentrations of Fe in solution above pH 3. Most of the complexes maintained Fe and Zn in concentrated nutrient solutions for irrigation systems, but Fe amino acid only maintained around 70% of the iron added. In general, the interactions of complexes with soils and soil components produced a high retention. The interaction of Fe lignosulfonate with peat, illite, and ferrihydrite, and Fe gluconate with peat and illite resulted in significant amounts of Fe to remain in solution, while for the Fe amino acid and humate the Fe remaining in solution was low. All Zn complexes were highly retained in an acidic peat, illite, and montmorillonite clays and soils, while no retention was observed on ferrihydrite. In conclusion, the stability of complexes in different conditions is related to the percentage of complexed element in the products. While complexes can be used to maintain micronutrients in solution in aqueous media (foliar and fertigation), their application to soil should be considered as a measure to increase metal availabilities but not their solubility.     

Soil solution aluminium activity related to theoretical A1 mineral solubilities in four Australian soils

Four soils were treated with HNO₃, CaCO₃ and K₂SO₄ to enable observation of the response of the soil solution composition and the solution A1 ion activity (Al³⁺) to the treatments and to time. The clay fraction of three of the soils was dominated by illite, kaolinite and quartz. The fourth was minated by kaolinite and iron oxides. The initial pH in 0.01 M CaCl₂ varied between 4.0 and 5.0 and the organic carbon content from 0.7 to 1.1%. The soil solutions from soils dominated by kaolinite, illite and quartz were generally supersaturated with respect to quartz and well ordered kaolinite, and unsaturated with respect to illite. The soil solutions from the soil dominated by kaolin and iron oxide were generally unsaturated with respect to quartz but still saturated with respect to ell crystallized kaolin. Within mineral groups such as Al₂SiO₅ compounds, A1₂Si₂O₅(OH)₄ (kaolinite group), and Al(OH)₃ (A1 oxide) minerals, the more soluble forms became less supersaturated or unsaturated with time for many treatments. Lime treatment usually increased the ion activity product of AI(OH)₃ in all soils, and of minerals with the composition, Al₂SiO₅, in the illite/kaolinite soils. Acid treatment reduced the apparent solubility of Al(OH)₃, and the A1 silicates in the Al₂SiO₅, and Al₂, Si₂, O₅,(OH)₄, mineral groups on all soils. These results are interpreted to indicate that lime treatment led to the formation of trace quantities of more soluble A1 minerals that subsequently controlled (Al³⁺), whereas acid treatment dissolved trace quantities of such minerals leaving less soluble minerals to control (Al³⁺). The results suggest that, in mineral soils such as these, (Al³⁺) is under the control of inorganic dissolution and precipitation processes. These processes conform to expectations given the free energy of various inorganic aluminium compounds. Furthermore the sequence of dissolution and formation processes appears to be governed by the Gay-Lussac—Ostwald step rule.     

Soil flooding and rice straw addition can increase isotopic exchangeable phosphorus in P‐deficient tropical soils

Soil flooding increases phosphorus (P) availability due to reductive dissolution of P‐bearing Fe(III) minerals. It is, however, unclear whether such processes also act in P‐deficient soils of the tropics that have large Fe/P ratios (dithionite‐ and oxalate‐extractable P and Fe). The objective was to identify the extent of P release induced by flooding in such soils and the soil characteristics involved. Six topsoils (0.4–5% Fe) from rice fields in Madagascar were incubated aerobically and anaerobically for 66 days amended with factorial combinations of (0, 50 mg P/kg); half of the flooded soils were also amended with 1 g rice straw/kg prior to flooding to stimulate soil oxygen depletion. The release of P after flooding was measured at day 40 with ³³P isotopic exchange, which detects both changes of labile P (exchangeable P) and changes in P solubility. Flooding increased labile P concentration in soil compared with aerobic soils by 1.4–60 mg P/kg, effects being significant in 6 of the 12 soil samples. Rice straw addition further increased the labile P in 5 of the 12 flooded soil samples by 2–27 mg P/kg. The release of labile P by flooding increased with soil oxalate‐extractable P concentration. Flooding combined with rice straw addition can increase the labile P in soil, even in soils with large amount of Fe; however, this release in unfertilized soils is likely insufficient for optimal nutrition of rice plants when evaluated against critical values for P solubility.