Organic acids are commonly found in soils and sediments, playing an important role in the alteration and weathering of minerals and influencing a series of geochemical processes such as soil fertility, metal cycling and pollutant migration. In order to better comprehend the reaction mechanisms of different layered silicate minerals with organic acids, three minerals with various structure types, namely montmorillonite, kaolinite and muscovite, were investigated in this work. In particular, the effects of interfacial reactions with oxalic acid on the crystal structure, chemical composition, morphology and specific surface area of minerals were compared. The composition and structure of montmorillonite, kaolinite and muscovite during the interfacial reaction with oxalic acid were characterised using powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and inductively coupled plasma-optical emission spectroscopy (ICP-OES) methods. It was shown that Si4+ and Al3+ were dissolved gradually during the interfacial reactions and that the changes in the properties of minerals depended on structural characteristics. After 300 days of the interfacial reactions with oxalic acid, the dissolution percentages of Si4+ and Al3+ in montmorillonite, kaolinite and muscovite were 12.7%, 8.4%, 3.8% and 62.1%, 30.7%, 6.1%, respectively. Moreover, the lamellar morphology of montmorillonite was destroyed upon the interfacial reaction with oxalic acid, and irregular particles with sizes of ~100–500 nm were formed on the surface. The diameter of kaolinite flake particles decreased from 400–1500 nm to 50–400 nm, and the surface of rod-shaped particles was ruptured. The small particles disappeared from the muscovite surface, and the initially sharp edges became blunted. The specific surface area and the total pore volume of montmorillonite and kaolinite increased after the interfacial reaction with oxalic acid, whereas the opposite results were obtained for muscovite. The differential dissolution of the minerals during their interfacial reaction with oxalic acid was mainly related to the differences between cation occupancies, structural types, chemical bond strengths and specific surface areas.

Kaolin waste dumps contain a huge volume of material that cannot be commercialized due to the presence of variable amounts of iron minerals, which impart a yellowish color to the kaolin. Elimination of iron from kaolin using either a chemical or a biological method was the aim of this study. The chemical leaching of iron from kaolin was carried out using response surface methodology to optimize the reaction conditions. Time was found to be the most influential variable, although oxalic acid must be present to leach 32% of the iron. Biological leaching was also assayed for 14 days using a Bacillus strain. The results of bacterial leaching of iron from kaolin showed <1% iron elimination.

Magnetite (Fe3O4) is a key economically valuable component in iron ore and is extracted by dissolution processes, but among the Fe (oxyhydr)oxides its solubility behavior is one of the least understood. The objective of this study was to improve understanding of magnetite dissolution mechanisms leading to thermodynamic equilibrium by comparing the dissolution of two solid samples, one synthetic and one industrial, using oxalic, sulfuric, and nitric acids at varying concentrations and temperatures. Of the three solid-liquid systems investigated, only the system consisting of magnetite and oxalic acid reached an equilibrium state within the duration of an individual experiment (6 h). In this system, increasing the acid concentration resulted in a significant increase in the equilibrium concentration of dissolved Fe. When dissolving synthetic and industrial magnetite, increasing the temperature not only increased the rate of reaction but also affected the concentration of dissolved Fe. Significant effects were observed when increasing the temperature from 15 to 35°C, but only slight differences were seen on further increases in temperature. Observations regarding the equilibrium state of the sulfuric and nitric acid systems could not be made because equilibrium was not reached. The most important individual observation regarding the equilibrium state of the nitric- and sulfuric-acid systems seems to be that in future studies a much longer reaction time is necessary, due to slow kinetics of the dissolution mechanism. A proton-based mechanism has been hypothesized as the one governing the dissolution of magnetite by these two acids, but only the dissolution of the industrial sample yielded results that were similar for these two acids and consistent with that hypothesis.

A china clay sample from Jharkhand State, India, containing 65.0 wt.% SiO2, 22.7% Al2O3, 1.77% Fe2O3 and 9.10% LOI was subjected to physical beneficiation and acid leaching studies to improve its quality. The clay was characterized by optical microscopy, XRD, and wet chemical analysis methods. Quartz and goethite are the two major impurities. High intensity magnetic separation removed only 10% of the total iron. Experiments with oxalic acid were carried out to establish the leaching kinetics of iron and the effects of acid concentration, time and temperature on iron leaching were also examined. The study demonstrated that ∼90% of total iron could be removed using 5% oxalic acid. The dissolution of iron from clay is best described by diffusion of ions through the product layer of constant size spherical particles. The activation energy of the leaching process over the temperature range was calculated to be 51.14 kJ/mol.

The percolation of water through waste landfill sites produces leachates with large amounts of pollutants. Clay barriers are often used to limit soil and underground water pollution. A better understanding of the interaction between ammonium smectite and carboxylic acids would contribute significantly to our understanding of such systems. The SWy-2 (Wyoming smectite) was exchanged with NH4+ and then batched with carboxylic acids (acetic, formic, chloroacetic and oxalic) in concentrations between 0.01 M and 1 M. The solid phases obtained were analysed chemically and characterized by infrared absorption spectroscopy (IR) and powder X-ray diffraction (XRD). Ionic chromatography was used for the quantitative measurement of ammonium ions in the solution after the interaction. For the four acids, the interaction was characterized by a cationic exchange of NH4+ to H3O+. A partial exchange to Al3+ due to a partial dissolution of the sample in strong acidic medium was observed with chloroacetic and oxalic acids for which adsorption of molecules on the clay sample occurs, mainly through H-bonding with the cation. Moreover, the intercalation of oxalic acid in the interlayer space was highlighted.

Biological weathering is a function of biotic energy expenditure. Growth and metabolism of organisms generates acids and chelators, selectively absorbs nutrient ions, and applies turgor pressure and other physical forces which, in concert, chemically and physically alter minerals. In unsaturated soil environments, plant roots normally form symbiotic mycorrhizal associations with fungi. The plants provide photosynthate-carbohydrate-energy to the fungi in return for nutrients absorbed from the soil and released from minerals. In ectomycorrhiza, one of the two major types of mycorrhiza of trees, roots are sheathed in fungus, and 15—30% of the net photosynthate of the plants passes through these fungi into the soil and virtually all of the water and nutrients taken up by the plants are supplied through the fungi. Here we show that ectomycorrhizal fungi actively forage for minerals and act as biosensors that discriminate between different grain sizes (53—90 μm, 500—1000 μm) and different minerals (apatite, biotite, quartz) to favour grains with a high surface-area to volume ratio and minerals with the highest P content. Growth and carbon allocation of the fungi is preferentially directed to intensively interact with these selected minerals to maximize resource foraging.

Lichen-dominated cryptoendolithic communities from the Dry Valleys of Antarctica have been the subject of much research over recent years owing to their potential as analogues of Martian life forms. Their ability to mobilize iron compounds and organize themselves into distinct coloured biotic zones suggests that they may alter the chemistry of their host rock. By conducting a major, minor and trace element study utilizing inductively coupled plasma atomic emission spectroscopy (ICP-AES) and mass spectrometry (ICP-MS) techniques, we have been investigating the relationship between the microbes and the chemistry of the sandstones. Different layers within a suite of sandstones collected from six localities in the Dry Valleys have been analysed to establish if or how the microbes influence or directly affect the chemical composition of the rocks. Background petrographic studies have shown significant differences in mineralogical maturity between rocks colonized by the communities and those that are not, and the chemistry results have shown significant elemental disparity between colonized and uncolonized rocks. By obtaining accurate percentages of the minerals present in each sample the differences in elemental concentrations could be construed to be caused by the differences in mineralogy between samples. The nature and extent of the concentration differences has led to the conclusion that either the cryptoendolith communities are able to alter their host rock by the solubilization and mobilization of elements that are then subsequently removed or that the organisms are simple opportunists that can only successfully colonize rocks that provide the ideal substrate, being mineralogically mature with ample pore space and less concentrated in the elements tested for.

A cultivation method was developed to enable exposure of ectomycorrhizal plants with intact extramatrical mycelium to solutions containing different concentrations of aluminium or heavy metals. Pinus sylvestris seedlings colonized by Suillus variegatus (two isolates), Rhizopogon roseolus or Paxillus involutus (two isolates) were used. Seedlings were transferred to Petri dishes containing glass beads and exposed to elevated concentrations of Al, Cd, Cu, or Ni in two ways: immediately following transfer; and after allowing mycorrhizal seedlings to develop an extraradical mycelium that colonized the interface between the upper surface of the beads and the metal- containing solution. Production of organic acids in mycorrhizal and non-mycorrhizal systems was measured by withdrawing samples from the solution and analyzing by HPLC. In most experiments, levels of oxalic acid were significantly higher in mycorrhizal treatments than in non-mycorrhizal controls. The measured levels of organic acids were variable, but the results obtained suggest that production of oxalic acid is stimulated by exposure to elevated Al in mycorrhizal seedlings colonized by S. variegatus and R. roseolus. Elevated Al concentrations also increased oxalic acid production by non-mycorrhizal seedlings significantly in two of four Al experiments performed, but the measured concentrations were significantly lower than in corresponding mycorrhizal treatments in both cases. Malonic acid was found in the culture solution of non-mycorrhizal and P. involutus- colonized seedlings, but only trace amounts were found in S. variegatus or R. roseolus-infected seedlings. Citric, shikimic, lactic, acetic, propionic, fumaric, formic, iso-butyric and butyric acid were found in variable concentrations. Production of oxalic acid by seedlings colonized by S. variegatus BL or P. involutus was not stimulated by exposure to 0.44 μM Cd or 17 μM Ni. Exposure to 0.157 mM Cu in two separate experiments using P. involutus 87.017 and two strains of S. variegatus (BL and I59) appeared to stimulate production of oxalic acid irrespective of mycorrhizal status or species.

Rumen microbial degradation is an important route for detoxification of secondary plant compounds encountered in the diets of free-grazing ruminants. Exposure to diets containing particular secondary plant compounds can lead to increased rates of secondary compound degradation in the rumen. An experiment was conducted to determine whether rumen adaptation to oxalic acid would influence the diet selection of goats offered choices between plant species differing in their oxalic acid content. Twelve adult female goats were divided into two groups of six animals each. One group received a daily oral dose, in gelatin capsules, of 0·6 mmol oxalic acid/kg live weight per d throughout the experiment while the other group received placebos consisting of empty gelatin capsules. After an adaptation period of 8 d, the animals were allowed to graze a mixture of spinach (rich in oxalic acid) and cabbage (low in oxalic acid) for 7 h/d on two consecutive days per week during four consecutive 1-week periods. Intervening days were spent on grass pasture. Diet composition and intake were measured using cuticular wax n−alkanes as internal markers. Results showed that adapted goats included a higher proportion of spinach in their diet (P < 0·05) although absolute intakes of spinach were the same for the two groups. Goats in the oxalic-acid-adapted group consumed less cabbage than control animals (P < 0·05) suggesting that adaptation to oxalic acid at the rumen level may have interfered with detoxification of cabbage-derived secondary plant compounds. Voluntary intake increased progressively through the four experimental periods (P < 0·001) with a tendency for higher intakes among control than among adapted animals (P < 0·1). The experiment demonstrates how differences in the rate of degradation of secondary plant compounds may influence diet selection in ruminants.

Within the overall objective of whether ruminants are able to form conditioned aversions (CFA) toward a food flavour associated with the administration of an aversive stimulus which occurs naturally in food plants (oxalic acid, OA), two specific objectives were tested: (1) whether the rate and degree of formation of CFA are dependent on the dose rate of OA administered and (2) whether the persistence of formed CFA depends on the previous dose rate of OA. Sheep were conditioned to associate the specific flavour of one of two novel foods with either the oral administration of OA or equivalent placebos. Four dose rates of OA were tested (0.06, 0.12, 0.18 and 0.24 g/kg sheep live weight per d), with twelve sheep per dose. Each conditioning period lasted for 8 d and was repeated four times. At the end of each conditioning period the preference for the two flavours was measured in short-term, 20min preference tests. The persistence of the CFA was measured at 0, 7, 21 and 49 d after the completion of the conditioning phase with long-term, 3 h preference tests. The results of the experiment indicated that: (1) the rate and degree of formation of CFA were dependent on the rate of administration of OA; (2) sheep required repeated exposures to the lower dose rates of OA in order to develop CFA and these CFA did not persist in the absence of continual reinforcement; (3) CFA to the higher dose rates of OA were developed after as little as one exposure and persisted over a period of at least 7 weeks. These findings are consistent with the expectation that ruminants should be able to select a diet which minimizes the risk of consumption of potentially harmful foods, whilst at the same time maintaining a degree of flexibility in their feeding behaviour.

Oxalic acid is found in high concentrations in some plants consumed by ruminants and may cause renal toxicity. To determine whether exposure to oxalic acid affects the capacity of the rumen of sheep and goats to degrade the compound, 20 animals (10 sheep and 10 goats) were dosed with free oxalic acid by gelatin capsule twice daily for 3 weeks at one of five levels (0·0, 0·3, 0·6, 0·9 and 1·2 mmol/kg live weight (M) per day). Rumen samples were collected by stomach tube in the week prior to the start of dosing and in each week of the 3-week experiment. Oxalic acid degradation capacity was measured by adding uC-labelled oxalic acid to rumen fluid in vitro and capturing evolved 14CO2. Rates of degradation increased with increasing level of administration (2·30, 4·71, 6·74, 9·83 and 13·90 mmol of oxalic acid degraded per I rumen fluid per day for doses 0·0, 0·3, 0·6, 0·9 and 1·2 mmol/kg M per day, respectively; P < 0·001). Rates of degradation increased during the dosing period (P < 0·001) with the largest increases occurring in the 1st week of dosing. Goats showed a greater response than sheep, with a higher mean oxalic acid degradation capacity (9·04 v. 5·95 mmol of oxalic acid degraded per I rumen fluid, P < 0·05). Oxalic acid administration did not influence plasma calcium concentration or cause renal function impairment as measured by plasma creatinine concentrations. The experiment demonstrated adaptation in the rumen to potential toxins in the host diet and suggests that the rumen micro-organisms of goats may have been more adapted to degrading oxalic acid than sheep.