Photocatalytic fixation of NOx in soils.

Nitrogen oxides (NOx = NO + NO2) are important atmospheric pollutants that are directly harmful to human health. Recently in urban and industrial areas, synthetic materials have been developed and deployed to photocatalytically oxidize NOx to nitrate (NO3-) in order to improve air quality. We show that the natural presence of small amounts (≤5%) of titanium oxides, such as anatase and rutile, can also drive NOx oxidation to nitrate in soils under UV-visible irradiation. The NO uptake coefficients ranged between 0.1 × 10-6 for sandy soils to 6.4 × 10-5 in the case of tropical clay soils; the latter comparable in efficiency to current industrial man-made catalysts. This photocatalytic N-fixation mechanism offers a new strategy for NOx mitigation from the atmosphere by transforming it into nitrate, and simultaneously provides an energy efficient source of essential fertilizer to agriculture.

Spatio-temporal assessment of soil properties immediately and eight months after a high intensity-controlled burn in the south of Spain.

In recent years, the use of fire as a means by which to manage forest ecosystems has become more frequent in Europe. Fire has a significant impact on the soil, and it is therefore necessary to understand how controlled burns affect this invaluable resource. The purpose of this study was to evaluate the main alterations in the physical-chemical and biological properties of the soil because of a high intensity-controlled burn in "Los Boquerones" area (Villaviciosa de Córdoba, Spain). Additionally, we assessed the spatial heterogeneity of the alterations of different soil properties. A grid of 12 points was established on a hillside in Sierra Morena (Córdoba). Thermocouples were placed at each point, and soil samples were collected at two depths (0-2 cm and 2-5 cm) before burning, immediately after burning and eight months later. Soil pH, electrical conductivity, nutrient content and/or availability, among others, and their spatio-temporal variations were analysed. Soil pH, increased in the first centimetres of the soil (0-2 cm) immediately after burning up to >2 units, and the increase was maintained eight months following the burn. Additionally, the high-intensity burn had a positive short-term effect on some of the soil properties, such as nutrient availability for plants, which was considerably increased. The magnitude of the alterations in the soil indicators assessed was spatially explained by the behaviour of the fire during the controlled burning. The burn also had both direct and indirect effects on soil microorganisms. In conclusion, the possible immediate and short-term effects of burning on the soil resource should be considered for a more holistic management of fire in forest ecosystems, as its functionality and capacity to provide ecosystem services is largely altered by these events as a function of their intensity.

Linking functional traits with tree growth and forest productivity in Quercus ilex forests along a climatic gradient.

Plant functional traits are highly plastic to changes in climatic factors and nutrient availability. However, the intraspecific plant response to abiotic factors and the overall effect on tree growth and productivity is still under debate. We studied forest productivity for 30 Quercus ilex subsp. ballota forests in Spain along a broad climatic gradient of aridity (mean annual precipitation from 321 to 858 mm). We used linear mixed models to quantify the effect of climatic and edaphic (soil nutrients, topography, and texture) factors on tree functional traits (leaf and branch traits), and subsequently, the effect of such functional traits and abiotic factors on the relative growth rate (RGR) of adult trees. We used piecewise structural equation models (SEMs) to determine the causal effect of intrinsic and extrinsic factors on forest productivity. Our results showed that tree functional traits were mainly explained by climatic and edaphic factors. Functional traits and tree biomass explained forest biomass and RGR, respectively, which ultimately explained forest productivity. In conclusion, intraspecific variability of functional traits has a significant effect on plant biomass and growth, which ultimately may explain forest productivity in Quercus ilex forests.

Photochemical emission and fixation of NOX gases in soils.

Gaseous nitrogen oxides (NOx), which result from the combustion of fossil fuels, volcanic eruptions, forest fires, and biological reactions in soils, not only affect air quality and the atmospheric concentration of ozone, but also contribute to global warming and acid rain. Soil NOx emissions have been largely ascribed to soil microbiological processes; but there is no proof of abiotic catalytic activity affecting soil NO emissions. We provide evidence of gas exchange in soils involving emissions of NOx by photochemical reactions, and their counterpart fixation through photocatalytic reactions under UV-visible irradiation. The catalytic activity promoting NOx capture as nitrate varied widely amongst different soil types, from low in quartzitic sandy soils to high in iron oxide and TiO2 rich soils. Clay soils with significant amounts of smectite also exhibited high rates of NOx sequestration and fixed amounts of N comparable to that of NO (nitric oxide) losses through biotic reactions. In these soils, a flux of 100 µg NNO m-2 h-1, as usually found in most ecosystems, could be reduced by these photochemical reactions by more than 60%. This mechanism of N fixation provides new insight into the nitrogen cycle and may inspire alternative strategies to reduce NO emissions from soils.

Chromium Displacement in Subtropical Soils Fertilized with Hydrolysed Leather: A Laboratory Study.

Prolonged use of biosolids with high metal content may result in diffuse pollution across large regions, especially if such ions can move freely through the soil profile and reach underground water sources. The objective of this study was to verify whether Cr added to the soil surface in the form of hydrolysed leather or a soluble salt would migrate over significant distances in four subtropical soils differing in physical, chemical and mineralogical properties. Horizontal and vertical mobility were assessed in Petri dishes and small pots, respectively, using low (12 mg kg-1 soil) and high Cr levels (150 mg kg-1 soil) added to the soil surface. Irrespective of concentration, soluble Cr salts were found to move more easily in soils with low organic matter and clay content. Contrarily, Cr added as hydrolysed leather exhibited negligible mobility and tended to accumulate in the vicinity of application.

Control of Earth-like magnetic fields on the transformation of ferrihydrite to hematite and goethite.

Hematite and goethite are the two most abundant iron oxides in natural environments. Their formation is controlled by multiple environmental factors; therefore, their relative concentration has been used widely to indicate climatic variations. In this study, we aimed to test whether hematite and goethite growth is influenced by ambient magnetic fields of Earth-like values. Ferrihydrite was aged at 95 °C in magnetic fields ranging from ~0 to ~100 µT. Our results indicate a large influence of the applied magnetic field on hematite and goethite growth from ferrihydrite. The synthesized products are a mixture of hematite and goethite for field intensities <~60 µT. Higher fields favour hematite formation by accelerating ferrimagnetic ferrihydrite aggregation. Additionally, hematite particles growing in a controlled magnetic field of ~100 µT appear to be arranged in chains, which may be reduced to magnetite keeping its original configuration, therefore, the presence of magnetic particles in chains in natural sediments cannot be used as an exclusive indicator of biogenic magnetite. Hematite vs. goethite formation in our experiments is influenced by field intensity values within the range of geomagnetic field variability. Thus, geomagnetic field intensity could be a source of variation when using iron (oxyhydr-)oxide concentrations in environmental magnetism.

Spatial heterogeneity of soil biochar content affects soil quality and wheat growth and yield.

Biochar (BC) is a carbonaceous material obtained by pyrolysis of organic waste materials and has been proposed as a soil management strategy to mitigate global warming and to improve crop productivity. Once BC has been applied to the soil, its imperfect and incomplete mixing with soil during the first few years and the standard agronomic practices (i.e. tillage, sowing) may generate spatial heterogeneity of the BC content in the soil, which may have implications for soil properties and their effects on plant growth. We investigated how, after two agronomic seasons, the spatial heterogeneity of olive-tree prunings BC applied to a vertisol affected soil characteristics and wheat growth and yield. During the second agronomic season and just before wheat germination, we determined the BC content in the soil by an in-situ visual categorization based on the soil darkening, which was strongly correlated to the BC content of the soil and the soil brightness. We found a high spatial heterogeneity in the BC plots, which affected soil characteristics and wheat growth and yield. Patches with high BC content showed reduced soil compaction and increased soil moisture, pH, electrical conductivity, and nutrient availability (P, Ca, K, Mn, Fe, and Zn); consequently, wheat had greater tillering and higher relative growth rate and grain yield. However, if the spatial heterogeneity of the soil BC content had not been taken into account in the data analysis, most of the effects of BC on wheat growth would not have been detected. Our study reveals the importance of taking into account the spatial heterogeneity of the BC content.

Mechanochemical synthesis of maghemite/silica nanocomposites: advanced materials for aqueous room-temperature catalysis.

A simple, environmentally friendly, and highly reproducible protocol has been developed for the mechanochemical preparation of advanced nanocatalytic materials in a one-pot process. The materials proved to have unprecedented activities in aqueous Suzuki couplings at room temperature, paving the way for a new generation of highly active and stable advanced nanocatalysts.

Pot evaluation of synthetic nanosiderite for the prevention of iron chlorosis.

BACKGROUND: Iron chlorosis is a problem that affects crops grown on calcareous soils. In this work, we assessed the effectiveness of nanosized siderite (FeCO3) to prevent iron chlorosis, the underlying hypothesis being that the oxidation products of siderite in soil are poorly crystalline, and hence plant-available, iron oxides. RESULTS: Nanosized siderite was prepared by mixing FeSO4 and K2CO3 solutions, either pure or doped with phosphate (siderite SID and SIDP, respectively). The average specific surface area was ∼140 m² g⁻¹ for SID and ∼220 m² g⁻¹ for SIDP. Experimental oxidation in a calcite suspension yielded goethite for SID and a mixture of lepidocrocite and goethite for SIDP. Two pot experiments in which a SID or SIDP suspension was applied to a calcareous soil at a rate of ∼2 g Fe kg⁻¹ showed nanosiderite to prevent iron chlorosis in chickpea. In a pot experiment with five successive crops, one initial application of ∼0.7 g Fe kg⁻¹ soil in the form of SID or SIDP was as effective as FeEDDHA in preventing Fe chlorosis. The residual effect of nanosiderite when applied to the first crop alone clearly exceeded that of FeEDDHA. CONCLUSION: Nanosiderite suspensions applied at rates of ∼0.7 g Fe kg⁻¹ soil were highly effective in preventing iron chlorosis and have a great residual effect.

Ordered ferrimagnetic form of ferrihydrite reveals links among structure, composition, and magnetism.

The natural nanomineral ferrihydrite is an important component of many environmental and soil systems and has been implicated as the inorganic core of ferritin in biological systems. Knowledge of its basic structure, composition, and extent of structural disorder is essential for understanding its reactivity, stability, and magnetic behavior, as well as changes in these properties during aging. Here we investigate compositional, structural, and magnetic changes that occur upon aging of "2-line" ferrihydrite in the presence of adsorbed citrate at elevated temperature. Whereas aging under these conditions ultimately results in the formation of hematite, analysis of the atomic pair distribution function and complementary physicochemical and magnetic data indicate formation of an intermediate ferrihydrite phase of larger particle size with few defects, more structural relaxation and electron spin ordering, and pronounced ferrimagnetism relative to its disordered ferrihydrite precursor. Our results represent an important conceptual advance in understanding the nature of structural disorder in ferrihydrite and its relation to the magnetic structure and also serve to validate a controversial, recently proposed structural model for this phase. In addition, the pathway we identify for forming ferrimagnetic ferrihydrite potentially explains the magnetic enhancement that typically precedes formation of hematite in aerobic soil and weathering environments. Such magnetic enhancement has been attributed to the formation of poorly understood, nano-sized ferrimagnets from a ferrihydrite precursor. Whereas elevated temperatures drive the transformation on timescales feasible for laboratory studies, our results also suggest that ferrimagnetic ferrihydrite could form naturally at ambient temperature given sufficient time.

Can the presence of structural phosphorus help to discriminate between abiogenic and biogenic magnetites?

The influence of phosphate on the competitive formation of magnetite and lepidocrocite and the properties of magnetite prepared from mixtures of Fe(II) and Fe(III) salts were studied. Products were prepared at 90 degrees C and pH 12.5 (series 1), 50 degrees C and pH 7 (series 2) and 20 degrees C and pH 8 (series 3). The P/Fe atomic ratio in the initial solution ranged from 0 to 3% and the pH was kept at the desired value with NaOH or KOH. Air was used as oxidant in series 2 and 3. All products, which were characterized by X-ray diffraction, transmission electron microscopy, chemical analysis and IR spectroscopy, contained a phase intermediate between magnetite and maghemite (referred to as magnetite in this paper). The products of series 1 consisted only of magnetite at all P/Fe ratios, whereas both magnetite and lepidocrocite formed in series 2 and 3 above a certain P/Fe ratio. On increasing the P/Fe ratio in the initial solution, the magnetite crystals became smaller and more oxidized (i.e. closer to maghemite) and the lepidocrocite/magnetite ratio increased. The P associated with magnetite was partly in the form of occluded P, i.e. non-surface-adsorbed phosphate. IR spectra suggested this P to be structural and occurring as low-symmetry PO(4) units. Because abiogenic magnetites produced in various environments incorporate structural P but some well-characterized biogenic magnetites seem to contain no P or be formed in P-poor environments, we hypothesize that natural magnetites containing occluded P are unlikely to be biogenic. However, more studies are needed to discard the presence of P in biogenic magnetites.