Animal manure phosphorus characterization by sequential chemical fractionation, release kinetics and 31P-NMR analysis

Phosphate release kinetics from manures are of global interest because sustainable plant nutrition with phosphate will be a major concern in the future. Although information on the bioavailability and chemical composition of P present in manure used as fertilizer are important to understand its dynamics in the soil, such studies are still scarce. Therefore, P extraction was evaluated in this study by sequential chemical fractionation, desorption with anion-cation exchange resin and 31P nuclear magnetic resonance (31P-NMR) spectroscopy to assess the P forms in three different dry manure types (i.e. poultry, cattle and swine manure). All three methods showed that the P forms in poultry, cattle and swine dry manures are mostly inorganic and highly bioavailable. The estimated P pools showed that organic and recalcitrant P forms were negligible and highly dependent on the Ca:P ratio in manures. The results obtained here showed that the extraction of P with these three different methods allows a better understanding and complete characterization of the P pools present in the manures.

Chemical and physical-hydric characterisation of a red latosol after five years of management during the summer between-crop season

Agricultural production systems that include the production of mulch for no-tillage farming and structural improvement of the soil can be considered key measures for agricultural activity in the Cerrado region without causing environmental degradation. In this respect, our work aimed to evaluate the chemical and physical-hydric properties of a dystrophic Red Latosol (Oxisol) in the municipality of Rio Verde, Goias, Brazil, under different soil management systems in the between-crop season of soybean cultivation five years after first planting. The following conditions were evaluated: Brachiaria brizantha cv. Marandu as a cover crop during the between-crop season; Second crop of maize intercropped with Brachiaria ruziziensis; Second crop of grain alone in a no-tillage system; Fallow soil after the soybean harvest; and Forest (natural vegetation) located in an adjacent area. Soil samples up to a depth of 40 cm were taken and used in the assessment of chemical properties and soil structure diagnostics. The results demonstrated that the conversion of native vegetation areas into agricultural fields altered the chemical and physical-hydric properties of the soil at all the depths evaluated, especially up to 10 cm, due to the activity of root systems in the soil structure. Cultivation of B. brizantha as a cover crop during the summer between-crop season increased soil water availability, which is important for agricultural activities in the region under study.

USE OF SCALED SEMIVARIOGRAMS IN THE PLANNING SAMPLE OF SOIL CHEMICAL PROPERTIES IN SOUTHERN AMAZONAS, BRAZIL

The lack of information concerning the variability of soil properties has been a major concern of researchers in the Amazon region. Thus, the aim of this study was to evaluate the spatial variability of soil chemical properties and determine minimal sampling density to characterize the variability of these properties in five environments located in the south of the State of Amazonas, Brazil. The five environments were archaeological dark earth (ADE), forest, pasture land, agroforestry operation, and sugarcane crop. Regular 70 × 70 m mesh grids were set up in these areas, with 64 sample points spaced at 10 m distance. Soil samples were collected at the 0.0-0.1 m depth. The chemical properties of pH in water, OM, P, K, Ca, Mg, H+Al, SB, CEC, and V were determined at these points. Data were analyzed by descriptive and geostatistical analyses. A large part of the data analyzed showed spatial dependence. Chemical properties were best fitted to the spherical model in almost all the environments evaluated, except for the sugarcane field with a better fit to the exponential model. ADE and sugarcane areas had greater heterogeneity of soil chemical properties, showing a greater range and higher sampling density; however, forest and agroforestry areas had less variability of chemical properties.

SOIL CHEMICAL PROPERTIES AND GROWTH OF SUNFLOWER (HELIANTHUS ANNUUS L.) AS AFFECTED BY THE APPLICATION OF ORGANIC FERTILIZERS AND INOCULATION WITH ARBUSCULAR MYCORRHIZAL FUNGI

The use of organic fertilizers and the inoculation of mycorrhizal fungi in the cultivation of oil crops is essential to reduce production costs and minimize negative impacts on natural resources. A field experiment was conducted in an Argissolo Amarelo (Ultisol) with the aim of evaluating the effects of fertilizer application and inoculation of arbuscular mycorrhizal fungi on the growth attributes of sunflower (Helianthus annuus L.) and on soil chemical properties. The experiment was conducted at the Federal University of Rio Grande do Norte, Brazil, using a randomized block design with three replicates in a 4 × 2 factorial arrangement consisting of four treatments in regard to application of organic fertilizer (liquid biofertilizer, cow urine, mineral fertilizer, and unfertilized control) and two treatments in regard to arbuscular mycorrhizal fungi (with and without mycorrhizal fungi). The results showed that the physiological attributes of relative growth rate and leaf weight ratio were positively influenced by fertilization, compared to the control treatment, likely brought about by the supply of nutrients from the fertilizers applied. The growth and productivity attributes were positively affected by mycorrhization.

EFFECT OF ALTERNATIVE MULTINUTRIENT SOURCES ON SOIL CHEMICAL PROPERTIES

The current high price of potassium chloride and the dependence of Brazil on imported materials to supply the domestic demand call for studies evaluating the efficiency of alternative sources of nutrients. The aim of this work was to evaluate the effect of silicate rock powder and a manganese mining by-product, and secondary materials originated from these two materials, on soil chemical properties and on brachiaria production. This greenhouse experiment was conducted in pots with 5 kg of soil (Latossolo Vermelho-Amarelo distrófico - Oxisol). The alternative nutrient sources were: verdete, verdete treated with NH4OH, phonolite, ultramafic rock, mining waste and the proportion of 75 % of these K fertilizers and 25 % lime. Mixtures containing 25 % of lime were heated at 800 ºC for 1 h. These sources were applied at rates of 0, 150, 300, 450 and 600 kg ha-1 K2O, and incubated for 45 days. The mixtures of heated silicate rocks with lime promoted higher increases in soil pH in decreasing order: ultramafic rock>verdete>phonolite>mining waste. Applying the mining waste-lime mixture increased soil exchangeable K, and available P when ultramafic rock was incorporated. When ultramafic rock was applied, the release of Ca2+ increased significantly. Mining subproduct released the highest amount of Zn2+ and Mn2+ to the soil. The application of alternative sources of K, with variable chemical composition, altered the nutrient availability and soil chemical properties, improving mainly plant development and K plant uptake, and are important nutrient sources.

Effects of Pig Slurry Application and Crops on Phosphorus Content in Soil and the Chemical Species in Solution

The application of pig slurry rates and plant cultivation can modify the soil phosphorus (P) content and distribution of chemical species in solution. The purpose of this study was to evaluate the total P, available P and P in solution, and the distribution of chemical P species in solution, in a soil under longstanding pig slurry applications and crop cultivation. The study was carried out in soil columns with undisturbed structure, collected in an experiment conducted for eight years in the experimental unit of the Universidade Federal de Santa Maria (UFSM), Santa Maria (RS). The soil was an Argissolo Vermelho distrófico arênico (Typic Hapludalf), subjected to applications of 0, 20, 40, and 80 m3 ha-1 pig slurry. Soil samples were collected from the layers 0-5, 5-10, 10-20, 20-30, 30-40, and 40-60 cm, before and after black oat and maize grown in a greenhouse, for the determination of available P, total P and P in the soil solution. In the solution, the concentration of the major cations, anions, dissolved organic carbon (DOC), and pH were determined. The distribution of chemical P species was determined by software Visual Minteq. The 21 pig slurry applications increased the total P content in the soil to a depth of 40 cm, and the P extracted by Mehlich-1 and from the solution to a depth of 30 cm. Successive applications of pig slurry changed the balance between the solid and liquid phases in the surface soil layers, increasing the proportion of the total amount of P present in the soil solution, aside from changing the chemical species in the solution, reducing the percentage complexed with Al and increasing the one complexed with Ca and Mg in the layers 0-5 and 5-10 cm. Black oat and maize cultivation increased pH in the solution, thereby increasing the proportion of HPO42- and reducing H2PO4- species.

Organic Matter Fractions and Quality of the Surface Layer of a Constructed and Vegetated Soil After Coal Mining. I - Humic Substances and Chemical Characterization

After open coal mining, soils are “constructed”, which usually contain low levels and quality of organic matter (OM). Therefore, the use of plant species for revegetation and reclamation of degraded areas is essential. This study evaluated the distribution of carbon (C) in the chemical fractions as well as the chemical characteristics and humification degree of OM in a soil constructed after coal mining under cultivation of perennial grasses. The experiment was established in 2003 with the following treatments: Hemarthria altissima (T1), Paspalum notatum (T2), Cynodon dactilon (T3), Urochloa brizantha (T4), bare constructed soil (T5), and natural soil (T6). In 2009, soil samples were collected from the 0.00-0.03 m layer and the total organic carbon stock (TOC) and C stock in the chemical fractions: acid extract (CHCl), fulvic acid (CFA), humic acid (CHA), and humin (CHU) were determined. The humic acid (HA) fraction was characterized by infrared spectroscopy and the laser-induced fluorescence index (ILIF) of OM was also calculated. After six years, differences were only observed in the CHA stocks, which were highest in T1 (0.89 Mg ha-1) and T4 (1.06 Mg ha-1). The infrared spectra of HA in T1, T2 and T4 were similar to T6, with greater contribution of aliphatic organic compounds than in the other treatments. In this way, ILIF decreased in the sequence T5>T3>T4>T1>T2>T6, indicating higher OM humification in T3 and T5 and more labile OM in the other treatments. Consequently, the potential of OM quality recovery in the constructed soil was greatest in treatments T1 and T4.

SPATIAL DEPENDENCE OF ELECTRICAL CONDUCTIVITY AND CHEMICAL PROPERTIES OF THE SOIL BY ELECTROMAGNETIC INDUCTION

Brazilian soils have natural high chemical variability; thus, apparent electrical conductivity (ECa) can assist interpretation of crop yield variations. We aimed to select soil chemical properties with the best linear and spatial correlations to explain ECa variation in the soil using a Profiler sensor (EMP-400). The study was carried out in Sidrolândia, MS, Brazil. We analyzed the following variables: electrical conductivity - EC (2, 7, and 15 kHz), organic matter, available K, base saturation, and cation exchange capacity (CEC). Soil ECa was measured with the aid of an all-terrain vehicle, which crossed the entire area in strips spaced at 0.45 m. Soil samples were collected at the 0-20 cm depth with a total of 36 samples within about 70 ha. Classical descriptive analysis was applied to each property via SAS software, and GS+ for spatial dependence analysis. The equipment was able to simultaneously detect ECa at the different frequencies. It was also possible to establish site-specific management zones through analysis of correlation with chemical properties. We observed that CEC was the property that had the best correlation with ECa at 15 kHz.

Chemical and Biochemical Properties of Oxisols after Sewage Sludge Application for 16 Years

ABSTRACT The large production of sewage sludge (SS), especially in large urban centers, has led to the suggestion of using this waste as fertilizer in agriculture. The economic viability of this action is great and contributes to improve the environment by cycling the nutrients present in this waste, including high contents of organic matter and plant nutrients. This study evaluated the chemical and biochemical properties of Dystrophic and EutroferricLatossolos Vermelhos (Oxisols) under corn and after SS application at different rates for 16 years. The field experiment was carried out in Jaboticabal, São Paulo State, Brazil, using a randomized block design with four treatments and five replications. Treatments consisted of control - T1 (mineral fertilization, without SS application), 5 Mg ha-1 SS - T2, 10 Mg ha-1 SS - T3, and 20 Mg ha-1 SS - T4 (dry weight base). The data were submitted to variance analysis and means were compared by the Duncan test at 5 %. Sewage sludge increased P extracted by resin in both theLatossolos Vermelhos, Dystrophic and Eutroferric, and the organic matter content in the Dystrophic Latossolo Vermelho. The waste at the rate 20 Mg ha-1 on a dry weight basis promoted increases in acid phosphatase activity in Eutroferric Latossolo Vermelho, basal respiration and metabolic quotient in DystrophicLatossolo Vermelho. The rate 20 Mg ha-1 sewage sludge on a dry weight basis did not alter the soil microbial biomass in both the Latossolos Vermelhos; in addition, it improved corn yields without inducing any symptoms of phytotoxicity or nutrient deficiency in the plants.

Chemical Functionalization of Bioceramics To Enhance Endothelial Cells Adhesion for Tissue Engineering.

To control the selective adhesion of human endothelial cells and human serum proteins to bioceramics of different compositions, a multifunctional ligand containing a cyclic arginine-glycine-aspartate (RGD) peptide, a tetraethylene glycol spacer, and a gallate moiety was designed, synthesized, and characterized. The binding of this ligand to alumina-based, hydroxyapatite-based, and calcium phosphate-based bioceramics was demonstrated. The conjugation of this ligand to the bioceramics induced a decrease in the nonselective and integrin-selective binding of human serum proteins, whereas the binding and adhesion of human endothelial cells was enhanced, dependent on the particular bioceramics.

Electrical Conductivity and Chemical Composition of Soil Solution: Comparison of Solution Samplers in Tropical Soils

ABSTRACT Soil solution samplers may have the same working principle, but they differ in relation to chemical and physical characteristics, cost and handling, and these aspects exert influence on the chemical composition of the soil solution obtained. This study was carried out to evaluate, over time, the chemical composition of solutions extracted by Suolo Acqua, with the hydrophilic membrane (HM) as a standard, using soils with contrasting characteristics, and to determine the relationship between electrical conductivity (EC) and concentration of ions and pH of soil solution samples. This study was carried out under laboratory conditions, using three soils samples with different clay and organic matter (OM) contents. Soil solution contents of F−, Cl−, NO−3, Br−, SO42−, Na+, NH4+, K+, Mg2+, Ca2+, were analyzed, as well as inorganic, organic, and total C contents, pH, and EC, in four successive sampling times. Soil solution chemical composition extracted by the Suolo Acqua sampler is similar to that collected by the HM, but the Suolo Acqua extracted more Na+ and soluble organic C than the HM solution. Solution EC, cation and anion concentrations, and soluble C levels are higher in the soil with greater clay and OM contents (Latossolo and Cambissolo in this case). Soil solution composition varied over time, with considerable changes in pH, EC, and nutrient concentrations, especially associated with soil OM. Thus, single and isolated sampling of the soil solution must be avoided, otherwise composition of the soil solution may not be correctly evaluated. Soil solution EC was regulated by pH, as well as the sum of cation and anion concentrations, and the C contents determined in the soil liquid phase.

Organic and Nitrogen Fertilization of Soil under ‘Syrah’ Grapevine: Effects on Soil Chemical Properties and Nitrate Concentration

ABSTRACT Viticulture is an activity of great social and economic importance in the lower-middle region of the São Francisco River valley in northeastern Brazil. In this region, the fertility of soils under vineyards is generally poor. To assess the effects of organic and nitrogen fertilization on chemical properties and nitrate concentrations in an Argissolo Vermelho-Amarelo (Typic Plinthustalf), a field experiment was carried out in Petrolina, Pernambuco, on Syrah grapevines. Treatments consisted of two rates of organic fertilizer (0 and 30 m3 ha-1) and five N rates (0, 10, 20, 40, and 80 kg ha-1), in a randomized block design arranged in split plots, with five replications. The organic fertilizer levels represented the main plots and the N levels, the subplots. The source of N was urea and the source of organic fertilizer was goat manure. Irrigation was applied through a drip system and N by fertigation. At the end of the third growing season, soil chemical properties were determined and nitrate concentration in the soil solution (extracted by porous cups) was determined. Organic fertilization increased organic matter, pH, EC, P, K, Ca, Mg, Mn, sum of bases, base saturation, and CEC, but decreased exchangeable Cu concentration in the soil by complexation of Cu in the organic matter. Organic fertilization raised the nitrate concentration in the 0.20-0.40 m soil layer, making it leachable. Nitrate concentration in the soil increased as N rates increased, up to more than 300 mg kg-1 in soil and nearly 800 mg L-1 in the soil solution, becoming prone to leaching losses.

Fluid-rock-strain feedbacks in extensional shear zones

La présence de fluide météorique synchrone à l'activité du détachement (Farmin, 2003 ; Mulch et al., 2007 ; Gébelin et al., 2011), implique que les zones de cisaillement sont des systèmes ouverts avec des cellules de convections à l'échelle crustale et un intense gradient géothermique au sein du détachement (Morrison et Anderson, 1998, Gottardi et al., 2011). De plus, les réactions métamorphiques liées à des infiltrations fluides dans les zones de cisaillement extensionnel peuvent influencer les paramètres rhéologiques du système (White and Knipe, 1978), et impliquer la localisation de la déformation dans la croûte. Dans ce manuscrit, deux zones de cisaillement infiltrées par des fluides météoriques sont étudiées, l'une étant largement quartzitique, et l'autre de nature granitique ; les relations entre déformation, fluides, et roches s'appuient sur des approches structurales, microstructurales, chimiques et isotopiques. L'étude du détachement du Columbia river (WA, USA) met en évidence que la déformation mylonitique se développe en un million d'années. La phase de cisaillement principal s'effectue à 365± 30°C d'après les compositions isotopiques en oxygène du quartz et de la muscovite. Ces minéraux atteignent l'équilibre isotopique lors de leur recristallisation dynamique contemporaine à la déformation. La zone de cisaillement enregistre une baisse de température, remplaçant le mécanisme de glissement par dislocation par celui de dissolution- précipitation dans les derniers stades de l'activité du détachement. La dynamique de circulation fluide bascule d'une circulation pervasive à chenalisée, ce qui engendre localement la rupture des équilibres d'échange isotopiques. La zone de cisaillement de Bitterroot (MT, USA) présente une zone mylonitique de 600m d'épaisseur, progressant des protomylonites aux ultramylonites. L'intensité de la localisation de la déformation se reflète directement sur l'hydratation des feldspaths, réaction métamorphique majeure dite de « rock softening ». Une étude sur roche totale indique des transferts de masse latéraux au sein des mylonites, et d'importantes pertes de volume dans les ultramylonites. La composition isotopique en hydrogène des phyllosilicates met en évidence la présence (1) d'une source magmatique/métamorphique originelle, caractérisée par les granodiorites ayant conservé leur foliation magmatique, jusqu'aux protomylonites, et (2) une source météorique qui tamponne les valeurs des phyllosilicates des fabriques mylonitiques jusqu'aux veines de quartz non-déformées. Les compositions isotopiques en oxygène des minéraux illustrent le tamponnement de la composition du fluide météorique par l'encaissant. Ce phénomène cesse lors du processus de chloritisation de la biotite, puisque les valeurs des chlorites sont extrêmement négatives (-10 per mil). La thermométrie isotopique indique une température d'équilibre isotopique de la granodiorite entre 600-500°C, entre 500-300°C dans les mylonites, et entre 300 et 200°C dans les fabriques cassantes (cataclasites et veines de quartz). Basé sur les résultats issus de ce travail, nous proposons un modèle général d'interactions fluide-roches-déformation dans les zones de détachements infiltrées par des fluides météoriques. Les zones de détachements évoluent rapidement (en quelques millions d'années) au travers de la transition fragile-ductile ; celle-ci étant partiellement contrôlée par l'effet thermique des circulations de fluide météoriques. Les systèmes de détachements sont des lieux où la déformation et les circulations fluides sont couplées ; évoluant rapidement vers une localisation de la déformation, et de ce fait, une exhumation efficace. - The presence of meteoric fluids synchronous with the activity of extensional detachment zones (Famin, 2004; Mulch et al., 2007; Gébelin et al., 2011) implies that extensional systems involve fluid convection at a crustal scale, which results in high geothermal gradients within active detachment zones (Morrison and Anderson, 1998, Gottardi et al., 2011). In addition, the metamorphic reactions related to fluid infiltration in extensional shear zones can influence the rheology of the system (White and Knipe, 1978) and ultimately how strain localizes in the crust. In this thesis, two shear zones that were permeated by meteoric fluids are studied, one quartzite-dominated, and the other of granitic composition; the relations between strain, fluid, and evolving rock composition are addressed using structural, microstructural, and chemical/isotopic measurements. The study of the Columbia River detachment that bounds the Kettle core complex (Washington, USA) demonstrates that the mylonitic fabrics in the 100 m thick quartzite- dominated detachment footwall developed within one million years. The main shearing stage occurred at 365 ± 30°C when oxygen isotopes of quartz and muscovite equilibrated owing to coeval deformation and dynamic recrystallization of these minerals. The detachment shear zone records a decrease in temperature, and dislocation creep during detachment shearing gave way to dissolution-precipitation and fracturing in the later stages of detachment activity. Fluid flow switched from pervasive to channelized, leading to isotopic disequilibrium between different minerals. The Bitterroot shear zone detachment (Montana, USA) developed a 600 m thick mylonite zone, with well-developed transitions from protomylonite to ultramylonite. The localization of deformation relates directly to the intensity of feldspar hydration, a major rock- softening metamorphic reaction. Bulk-rock analyses of the mylonitic series indicate lateral mass transfer in the mylonite (no volume change), and significant volume loss in ultramylonite. The hydrogen isotope composition of phyllosilicates shows (1) the presence of an initial magmatic/metamorphic source characterized by the granodiorite in which a magmatic, and gneissic (protomylonite) foliation developed, and (2) a meteoric source that buffers the values of phyllosilicates in mylonite, ultramylonite, cataclasite, and deformed and undeformed quartz veins. The mineral oxygen isotope compositions were buffered by the host-rock compositions until chloritization of biotite started; the chlorite oxygen isotope values are negative (-10 per mil). Isotope thermometry indicates a temperature of isotopic equilibrium of the granodiorite between 600-500°C, between 500-300°C in the mylonite, and between 300 and 200°C for brittle fabrics (cataclasite and quartz veins). Results from this work suggest a general model for fluid-rock-strain feedbacks in detachment systems that are permeated by meteoric fluids. Phyllosilicates have preserved in their hydrogen isotope values evidence for the interaction between rock and meteoric fluids during mylonite development. Fluid flow generates mass transfer along the tectonic anisotropy, and mylonites do not undergo significant volume change, except locally in ultramylonite zones. Hydration of detachment shear zones attends mechanical grain size reduction and enhances strain softening and localization. Self-exhuming detachment shear zones evolve rapidly (a few million years) through the transition from ductile to brittle, which is partly controlled by the thermal effect of circulating surface fluids. Detachment systems are zones in the crust where strain and fluid flow are coupled; these systems. evolve rapidly toward strain localization and therefore efficient exhumation.

Evaluation of Microcracking and Chemical Deterioration in Concrete Pavements Final Report, October 31, 1995

The major objective of this research project was to investigate the chemistry and morphology of portland cement concrete pavements in Iowa. The integrity of the various pavements was evaluated qualitatively, based on the presence or absence of microcracks, the presence or absence of sulfate minerals, and the presence or absence of alkali-silica gel(s). Major equipment delays and subsequent equipment replacements resulted in significant delays over the course of this research project. However, all these details were resolved and the equipment is currently in place and fully operational. The equipment that was purchased for this project included: ( I ) a LECO VP 50, 12-inch diameter, variable speed grinder/polisher: (2) a Hitachi S-2460N variable pressure scanning electron microscope; and (3) a OXFORD Instruments Link ISIS microanalysis system with a GEM (high-purity germanium) X-ray detector. This study has indicated that many of the concrete pavements contained evidence of multiple deterioration mechanisms: and hence, the identification of a single reason for the distress that was observed in any given pavement typically had to be based on opinion rather than empirical evidence.