Développement d'un senseur électrochimique pour le dosage des nitrates en laboratoire et en pépinière forestière

Le lessivage des nitrates, la contamination de la nappe phréatique et l’eutrophisation des cours d’eau figurent parmi les enjeux planétaires qui affectent la durabilité de l’agriculture et des ressources naturelles. Ce mémoire présente le développement d’une première génération d’un nouveau senseur électrochimique pour le dosage de précisions des nitrates. Celui-ci est basé sur la spectroscopie d’impédance électrochimique d’une membrane polymérique sélective aux ions. Grâce à cette approche, un senseur compact et abordable a été produit. Par son utilisation en solutions aqueuses et en substrats de croissance saturés, il a été montré que le senseur permettait de quantifier des ajouts contrôlés de nitrates allant de 0,6 ppm à 60 ppm. La mise en application en substrat de croissance a pu être étudiée en comparaison avec des méthodes certifiées ISO 17025 visant l’analyse de ces substrats. Le senseur a aussi montré une grande versatilité par son utilisation sur divers appareils de mesure d’impédance. En plus, il a démontré une stabilité possible suite à une implantation d’un mois directement en substrat de croissance sous les variables environnementales d’une pépinière forestière. Par l’étude du spectre d’impédance du senseur en solutions pures de différentes concentrations, il a aussi été possible de proposer le circuit électrique équivalent du système, qui met en évidence deux parcours compétitifs du courant, un au coeur de la membrane et un deuxième en solution. Les résultats de ces travaux sont au coeur de deux publications scientifiques dont le manuscrit est inclus à ce mémoire. Pour finir cette étude, des suggestions seront faites pour guider l’amélioration du senseur par le développement d’une deuxième génération de celui-ci.

Adubação de sistemas: antecipação de adubação nitrogenada para a cultura do milho em integração lavoura-pecuária

Traditionally in no-tillage systems, fertilization is done to the catch crop. In general nutrient cycling in crop systems has not been treated as an important tool in the process of nutrient supplying for plants. The type and the condition in which vegetable residuesis decomposed can affect the efficiency of nutrient cycling.This study assessed the effect of anticipated nitrogen fertilization in crop-livestock systems on cultivated cornproduction, rate ofnutrient release from plant residue, and theN-minerallevels of soil. The study was carried out in the city Abelardo Luz (SC) in a Clayey Oxisol. The experimental design was a randomized block design with three replications. The treatments were arranged in a 2 x 2 factorial arrangement. The first factor was N Fertilization Time: in the N-Pasture level, nitrogen (200 kg ha-1 N) and N-Grains level, no nitrogen was applied. The second factor was the Grazing Height, characterized by two sward heights of oat at 15 cm (Low Height Pasture) and at 30 cm (High Height Pasture). Corn hybrid ‘Máximus’ was sowed in 10thOctober, 31 days after the removal of animals. In the twelve resulting plots from the combination of treatments on pasture phase (N Fertilization Time x Grazing Height) rates of N-fertilizer (0, 100, 200 e 300 Kg ha-1 of N) as urea were allocated in the split plot.We conclude that anticipated N fertilization of winter cover crop pasture to provide high-quality forage and carry-over N to the subsequent corn crop and may eventually replace side drees nitrogen fertilization on corn and can improve overall N fertilizer efficiency use in integrated crop-livestock systems.The rate of K release from plant residues is very fast, releasing large quantities in the first days after plant desiccation.Despite of considerably high nitrogen dose used in both the pasture and at the grain crop it was not observed nitrate leaching risks during the study period.

Microbiologia do ciclo do nitrogênio em solos do cerrado

Dissertação (mestrado)—Universidade de Brasília, Instituto de Ciências Biológicas, Programa de Pós-Graduação em Biologia Microbiana, 2016.

Nitrogen use efficiency and optimization of nitrogen fertilizer application for stable yields and high quality of cereals grown in conservation agriculture

In most agroecosystems, nitrogen (N) is the most important nutrient limiting plant growth. One management strategy that affects N cycling and N use efficiency (NUE) is conservation agriculture (CA), an agricultural system based on a combination of minimum tillage, crop residue retention and crop rotation. Available results on the optimization of NUE in CA are inconsistent and studies that cover all three components of CA are scarce. Presently, CA is promoted in the Yaqui Valley in Northern Mexico, the country´s major wheat-producing area in which from 1968 to 1995, fertilizer application rates for the cultivation of irrigated durum wheat (Triticum durum L.) at 6 t ha-1 increased from 80 to 250 kg ha-1, demonstrating the high intensification potential in this region. Given major knowledge gaps on N availability in CA this thesis summarizes the current knowledge of N management in CA and provides insights in the effects of tillage practice, residue management and crop rotation on wheat grain quality and N cycling. Major aims of the study were to identify N fertilizer application strategies that improve N use efficiency and reduce N immobilization in CA with the ultimate goal to stabilize cereal yields, maintain grain quality, minimize N losses into the environment and reduce farmers’ input costs. Soil physical and chemical properties in CA were measured and compared with those in conventional systems and permanent beds with residue burning focusing on their relationship to plant N uptake and N cycling in the soil and how they are affected by tillage and N fertilizer timing, method and doses. For N fertilizer management, we analyzed how placement, time and amount of N fertilizer influenced yield and quality parameters of durum and bread wheat in CA systems. Overall, grain quality parameters, in particular grain protein concentration decreased with zero-tillage and increasing amount of residues left on the field compared with conventional systems. The second part of the dissertation provides an overview of applied methodologies to measure NUE and its components. We evaluated the methodology of ion exchange resin cartridges under irrigated, intensive agricultural cropping systems on Vertisols to measure nitrate leaching losses which through drainage channels ultimately end up in the Sea of Cortez where they lead to algae blooming. A throughout analysis of N inputs and outputs was conducted to calculate N balances in three different tillage-straw systems. As fertilizer inputs are high, N balances were positive in all treatments indicating the risk of N leaching or volatilization during or in subsequent cropping seasons and during heavy rain fall in summer. Contrary to common belief, we did not find negative effects of residue burning on soil nutrient status, yield or N uptake. A labeled fertilizer experiment with urea 15N was implemented in micro-plots to measure N fertilizer recovery and the effects of residual fertilizer N in the soil from summer maize on the following winter crop wheat. Obtained N fertilizer recovery rates for maize grain were with an average of 11% very low for all treatments.

Leaching of nitrate from cropped rainfed terraces in the mid-hills of Nepal

Intensification of crop production in the mid-hills of Nepal has led to concerns that nitrogen loss by leaching may increase. This study estimated the amount of N leached during two years from rainfed terraces (bari-land) at three locations in Nepal. Maize or upland rice grown in the monsoon season was given either no nutrient inputs or inputs via either nitrogen fertilizer or farmyard manure. Nitrate concentration in soil solution was measured regularly with porous ceramic cup samplers and drainage estimated from a simple soil water balance. Estimated losses of nitrogen by leaching ranged from 0 to 63.5 kg N ha(-1) depending on location and the form of nitrogen applied. Losses from plots receiving no nutrient inputs were generally small (range: 0-35 kg N ha(-1)) and losses from plots where nitrogen was applied as manure (range: 2-41 kg N ha(-1)) were typically half those from plots with nitrogen applied as fertilizer. Losses during the post-monsoon crops of finger millet were small (typically <5% of total loss) although losses from the one site with blackgram were larger (about 13%). The highest concentrations of nitrate in solution were measured early in the season as the monsoon rains began and immediately following fertilizer applications. Leaching losses are likely to be minimised if manure is applied as a basal nutrient dressing followed by fertilizer nitrogen later in the season.

Nitrate role in basic cation leaching under no-till

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Leaching of nitrate and ammonium from cover crop straws as affected by rainfall

Nitrogen (N) mineralization dynamics in no-till systems is affected, among other factors, by N amount and quality in the mulch and by climatic conditions. Leaching of NO3-N and NH4-N from six plant species used as soil cover crops in tropical environments were evaluated when the straw was submitted to rainfall after chemical desiccation. Millet (Pennisetum glaucum), guinea sorghum (Sorghum vulgare), black oat (Avena strigosa), triticale (Triticum secale), Indian hemp (Crotalaria juncea), and brachiaria (Brachiaria decumbens) were grown in a greenhouse, in Botucatu-SP, Brazil. Forty-five days after emergence, the plants were cut at the root collar, oven-dried, and submitted to simulated rainfalls of 4.4, 8.7, 17.04, 34.9, and 69.8 mm, considering an amount of straw equivalent to 8 t ha(-1) of dry matter. The amounts of N-NO3- extracted from the straw by rainwater were very small. However, accumulated rainfall around 70 mm caused ammonium leaching ranging from 2.5 to 9.5kg ha(-1), depending on the species. Plant residues of triticale and black oat (grasses) and Indian hemp (legume) showed high N leaching intensity with the first rains after chemical desiccation. The amount of N leached from straw was highly correlated with N tissue content.

Modelling stream and soil water nitrate dynamics during experimentally increased nitrogen deposition in a coniferous forest catchment at Gardsjon, Sweden

Increased atmospheric deposition of inorganic nitrogen (N) may lead to increased leaching of nitrate (NO3-) to surface waters. The mechanisms responsible for, and controls on, this leaching are matters of debate. An experimental N addition has been conducted at Gardsjon, Sweden to determine the magnitude and identify the mechanisms of N leaching from forested catchments within the EU funded project NITREX. The ability of INCA-N, a simple process-based model of catchment N dynamics, to simulate catchment-scale inorganic N dynamics in soil and stream water during the course of the experimental addition is evaluated. Simulations were performed for 1990-2002. Experimental N addition began in 1991. INCA-N was able to successfully reproduce stream and soil water dynamics before and during the experiment. While INCA-N did not correctly simulate the lag between the start of N addition and NO 2 3 breakthrough, the model was able to simulate the state change resulting from increased N deposition. Sensitivity analysis showed that model behaviour was controlled primarily by parameters related to hydrology and vegetation dynamics and secondarily by in-soil processes.

Stable N isotope composition of nitrate reflects N transformations during the passage of water through a montane rain forest in Ecuador

Knowledge of the fate of deposited N in the possibly N-limited, highly biodiverse north Andean forests is important because of the possible effects of N inputs on plant performance and species composition. We analyzed concentrations and fluxes of NO3 −–N, NH4 +–N and dissolved organic N (DON) in rainfall, throughfall, litter leachate, mineral soil solutions (0.15–0.30 m depths) and stream water in a montane forest in Ecuador during four consecutive quarters and used the natural 15N abundance in NO3 − during the passage of rain water through the ecosystem and bulk δ15N values in soil to detect N transformations. Depletion of 15N in NO3 − and increased NO3 −–N fluxes during the passage through the canopy and the organic layer indicated nitrification in these compartments. During leaching from the organic layer to mineral soil and stream, NO3 − concentrations progressively decreased and were enriched in 15N but did not reach the δ15N values of solid phase organic matter (δ15N = 5.6–6.7‰). This suggested a combination of nitrification and denitrification in mineral soil. In the wettest quarter, the δ15N value of NO3 − in litter leachate was smaller (δ15N = −1.58‰) than in the other quarters (δ15N = −9.38 ± SE 0.46‰) probably because of reduced mineralization and associated fractionation against 15N. Nitrogen isotope fractionation of NO3 − between litter leachate and stream water was smaller in the wettest period than in the other periods probably because of a higher rate of denitrification and continuous dilution by isotopically lighter NO3 −–N from throughfall and nitrification in the organic layer during the wettest period. The stable N isotope composition of NO3 − gave valuable indications of N transformations during the passage of water through the forest ecosystem from rainfall to the stream.

Using quantity/intensity relationships to assess the potential for ammonium leaching in a Vertosol

High concentrations of ammonium (up to 0.1 cmol/kg) have been observed below 1 m depth in a Vertosol soil near Warra in south-eastern Queensland. This study examined whether ammonium leaching could be responsible for the ammonium accumulation observed in the Warra soil. This was done by using quantity/intensity (Q/I) relationships to compare the ammonium retention capacity of the Warra soil with other similar soils throughout the region that did not contain elevated subsoil ammonium concentrations. Analysis of Q/I curves revealed that in the concentration range studied, the amount of ammonium retained on high affinity adsorption sites in all 3 soils was low, and the Warra soil was not significantly different from the other 2 soils. The ability of the soils to retain ammonium in the soil solution against leaching [i.e. their potential buffer capacity (PBC)] did differ between soils and was greatest at Warra. This indicates that at any one time the Warra soil holds more ammonium on the exchange complex and less in solution than the other soils examined. It was concluded that ammonium is no more likely to leach through the surface horizons of the Warra soil than the other soils examined. Indeed, the data indicated that the Warra soil probably has greater capacity to retain ammonium against leaching due to its greater PBC. Consequently, it is considered unlikely that leaching of ammonium has been a major contributor to the subsoil ammonium concentrations at Warra.

Simulated rainwater effects on anion exchange capacity and nitrate retention in Ferrosols

Nitrate (NO3) accumulations (up to 1880 kg NO3-N/ha for a 12-m profile) in the soils of the Johnstone River catchment (JRC) may pose a serious environmental threat to the Great Barrier Reef lagoon if the NO3 were released. The: leaching of artificial rainwater through repacked soil columns was investigated to determine the effect of low NO3/low ionic strength inputs on the NO3 Chemistry of the JRC profiles. Repacked soil columns were used to simulate the 11.5-m profiles, and the soil solution anion and cation concentrations were monitored at 10 points throughout the soil column. As the rainwater was applied, NO3 leached down the profile, with substantial quantities exiting the columns. Anion exchange was discounted as the major mechanism of NO3 release due to the substantial net loss of anions from the system (up to 2740 kg NO3-N/ha over the experimental period). As the soils were dominated by variable charge minerals, the effect of changing pH and ionic strength on the surface charge density was investigated in relation to the release of NO3 from the exchange. It was concluded that the equilibration of the soil solution with the low ionic strength rainwater solution resulted in a lessening of both the positive and negative surface charge. Nitrate was released into the soil solution and subsequently leached due to the lessening of the positive surface charge. Loss of NO3 from the soil profile was slow, with equivalent field release times estimated to be tens of years. Although annual release rates were high in absolute terms (up to 175 kg NO3-N/ha.year), they are only slightly greater than the current loss rates from fertilised sugarcane production (up to 50 kg NO3-N/ha.year). In addition to this, the large-scale release of NO3 from the accumulations will only occur until a new equilibrium is established with the input rainwater solution.

The effect of ionic strength variation and anion competition on the development of nitrate accumulations in variable charge subsoils

The leaching of N fertilisers has led to the formation of nitrate (NO3) accumulations in deep subsoils (>5 m depth) of the Johnstone River catchment. This paper outlines the chemical mechanism by which these NO3 accumulations are formed and maintained. This was achieved via a series of column experiments designed to investigate NO3 leaching in relation to the soil charge chemistry and the competition of anions for exchange sites. The presence of variable charge minerals has led to the formation positive surface charge within these profiles. An increase in the soil solution ionic strength accompanying the fertiliser leaching front acts to increase the positive (and negative) charge density, thus providing adsorption sites for NO3. A decrease in the soil solution ionic strength occurs after the fertiliser pulse moves past a point in the profile, due to dilution with incoming rainwater. Nitrate is then released from the exchange back into the soil solution, thus buffering the decrease in the soil solution ionic strength. Since NO3 was adsorbed throughout the profile in this experiment it does not effectively explain the situation occurring in the field. Previous observations of the sulfate (SO4) profile distribution indicated that large SO4 accumulations in the upper profile may influence the NO3 distribution through competition for adsorption sites. A subsequent experiment investigating the effect of SO4 additions on NO3 leaching showed that NO3 adsorption was minimal in the upper profile. Adsorption of NO3 did occur, though only in the region of the profile where SO4 occupancy was low, i.e. in the lower profile. Therefore, the formation of the NO3 accumulations is dependent on the variable charge mineralogy, the variation of charge density with soil solution ionic strength, and the effects of SO4 competition for adsorption sites.

Organic and nitrogen fertilization of soil under Syrah grapevine: effects on soil chemical properties and nitrate concentration.

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.

Near-infrared spectroscopic study of basic aluminum sulfate and nitrate

The tridecameric Al-polymer [AlO4Al12(OH)24(H2O)12]7+ was prepared by forced hydrolysis of Al3+ up to an OH/Al molar ratio of 2.2. Under slow evaporation crystals were formed of Al13-nitrate. Upon addition of sulfate the tridecamer crystallised as the monoclinic Al13-sulfate. These crystals have been studied using near-infrared spectroscopy and compared to Al2(SO4)3.16H2O. Although the near-infrared spectra of the Al13-sulfate and nitrate are very similar indicating similar crystal structures, there are minor differences related to the strength with which the crystal water molecules are bonded to the salt groups. The interaction between crystal water and nitrate is stronger than with the sulfate as reflected by the shift of the crystal water band positions from 6213, 4874 and 4553 cm–1 for the Al13 sulfate towards 5925, 4848 and 4532 cm–1 for the nitrate. A reversed shift from 5079 and 5037 cm–1 for the sulfate towards 5238 and 5040 cm–1 for the nitrate for the water molecules in the Al13 indicate that the nitrate-Al13 bond is weakened due to the influence of the crystal water on the nitrate. The Al-OH bond in the Al13 complex is not influenced by changing the salt group due to the shielding by the water molecules of the Al13 complex.

Polyurethane (PU) scaffolds prepared by solvent casting/particulate leaching (SCPL) combined with centrifugation

This article reports an enhanced solvent casting/particulate (salt) leaching (SCPL) method developed for preparing three-dimensional porous polyurethane (PU) scaffolds for cardiac tissue engineering. The solvent for the preparation of the PU scaffolds was a mixture of dimethylformamide (DFM) and tetrahydrofuran (THF). The enhanced method involved the combination of a conventional SCPL method and a step of centrifugation, with the centrifugation being employed to improve the pore uniformity and the pore interconnectivity of scaffolds. Highly porous three-dimensional scaffolds with a well interconnected porous structure could be achieved at the polymer solution concentration of up to 20% by air or vacuum drying to remove the solvent. When the salt particle sizes of 212-295, 295-425, or 425-531 µm and a 15% w/v polymer solution concentration were used, the porosity of the scaffolds was between 83-92% and the compression moduli of the scaffolds were between 13 kPa and 28 kPa. Type I collagen acidic solution was introduced into the pores of a PU scaffold to coat the collagen onto the pore walls throughout the whole PU scaffold. The human aortic endothelial cells (HAECs) cultured in the collagen-coated PU scaffold for 2 weeks were observed by scanning electron microscopy (SEM). It was shown that the enhanced SCPL method and the collagen coating resulted in a spatially uniform distribution of cells throughout the collagen-coated PU scaffold.