Nitrogen fluxes from the landscape are controlled by net anthropogenic nitrogen inputs and by climate

The flux of nitrogen (N) to coastal marine ecosystems is strongly correlated with the “net anthropogenic nitrogen inputs” (NANI) to the landscape across 154 watersheds, ranging in size from 16 km2 to 279 000 km2, in the US and Europe. When NANI values are greater than 1070 kg N km−2 yr−1, an average of 25% of the NANI is exported from those watersheds in rivers. Our analysis suggests a possible threshold at lower NANI levels, with a smaller fraction exported when NANI values are below 1070 kg N km−2 yr−1. Synthetic fertilizer is the largest component of NANI in many watersheds, but other inputs also contribute substantially to the N fluxes; in some regions, atmospheric deposition of N is the major component. The flux of N to coastal areas is controlled in part by climate, and a higher percentage of NANI is exported in rivers, from watersheds that have higher freshwater discharge.

Nitrogen flows from European watersheds to coastal marine waters

Nitrogen flows from European watersheds to coastal marine waters Executive summary Nature of the problem • Most regional watersheds in Europe constitute managed human territories importing large amounts of new reactive nitrogen. • As a consequence, groundwater, surface freshwater and coastal seawater are undergoing severe nitrogen contamination and/or eutrophication problems. Approaches • A comprehensive evaluation of net anthropogenic inputs of reactive nitrogen (NANI) through atmospheric deposition, crop N fixation,fertiliser use and import of food and feed has been carried out for all European watersheds. A database on N, P and Si fluxes delivered at the basin outlets has been assembled. • A number of modelling approaches based on either statistical regression analysis or mechanistic description of the processes involved in nitrogen transfer and transformations have been developed for relating N inputs to watersheds to outputs into coastal marine ecosystems. Key findings/state of knowledge • Throughout Europe, NANI represents 3700 kgN/km2/yr (range, 0–8400 depending on the watershed), i.e. five times the background rate of natural N2 fixation. • A mean of approximately 78% of NANI does not reach the basin outlet, but instead is stored (in soils, sediments or ground water) or eliminated to the atmosphere as reactive N forms or as N2. • N delivery to the European marine coastal zone totals 810 kgN/km2/yr (range, 200–4000 depending on the watershed), about four times the natural background. In areas of limited availability of silica, these inputs cause harmful algal blooms. Major uncertainties/challenges • The exact dimension of anthropogenic N inputs to watersheds is still imperfectly known and requires pursuing monitoring programmes and data integration at the international level. • The exact nature of ‘retention’ processes, which potentially represent a major management lever for reducing N contamination of water resources, is still poorly understood. • Coastal marine eutrophication depends to a large degree on local morphological and hydrographic conditions as well as on estuarine processes, which are also imperfectly known. Recommendations • Better control and management of the nitrogen cascade at the watershed scale is required to reduce N contamination of ground- and surface water, as well as coastal eutrophication. • In spite of the potential of these management measures, there is no choice at the European scale but to reduce the primary inputs of reactive nitrogen to watersheds, through changes in agriculture, human diet and other N flows related to human activity.

The effects of a changing pollution climate on throughfall deposition and cycling in a forested area in southern England

This study compares two sets of measurements of the composition of bulk precipitation and throughfall at a site in southern England with a 20-year gap between them. During this time, SO2 emissions from the UK fell by 82%, NOx emissions by 35% and NH3 emissions by 7%. These reductions were partly reflected in bulk precipitation, with deposition reductions of 56% in SO4,38% in NO3, 32% in NH4, and 73% in H+. In throughfall under Scots pine, the effects were more dramatic, with an 89% reduction in SO4 deposition and a 98% reduction in H+ deposition. The mean pH under these trees increased from 2.85 to 4.30. Nitrate and ammonium deposition in throughfall increased slightly, however. In the earlier period, the Scots pines were unable to neutralise the high flux of acidity associated with sulphur deposition, even though this was not a highly polluted part of the UK, and deciduous trees (oak and birch) were only able to neutralise it in summer when the leaves were present. In the later period, the sulphur flux had reduced to the point where the acidity could be neutralised by all species — the neutralisation mechanism is thus likely to be largely leaching of base cations and buffering substances from the foliage. The high fluxes are partly due to the fact that these are 60–80 year old trees growing in an open forest structure. The increase in NO3 and NH4 in throughfall in spite of decreased deposition seems likely due to a decrease in foliar uptake, perhaps due to the increasing nitrogen saturation of the catchment soils. These changes may increase the rate of soil microbial activity as nitrogen increases and acidity declines, with consequent effects on water quality of the catchment drainage stream.

Dynamics of Dissolved Forms of Carbon and Inorganic Nitrogen in Small Watersheds of the Coastal Atlantic Forest in Southeast Brazil

Based on the fact that streamwater quality reflects landscape conditions, the objectives of this study were: to investigate nitrogen (N), carbon (C), and major ion concentrations in six streams crossing minimally disturbed Atlantic Forest areas, with similar geomorphological characteristics; to determine N and C fluxes in one of these pristine streams (Indaia); and assess the impact of human activity on the biogeochemistry of two other streams in the same region, crossing urbanized areas. The distribution pattern of carbon and inorganic nitrogen dissolved forms, as well as the major ion and biogenic gas concentrations in the streamwater, was similar in pristine streams, indicating that the C and N dynamics were determined by influence of some factors, such as climate, atmospheric deposition, geology, soil type, and land covering, which were analogous in the forested watersheds. The urban streams were significantly different from the pristine streams, showing low dissolved oxygen concentrations, high respiration rates, and high concentrations of carbon dioxide, dissolved inorganic nitrogen, dissolved inorganic carbon, and major ion. These differences were attributed to anthropogenic impact on water quality, especially domestic sewage discharge. Additionally, in the Indaia stream, it was possible to observe the importance of rainfall over temporal dynamics of dissolved carbon forms, and also, the obtained specific flux of dissolved inorganic nitrogen was relatively elevated (approximately 11 kg ha(-1) year(-1)). These results reveal the influence of human activity over the biogeochemistry of coastal streams and also indicate the importance N export of Atlantic Forest to the ocean.

Chemical bonding and composition of silicon nitride films prepared by inductively coupled plasma chemical vapor deposition

Thin silicon nitride films were prepared at 350 degrees C by inductively coupled plasma chemical vapor deposition on Si(100) substrates under different NH(3)/SiH(4) or N(2)/SiH(4) gas mixture. The chemical composition and bonding structure of the deposited films were investigated as a function of the process parameters, such as the gas flow ratio NH(3)/SiH(4) or N(2)/SiH(4) and the RF power, using X-ray photoelectron spectroscopy (XPS). The gas flow ratio was 1.4, 4.3, 7.2 or 9.5 and the RF power, 50 or 100 W. Decomposition results of Si 2p XPS spectra indicated the presence of bulk Si, under-stoichiometric nitride, stoichiometric nitride Si(3)N(4), oxynitride SiN(x)O(y), and stoichiometric oxide SiO(2), and the amounts of these compounds were strongly influenced by the two process parameters. These results were consistent with those obtained from N 1s XPS spectra. The chemical composition ratio N/Si in the film increased with increasing the gas flow ratio until the gas flow ratio reached 4.3, reflecting the high reactivity of nitrogen, and stayed almost constant for further increase in gas flow ratio, the excess nitrogen being rejected from the growing film. A considerable and unexpected incorporation of contaminant oxygen and carbon into the depositing film was observed and attributed to their high chemical reactivity. (C) 2010 Elsevier B.V. All rights reserved.

X-ray photoelectron spectroscopy analysis of zirconium nitride-like films prepared on Si(100) substrates by ion beam assisted deposition

Thin zirconium nitride films were prepared on Si(l 00) substrates at room temperature by ion beam assisted deposition with a 2 keV nitrogen ion beam. Arrival rate ratios ARR(N/Zr) used were 0.19, 0.39, 0.92, and 1.86. The chemical composition and bonding structure of the films were analyzed with X-ray photoelectron spectroscopy (XPS). Deconvolution results for Zr 3d, Zr 3p(3/2), N 1s, O 1s, and C 1s XPS spectra indicated self-consistently the presence of metal Zr-0, nitride ZrN, oxide ZrO2, oxymnide Zr2N2O, and carbide ZrC phases, and the amounts of these compounds were influenced by ARR(N/Zr). The chemical composition ratio N/Zr in the film increased with increasing ARR(N/Zr) until ARR(N/Zr) reached 0.92, reflecting the high reactivity of nitrogen in the ion beam, and stayed almost constant for ARR(N/Zr) >= 1, the excess nitrogen being rejected from the growing film. A considerable incorporation of contaminant oxygen and carbon into the depositing film was attributed to the getter effect of zirconium. (C) 2007 Elsevier B.V. All rights reserved.

P-T-Fluid evolution and graphite deposition during retrograde metamorphism in Ribeira Fold Belt, SE Brazil: Oxygen fugacity, fluid inclusions and C-O-H isotopic evidence

Combined fluid inclusion (FI) microthermometry, Raman spectroscopy, X-ray diffraction, C-O-H isotopes and oxygen fugacities of granulites from central Ribeira Fold Belt, SE Brazil, provided the following results: i) Magnetite-Hematite fO(2) estimates range from 10(-11.5) bar (QFM + 1) to 10(-18.3) bar (QFM - 1) for the temperature range of 896 degrees C-656 degrees C, implying fO(2) decrease from metamorphic peak temperatures to retrograde conditions; ii) 5 main types of fluid inclusions were observed: a) CO(2) and CO(2)-N(2) (0-11 mol%) high to medium density (1.01-0.59 g/cm(3)) FI; b) CO(2) and CO(2)-N(2) (0-36 mol%) low density (0.19-0.29 g/cm(3)) FI; c) CO(2) (94-95 mol%)-N(2) (3 mol%)-CH(4) (2-3 mol%)-H(2)O (water phi(v) (25 degrees C) = 0.1) FI; d) low-salinity H(2)O-CO(2) FI; and e) late low-salinity H(2)O FI; iii) Raman analyses evidence two graphite types in khondalites: an early highly ordered graphite (T similar to 450 degrees C) overgrown by a disordered kind (T similar to 330 degrees C); iv) delta(18)O quartz results of 10.3-10.7 parts per thousand, imply high-temperature CO(2) delta(18)O values of 14.4-14.8 parts per thousand, suggesting the involvement of a metamorphic fluid, whereas lower temperature biotite delta(18)O and delta D results of 7.5-8.5 parts per thousand and -54 to -67 parts per thousand respectively imply H(2)O delta(18)O values of 10-11 parts per thousand and delta D(H2O) of -23 to -36 parts per thousand suggesting delta(18)O depletion and increasing fluid/rock ratio from metamorphic peak to retrograde conditions. Isotopic results are compatible with low-temperature H(2)O influx and fO(2) decrease that promoted graphite deposition in retrograde granulites, simultaneous with low density CO(2), CO(2)-N(2) and CO(2)-N(2)-CH(4)-H(2)O fluid inclusions at T = 450-330 degrees C. Graphite delta(13)C results of -10.9 to -11.4 parts per thousand imply CO(2) delta(13)C values of -0.8 to -1.3 parts per thousand suggesting decarbonation of Cambrian marine carbonates with small admixture of lighter biogenic or mantle derived fluids. Based on these results, it is suggested that metamorphic fluids from the central segment of Ribeira Fold Belt evolved to CO(2)-N(2) fluids during granulitic metamorphism at high fO(2), followed by rapid pressure drop at T similar to 400-450 degrees C during late exhumation that caused fO(2) reduction induced by temperature decrease and water influx, turning carbonic fluids into CO(2)-H(2)O (depleting biotite delta(18)O and delta D values), and progressively into H(2)O. When fO(2) decreased substantially by mixture of carbonic and aqueous fluids, graphite deposited forming khondalites. (C) 2010 Elsevier Ltd. All rights reserved.

Electrodeposition and characterization of undoped and nitrogen-doped ZnSe films

Semiconducting films of (n-type) ZnSe and (p-type) nitrogen-doped ZnSe were electrodeposited by a linear-sweep voltammetric technique on to a substrate of fluorine-tin oxide (FM) glass ceramics. The films were characterized by scanning electron microscopy, energy-dispersive X-ray analysis and grazing-incidence X-ray diffraction. The results indicated that the material was deposited uniformly over the substrate, forming clusters when the Zn content of the bath was 0.1 mol L(-1) and a film when it was 0.2 or 0.3 mol L(-1). The effectiveness of doping the films with nitrogen by adding ammonium sulfate to the deposition solution was assessed by measuring the film-electrolyte interface capacitance (C) at various applied potentials (E(ap)) and plotting Mott-Schottky curves (C(-2) vs E(ap)), whose slope sign was used to identify p-type ZnSe. (C) 2009 Elsevier B.V. All rights reserved.

Fertilizer distribution mechanisms and side dress nitrogen fertilization in upland rice under no-tillage system

Algumas culturas têm pouca adaptação ao sistema plantio direto (SPD), em vista da alta compactação da camada superficial do solo. Nesse caso, o mecanismo utilizado na semeadora para a abertura dos sulcos para deposição do fertilizante pode ter grande importância no sentido de facilitar a penetração das raízes. Avaliouse a influência do mecanismo de distribuição de fertilizante e da adubação nitrogenada na cultura do arroz de terras altas (Oryza sativa) no sistema plantio direto. O experimento foi conduzido nos anos agrícolas 2001/2002 e 2002/2003, em Botucatu-SP, Brasil. O delineamento experimental foi em blocos casualizados, com parcelas subdivididas e quatro repetições. As parcelas foram constituídas por dois mecanismos de distribuição de fertilizantes (haste sulcadora e disco duplo). Nas subparcelas, quatro níveis de N foram aplicados em cobertura (0, 40, 80 e 120 kg ha-1). Avaliou-se a profundidade de abertura do sulco e de deposição das sementes, a população de plantas, a altura de plantas, o número de colmos e de panículas m-2, o número total de espiguetas por panícula, a fertilidade das espiguetas, a massa de 1.000 grãos, a matéria seca da parte aérea, a produtividade e o teor de N na folha bandeira. O sucesso no estabelecimento da cultura do arroz de terras altas no SPD nas regiões de inverno seco do Brasil está diretamente ligado ao mecanismo de distribuição das semeadoras-adubadoras. A haste sulcadora promoveu maior profundidade de deposição de sementes, conseqüentemente reduzindo o estande, o número de panículas por área e a produtividade. A aplicação de N em cobertura no arroz de terras altas em SPD proporciona maiores produtividades quando a semeadura é realizada com mecanismo de disco duplo.

Amorphous carbon nitrogenated films prepared by plasma immersion ion implantation and deposition

In this work, an investigation was conducted on amorphous hydrogenated-nitrogenated carbon films prepared by plasma immersion ion implantation and deposition. Glow discharge was excited by radiofrequency power (13.56 MHz, 40 W) whereas the substrate-holder was biased with 25 kV negative pulses. The films were deposited from benzene, nitrogen and argon mixtures. The proportion of nitrogen in the chamber feed (R-N) was varied against that of argon, while keeping the total pressure constant (1.3 Pa). From infrared reflectance-absorbance spectroscopy it was observed that the molecular structure of the benzene is not preserved in the film. Nitrogen was incorporated from the plasma while oxygen arose as a contaminant. X-ray photoelectron spectroscopy revealed that N/C and O/C atomic ratios change slightly with R-N. Water wettability decreased as the proportion of N in the gas phase increased while surface toughness underwent just small changes. Nanoindentation measurements showed that film deposition by means of ion bombardment was beneficial to the mechanical properties of the film-substrate interface. The intensity of the modifications correlates well with the degree of ion bombardment. (c) 2006 Elsevier B.V. All rights reserved.

Plasma-polymerized hexamethyldisilazane treated by nitrogen plasma immersion ion implantation technique

This paper describes the effect of nitrogen Plasma Immersion Ion Implantation (PIII) on chemical structure, refraction index and surface hardness of plasma-polymerized hexamethyldisilazane (PPHMDSN) thin films. Firstly, polymeric films were deposited at 13.56 MHz radiofrequency (RF) Plasma Enhanced Chemical Vapour Deposition (PECVD) and then, were treated by nitrogen PIII from 15 to 60 min. Fourier Transformed Infrared (FTIR) spectroscopy was employed to analyse the molecular structure of the samples, and it revealed that vibrations modes at 3350 cm(-1), 2960 cm(-1), 1650 cm(-1), 1250 cm(-1) and 1050 cm(-1) were altered by nitrogen PIII. Visible-ultraviolet (vis-UV) spectroscopy was used to evaluate film refractive index and the results showed a slight increase from 1.6 to 1.8 following the implantation time. Nanoindentation revealed a surface hardness rise from 0.5 to 2.3 GPa as PIII treatment time increased. These results indicate nitrogen PIII is very promising in improving optical and mechanical properties of PPHMDSN films.

Straw decomposition of nitrogen-fertilized grasses intercropped with irrigated maize in an integrated crop-livestock system

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Low-temperature, self-nucleated growth of indium-tin oxide nanostructures by pulsed laser deposition on amorphous substrates

Indium-tin oxide nanostructures were deposited by excimer laser ablation in a nitrogen atmosphere using catalyst-free oxidized silicon substrates at 500 degrees C. Up to 1 mbar, nanowires grew by the vapor-liquid-solid (VLS) mechanism, with the amount of liquid material decreasing as the deposition pressure increased. The nanowires present the single-crystalline cubic bixbyite structure, oriented < 100 >. For the highest pressure used, pyramids were formed and no sign of liquid material could be observed, indicating that these structures grew by a vapor-solid mechanism. (c) 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Effects of nitrogen ion irradiation on plasma polymerized films produced from titanium tetraiso pro poxide-oxygen-helium mixtures

In this work films were produced by the plasma enhanced chemical vapor deposition (PECVD) of titanium tetraisopropoxide-oxygen-helium mixtures and irradiated with 150 keV singly-charged nitrogen ions (N(+)) at fluences, phi, between 10(14) and 10(16) cm(-2). Irradiation resulted in compaction, which reached about 40% (measured via the film thickness) at the highest fluence. Infrared reflection-absorption spectroscopy (IRRAS) revealed the presence of Ti-O bonds in all films. Both O-H and C-H groups were present in the as-deposited films, but the density of each of these decreased with increasing phi and was absent at high phi, indicating a loss of hydrogen. X-ray photoelectron spectroscopy (XPS) analyses revealed an increase in the C to Ti atomic ratio as phi increased, while the O to Ti ratio hardly altered, remaining at around 2.8. The optical gap of the films, derived from data obtained by ultraviolet-visible spectroscopy (UVS), remained at about 3.6 eV for all fluences except the highest, for which an abrupt fall to around 1.0 eV was observed. For the irradiated films, the electrical conductivity, measured using the two-point method, showed a systematic increase with increasing phi. (c) 2008 Elsevier B.V. All rights reserved.

Intravenous versus nebulized ceftazidime in ventilated piglets with and without experimental bronchopneumonia: Comparative effects of helium and nitrogen

Background: Lung deposition of intravenous cephalosporins is low. The lung deposition of equivalent doses of ceftazidime administered either intravenously or by ultrasonic nebulization using either nitrogen-oxygen or helium-oxygen as the carrying gas of the aerosol was compared in ventilated piglets with and without experimental bronchopneumonia. Methods: Five piglets with noninfected lungs and 5 piglets with Pseudomonas aeruginosa experimental bronchopneumonia received 33 mg/kg ceftazidime intravenously. Ten piglets with noninfected lungs and 10 others with experimental P. aeruginosa bronchopneumonia received 50 mg/kg ceftazidime by ultrasonic nebulization. In each group, the ventilator was operated in half of the animals with a 65%/35% helium-oxygen or nitrogen-oxygen mixture. Animals were killed, and multiple lung specimens were sampled for measuring ceftazidime lung tissue concentrations by high-performance liquid chromatography. Results: As compared with intravenous administration, nebulization of ceftazidime significantly increased lung tissue concentrations (17 ± 13 vs. 383 ± 84 μg/g in noninfected piglets and 10 ± 3 vs. 129 ± 108 μg/g in piglets with experimental bronchopneumonia; P < 0.001). The use of a 65%/35% helium-oxygen mixture induced a 33% additional increase in lung tissue concentrations in noninfected piglets (576 ± 141 μg/g; P < 0.001) and no significant change in infected piglets (111 ± 104 μg/g). Conclusion: Nebulization of ceftazidime induced a 5- to 30-fold increase in lung tissue concentrations as compared with intravenous administration. Using a helium-oxygen mixture as the carrying gas of the aerosol induced a substantial additional increase in lung deposition in noninfected piglets but not in piglets with experimental bronchopneumonia. © 2005 American Society of Anesthesiologists, Inc. Lippincott Williams & Wilkins, Inc.