Uranium chemistry of oceanic basalts

Measurements of uranium concentration and the 234U/238 U activity ratio in oceanic basalts which have undergone low-temperature seafloor alteration indicate that uranium uptake is a pervasive occurrence but that the various phases involved behave differently with respect to this process. Palagonite exhibits uranium contents 8-20 times higher than unaltered glass coupled with low 234U/238U, suggesting ongoing preferential leaching of 234U. Altered crystalline interiors of several old basalts have 234U/238U > 1, indicative of recent uranium exchange with seawater. The data also provide evidence for uranium sources with 234U/238U higher than the seawater value of 1.14. Manganese crusts on basalts of a variety of ages have isotopic ratios indicating that they either are recent deposits or also have experienced continuing uranium exchange with seawater.

Sedimentology and geochemistry of ODP Leg 129 siliceous deposits

Siliceous deposits drilled on Ocean Drilling Program Leg 129 accumulated within a few degrees of the equator during the Jurassic through early Tertiary, as constrained by paleomagnetic data. During the Jurassic and Early Cretaceous, radiolarian ooze, mixed with a minor amount of pelagic clay, was deposited near the equator, and overall accumulation rates were moderate to low. At a smaller scale, in more detail, periods of relatively higher accumulation rates alternated with periods of very low accumulation rates. Higher rates are represented by radiolarite and limestone; lower rates are represented by radiolarian claystone. Our limited data from Leg 129 suggests that accumulation of biogenic deposits was not symmetrical about the equator or consistent over time. In the Jurassic, sedimentation was siliceous; in the Cretaceous there was significant calcareous deposition; in the Tertiary claystone indicates significantly lower accumulation rates at least the northern part of the equatorial zone. Accumulation rates for Leg 129 deposits in the Cretaceous were higher in the southern part of the equatorial zone than in the northern part, and the southern side of this high productivity zone extended to approximately 15°S, while the northern side extended only to about 5°N. Accumulation rates are influenced by relative contributions from various sediment sources. Several elements and element ratios are useful for discriminating sedimentary sources for the equatorial depositional environments. Silica partitioning calculations indicate that silica is dominantly of biogenic origin, with a detrital component in the volcaniclastic turbidite units, and a small hydrothermal component in the basal sediments on spreading ridge basement of Jurassic age at Site 801. Iron in Leg 129 sediments is dominantly of detrital origin, highest in the volcaniclastic units, with a minor hydrothermal component in the basal sediments at Site 801. Manganese concentrations are highest in the units with the lowest accumulation rates. Fe/Mn ratios are >3 in all units, indicating negligible hydrothermal influence. Magnesium and aluminum concentrations are highest in the volcaniclastic units and in the basal sediments at Site 801. Phosphorous is very low in abundance and may be detrital, derived from fish parts. Boron is virtually absent, as is typical of deep-water deposits. Rare earth element concentrations are slightly higher in the volcaniclastic deposits, suggesting a detrital source, and lower in the rest of the lithologic units. Rare earth element abundances are also low relative to "average shale." Rare earth element patterns indicate all samples are light rare earth element enriched. Siliceous deposits in the volcaniclastic units have patterns which lack a cerium anomaly, suggesting some input of rare earth elements from a detrital source; most other units have a distinct negative Ce anomaly similar to seawater, suggesting a seawater source, through adsorption either onto biogenic tests or incorporation into authigenic minerals for Ce in these units. The Al/(Al + Fe + Mn) ratio indicates that there is some detrital component in all the units sampled. This ratio plotted against Fe/Ti shows that all samples plot near the detrital and basalt end-members, except for the basal samples from Site 801, which show a clear trend toward the hydrothermal end-member. The results of these plots and the association of high Fe with high Mg and Al indicate the detrital component is dominantly volcaniclastic, but the presence of potassium in some samples suggests some terrigenous material may also be present, most likely in the form of eolian clay. On Al-Fe-Mn ternary plots, samples from all three sites show a trend from biogenic ooze at the top of the section downhole to oceanic basalt. On Si-Fe-Mn ternary plots, the samples from all three sites fall on a trend between equatorial mid-ocean spreading ridges and north Pacific red clay. Copper-barium ratios show units that have low accumulation rates plot in the authigenic field, and radiolarite and limestone samples that have high accumulation rates fall in the biogenic field.

(Table 1) B content, d11B, d18O, degree of alteration, and lithology of basalts from ODP Hole 504B

Boron contents and boron isotopic compositions were determined for the uppermost 1.3 km section of typical 6.2 Ma oceanic crust from DSDP/ODP Hole 504B, Costa Rica Rift, Galapagos Spreading Center. Both the boron content and the d11B value in the oceanic crust are controlled by two types of alteration: 1. (1) low-temperature alteration (0 to 60°C; Zones I and II) and 2. (2) high-temperature hydrothermal alteration (200 to 400°C; Zones III and IV). Basalts subjected to the low-temperature alteration are characterized by their relatively high boron contents (0.69 to 19.3 ppm) and high d11B values (+2.2 to +10.6?), indicating uptake of boron into secondary phases in equilibrium with seawater or evolved seawater. Hydrothermally altered basalts contain less abundant boron (0.17 to 0.52 ppm) and relatively constant d11B values (?0.1 to +1.0?). Although basalts from the upper part of these hydrothermal zones (<1300 mbsf) show equilibrated boron content and d11B value with aqueous fluid, effective leaching of boron from basalt is predominant in the lower part (>1300 mbsf). Original boron content and d11B value of the Hole 504B MORB were 0.35 ppm and +0.2?, respectively. The present data provide fundamental information in understanding of the distribution of boron and boron isotopes in the oceanic crust.

Fractal Behaviour and Irregularity of Wetting Fronts in Heterogeneous Porous Media

The wetting front is the zone where water invades and advances into an initially dry porous material and it plays a crucial role in solute transport through the unsaturated zone. Water is an essential part of the physiological process of all plants. Through water, necessary minerals are moved from the roots to the parts of the plants that require them. Water moves chemicals from one part of the plant to another. It is also required for photosynthesis, for metabolism and for transpiration. The leaching of chemicals by wetting fronts is influenced by two major factors, namely: the irregularity of the fronts and heterogeneity in the distribution of chemicals, both of which have been described by using fractal techniques. Soil structure can significantly modify infiltration rates and flow pathways in soils. Relations between features of soil structure and features of infiltration could be elucidated from the velocities and the structure of wetting fronts. When rainwater falls onto soil, it doesn?t just pool on surfaces. Water ?or another fluid- acts differently on porous surfaces. If the surface is permeable (porous) it seeps down through layers of soil, filling that layer to capacity. Once that layer is filled, it moves down into the next layer. In sandy soil, water moves quickly, while it moves much slower through clay soil. The movement of water through soil layers is called the the wetting front. Our research concerns the motion of a liquid into an initially dry porous medium. Our work presents a theoretical framework for studying the physical interplay between a stationary wetting front of fractal dimension D with different porous materials. The aim was to model the mass geometry interplay by using the fractal dimension D of a stationary wetting front. The plane corresponding to the image is divided in several squares (the minimum correspond to the pixel size) of size length ". We acknowledge the help of Prof. M. García Velarde and the facilities offered by the Pluri-Disciplinary Institute of the Complutense University of Madrid. We also acknowledge the help of European Community under project Multi-scale complex fluid flows and interfacial phenomena (PITN-GA-2008-214919). Thanks are also due to ERCOFTAC (PELNoT, SIG 14)

Sustainability of irrigated farming systems in a Tunisian region: A recursive stochastic programming analysis

The aim of this study was to evaluate the sustainability of farm irrigation systems in the Cébalat district in northern Tunisia. It addressed the challenging topic of sustainable agriculture through a bio-economic approach linking a biophysical model to an economic optimisation model. A crop growth simulation model (CropSyst) was used to build a database to determine the relationships between agricultural practices, crop yields and environmental effects (salt accumulation in soil and leaching of nitrates) in a context of high climatic variability. The database was then fed into a recursive stochastic model set for a 10-year plan that allowed analysing the effects of cropping patterns on farm income, salt accumulation and nitrate leaching. We assumed that the long-term sustainability of soil productivity might be in conflict with farm profitability in the short-term. Assuming a discount rate of 10% (for the base scenario), the model closely reproduced the current system and allowed to predict the degradation of soil quality due to long-term salt accumulation. The results showed that there was more accumulation of salt in the soil for the base scenario than for the alternative scenario (discount rate of 0%). This result was induced by applying a higher quantity of water per hectare for the alternative as compared to a base scenario. The results also showed that nitrogen leaching is very low for the two discount rates and all climate scenarios. In conclusion, the results show that the difference in farm income between the alternative and base scenarios increases over time to attain 45% after 10 years.

Analysis of the surface state of epi-ready Ge wafers

The surface state of Ge epi-ready wafers (such as those used on III-V multijunction solar cells) supplied by two different vendors has been studied using X-ray photoemission spectroscopy. Our experimental results show that the oxide layer on the wafer surface is formed by GeO and GeO2. This oxide layer thickness differs among wafers coming from different suppliers. Besides, several contaminants appear on the wafer surfaces, carbon and probably chlorine being common to every wafer, irrespective of its origin. Wafers from one of the vendors show the presence of carbonates at their surfaces. On such wafers, traces of potassium seem to be present too.

Cover crops effect on farm benefits and nitrate leaching: Linking economic and environmental analysis.

Introducing cover crops (CC) interspersed with intensively fertilized crops in rotation has the potential to reduce nitrate leaching. This paper evaluates various strategies involving CC between maize and compares the economic and environmental results with respect to a typical maize?fallow rotation. The comparison is performed through stochastic (Monte-Carlo) simulation models of farms? profits using probability distribution functions (pdfs) of yield and N fertilizer saving fitted with data collected from various field trials and pdfs of crop prices and the cost of fertilizer fitted from statistical sources. Stochastic dominance relationships are obtained to rank the most profitable strategies from a farm financial perspective. A two-criterion comparison scheme is proposed to rank alternative strategies based on farm profit and nitrate leaching levels, taking the baseline scenario as the maize?fallow rotation. The results show that when CC biomass is sold as forage instead of keeping it in the soil, greater profit and less leaching of nitrates are achieved than in the baseline scenario. While the fertilizer saving will be lower if CC is sold than if it is kept in the soil, the revenue obtained from the sale of the CC compensates for the reduced fertilizer savings. The results show that CC would perhaps provide a double dividend of greater profit and reduced nitrate leaching in intensive irrigated cropping systems in Mediterranean regions.

Effects of biochar prepared from organic waste on soil properties

Biochar is a carbon-rich solid obtained by the thermal decomposition of organic matter under a limited supply of oxygen and at relatively low temperatures. Biochar can be prepared from the pyrolysis of different organic feed- stocks, such as wood and biomass crops, agricultural by-products, different types of waste or paper industry waste materials . The pyrolysis procedure of waste, i.e. sewage sludge, has mainly two advantages, firstly, it removes pathogens from waste and, secondly, biochar can reduce the leaching of heavy metals present in raw sewage sludge. This trend of the use of waste material as feedstocks to the preparation of biochar is increasing in the last years due to industrial development and economic growth imply an increase in waste generation. The application of biochar may have positive effects on soil physical properties as water holding capacity and structure or on soil biological activity and soil quality. Also, biochar can be used to remove water pollutants and can be used in multiple ways in soil remediation due to its adsorption of pesticides or metals. Also, biochar contribute to carbon sequestration due to carbon stability of biochar materials. The objective of this presentation is to review the positive effects of the biochar prepared from organic waste on soil properties.

Calcium regulation of a slow post-spike hyperpolarization in vagal afferent neurons

Activation of distinct classes of potassium channels can dramatically affect the frequency and the pattern of neuronal firing. In a subpopulation of vagal afferent neurons (nodose ganglion neurons), the pattern of impulse activity is effectively modulated by a Ca2+-dependent K+ current. This current produces a post-spike hyperpolarization (AHPslow) that plays a critical role in the regulation of membrane excitability and is responsible for spike-frequency accommodation in these neurons. Inhibition of the AHPslow by a number of endogenous autacoids (e.g., histamine, serotonin, prostanoids, and bradykinin) results in an increase in the firing frequency of vagal afferent neurons from <0.1 to >10 Hz. After a single action potential, the AHPslow in nodose neurons displays a slow rise time to peak (0.3–0.5 s) and a long duration (3–15 s). The slow kinetics of the AHPslow are due, in part, to Ca2+ discharge from an intracellular Ca2+-induced Ca2+ release (CICR) pool. Action potential-evoked Ca2+ influx via either L or N type Ca2+ channels triggers CICR. Surprisingly, although L type channels generate 60% of action potential-induced CICR, only Ca2+ influx through N type Ca2+ channels can trigger the CICR-dependent AHPslow. These observations suggest that a close physical proximity exists between endoplasmic reticulum ryanodine receptors and plasma membrane N type Ca2+ channels and AHPslow potassium channels. Such an anatomical relation might be particularly beneficial for modulation of spike-frequency adaptation in vagal afferent neurons.

Nitric oxide inhibits the release of norepinephrine and dopamine from the medial basal hypothalamus of the rat.

Previous research indicates that norepinephrine and dopamine stimulate release of luteinizing hormone (LH)-releasing hormone (LHRH), which then reaches the adenohypophysis via the hypophyseal portal vessels to release LH. Norepinephrine exerts its effect via alpha 1-adrenergic receptors, which stimulate the release of nitric oxide (NO) from nitricoxidergic (NOergic) neurons in the medial basal hypothalamus (MBH). The NO activates guanylate cyclase and cyclooxygenase, thereby inducing release of LHRH into the hypophyseal portal vessels. We tested the hypothesis that these two catecholamines modulate NO release by local feedback. MBH explants were incubated in the presence of sodium nitroprusside (NP), a releaser of NO, and the effect on release of catecholamines was determined. NP inhibited release of norepinephrine. Basal release was increased by incubation of the tissue with the NO scavenger hemoglobin (20 micrograms/ml). Hemoglobin also blocked the inhibitory effect of NP. In the presence of high-potassium (40 mM) medium to depolarize cell membranes, norepinephrine release was increased by a factor of 3, and this was significantly inhibited by NP. Hemoglobin again produced a further increase in norepinephrine release and also blocked the action of NP. When constitutive NO synthase was inhibited by the competitive inhibitor NG-monomethyl-L-arginine (NMMA) at 300 microM, basal release of norepinephrine was increased, as was potassium-evoked release, and this was associated in the latter instance with a decrease in tissue concentration, presumably because synthesis did not keep up with the increased release in the presence of NMMA. The results were very similar with dopamine, except that reduction of potassium-evoked dopamine release by NP was not significant. However, the increase following incubation with hemoglobin was significant, and hemoglobin, when incubated with NP, caused a significant elevation in dopamine release above that with NP alone. In this case, NP increased tissue concentration of dopamine along with inhibiting release, suggesting that synthesis continued, thereby raising the tissue concentration in the face of diminished release. When the tissue was incubated with NP plus hemoglobin, which caused an increase in release above that obtained with NP alone, the tissue concentration decreased significantly compared with that in the absence of hemoglobin, indicating that, with increased release, release exceeded synthesis, causing a fall in tissue concentration. When NO synthase was blocked by NMMA, the release of dopamine, under either basal or potassium-evoked conditions, was increased. Again, in the latter instance the tissue concentration declined significantly, presumably because synthesis did not match release. Therefore, the results were very similar with both catecholamines and indicate that NO acts to suppress release of both amines. Since both catecholamines activate the release of LHRH, the inhibition of their release by NO serves as an ultra-short-loop negative feedback by which NO inhibits the release of the catecholamines, thereby reducing the activation of the NOergic neurons and decreasing the release of LHRH. This may be an important means for terminating the pulses of release of LHRH, which generate the pulsatile release of LH that stimulates gonadal function in both male and female mammals.

Resposta do cafeeiro arábica ao magnésio em solos fertilizados com altas doses de potássio

O aumento das doses de potássio (K) para atender a demanda nutricional desse nutriente em cafezais produtivos induz a deficiência de Mg. Esta pesquisa foi realizada com o objetivo de compreender como a classe de solo interfere na interação entre esses nutrientes (K e Mg), de maneira que a aplicação de alta dose de K não afete a nutrição da planta em relação ao Mg. Dois experimentos foram conduzidos em duas classes de solo: Latossolo, com textura muito argilosa, em Machado-MG, e Argissolo, com textura media sobre argilosa, em Monte Santo de Minas-MG. Adotou-se delineamento fatorial com três doses de K (110, 260 e 390 kg ha-1 K2O) x cinco doses de Mg (0, 81, 162, 324 e 405 kg ha-1 MgO), com três repetições. No Argissolo, a lixiviação de K impediu a redução da concentração foliar de Mg, independentemente da dose de K. No Latossolo, a concentração de Mg foliar variou com a dose de K, e apresentou ajuste quadrático. A concentração foliar de Mg aumentou linearmente com a dose desse nutriente, independentemente da classe de solo e da dose de K.

Ultrasound-assisted selective hydrogenation of C-5 acetylene alcohols with Lindlar catalysts

The selective hydrogenation of 2-methyl-3-butyn-2-ol (MBY) was performed in the presence of Lindlar catalyst, comparing conventional stirring with sonication at different frequencies of 40, 380 and 850 kHz. Under conventional stirring, the reaction rates were limited by intrinsic kinetics, while in the case of sonication, the reaction rates were 50–90% slower. However, the apparent reaction rates were found to be significantly frequency dependent with the highest rate observed at 40 kHz. The original and the recovered catalysts after the hydrogenation reaction were compared using bulk elemental analysis, powder X-ray diffraction and scanning and transmission electron microscopy coupled with energy-dispersive X-ray analysis. The studies showed that sonication led to the frequency-dependent fracturing of polycrystalline support particles with the highest impact caused by 40 kHz sonication, while monocrystals were undamaged. In contrast, the leaching of Pd/Pb particles did not depend on the frequency, which suggests that sonication removed only loosely-bound catalyst particles.

Solute losses from various shoot parts of field-grown wheat by leakage in the rain

Leakage from field-grown wheat was investigated during two seasons differing considerably in their rainfall patterns. For all solutes analyzed, these losses were low from non-senescing plant parts, increased after the onset of senescence and became maximal in fully senesced (dry, brown) organs. The cumulative losses of potassium by leakage in the rain were 65% of the content at anthesis for the flag leaf and 95% for the third leaf from the top, while these relative values were lower for magnesium (50 to 80%) and calcium (around 55%) and extremely low for sodium (<10%). The differences between potassium and sodium may be due to a different compartmentation on the tissue level or on the subcellular level. It became evident that for certain nutrients (e.g. potassium or magnesium) leakage in the rain may represent a major loss from senescing leaves and can be a relevant flux in maturing wheat.

Nd isotope ratios of surface sediments from the Pacific Ocean (Table 2)

The neodymium isotopic composition of the silicate fraction of Holocene pelagic sediments from the North Pacific define two provinces: a central North Pacific province characterized by unradiogenic and remarkably homogeneous end (-10.2 +/- 0.5) and a narrow circum-Pacific marginal province characterized by more radiogenic and variable end (-4.2 +/- 3.8). The silicate fraction in the central North Pacific is exclusively eolian; based on prevailing wind patterns, meteorological data, and neodymium isotopic data, the only significant sediment source is Chinese loess. Leaching experiments on Chinese loess confirm that leachable Nd is isotopically indistinguishable from bulk and residual silicate Nd. Silicates in the circum-North Pacific marginal province comprise eolian loess, volcanic ash, and hemipelagic sediments derived from volcanic arcs. A compilation of Pacific seawater and Mn nodule epsilon-Nd data shows no clear spatial variation except for a general decrease from surface to deep waters from -3 to -4 and slightly lower epsilon-Nd in bottom waters along the western North Pacific due to the incursion of Antarctic Bottom Water. The relative homogeneity of bottom water epsilon-Nd, which contrasts sharply with the distinctive variation in sediment epsilon-Nd, plus the large difference between the average end of bottom waters and the central North Pacific eolian silicates (-4 vs. -10), suggests that any contribution of REE to seawater from eolian materials is insignificant. Furthermore, leaching of REE from eolian particles as they sink though the water column must be insignificant because Nd in shallow waters is more radiogenic than Nd in deeper waters. That there is no contrast in the Nd isotopic composition of bottom waters that overlie the central and marginal sediment provinces suggests that the ash and hemipelagic sediments derived from Pacific rim volcanic arcs also contribute minimal REE to seawater. The elimination of eolian, ash, and hemipelagic sediments leaves only near-shore riverine particulates as a possibly significant particulate source of REE to seawater.

Modelling the fate of chromated copper arsenate in a sandy soil

A pulse of chromated copper arsenate (CCA, a timber preservative) was applied in irrigation water to an undisturbed field soil in a laboratory column. Concentrations of various elements in the leachate from the column were measured during the experiment. Also, the remnants within the soil were measured at the end of the experiment. The geochemical modelling package, PHREEQC-2, was used to simulate the experimental data. Processes included in the CCA transport modelling were advection, dispersion, non-specific adsorption (cation exchange) and specific adsorption by clay minerals and organic matter, as well as other possible chemical reactions such as precipitation/dissolution. The modelling effort highlighted the possible complexities in CCA transport and reaction experiments. For example, the uneven dosing of CCA as well as incomplete knowledge of the soil properties resulted in simulations that gave only partial, although reasonable, agreement with the experimental data. Both the experimental data and simulations show that As and Cu are strongly adsorbed and therefore, will mostly remain at the top of the soil profile, with a small proportion appearing in leachate. On the other hand, Cr is more mobile and thus it is present in the soil column leachate. Further simulations show that both the quantity of CCA added to the soil and the pH of the irrigation water will influence CCA transport. Simulations suggest that application of larger doses of CCA to the soil will result in higher leachate concentrations, especially for Cu and As. Irrigation water with a lower pH will dramatically increase leaching of Cu. These results indicate that acidic rainfall or significant accidental spillage of CCA will increase the risk of groundwater pollution.