Uptake of carbon, nitrogen and phosphorus by phytoplankton along the 20 degrees W meridian in the NE Atlantic between 57.5 degrees N and 37 degrees N

Phytoplankton biomass and rate of production were measured along a transect from 57.54 degreesN to 37.01 degreesN in the northeast Atlantic during July 1996 and at a series of stations over a 7-day period at 37 degreesN 20 degreesW. Surface nutrient concentrations ranged from 4 mu mol l(-1) NO3-, and 0.35 mu mol l(-1) PO43- at 57.54 degreesN to <10 nmol l(-1) NO3- and similar to 10 nmol l(-1) PO43- at 37.01 degreesN. The greatest phytoplankton biomass and production were measured in the vicinity of a frontal system at 50 degreesN, and there was a general decline in total phytoplankton biomass and production to the south of the transect. Production was measured in three size fractions. At the station with the highest chlorophyll concentrations (50.34 degreesN), phytoplankton cells larger than 5 mum dominated the assemblage, accounting for 72% of the chlorophyll concentration (22.9 mg m(-2)) and 51% of primary production (54.1 mmol Cm-2 d(-1)), but picophytoplankton production was also high (43%). At 57 degreesN, carbon fixation by the > 5 mum fraction accounted for 75% of the daily production of 60.75 mmol Cm-2 d(-1). At 37 degreesN, picophytoplankton was the dominant group, accounting for similar to 58% (10 mg m(-2)) of chlorophyll and similar to 64% (46 mmol Cm-2 d(-1)), of primary production. Nitrate, ammonium and phosphate uptake rates also were determined. Although high nitrate uptake rates were measured in the surface water at similar to 50 degreesN, the greatest uptake rates of both depth-integrated nitrate and ammonium were at the south of the transect. At 37 degreesN, a deep euphotic zone was present and light penetrated through the nitracline; total nitrate uptake was enhanced because of assimilation at the base of the euphotic zone. As a consequence, high values of depth-integrated f-ratio were measured in the oligotrophic waters at the south of the transect. Phosphate was predominantly incorporated into the picoplankton fraction, which included heterotrophic and autotrophic components, at all stations and a significant proportion of phosphate uptake occurred in the dark. The C:N:P assimilation ratios were variable throughout the region; phosphate uptake was generally greater than would be expected if nutrient assimilation were in proportion to the Redfield ratio. (C) 2001 Elsevier Science Ltd. All rights reserved.

Cycloalkenyl Halide Substitution Reactions of Enantiopure Arene cis-Tetrahydrodiols with Boron, Nitrogen and Phosphorus Nucleophiles

Enantiopure arene cis-tetrahydrodiols of bromobenzene and iodobenzene have been obtained in good yields, from chemoselective hydrogenation (rhodium-graphite) of the corresponding cis-dihydrodiol metabolites. Palladium-catalysed substitution of the halogen, by hydrogen, boron, nitrogen and phosphorus nucleophiles, in the acetonide derivatives, has yielded highly functionalised products for application in synthesis with potential as scaffolds for chiral ligands.

Liquid nitrogen and salicylic/lactic acid paint in the treatment of cutaneous warts in general practice

Patients with common hand warts and simple plantar warts attending a general practice wart clinic in Northern Ireland were assigned to one of three treatment groups - liquid nitrogen applied weekly, daily application of wart paint (lactic acid one part, salicylic acid one part, collodion four parts), or a combination of the two. Combination therapy cured 87% of common hand warts over a six week period, and was significantly more effective than either agent used separately (P

Reactions of nitrogen and oxygen surface groups in nanoporous carbons under inert and reducing atmospheres

The reactions of surface functional groups have an important role in controlling conversion of char nitrogen to NOx during coal combustion. This study involved an investigation of the thermal stability and reactions of nitrogen surface functional groups in nanoporous carbons. Four suites of carbons, which were used as models for coal chars, were prepared with a wide range of nitrogen and oxygen contents and types of functional groups. The porous structures of the carbons were characterized by gas adsorption methods while chemical analysis, X-ray photoelectron spectroscopy, and X-ray near edge structure spectroscopy were used to characterize the surface functional groups. Temperature programmed desorption and temperature programmed reduction methods were used to study the reactivity of the surface functional groups during heat treatment under inert and reducing conditions. Heat treatment studies show that the order of stability of the functional groups is quaternary nitrogen > pyridinic > pyrrolic > pyridine N-oxide. Pyridine N-oxide surface groups desorb NO and form N-2 via surface reactions at low temperature. Pyrrolic and pyridinic functional groups decompose and react with surface species to give NH3, HCN, and N-2 as desorption products, but most pyrrolic groups are preferentially converted to pyridinic and quaternary nitrogen. The main desorption product is N-2. Approximately 15-40 wt % of the original nitrogen was retained in the carbons mainly as quaternary nitrogen after heat treatment to 1673 K. The results are discussed in terms of decomposition ranges for surface functional groups and reaction mechanisms of surface species.

Availability and transfer to grain of As, Cd, Cu, Ni, Pb and Zn in a barley agri-system: Impact of biochar, organic and mineral fertilizers

With biochar becoming an emerging soil amendment and a tool to mitigate climate change, there are only a few studies documenting its effects on trace element cycling in agriculture. Zn and Cu are deficient in many human diets, whilst exposures to As, Pb and Cd need to be decreased. Biochar has been shown to affect many of them mainly at a bench or greenhouse scale, but field research is not available. In our experiment we studied the impact of biochar, as well as its interactions with organic (compost and sewage sludge) and mineral fertilisers (NPK and nitrosulfate), on trace element mobility in a Mediterranean agricultural field (east of Madrid, Spain) cropped with barley. At harvesting time, we analysed the soluble fraction, the available fraction (assessed with the diffusive gradients in thin gels technique, DGT) and the concentration of trace elements in barley grain. No treatment was able to significantly increase Zn, Cu or Ni concentration in barley grain, limiting the application for cereal fortification. Biochar helped to reduce Cd and Pb in grain, whereas As concentration slightly increased. Overall biochar amendments demonstrated a potential to decrease Cd uptake in cereals, a substantial pathway of exposure in the Spanish population, whereas mineral fertilisation and sewage sludge increased grain Cd and Pb. In the soil, biochar helped to stabilise Pb and Cd, while marginally increasing As release/mobilisation. Some of the fertilisation practises or treatments increased toxic metals and As solubility in soil, but never to an extent high enough to be considered an environmental risk. Future research may try to fortify Zn, Cu and Ni using other combinations of organic amendments and different parent biomass to produce enriched biochars.

More nitrogen rich B-type stars in the SMC cluster, NGC 330

High resolution spectra of seven early B-type giant/supergiant stars in the SMC cluster NGC330 are analysed to obtain their chemical compositions relative to SMC field and Galactic B-type stars. It is found that all seven stars are nitrogen rich with an abundance approximately 1.3 dex higher than an SMC main- sequence field B-type star, AV304. They also display evidence for deficiencies in carbon, but other metals have abundances typical of the SMC. Given the number of B-type stars with low projected rotational velocities in NGC330 (all our targets have v sin i <50 km s(-1)), we suggest that it is unlikely that the stars in our sample are seen almost pole-on, but rather that they are intrinsically slow rotators. Furthermore, none of our objects displays any evidence of significant Balmer emission excluding the possibility that these are Be stars observed pole-on. Comparing these results with the predictions of stellar evolution models including the effects of rotationally induced mixing, we conclude that while the abundance patterns may indeed be reproduced by these models, serious discrepancies exist. Most importantly, models including the effects of initially large rotational velocities do not reproduce the observed range of effective temperatures of our sample, nor the currently observed rotational velocities. Binary models may be able to produce stars in the observed temperature range but again may be incapable of producing suitable analogues with low rotational velocities. We also discuss the clear need for stellar evolution calculations employing the correct chemical mix of carbon, nitrogen and oxygen for the SMC.

The human micro-vascular enclothelial cells in vitro interaction with atomic-nitrogen-doped diamond-like carbon thin films

This paper reports the initial response of atomic nitrogen doped diamond like carbon (DLC) to endothelial cells in vitro. The introduction of nitrogen atoms/molecules to the diamond like carbon structures leads to an atomic structural change favorable to the attachment of human micro-vascular enclothelial cells. Whilst the semi-conductivity induced by nitrogen in DLC is thought to play a part, the increase in the inion-bonded N atoms and N-2 molecules in the atomic doped species (with the exclusion of the charged species) seems to contribute to the improved attachment of human microvascular endothelial cells. The increased endothelial attachment is associated with a lower work function and slightly higher water contact angle in the atomic doped films, where the heavy charged particles are excluded. The films used in the study were synthesized by the RF PECVD technique followed by post deposition doping with nitrogen, and afterwards the films were characterized by XPS, Raman spectroscopy, SIMS and Kelvin probe. The water contact angles were measured, and the counts of the adherent endothelial cells on the samples were carried out. This study is relevant and contributory to improving biocompatibility of surgical implants and prostheses.

The electrochemical oxidation and reduction of nitrate ions in the room temperature ionic liquid [C(2)mim][NTf2]; the latter behaves as a 'melt' rather than an 'organic solvent'

The electrochemical oxidation of 1-butyl-3-methylimidazolium nitrate [C(4)mim][NO3] was studied by cyclic voltammetry in the room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [C(2)mim][NTf2]. A sharp peak was observed on a Pt microelectrode (d = 10 mu m), and a diffusion coefficient at infinite dilution of ca. 2.0 x 10(-11) m(2) s(-1) was obtained. Next, the cyclic voltammetry of sodium nitrate (NaNO3) and potassium nitrate (KNO3) was studied, by dissolving small amounts of solid into the RTIL [ C2mim][ NTf2]. Similar oxidation peaks were observed, revealing diffusion coefficients of ca. 8.8 and 9.0 x 10(-12) m(2) s(-1) and solubilities of 11.9 and 10.8 mM for NaNO3 and KNO3, respectively. The smaller diffusion coefficients for NaNO3 and KNO3 (compared to [C(4)mim][NO3]) may indicate that NO3- is ion-paired with Na+ or K+. This work may have applications in the electroanalytical determination of nitrate in RTIL solutions. Furthermore, a reduction feature was observed for both NaNO3 and KNO3, with additional anodic peaks indicating the formation of oxides, peroxides, superoxides and nitrites. This behaviour is surprisingly similar to that obtained from melts of NaNO3 and KNO3 at high temperatures ( ca. 350 - 500 degrees C), and this observation could significantly simplify experimental conditions required to investigate these compounds. We then used X-ray photoelectron spectroscopy (XPS) to suggest that disodium( I) oxide (Na2O), which has found use as a storage compound for hydrogen, was deposited on a Pt electrode surface following the reduction of NaNO3.

Reactivity of the 4d transition metals toward N hydrogenation and NH dissociation: A DFT-based HSAB analysis

The density functional theory (DFT) based hard-soft acid-base (HSAB) reactivity indices, including the electrophilicity index, have been successfully applied to many areas of molecular chemistry. In this work we test the applicability of such an approach to fundamental surface chemistry. We have considered, as prototypical surface reactions, both the hydrogenation of atomic nitrogen and the dissociative adsorption of the NH molecular radical. By use of a DFT methodology, the minimum energy reaction pathways, and corresponding reaction barriers, of the above reactions over Zr(001), Nb(110), Mo(110), Tc(001), Ru(001), Rh(111), and Pd(111) have been determined. By consideration of the chemical potential and chemical hardness of the surface metal atoms, and the principle of electronegativity equalization, it is found that the charge transferred to the NH radical during the process of dissociative adsorption correlates very well with that determined by Mulliken population analysis. Furthermore, it is found that the stability of the NH/surface transition state complex relates directly to this charge transfer and that the trend in transition state stability predicted by a HSAB; treatment correlates very strongly with that determined by DFT calculations. With regards to N hydrogenation, we find that during the course of the reaction, H loses cohesion to the surface, as it must migrate from a 3-fold hollow site to either a bridge or top site, to react with N. Partial density of states (PDOS) and Mulliken population analysis reveal that this loss of bonding is accompanied by charge transfer from H to the surface metal atoms. Moreover, by simple modeling, we show that the reaction barriers are directly proportional to this mandatory charge transfer. Indeed, it is found that the reaction barriers correlate very well with the electrophilicity index of the metal atoms.

High-density and low electron temperature direct current reflex plasma source

A new type of direct current, high-density, and low electron temperature reflex plasma source, obtained as a hybrid between a modified hollow-cathode discharge and a Penning ionization gauge discharge is presented. The plasma source was tested in argon, nitrogen, and oxygen over a range pressure of 1.0-10(-3) mbar, discharge currents 20-200 mA, and magnetic field 0-120 Gauss. Both external parameters, such as breakdown potential and the discharge voltage-current characteristic, and its internal parameters, like the electron energy distribution function, electron and ion densities, and electron temperature, were measured. Due to the enhanced hollow-cathode effect by the magnetic trapping of electrons, the density of the bulk plasma is as high as 10(18) m(-3), and the electron temperature is as low as a few tenths of electron volts. The plasma density scales with the dissipated power. Another important feature of this reflex plasma source is its high degree of uniformity, while the discharge bulk region is free of an electric field. (C) 2004 American Institute of Physics.

Measurement of Quenching Coefficients and Developement of Calibration Methods for Quantitative Spectroscopy of Plasma at Elevated Pressures

Measurements of collisional de-excitation (quenching) coefficients required for the interpretation of emission and fluorescence spectroscopic measurements are reported. Particular attention is turned on argon transitions which are of interest for actinometric determinations of atomic ground state populations and on fluorescence lines originating from excited atoms and noble gases in connection with two-photon excitation (TALIF) of atomic radicals. A novel method is described which allows to infer quenching coefficients for collisions with molecular hydrogen of noble gas states in the energy range up to 24 eV. The excitation is performed in these experiments by collisions of energetic electrons in the sheath of an RF excited hydrogen plasma during the field reversal phase which lasts about 10 ns. We describe in addition a calibration method - including quenching effects - for the determination by TALIF of absolute atomic radical densities of hydrogen, nitrogen and oxygen using two-photon resonances in noble gases close by the resonances of the species mentioned. The paper closes with first ideas on a novel technique to bypass quenching effects in TALIF by introducing an additional, controllable loss by photoionization that will allow quenching-free determination of absolute atomic densities with prevalent nanosecond laser systems in situations where collisional de-excitation dominates over spontaneous emission.

Density-Enhanced Gas and Dust Shells in a New Chemical Model for IRC+10216

A new chemical model is presented for the carbon-rich circumstellar envelope (CSE) of the asymptotic giant branch star IRC+10216. The model includes shells of matter with densities that are enhanced relative to the surrounding circumstellar medium. The chemical model uses an updated reaction network including reactions from the RATE06 database and a more detailed anion chemistry. In particular, new mechanisms are considered for the formation of CN-, C3N-, and C2H-, and for the reactions of hydrocarbon anions with atomic nitrogen and with the most abundant cations in the CSE. New reactions involving H- are included which result in the production of significant amounts of C2H- and CN- in the inner envelope. The calculated radial molecular abundance profiles for the hydrocarbons C2H, C4H, and C6H and the cyanopolyynes HC3N and HC5N show narrow peaks which are in better agreement with observations than previous models. Thus, the narrow rings observed in molecular microwave emission surrounding IRC+10216 are interpreted as arising in regions of the envelope where the gas and dust densities are greater than the surrounding circumstellar medium. Our models show that CN- and C2H- may be detectable in IRC+10216 despite the very low theorized radiative electron attachment rates of their parent neutral species. We also show that magnesium isocyanide (MgNC) can be formed in the outer envelope through radiative association involving Mg+ and the cyanopolyyne species.