Challenges in quantifying biosphere-atmosphere exchange of nitrogen species

Recent research in nitrogen exchange with the atmosphere has separated research communities according to N form. The integrated perspective needed to quantify the net effect of N on greenhouse-gas balance is being addressed by the NitroEurope Integrated Project (NEU). Recent advances have depended on improved methodologies, while ongoing challenges include gas-aerosol interactions, organic nitrogen and N(2) fluxes. The NEU strategy applies a 3-tier Flux Network together with a Manipulation Network of global-change experiments, linked by common protocols to facilitate model application. Substantial progress has been made in modelling N fluxes, especially for N(2)O, NO and bi-directional NH(3) exchange. Landscape analysis represents an emerging challenge to address the spatial interactions between farms, fields, ecosystems, catchments and air dispersion/deposition. European up-scaling of N fluxes is highly uncertain and a key priority is for better data on agricultural practices. Finally, attention is needed to develop N flux verification procedures to assess compliance with international protocols.     

Analysis and residue levels of forchlorfenuron (CPPU) in watermelons

This paper describes the application of liquid chromatography-tandem mass spectrometry (LC/MS-MS) for analysis of residues of forchlorfenuron (CPPU), a new plant growth regulator, in watermelons, after a sample preparation step based on the buffered Quick, Easy, Cheap, Effective, Rugged and Safe extraction method. Analytical determinations were carried out in a triple quadrupole system fitted with an electrospray interphase operating in the positive ionisation mode (ESI+). Three simultaneous MS-MS transitions of the quasi-molecular ion m/z 248 (precursor ion) were monitored for data acquisition (248 > 129, 248 > 155, and 248 > 248), using the transition 248 > 129 for quantitation. Recovery studies on watermelons at levels of 1-200 microg/kg, performing five replicates at each level and using bracketing single-level calibration with matrix-matched standards for quantitation, gave forchlorfenuron mean recoveries ranging from 82 to 106% with relative standard deviations (RSD) lower than 18%. The limit of determination was established at 1 microg/kg. The method was applied to evaluate the persistence of forchlorfenuron residues in watermelons grown in plastic greenhouses, after applying an individual spray treatment to the flower ovary at the anthesis stage (45 mu g/flower and 60 mu g/flower for cv "Extazy" and cv "reina de corazones" watermelons, respectively). One month after treatment, 20 "Extazy" watermelon units (1.5-2 kg/unit) and 20 "Reina de corazones" watermelon units (4-5 kg/unit) were collected and analyzed individually. None of the samples contained forchlorfenuron residues higher than 1 microg/kg.     

Effect of Fe (III) on acid degradation of methylparathion

A study was undertaken to determine the transformation kinetic of methylparathion (O, O, -dimethyl O-4 nitrophenylphosphorotioate) in the presence of Fe(III) between pH 2 and 7. The Fe(III) was not electroactive under the conditions used in this study, and polarographic signals were exhibited by methylparathion and main degradation product only. Data suggest that hydrolysis of methylparathion in an acid medium is catalyzed by Fe(III) and the pesticide did not degrade in this medium without this cation. Methylparathion degradation was observed at all the pHs studied and was independent of the predominant chemical form of Fe(III) in the aqueous medium. The reaction was first-order with pH-dependent rate constant (k) values ranging from 3.3 x 10(- 3) h(- 1) to 7.0 x 10(- 3) h(- 1). The k values increased as pH decreased, suggesting that Fe(III) acted as an electrophile in the reaction mechanism.     

High chrome exhaustion in a non-float tanning process using a sulphonic aromatic acid

Tanning processes performed in drums consume large amounts of water and chemicals, most of which end up in the wastewater. This study explores an alternative approach at an industrial scale to the traditional pickle-chrome tanning method. The new method replaces formic and sulphuric acids with sulphonic aromatic acid. Because it is done without float, there is a sizeable reduction in the amount of added salt and chrome salt as well as an increase in temperatures at the end of the tanning process. From an environmental perspective, the new method offers important advantages. For instance, there is no float addition in the tannage. Also, there are reductions of 94% and 99%, respectively, in the discharge of chlorides and chrome, as well as a 75% reduction in the residual float. Our financial assessment demonstrated that the new method is 42% cheaper than a traditional approach.     

Antibacterial behavior of silver-modified clinoptilolite-heulandite rich tuff on coliform microorganisms from wastewater in a column system

The water disinfecting behavior of silver-modified clinoptilolite–heulandite rich tuff (ZSAg) as an antibacterial agent against coliform microorganisms from water in a continuous mode was investigated. Silver recovery from the disinfected effluents by the sodium-modified clinoptilolite–heulandite rich tuff (ZSNa) was also considered. Escherichia coli (ATCC 8739) and total coliform microorganisms, as indicators of microbiological contamination of water, were chosen to achieve the disinfection of synthetic wastewater or municipal wastewater. Ammonium (NH₄⁺) and chloride (Cl⁻) ions were added to the synthetic wastewater as an interfering chemical species on the disinfection processes. The antibacterial activity of the ZSAg as a bactericide was measured by the coliform concentration as evaluated by the APHA method. The amount of silver in the disinfected effluents was determined using atomic absorption spectroscopy. The inactivation of the ZSAg was calculated from the breakthrough curves based on the model reported by Gupta et al. It was found that when the silver concentration in the effluent is less than 0.6 μg/mL, the bacterial survival percentage increased and the volume of disinfected water diminished. The total silver amounts found in the effluent at the end of the disinfection processes varied depending on the water treated (synthetic or municipal wastewater). The presence of NH₄⁺ ions in synthetic wastewater influent notably improved the disinfected water volume (zero NVC/100 mL), in comparison to the disinfection of the same influent without NH₄⁺ ions. A contrary water disinfection behavior was observed in the presence of Cl⁻ ions. The silver recovery does not depend on the mass of the sodium zeolitic bed according with the wastewater to be treated (synthetic or municipal wastewater) and the presence of NH₄⁺ or Cl⁻ ions in the influent also influenced the silver recovery from wastewater. The ZSNa did not have antibacterial activity. Therefore the amount of bactericide agent (silver-modified natural zeolite), coliform microorganisms from water (E. coli or consort of coliform microorganisms) as well as the water quality (synthetic wastewater or municipal wastewater) influenced both the disinfection process and the silver recovery in a column system.     

Inverse modeling of multicomponent reactive transport through single and dual porosity media

Compacted bentonite is foreseen as buffer material for high-level radioactive waste in deep geological repositories because it provides hydraulic isolation, chemical stability, and radionuclide sorption. A wide range of laboratory tests were performed within the framework of FEBEX (Full-scale Engineered Barrier EXperiment) project to characterize buffer properties and develop numerical models for FEBEX bentonite. Here we present inverse single and dual-continuum multicomponent reactive transport models of a long-term permeation test performed on a 2.5 cm long sample of FEBEX bentonite. Initial saline bentonite porewater was flushed with 5.5 pore volumes of fresh granitic water. Water flux and chemical composition of effluent waters were monitored during almost 4 years. The model accounts for solute advection and diffusion and geochemical reactions such as aqueous complexation, acid-base, cation exchange, protonation/deprotonation by surface complexation and dissolution/precipitation of calcite, chalcedony and gypsum. All of these processes are assumed at local equilibrium. Similar to previous studies of bentonite porewater chemistry on batch systems which attest the relevance of protonation/deprotonation on buffering pH, our results confirm that protonation/deprotonation is a key process in maintaining a stable pH under dynamic transport conditions. Breakthrough curves of reactive species are more sensitive to initial porewater concentration than to effective diffusion coefficient. Optimum estimates of initial porewater chemistry of saturated compacted FEBEX bentonite are obtained by solving the inverse problem of multicomponent reactive transport. While the single-continuum model reproduces the trends of measured data for most chemical species, it fails to match properly the long tails of most breakthrough curves. Such limitation is overcome by resorting to a dual-continuum reactive transport model.     

Chemosensory discrimination of familiar and unfamiliar conspecifics by lizards: implications of field spatial relationships between males

The ability of territorial lizards to discriminate between scents of neighbors and non-neighbors might contribute to decreasing the costs of aggressive interactions. To test this hypothesis, we conducted a field study to analyze the spatial relationships between male Iberian rock-lizards, Lacerta monticola. We then used the same individuals in a laboratory experiment to test whether male lizards can use chemical cues to discriminate between familiar conspecific males (those whose home ranges overlapped) and unfamiliar conspecific males (those whose home ranges did not overlap, and whose home range centers were at least 50 m apart). Differences in tongue-flick rates in the presence of chemical cues suggested that male L. monticola discriminated between odors of familiar and unfamiliar males. The behavioral responses were also dependent on relative differences in body size between the responding male and the unfamiliar male that donated the scent: There was a significant negative correlation between tongue-flick rates emitted in cages of unfamiliar males and the body size differences between males. In contrast, when the donor of the scent was a familiar male, the tongue-flick rate was not dependent on body size differences. These results are compatible with individual discrimination through chemical cues in male L. monticola.