Kinetic behavior of anti-inflammatory drug ibuprofen in aqueous medium during its degradation by electrochemical advanced oxidation

The electrochemical abatement of the drug ibuprofen (2-(4-isobutylphenyl)propionic acid) from aqueous solution has been carried out by anodic oxidation. The electrolyses have been performed at constant current using a small, undivided cell equipped with a Pt or thin-film boron-doped diamond (BDD) anode and a carbon-felt cathode. The results have shown that ibuprofen has been destroyed under all the conditions tested, following pseudo-first-order kinetics; however, BDD enables higher removal rates than Pt, because the former produces greater quantity of ^?OH. Using BDD anode, the pseudo-first-order rate constant increased with applied current and when NaCl replaced Na₂SO₄ as supporting electrolyte, while it is almost unaffected by ibuprofen concentration. Mineralization of ibuprofen aqueous solutions was followed by total organic carbon (TOC) measurements. After 8 h of electrolysis, TOC removal varied from 91 % to 96 % applying a current in the range of 50–500 mA. The reaction by-products were quantified by chromatographic techniques, and in particular, aliphatic acids (oxalic, glyoxylic, formic, acetic, and pyruvic) have been the main intermediates formed during the electrolyses. The absolute rate constant for the oxidative degradation of ibuprofen have also been determined, by competition kinetic method, as 6.41?×?10⁹ M^?1?s^?1.     

Nutrient leaching in a Colombian savanna Oxisol amended with biochar

Nutrient leaching in highly weathered tropical soils often poses a challenge for crop production. We investigated the effects of applying 20 t ha biochar (BC) to a Colombian savanna Oxisol on soil hydrology and nutrient leaching in field experiments. Measurements were made over the third and fourth years after a single BC application. Nutrient contents in the soil solution were measured under one maize and one soybean crop each year that were routinely fertilized with mineral fertilizers. Leaching by unsaturated water flux was calculated using soil solution sampled with suction cup lysimeters and water flux estimates generated by the model HYDRUS 1-D. No significant difference ( > 0.05) was observed in surface-saturated hydraulic conductivity or soil water retention curves, resulting in no relevant changes in water percolation after BC additions in the studied soils. However, due to differences in soil solution concentrations, leaching of inorganic N, Ca, Mg, and K measured up to a depth of 0.6 m increased ( < 0.05), whereas P leaching decreased, and leaching of all nutrients (except P) at a depth of 1.2 m was significantly reduced with BC application. Changes in leaching at 2.0 m depth with BC additions were about one order of magnitude lower than at other depths, except for P. Biochar applications increased soil solution concentrations and downward movement of nutrients in the root zone and decreased leaching of Ca, Mg, and Sr at 1.2 m, possibly by a combination of retention and crop nutrient uptake.     

Carbon deposition in soil rhizosphere following amendments with compost and its soluble fractions, as evaluated by combined soil-plant rhizobox and reporter gene systems

We determined the organic carbon released by roots of maize plants (Zea mays L.) when grown in soils amended with compost and its soluble fractions. In rhizobox systems, soil and roots are separated from the soil of a lower compartment by a nylon membrane. Treatments are applied to the upper compartment, while in the lower compartment luminescent biosensors measure the bioavailable organic carbon released by roots (rhizodeposition). The rhizobox-plants systems were amended with a compost (COM), its water extract (TEA), the hydrophobic (HoDOM) and hydrophilic (HiDOM) fractions of the dissolved organic matter (DOM) extracted from the compost. After root development, the lower untreated compartments were sampled and sliced into thin layers. The bioavailable organic carbon in each layer was assessed with the lux-marked biosensor Pseudomonas fluorescens 10586 pUCD607, and compared with total organic carbon (TOC) analyses. The TOC values ranged between 8.4 and 9.6 g kg(-1) and did not show any significant differences between bulk and rhizosphere soil samples in any treatment. Conversely, the biosensor detected significant differences in available C compounds for rhizosphere soils amended with various organic materials. Concentrations of available organic compounds in the first 2 mm of soil rhizosphere were 1.69 (control), 1.09 (COM), 2.87 (HiDOM), 4.73 (HoDOM) and 2.14 (TEA)micromol Cg(-1) soil g(-1) roots. The applied rhizobox-biosensor integrated method was successful in detecting and quantifying effects of organic amendments on organic carbon released by maize plant roots. This approach may become important in assessing the carbon cycle in agricultural soils and soil-atmosphere compartments.     

A comparison of sediment quality guidelines for toxicity assessment in the Sunderban wetlands (Bay of Bengal, India)

The aim of this paper was to obtain the first screening ecotoxicological risk evaluation in the Sunderban wetlands, the largest prograding delta in the estuarine phase of the River Ganges. The characterization of exposure was conducted by means of an extensive survey of several persistent organic pollutants (PAHs, PCBs, DDTs, PBDEs, HCHs, HCB) measured in seven core sediments from the Sunderban wetlands, obtaining a dataset with more than 2200 analyses. The pollutant effects were assessed by the use of three different sediment quality guidelines (SQGs) previously developed in the literature to evaluate toxicity induced in sediment-dwelling organisms. The three different approaches chosen for risk assessment of the Sunderban were the consensus SQGs obtained by TEC (threshold effect concentration), PEC (probable effect concentration) and EEC (extreme effect concentration), the threshold/probable effect level (TEL/PEL) approach and, finally, the ERL-ERM guidelines, including the m-ERM-Q (mean ERM quotient). The evaluation of the toxicity induced by a mixture of the target pollutants indicated the importance of gamma-HCH contamination in the Sunderban sediments despite the very low concentrations measured in core sediments. A different sensitivity for toxicity assessment due to quality guidelines was obtained, as the consensus SQGs based on TEC were less conservative and protective than the TEL and ERL approaches, while the use of m-ERM-Q seems to be the most powerful tool to predict the toxicity related to a contaminant mixture.     

Avian Conservation under the Endangered Species Act: Expenditures versus Recovery Priorities

Abstract: Budget constraints require the U.S. Fish and Wildlife Service to prioritize species for recovery spending. Each listed species is ranked according to the degree of threat it faces, its recovery potential, and its taxonomic distinctness. We analyzed state and federal government expenditures for recovery of threatened and endangered birds ( n = 85 species) from 1992 to 1995 to determine if the priority system was being followed. Although recovery spending correlated with priority rank, priority rank explained <5% of the variation in spending. A small number of the same moderately ranked species dominated expenditures each year (41–79% of total annual budgets). Species with wide distributions, high recovery potential, and captive breeding programs received the most funding, and more funding than their priority ranks dictated. Island species received significantly less funding than expected based on priority rank. Twelve species, 10 of which resided on islands, received <$5000 at least once from 1992 to 1995. Recovery spending was unrelated to degree of threat, taxonomic distinctness, and migratory status. There also was no relationship between land-purchase expenditures and priority ranks. To improve the relationship between recovery spending on threatened and endangered birds and their priority rank, significant changes need to be made within the private sector ( less litigation and special-interest lobbying  ), U.S. Congress (increased budget and reduced earmarking  ), and the U.S. Fish and Wildlife Service (restructuring of regional offices and increased accountability).     

Sellers' Hedging Incentives at EPA's Emission Trading Auction

Cason (1993, J. Environ. Econom. Management25, 177–195, doi:10.1006/jeem 1993.1041) argued that the auction which the EPA used in order to start the market for sulfur allowances may reduce the efficiency of the market since it gives sellers an incentive to understate their valuation. In this paper we show that the sellers' incentives are even more perverse than Cason suggested when we take into account that sellers can also submit a bid. We show that sellers have an incentive to set their asking price equal to 0 while simultaneously hedging their bets by submitting a positive bid.     

Monitoring of marine mucilage formation in Italian seas investigated by infrared spectroscopy and independent component analysis

The aim of this study is to present and to discuss some characteristics of recalcitrant organic matter mechanism and formation. These aggregates called mucilages that are produced by the degradation reactions of several algae, have been investigated by infrared (FTIR) spectroscopy. FTIR spectra of macroaggregates produced by different algal samples have been daily collected in order to investigate the steps of aggregation. Afterwards, they have been elaborated by means of Independent Component Analysis (ICA). ICA investigation of FTIR spectra showed that the global aggregation process of marine mucilage always consisted of two different phases or independent components (ICs). One IC is related to the first degradation step of algal cells leading to the production of mono and oligosaccharides with aminoacids and oligopeptides. The second IC is related to the polymerization of oligosaccharides with aminoacids and oligopeptides and to their interaction with less polar compounds such as lipids thus producing supramolecular structures. The emerging mechanisms of anomalous size aggregates of organic matter match those of natural organic matter aggregation. The approach we suggest is to use synthetic mucilages which allows to monitor the macroaggregates formation because it can hardly be performed by means of natural marine macroaggregates.     

The BIOTA Biodiversity Observatories in Africa—a standardized framework for large-scale environmental monitoring

The international, interdisciplinary biodiversity research project BIOTA AFRICA initiated a standardized biodiversity monitoring network along climatic gradients across the African continent. Due to an identified lack of adequate monitoring designs, BIOTA AFRICA developed and implemented the standardized BIOTA Biodiversity Observatories, that meet the following criteria (a) enable long-term monitoring of biodiversity, potential driving factors, and relevant indicators with adequate spatial and temporal resolution, (b) facilitate comparability of data generated within different ecosystems, (c) allow integration of many disciplines, (d) allow spatial up-scaling, and (e) be applicable within a network approach. A BIOTA Observatory encompasses an area of 1?km² and is subdivided into 100 1-ha plots. For meeting the needs of sampling of different organism groups, the hectare plot is again subdivided into standardized subplots, whose sizes follow a geometric series. To allow for different sampling intensities but at the same time to characterize the whole square kilometer, the number of hectare plots to be sampled depends on the requirements of the respective discipline. A hierarchical ranking of the hectare plots ensures that all disciplines monitor as many hectare plots jointly as possible. The BIOTA Observatory design assures repeated, multidisciplinary standardized inventories of biodiversity and its environmental drivers, including options for spatial up- and downscaling and different sampling intensities. BIOTA Observatories have been installed along climatic and landscape gradients in Morocco, West Africa, and southern Africa. In regions with varying land use, several BIOTA Observatories are situated close to each other to analyze management effects.     

A simple linear model for estimating ozone AOT40 at forest sites from raw passive sampling data

A rapid, empirical method is described for estimating weekly AOT40 from ozone concentrations measured with passive samplers at forest sites. The method is based on linear regression and was developed after three years of measurements in Trentino (northern Italy). It was tested against an independent set of data from passive sampler sites across Italy. It provides good weekly estimates compared with those measured by conventional monitors (0.85 ≤R(2)≤ 0.970; 97 ≤ RMSE ≤ 302). Estimates obtained using passive sampling at forest sites are comparable to those obtained by another estimation method based on modelling hourly concentrations (R(2) = 0.94; 131 ≤ RMSE ≤ 351). Regression coefficients of passive sampling are similar to those obtained with conventional monitors at forest sites. Testing against an independent dataset generated by passive sampling provided similar results (0.86 ≤R(2)≤ 0.99; 65 ≤ RMSE ≤ 478). Errors tend to accumulate when weekly AOT40 estimates are summed to obtain the total AOT40 over the May-July period, and the median deviation between the two estimation methods based on passive sampling is 11%. The method proposed does not require any assumptions, complex calculation or modelling technique, and can be useful when other estimation methods are not feasible, either in principle or in practice. However, the method is not useful when estimates of hourly concentrations are of interest.