Photophysical and photochemical properties of the pharmaceutical compound salbutamol in aqueous solutions

Salbutamol is a potent β₂-adrenergic receptor agonist widely used in the treatment of bronchial asthma and chronic obstructive pulmonary disease. An increasing number of studies have detected salbutamol in natural water systems worldwide. Studies have shown that sunlight degrades salbutamol resulting in the formation of products; some showing higher toxicity to bacteria Vibrio fischeri than the parent compound. In this contribution, steady-state absorption and emission techniques, high-performance liquid chromatography, and transient absorption spectroscopy are used to investigate the photochemistry of salbutamol in aqueous buffer solutions at controlled pH values. Ground- and excited-state calculations that include solvent effects are performed to guide the interpretation of the experimental results. Salbutamol is sensitive to UVB light absorption in the pH range from 3 to 12, forming products that absorb light at longer wavelengths than the parent compound. Quantum yields of degradation reveal that the deprotonated species is 10-fold more photo-active than the protonated species. In line with this result, the fluorescence quantum yield of the protonated species is more than an order of magnitude higher than that of the deprotonated species. Transient absorption spectroscopy shows that population of the triplet state occurs with a rate constant of 7.1 × 10⁸ s⁻¹ in the protonated species, while a rate constant of 1.7 × 10¹⁰ s⁻¹ is measured for the deprotonated species. While degradation of the deprotonated species is not affected by the presence of molecular oxygen, a twofold increase in the photodegradation yield of the protonated species in air-saturated conditions is observed.     

Transport of chlorinated dioxins and furans in soil columns: modeling pentachlorophenol pole-treating oil influence

Column experiments were conducted to validate a screening model predicting the influence of pentachlorophenol (PCP) pole-treating oil on the vertical migration of its impurities, chlorinated dioxins and furans (PCDD/Fs). PCP pole-treating oil (15 mL d⁻¹) and water (20 mL d⁻¹) were added daily to the top of sand and organic soil columns during 35 d. Column soil samples were analyzed to determine concentrations of hydrocarbons and PCDD/Fs at several depths in the columns (0-30 cm) and their evolution in time (7, 14, 21 and 35 d).The model predicted a significant vertical migration of PCDD/Fs due to the presence of oil as a free phase and PCDD/Fs were found in the different column layers at concentrations consistent with model predictions (same order of magnitude). Measured PCDD/Fs concentrations are in total disagreement with literature data and with model prediction in the absence of oil free phase, which implies PCDD/F properties alone cannot be used to predict their fate in the current context: the influence of PCP pole-treating oil must be accounted for to properly explain their migration.     

Biodegradation of aromatic hydrocarbons by Haloarchaea and their use for the reduction of the chemical oxygen demand of hypersaline petroleum produced water

Ten halophilic Archaea (Haloarchaea) strains able to degrade aromatic compounds were isolated from five hypersaline locations; salt marshes in the Uyuni salt flats in Bolivia, crystallizer ponds in Chile and Cabo Rojo (Puerto Rico), and sabkhas (salt flats) in the Persian Gulf (Saudi Arabia) and the Dead Sea (Israel and Jordan). Phylogenetic identification of the isolates was determined by 16S rRNA gene sequence analysis. The isolated Haloarchaea strains were able to grow on a mixture of benzoic acid, p-hydroxybenzoic acid, and salicylic acid (1.5 mM each) and a mixture of the polycyclic aromatic hydrocarbons, naphthalene, anthracene, phenanthrene, pyrene and benzo[a]anthracene (0.3 mM each). Evaluation of the extent of degradation of the mixed aromatic hydrocarbons demonstrated that the isolates could degrade these compounds in hypersaline media containing 20% NaCl. The strains were shown to reduce the COD of hypersaline crude oil reservoir produced waters significantly beyond that achieved using standard hydrogen peroxide treatment alone.     

Remediation of metal-contaminated soils with the addition of materials--part I: characterization and viability studies for the selection of non-hazardous waste materials and silicates

Contamination episodes in soils require interventions to attenuate their impact. These actions are often based on the addition of materials to increase contaminant retention in the soil and to dilute the contaminant concentration. Here, non-hazardous wastes (such as sugar foam, fly ash and a material produced by the zeolitization of fly ash) and silicates (including bentonites) were tested and fully characterized in the laboratory to select suitable materials for remediating metal-contaminated soils. Data from X-ray fluorescence (XRF), N₂ adsorption/desorption isotherms, X-ray diffraction (XRD) and scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM-EDX) analyses revealed the chemical composition, specific surface area and the phases appearing in the materials. A pH titration test allowed the calculation of their acid neutralization capacity (ANC). The metal sorption and desorption capacities of the waste materials and silicates were also estimated. Sugar foam, fly ash and the zeolitic material were the best candidate materials. Sugar foam was selected because of its high ANC (17 000 meq kg⁻¹), and the others were selected because of their larger distribution coefficients and lower sorption reversibilities than those predicted in the contaminated soils.     

Two‐dimensional transport of lactate‐modified nanoscale iron particles in porous media

This study investigates the two‐dimensional transport of nanoscale iron particles (NIP) and lactate‐modified NIP (LMNIP) in homogeneous and heterogeneous porous media under typical pressurized groundwater flow conditions. A two‐dimensional bench‐scale test setup was developed and a series of experiments was conducted simulating homogeneous sand profile and two‐layer profile with two different sands. NIP and LMNIP at a concentration of 4 g/L were prepared in electrolyte simulating groundwater conditions and were injected at the inlet of the test setup under different pressure gradients (0.5. 0.8, 1, and 2 pounds per square inch). During the testing, effluent was collected and its volume and nanoiron concentrations were measured. At the end of the testing, soil cores were obtained at different distances from the inlet and were used to measure nanoiron concentrations and magnetic susceptibility values. Results showed that the transport of NIP and LMNIP was enhanced by increased pressure gradient. LMNIP transport occurred more uniformly as compared to bare NIP. The iron concentrations decreased with distance from the inlet to the outlet and increased from the top to the bottom of the test cell. The data indicate that, as the particles were transported, they underwent aggregation and sedimentation, which resulted in the observed non‐uniform spatial distribution of iron. The NIP and LMNIP transported through the high‐porosity and high‐permeability soil layer in the heterogeneous soil profile, implying that the transport occurred predominantly along the path of least resistance for the flow. Magnetic susceptibility values are found to have good correlation with the iron content in the soil and are helpful to characterize the transport of NIP and LMNIP. Overall, this study shows that the non‐uniform distribution of NIP and LMNIP occurs under two‐dimensional transport conditions and the soil heterogeneities can significantly impact the transport of NIP and LMNIP. The design of field delivery systems should consider such conditions and optimize the pressurized injection systems. © 2011 Wiley Periodicals, Inc.     

Climate change impacts on vegetation and water cycle in the Euro-Mediterranean region,studied by a likelihood approach

Scientific community and policy-makers share the common interest in identifying and evaluating potential impacts of climate change on ecosystems, relying mainly on probabilistic methods of exploring the risks. In this perspective, the concept of ensemble forecasting makes possible to handle uncertainties associated with climate risk analysis by focusing on a range of potential or probable impact scenarios rather than actualizing a single case. In this paper, an ensemble of simulations based on the Lund-Potsdam-Jena (LPJ) model was used to investigate the uncertainty upon predictions of the future Euro-Mediterranean vegetation distribution, carbon dynamics, and water budget. Twenty simulations from past to future were based on the combination of different climate inputs, vegetation model parameterizations, and configurations. The evaluation of results combined the separate deterministic future projections from the LPJ model into a single probabilistic projection, associating a likelihood degree in accordance with the most recent Intergovernmental Panel on Climate Change terminology. Results projected a general critical situation in terms of water availability, made more serious if considering that also the occurrence of extreme-related events, e.g., fires, is expected to become more frequent as favored by more recurrent drought episodes. Although more uncomfortable climate conditions were projected for vegetation, net primary production (NPP) was predicted to increase due to the potential enrichment of CO₂ in atmosphere and its fertilization effects on vegetation. The combination of rising NPP and fire frequency may shape the carbon cycle components, as the carbon losses by fire also were projected to increase.