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.     

Chitosan/albumin/CaCO3 as mimics for membrane bioreactor fouling: genesis of structural mineralized-EPS-building blocks and cake layer compressibility

Membrane bioreactor biofouling is usually described as an extracellular matrix in which biopolymers, inorganic salts and active microbes co-exist. For that reason, biomineralization (BM) models can be useful to describe the spatial organization and environmental constraints within the referred scenario. BM arguments were utilized as background in order to (1) evaluate CaCO₃ influence on flux decline; pore blocking and cake layer properties (resistance, permeability and compressibility) in a wide range of Chitosan/Bovine serum albumin (BSA) mixtures during step-pressure runs and, (2) perform membrane autopsies in order to explore the genesis of mineralized extracellular building blocks (MEBB) during cake layer build up. Using low molecular weight chitosan (LC) and BSA, 2 L of 5 LC/BSA mixtures (0.25-1.85 ratio) were pumped to an external ultra filtration (UF) membrane (23.5 cm², hydrophobic, piezoelectric, 100 kDa as molecular weight cut-off). Eight different pressure steps (40 ± 7 to 540 ± 21 kPa) were applied. Each pressure step was held for 900 s. CaCO₃ was added to LC/BSA mixtures at 0.5, 1.5 and 3 mM in order to create MEBB during the filtration tests. Membrane autopsies were performed after the filtration tests using thermo gravimetric, scanning microscopy and specific membrane mass (mg cm⁻²) analyses. Biopolymer-CaCO₃ step-pressure filtration created compressible cake layers (with inner voids). The formation of an internal skeleton of MEBB may contribute to irreversible fouling consolidation. A hypothesis for MEBB genesis and development was set forth.     

Phenol depletion by thermally activated peroxydisulfate at 70°C

The ability of thermal activated peroxydisulfate (PS) of mineralizing phenol at 70 °C from contaminated waters is investigated. Phenol in concentrations of 10⁻⁴ to 5 × 10⁻⁴ M is quantitatively depleted by 5 × 10⁻³ to 10⁻² M activated PS in 15 min of reaction. However, mineralization of the organic carbon is not observed. Instead, an insoluble phenol polymer-type product is formed. A reaction mechanism including the formation of phenoxyl radicals and validated by computer simulations is proposed. High molecular weight phenolic products are formed by phenoxyl radical H-abstraction reactions. This is not the case for the room temperature degradation of phenol by sulfate radicals where sulfate addition to the aromatic ring mainly leads to the generation of hydroxycyclohexadienyl radicals leading to hydroxybenzenes and oxidized open chain products. Therefore, a change in the reaction mechanism is observed with increasing temperature, and thermal activation of PS at 70 °C does not lead to the mineralization of phenol. Thus PS activation at 70 °C may be considered a potential method to reduce the load of phenol in polluted waters by polymerization.     

A national inventory to estimate release of polychlorinated dibenzo-p-dioxins and dibenzofurans in Portugal

Taking into account current environmental concerns, the main objective of this work focused a national inventory aiming to estimate the amount of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF) released in Portugal in 2006. The methodology used was based on the Standardized Toolkit for Identification and Quantification of Dioxins and Furan Releases, developed by UNEP Chemicals, in 2005. The method allows the assessment of the amount of PCDD/PCDF released into the environment along five vectors involving air, water, land, products and residues. Facing some difficulties mainly regarding to the availability of data for some activities known to produce PCDD/PCDF, three scenarios (Sc1 to Sc3) corresponding to lower, central and upper estimates were established. The Sc1 scenario (lower estimate) includes the situations where in case of doubt or scarce information, reduced or none emission values were assumed, Sc2 refers to a central estimate, which is believed to be the most realistic for the Portuguese situation, while Sc3 corresponds to the worst case (upper estimate). The results obtained pointed out that the total amount of PCDD/PCDF emitted in Portugal during the period under analysis was in the range of 51.2-217.9 g TEQ year⁻¹, with the most likely value of 95.2 g TEQ year⁻¹ achieved under the Sc2 scenario. This study also showed that the methodology developed by UNEP Chemicals is a very simple one, and the main difficulty is the availability of data. The main indicators calculated in this study were 8.98 μg TEQ/(year person) by taking into account the total amount of PCDD/PCDF released, and 3.63 μg TEQ/(year person) when only air emissions were considered.     

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.     

Salinity increases mobility of heavy metals in soils

The effect of salinity induced by CaCl₂, MgCl₂, NaCl and Na₂SO₄ on the mobility of Cu, Cd, Pb and Zn was studied. An increase of ionic strength by any salts promoted a higher release of Cd than the others metals. When CaCl₂ and NaCl were applied, Cd and Pb showed the highest degree of mobilization. When MgCl₂ was applied, Cd and Cu were mobilized the most. Finally, an increase of Na₂SO₄ also promoted the strongest mobilization of Cd and Cu.As the total heavy metal content was higher, the percentage of Pb and Cu released upon salinization decreased, indicating that these metals are strongly bound to soil constituents. An increase of carbonates in the soil promoted a higher release of Pb for all used salts and for Zn when MgCl₂ and NaCl were used. This indicates that Pb and Zn are adsorbed on the surface of carbonate crystals. An increase of fine particles promoted a decrease of percentage of released Cd for all salts, indicating that Cd is strongly retained in the fine fractions.The main mechanism regulating Pb and Cd mobility was competition with Ca²⁺ for sorption sites followed for metal chloro-complexation, association between the Cd/Pb-sulfates and competition with Mg²⁺. The main mechanism regulating Cu mobility was the formation of Cu-sulfate, followed by competition with cations (Mg > Ca) and chloride. For Zn, competition with Ca²⁺ for sorption sites was the most important process for its mobility; followed by Zn-sulfate association and, finally, chloride and competition with Mg with the same effect.     

Socio-cultural valuation of ecosystem services in a transhumance social-ecological network

The ecosystem services framework is receiving increasing attention in the fields of policy and research. The assessment of human attitudes and perceptions regarding ecosystem services has been proposed as a promising tool for addressing complex problems associated with environmental change, particularly in the context of cultural landscapes. Transhumance is not only a farming practice responsible for shaping cultural landscapes but also an adaptive strategy based on mobility that may represent a useful approach to overcoming the growing challenges posed by accelerated environmental change. A socio-cultural valuation of ecosystem services associated with the Conquense Drove Road, one of the major transhumant networks still in use in Mediterranean Spain, was conducted via the distribution of questionnaires to 416 local residents and visitors to capture their perceptions regarding the importance of 34 ecosystem services (10 provisioning, 12 regulating, and 12 cultural) for both social and personal well-being. Overall, the ecosystem services considered to be the most important for social well-being were fire prevention, air purification and livestock. Most of the ecosystem services in question were perceived as declining, with the exception of those associated with recreation, scientific knowledge and environmental education. This study revealed that perceptions regarding the value of ecosystem services differed among respondents, depending on their age, place of origin and gender. Several methodological issues, as well as the implications of socio-cultural valuation for policy making, are also discussed here.     

Spatial variability of precipitation in Spain

The spatial variability of annual and seasonal precipitation in the conterminous land of Spain has been evaluated by using correlation decay distance analysis (CDD). The CDD analysis essentially explores how the correlation between neighbouring stations varies according to distance. We analysed CDD independently for the decades 1956–1965, 1966–1975, 1976–1985, 1986–1995, and 1996–2005 using only those stations with no missing values for each decade. To this end, 972, 1,174, 1,242, 773 and 695 complete series were used for each decade, respectively. In particular, for each station and decade, we calculated the threshold distance at which the common variance between target (i) and neighbour series is higher than 50 % (r ²  = 0.5) to evaluate whether current density of the climate data set captures the spatial variability of precipitation within the study area. Results indicate that, at an annual scale, neighbouring stations with 50 % of common variance are restricted on average to about 105 km, but this distance can vary from 28 to 251 km within the study area. The lowest variability is located to the SW and in winter, while the higher spatial variability is found to the north, in the Cantabrian area, and to the east, in the Mediterranean and Pyrenees, during summer. Our results suggest that current density of climate stations (those operating in 2005) is good enough to study precipitation variability at an annual scale for winter, spring and autumn, but not enough for summer.     

Looking beyond the average agricultural impacts in defining adaptation needs in Europe

The effects of climate change on agriculture are often characterised by changes in the average productivity of crops; however, these indicators provide limited information regarding the risks associated with fluctuations in productivity resulting from future changes in climate variability that may also affect agriculture. In this context, this study evaluates the combined effects of the risks associated with anomalies reflected by changes in the mean crop yield and the variability of productivity in European agro-climatic regions under future climate change scenarios. The objective of this study is to evaluate adaptation needs and to identify regional effects that should be addressed with greater urgency in the light of the risks and opportunities that are identified. The results show differential effects on regional agriculture and highlight the importance of considering both regional average impacts and the variability in crop productivity in setting priorities for the adaptation and maintenance of rural incomes and agricultural insurance programmes.     

Agricultural adjustment,population dynamics and forests redistribution in a subtropical watershed of NW Argentina

Patterns of land-use and land-cover change are usually grouped into one of two categories defined by the dominant trend: (1) deforestation resulting from expanding agriculture and (2) forest expansion, usually related to the abandonment of marginal lands. At regional scale, however, both processes can occur simultaneously even in the absence of net change. Given the focus on net change, such redistribution of agricultural and natural and seminatural lands has been generally overlooked. The interaction between agriculture modernization, human demography and complex topographic gradients of northwestern Argentina has resulted in processes of both forest recovery and deforestation, thus providing the opportunity to analyze patterns and driving forces of land-cover redistribution. We analyzed 20 years (1986–2006) of land-cover change in a subtropical watershed in relation to topographic and demographic variables. Although net forest change represented <1 %, forests redistribution affected 7 % of forest lands. There was a consistent geographic segregation of deforestation and forest recovery, with forests expanding over steep highlands and agriculture expanding over lowland irrigated areas. Population trends were not associated to forest expansion in lowlands but they explained 32 % of forest recovery in highlands. Highland forest expansion and lowland deforestation, respectively, imply conservation opportunities for humid montane forests and the environmental services they provide (e.g., watershed conservation) and threats for the conservation of dry forests and its biodiversity. Our study exemplifies the importance of land-use redistribution (rather than net change) with relevant environmental consequences at regional scale.