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.     

Effects of the organophosphate insecticide azinphos-methyl on the reproduction and cholinesterase activity of Biomphalaria glabrata

Azinphos-methyl is an organophosphate insecticide used for pest control on a number of food crops in many parts of the world. The snail Biomphalaria glabrata is a freshwater gastropod widely distributed in South America, Central America and Africa. The aim of the present work was to investigate whether azinphos-methyl causes alterations in the reproduction of B. glabrata. To this end, gastropod pigmented specimens were exposed to various concentrations of the insecticide (0.021, 0.5, 2.5, and 5 mg L⁻¹) for either 2 or 14 d. Along 14 d, several reproduction parameters and cholinesterase (ChE) activity were evaluated. In each group, the number of egg masses, the number of eggs per mass, the number of hatchings, the time to hatching, and the survival of the offspring after one month of treatment was evaluated. The results showed that, depending on the concentration and time of exposure, azinphos-methyl induced alterations in the reproduction of B. glabrata. These alterations were mainly represented by a decrease in the number of egg masses, and, in some cases, by a lower number or even the total absence of hatchings. Thus, the gastropods exposed to 2.5 and 5 mg L⁻¹ of azinphos-methyl for 14 d showed ChE inhibitions higher than 35% along time and completely lost their ability to reproduce. On the other hand, exposure to high acute concentrations or exposure to low concentrations for 14 d resulted in ChE inhibition equal to or lower than 35% between 7 and 14 d of treatment and similar alterations in reproduction. These were represented by a decrease in the number of egg masses. At low pestice levels, the number of egg masses and the number of offspring resulted to be more sensitive biomarkers than ChE inhibition. It is concluded that the insecticide azinphos-methyl can cause a decline in the reproductive performance of B. glabrata.     

Biodegradable chelate enhances the phytoextraction of copper by Oenothera picensis grown in copper-contaminated acid soils

Oenothera picensis plants (Fragrant Evening Primrose) grow in the acid soils contaminated by copper smelting in the coastal region of central Chile. We evaluated the effects of the biodegradable chelate MGDA (methylglycinediacetic acid) on copper extraction by O. picensis and on leaching of copper through the soil profile, using an ex situ experiment with soil columns of varying heights. MGDA was applied in four rates: 0 (control), 2, 6 and 10 mmol plant⁻¹. MGDA application significantly increased biomass production and foliar concentration, permitting an effective increase in copper extraction, from 0.09 mg plant⁻¹ in the control, to 1.3 mg plant⁻¹ in the 6 and 10 mmol plant⁻¹ treatments. With 10 mmol plant⁻¹ rate of MGDA, the copper concentration in the leachate from the 30 cm columns was 20 times higher than in the control. For the 60 cm columns, copper concentration was 2 times higher than the control. It can be concluded that at increased soil depths, copper leaching would be minimal and that MGDA applications at the studied rates would not pose a high risk for leaching into groundwater. It can thus be stated that applications of MGDA are an effective and environmentally safe way to improve copper extraction by O. picensis in these soils.     

Assessment of oral bioaccessibility of arsenic in playground soil in Madrid (Spain): a three-method comparison and implications for risk assessment

Three methodologies to assess As bioaccessibility were evaluated using playground soil collected from 16 playgrounds in Madrid, Spain: two (Simplified Bioaccessibility Extraction Test: SBET, and hydrochloric acid-extraction: HCl) assess gastric-only bioaccessibility and the third (Physiologically Based Extraction Test: PBET) evaluates mouth-gastric-intestinal bioaccessibility. Aqua regia-extractable (pseudo total) As contents, which are routinely employed in risk assessments, were used as the reference to establish the following percentages of bioaccessibility: SBET - 63.1; HCl - 51.8; PBET - 41.6, the highest values associated with the gastric-only extractions. For Madrid playground soils - characterised by a very uniform, weakly alkaline pH, and low Fe oxide and organic matter contents - the statistical analysis of the results indicates that, in contrast with other studies, the highest percentage of As in the samples was bound to carbonates and/or present as calcium arsenate. As opposed to the As bound to Fe oxides, this As is readily released in the gastric environment as the carbonate matrix is decomposed and calcium arsenate is dissolved, but some of it is subsequently sequestered in unavailable forms as the pH is raised to 5.5 to mimic intestinal conditions. The HCl extraction can be used as a simple and reliable (i.e. low residual standard error) proxy for the more expensive, time consuming, and error-prone PBET methodology. The HCl method would essentially halve the estimate of carcinogenic risk for children playing in Madrid playground soils, providing a more representative value of associated risk than the pseudo-total concentrations used at present.     

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.     

Polychlorinated dibenzo-p-dioxin and dibenzofuran in urban air of an Andean city

Particle-bound polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in ambient air were monitored together with particulate matter less than 10 μm (PM₁₀) at three sampling sites of the Andean city of Manizales, Colombia; during September 2009 and July 2010. PCDD/Fs ambient air emissions ranged from 1 fg WHO-TEQ m⁻³ to 52 fg WHO-TEQ m⁻³ in particulate fraction. The PM₁₀ concentrations ranged from 23 μg m⁻³ to 54 μg m⁻³. Concentrations of PM₁₀ and PCDD/Fs in ambient air observed for Manizales - a medium sized city with a population of 380 000 - were comparable to concentrations in larger cities. The highest concentrations of PCDD/Fs and PM₁₀ found in this study were determined at the central zone of the city, characterized by public transportation density, where diesel as principal fuel is used. In addition, hypothetical gas fractions of PCDD/Fs were calculated from theoretical K_p data. Congener profiles of PCDD/Fs exhibited ratios associated with different combustion sources at the different sampling locations, ranging from steel recycling to gasoline and diesel engines. Taking into account particle and gas hypothetical fraction of PCDD/Fs, Manizales exhibited values of PCDD/Fs equivalent to rural and urban-industrial sites in the southeast and center of the city respectively. Poor correlation of PCDDs with PM₁₀ (r = −0.55 and r = 0.52) suggests ambient air PCDDs were derived from various combustion sources. Stronger correlation was observed of PCDFs with PM₁₀. Poor correlation between precipitation and reduced PM₁₀ concentration in ambient air (r = −0.45) suggested low PM₁₀ removal by rainfall.     

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.     

Temporal analysis of PM10 in Metropolitan Monterrey, México

The Monterrey Metropolitan Area (MMA) is the third largest city in Mexico. Few studies have been carried out regarding its air pollution. The aim of this study was to analyze the temporal behavior of PM10 (particulate matter < or =10 microm in aerodynamic diameter). Data reported by the "Sistema Integral de Monitoreo Ambiental" (Integrated Environmental Monitoring System) network from 2006 to 2008 were used. PM10 levels were compared among the stations by year, season, and day of week. A bootstrap technique was used to obtain subsamples to which Student's t test and ANOVA were applied. PM10 levels were high and exceeded the annual limit of 50 microg/m3 set up by the Mexican standard Norma Oficial Mexicana NOM-025-SSA1-1993. These levels could have serious health effects. The southwest zone of MMA had the highest levels of PM10 during the period studied. Winter was the most polluted season, and summer was the least polluted season. Thursday and Friday were the most polluted days, and Sunday was the least polluted day. The hours with the highest levels of PM10 were 8:00 to 10:00 a.m., whereas nighttime hours were the cleanest.