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.     

Biochemical biomarkers in Nile tilapia (Oreochromis niloticus) after short-term exposure to diesel oil, pure biodiesel and biodiesel blends

Fossil fuels such as diesel are being gradually replaced by biodiesel, a renewable energy source, cheaper and less polluting. However, little is known about the toxic effects of this new energy source on aquatic organisms. Thus, we evaluated biochemical biomarkers related to oxidative stress in Nile tilapia (Oreochromis niloticus) after two and seven exposure days to diesel and pure biodiesel (B100) and blends B5 and B20 at concentrations of 0.01 and 0.1 mL L⁻¹. The hepatic ethoxyresorufin-O-deethylase activity was highly induced in all groups, except for those animals exposed to B100. There was an increase in lipid peroxidation in liver and gills in the group exposed to the higher concentration of B5. All treatments caused a significant increase in the levels of 1-hydroxypyrene excreted in the bile after 2 and 7 d, except for those fish exposed to B100. The hepatic glutathione-S-transferase increased after 7 d in animals exposed to the higher concentration of diesel and in the gill of fish exposed to the higher concentration of pure diesel and B5, but decreased for the two tested concentrations of B100. Superoxide dismutase, catalase and glutathione peroxidase also presented significant changes according to the treatments for all groups, including B100. Biodiesel B20 in the conditions tested had fewer adverse effects than diesel and B5 for the Nile tilapia, and can be suggested as a less harmful fuel in substitution to diesel. However, even B100 could activate biochemical responses in fish, at the experimental conditions tested, indicating that this fuel can also represent a risk to the aquatic biota.     

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.     

Bromination of selected pharmaceuticals in water matrices

The bromination of five selected pharmaceuticals (metoprolol, naproxen, amoxicillin, phenacetin, and hydrochlorothiazide) was studied with these compounds individually dissolved in ultra-pure water. The apparent rate constants for the bromination reaction were determined as a function of the pH, obtaining the sequence amoxicillin > naproxen ? hydrochlorothiazide ≈ phenacetin ≈ metoprolol. A kinetic mechanism specifying the dissociation reactions and the species formed for each compound according to its pK_a value and the pH allowed the intrinsic rate constants to be determined for each elementary reaction. There was fairly good agreement between the experimental and calculated values of the apparent rate constants, confirming the goodness of the proposed reaction mechanism.In a second stage, the bromination of the selected pharmaceuticals simultaneously dissolved in three water matrices (a groundwater, a surface water from a public reservoir, and a secondary effluent from a WWTP) was investigated. The pharmaceutical elimination trend agreed with the previously determined rate constants. The influence of the main operating conditions (pH, initial bromine dose, and characteristics of the water matrix) on the degradation of the pharmaceuticals was established. An elimination concentration profile for each pharmaceutical in the water matrices was proposed based on the use of the previously evaluated apparent rate constants, and the theoretical results agreed satisfactorily with experiment. Finally, chlorination experiments performed in the presence of bromide showed that low bromide concentrations slightly accelerate the oxidation of the selected pharmaceuticals during chlorine disinfection.     

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.     

Dietary uptake of polybrominated diphenyl ethers (PBDEs), occurrence and profiles, in aquacultured turbots (Psetta maxima) from Galicia, Spain

Polybromodiphenyl ethers (PBDEs) are one of the many toxic chemicals present in the environment and in the food we eat every day, being fish one of the main sources of persistent organic pollutants in our diet; like other lipid-related contaminants, they are of concern since they can bioaccumulate and biomagnify through the trophic chain. We published a study focused on the dietary uptake of dioxins and furans (PCDD/Fs) and dioxin-like polychlorobiphenyls (dl-PCBs) in a set of samples of Spanish farmed turbot (Blanco et al., 2007). In the present paper, we extend the study to PBDEs to provide more information about the uptake and transfer from feed to fish of halogenated contaminants. PBDEs in the feeds (2.35-4.76 ng g(-1)) were reflected in turbot fillets (0.54-2.05 ng g(-1)): predominant congeners were tetra-BDE 47, penta-BDEs 99 and 100. It is remarkable that tetra-BDE 49, accounting for only 2% in the feed, contributed to 15% of total PBDEs in turbot fillets. Dietary net accumulation values, 30-45%, showed that tri-, tetra-, penta- and hexa-BDEs were as efficiently transferred into turbot as dl-PCBs and tetra- and penta-chlorinated PCDD/Fs. Lipid-normalized biomagnification factors relating concentration in fish and in feed, BMFs>1 were obtained, except for BDE 209. BDE 49 accumulation, 90%, was possibly contributed by metabolism of higher brominated BDEs. Implication in aquaculture management is a need for uncontaminated fish feed to offer safe products.     

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.     

Use of recycled fine aggregate in concretes with durable requirements

The use of construction waste materials as aggregates for concrete production is highly attractive compared to the use of non-renewable natural resources, promoting environmental protection and allowing the development of a new raw material. Several countries have recommendations for the use of recycled coarse aggregate in structural concrete, whereas the use of the fine fraction is limited because it may produce significant changes in some properties of concrete. However, during the last decade the use of recycled fine aggregates (RFA) has achieved a great international interest, mainly because of economic implications related to the shortage of natural sands suitable for the production of concrete, besides to allow an integral use of this type of waste. In this study, the durable behaviour of structural concretes made with different percentage of RFA (0%, 20%, and 30%) is evaluated. Different properties related to the durability of concretes such as absorption, sorptivity, water penetration under pressure, and carbonation are determined. In addition, the results of compressive strength, static modulus of elasticity and drying shrinkage are presented. The obtained results indicate that the recycled concretes have a suitable resistant and durable behaviour, according to the limits indicated by different international codes for structural concrete.     

Larvicidal and pupicidal activities of eco-friendly phenolic lipid products from Anacardium occidentale nutshell against arbovirus vectors

Environmental Science and Pollution Research - Aedes aegypti and Culex quinquefasciatus are vectors of diseases that constitute public health problems. The discovery of products capable of...