Polymer biodegradation: mechanisms and estimation techniques

Within the frame of the sustainable development, new materials are being conceived in order to increase their biodegradability properties. Biodegradation is considered to take place throughout three stages: biodeterioration, biofragmentation and assimilation, without neglect the participation of abiotic factors. However, most of the techniques used by researchers in this area are inadequate to provide evidence of the final stage: assimilation. In this review, we describe the different stages of biodegradation and we state several techniques used by some authors working in this domain. Validate assimilation (including mineralisation) is an important aspect to guarantee the real biodegradability of items of consumption (in particular friendly environmental new materials). The aim of this review is to emphasise the importance of measure as well as possible, the last stage of the biodegradation, in order to certify the integration of new materials into the biogeochemical cycles. Finally, we give a perspective to use the natural labelling of stable isotopes in the environment, by means of a new methodology based on the isotopic fractionation to validate assimilation by microorganisms.     

Photodegradation of the steroid hormones 17beta-estradiol (E2) and 17alpha-ethinylestradiol (EE2) in dilute aqueous solution

The photochemical transformation of natural estrogenic steroid 17beta-estradiol (E2) and the synthetic oral contraceptive 17alpha-ethinylestradiol (EE2) has been studied in dilute non buffered aqueous solution (pH 5.5-6.0) upon monochromatic (254 nm) and polychromatic (lambda>290 nm) irradiation. Upon irradiation at 254 nm, the quantum yields of E2 and EE2 photolysis were similar and evaluated to be 0.067+/-0.007 and 0.062+/-0.007, respectively. Upon polychromatic excitation, and by using phenol as chemical actinometer, the photolysis efficiencies have been determined to be 0.07+/-0.01 and 0.08+/-0.01 for E2 and EE2, respectively. For both estrogens, photodegradation by-products were identified with GC/MS and LC/MS. In a first step, a model compound--5,6,7,8-tetrahydro-2-naphthol (THN)--, which represents the photoactive phenolic group, was used to obtain basic photoproduct structural informations. Numerous primary and secondary products were observed, corresponding to hydroxylated phenolic- or quinone-type compounds.     

Polycyclic aromatic hydrocarbon sampling in wastewaters using semipermeable membrane devices: accuracy of time-weighted average concentration estimations of truly dissolved compounds

Semipermeable membrane devices (SPMDs) previously spiked with performance reference compounds were exposed in wastewater. After 6 days of exposure, 13 polycyclic aromatic hydrocarbons (PAHs) were quantified in SPMDs. Exchange rate constants and time-weighted average (TWA) concentrations of SPMD-available PAHs in water were calculated. The bias of using SPMDs to estimate an actual TWA concentration if the concentration in water fluctuates, as can be expected in wastewater, was studied with numerical simulations. The bias increased with the exchange rate constant. However, most exchange rate constants evaluated in SPMDs exposed in wastewater were small enough for SPMDs to estimate a TWA concentration of PAHs even when the water concentration varied. TWA-SPMD-available concentrations were always below total dissolved (operationally defined as 0.7 microm) concentrations, indicating that part of the dissolved PAHs was not available for sampling. In situ partitioning coefficients K(DOC) were computed and found to be slightly higher than data from the literature. This confirms that only truly dissolved PAHs should be sampled by SPMDs in wastewater.     

Monitoring PCDD/Fs, PCBs and metals in the ambient air of an industrial area of Catalonia, Spain

In 2005 and 2006, the levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and metals (As, Be, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sn, Tl and V) were measured in air samples collected in an industrial area of Sant Adrià del Besòs (Barcelona, Catalonia, Spain) where a municipal solid waste incinerator (MSWI) is placed, and in a background/control area. In general terms, concentrations of all environmental pollutants were higher at the industrial site. No significant seasonal/temporal variations were observed in any of the areas. No Pearson correlation was found between the PCDD/F concentrations and the environmental conditions of the two sampling periods considered. Principal component analyses (PCA) were performed to get information on the relationship among samples, pollutants, and emission sources. The results indicate that the MSWI of S. Adrià de Besòs is not a significant emission source of the above compounds for the area under its direct influence. Moreover, a notable difference in the PCDD/F congener profiles was found between ambient air and stack gas emissions, indicating that the current levels of PCDD/Fs are more related to other potential emissions sources rather than to those from the MSWI.     

Inverse modeling of multicomponent reactive transport through single and dual porosity media

Compacted bentonite is foreseen as buffer material for high-level radioactive waste in deep geological repositories because it provides hydraulic isolation, chemical stability, and radionuclide sorption. A wide range of laboratory tests were performed within the framework of FEBEX (Full-scale Engineered Barrier EXperiment) project to characterize buffer properties and develop numerical models for FEBEX bentonite. Here we present inverse single and dual-continuum multicomponent reactive transport models of a long-term permeation test performed on a 2.5 cm long sample of FEBEX bentonite. Initial saline bentonite porewater was flushed with 5.5 pore volumes of fresh granitic water. Water flux and chemical composition of effluent waters were monitored during almost 4 years. The model accounts for solute advection and diffusion and geochemical reactions such as aqueous complexation, acid-base, cation exchange, protonation/deprotonation by surface complexation and dissolution/precipitation of calcite, chalcedony and gypsum. All of these processes are assumed at local equilibrium. Similar to previous studies of bentonite porewater chemistry on batch systems which attest the relevance of protonation/deprotonation on buffering pH, our results confirm that protonation/deprotonation is a key process in maintaining a stable pH under dynamic transport conditions. Breakthrough curves of reactive species are more sensitive to initial porewater concentration than to effective diffusion coefficient. Optimum estimates of initial porewater chemistry of saturated compacted FEBEX bentonite are obtained by solving the inverse problem of multicomponent reactive transport. While the single-continuum model reproduces the trends of measured data for most chemical species, it fails to match properly the long tails of most breakthrough curves. Such limitation is overcome by resorting to a dual-continuum reactive transport model.     

Construction demolition wastes, Waelz slag and MSWI bottom ash: a comparative technical analysis as material for road construction

The objective of the study is to analyze the technical suitability of using secondary materials from three waste flows (construction and demolition waste (CDW), Waelz slag and municipal solid waste incineration (MSWI) bottom ash), under the regulations and standards governing the use of materials for road construction. A detailed technical characterization of the materials was carried out according to Spanish General Technical Specifications for Road Construction (PG3). The results show that Waelz slag can be adequate for using in granular structural layers, while CDW fits better as granular material in roadbeds. Likewise, fresh MSWI bottom ash can be used as roadbed material as long as it does not contain a high concentration of soluble salts. This paper also discusses the adequacy of using certain traditional test methods for natural soils when characterizing secondary materials for use as aggregates in road construction.     

Characterization of food waste and bulking agents for composting

The characterization of food waste (FW) and locally available bulking agents (BA) are a prerequisite to optimizing compost recipes. This study measured the variation in FW characteristics (pH, dry matter (DM), carbon (C), wet bulk density and Total Kjeldahl Nitrogen (TKN)) produced by a restaurant and a community kitchen in downtown Montreal, Canada from May to August 2004. The project also measured the mass of FW produced by another restaurant and a group of 20-48 households, from June to August 2004. Locally available BA (hay, straw, pine wood shavings, cardboard, left over cattle feed and wheat residue pellets) were also characterized to formulate composting recipes based on the FW characteristics observed during a period representative of winter and summer conditions. Residential and restaurant FW characteristics varied significantly over the summer months, although the mass produced remained constant at 0.61 and 0.56 kg capita(-1)day(-1), respectively. In addition, the number of customers served by the restaurant increased by nearly 50% from June to August. The BA with the highest moisture adsorption capacity was found to be the wheat residue pellets, followed by chopped straw. Wheat residue pellets, chopped hay and left over cattle feed all presented a balanced C/N ratio. Wheat residue pellets and wheat straw, chopped hay and cardboard demonstrated neutral pH values. Based on the variable FW characteristics and monthly production rates, the formulation of recipes indicates that compost facilities must be flexible enough to handle seasonal variations of as much as 50% by volume.     

Seasonal evolution of beach waste and litter during the bathing season on the Catalan coast

Beach waste and litter composition and evolution on popular urban (located in the main nucleus of the municipality) and urbanized (located in residential areas outside the main nucleus) beaches of the Costa Brava (Catalan coast) were assessed during the bathing season. Waste and litter production (amount and composition) were affected by urbanization and varied during the summer. Urban beaches had higher densities of waste deposition and lower percentages of organic, domestic and other miscellaneous waste than urbanized beaches. Litter characteristics were also influenced by type of beach, and varied during the season as a consequence of beach use and cleaning practices, but not environmental factors. Urbanized beaches obtained higher scores for aesthetic quality of sand than urban beaches, and small-sized litter tended to accumulate during the season in the beach of Lloret Centre. The most important problems are management of recyclable materials, litter left by users on the sand, and separation of sand from litter. In addition, current efficiency of mechanical cleaning is low, especially in the withdrawal of cigarette butts. These analyses highlight problems that should be addressed in future management of area beaches.     

Chemosensory discrimination of familiar and unfamiliar conspecifics by lizards: implications of field spatial relationships between males

The ability of territorial lizards to discriminate between scents of neighbors and non-neighbors might contribute to decreasing the costs of aggressive interactions. To test this hypothesis, we conducted a field study to analyze the spatial relationships between male Iberian rock-lizards, Lacerta monticola. We then used the same individuals in a laboratory experiment to test whether male lizards can use chemical cues to discriminate between familiar conspecific males (those whose home ranges overlapped) and unfamiliar conspecific males (those whose home ranges did not overlap, and whose home range centers were at least 50 m apart). Differences in tongue-flick rates in the presence of chemical cues suggested that male L. monticola discriminated between odors of familiar and unfamiliar males. The behavioral responses were also dependent on relative differences in body size between the responding male and the unfamiliar male that donated the scent: There was a significant negative correlation between tongue-flick rates emitted in cages of unfamiliar males and the body size differences between males. In contrast, when the donor of the scent was a familiar male, the tongue-flick rate was not dependent on body size differences. These results are compatible with individual discrimination through chemical cues in male L. monticola.     

Estimation of pollutant partition in sandy soils with different water contents

The objectives of this work were: (1) to identify an isotherm model to relate the contaminant contents in the gas phase with those in the solid and non-aqueous liquid phases; (2) to develop a methodology for the estimation of the contaminant distribution in the different phases of the soil; and (3) to evaluate the influence of soil water content on the contaminant distribution in soil. For sandy soils with negligible contents of clay and natural organic matter, contaminated with benzene, toluene, ethylbenzene, xylene, trichloroethylene (TCE), and perchloroethylene (PCE), it was concluded that: (1) Freundlich’s model showed to be adequate to relate the contaminant contents in the gas phase with those in the solid and non-aqueous liquid phases; (2) the distribution of the contaminants in the different phases present in the soil could be estimated with differences lower than 10% for 83% of the cases; and (3) an increase of the soil water content led to a decrease of the amount of contaminant in the solid and non-aqueous liquid phases, increasing the amount in the other phases.