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.     

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.     

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.     

Effects of a selenium-enriched diet on antioxidant response in adult crayfish (Procambarus clarkii)

Many diets employed in aquaculture are enriched with selenium to improve the diet quality and its conservation. The aim of the study was to investigate the effects of a diet enriched in selenium (1.21 mg kg(-1)) on the antioxidant response of Procambarus clarkii (Girard, 1852). Crayfish fed a diet with lower selenium content (0.30 mg kg(-1)) were the control. Selenium accumulation, enzymatic activities, and total glutathione were evaluated in hepatopancreas of adults of both sexes fed with both diets for 50 days at two experimental times (T(30), T(50) days). Treated females exhibited the highest selenium bioaccumulation during both experimental times, while treated males displayed the highest selenium concentration after 30 days, compared to control crayfish. A sex-related difference was found for the response of the analyzed enzymes in the selenium diet-treated specimens. In fact, superoxide dismutase, glutathione peroxidase and glyoxalase I activities in males were more sensitive compared with females, showing depleted activities in both experimental times. Catalase activity was induced in females (T(50)), while glutathione S-transferase activity was the highest in treated females and the lowest in treated males, compared with own controls. Only glutathione reductase activity and glutathione content showed the same trend in both sexes, which were both lowered in treated specimens, when compared with control crayfish. This result might be due to the effect of selenium toxicity on this freshwater species. Males and females of P. clarkii showed a different susceptibility to the prooxidant effects in a Se-enriched diet.     

Solubility of toluene, benzene and TCE in high-microbial concentration systems

We report measurements of solubility limits for benzene, toluene, and TCE in systems that contain varying levels of biomass up to 0.13 g mL⁻¹ for TCE and 0.25 g mL⁻¹ for benzene and toluene. The solubility limit increased from 21 to 48 mM when biomass (in the form of yeast) was added to aqueous batch systems containing benzene. The toluene solubility limit increased from 4.9 to greater than 20 mM. For TCE, the solubility increased from 8 mM to more than 1000 mM. Solubility for TCE (trichloroethylene) was most heavily impacted by biomass levels, changing by two orders of magnitude as the microbial concentrations approach those in biofilms.     

Processing and Properties of Mixtures of PHB-V with Post-consumer LDPE

Mixtures of poly-β-(hydroxybutyrate-co-valerate) PHB-V with virgin and post-consumer low density polyethylene (LDPE) were prepared by melt mixing in proportions of 100/0, 90/10, 80/20, 70/30 and 0/100 (wt/wt%). The mixtures were analysed by infrared spectroscopy, differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), melting flow index (MFI), tensile tests, scanning electron microscopy (SEM) and biodegradation in simulated soil. The DMTA and DSC curves of post-consumer LDPE suggested that this polymer was a mixture of LDPE and linear low density polyethylene (LLDPE). Virgin and post-consumer LDPE had lower MFI than PHB-V, but the blends showed higher index as the content of LDPE increased. The addition of LDPE reduced the tensile strength and Young’s modulus of the mixtures compared with PHB-V. SEM indicated poor interfacial adhesion between PHB-V and LDPE. PHB-V degraded slow and gradually, while both LDPE showed virtually no degradation under the conditions studied. The biodegradability of the blends depended on their composition and of the type of LDPE. LDPE improved the biodegradability of the mixtures.     

Influence of Technological Process on Biodegradation of PVA/Waxy Starch Blends in an Aerobic and Anaerobic Environment

Improving biodegradability of PVA/starch blends is a reality already documented by a number of works. Admittedly, mechanical properties of products (for example, tensile strength) are somewhat worse, but suitable composition optimizing or chemical modifying of starch may eliminate the problem to a large degree. This work is an attempt to find another potential effect influencing biodegradability, that of technological procedure for producing films from these blends on an extruder. The procedure with a so-called pre-extrusion step (two-stage) and dry-blend (single-stage) produced blends of slightest differences in achieved biodegradability (virtually within limits of experimental error) in aerobic (76 vs. 79%) as well as anaerobic breakdown (48 vs. 52%). Conversely, morphological analysis exhibited superior homogeneity of films prepared by the two-stage process; their tensile strength was also higher.     

Dairy washwater treatment using a horizontal flow biofilm system

In Ireland, dairy farmyard washwater commonly comprises farmyard run-off and dairy parlour washings. Land-spreading is the most widely used method for treating this wastewater. However, this method can be labour intensive and can cause, in some cases, the degradation of surface and ground waters, mainly due to nitrogen contamination. In this study, a horizontal flow biofilm reactor (HFBR) with step-feed was constructed and tested in the laboratory, to remove organic carbon and nitrogen from a agricultural strength synthetic washwater (SWW). The HFBR had an average top plan surface area (TPSA) of 0.1002 m(2) and consisted of a stack of 45 polystyrene horizontal sheets--15 sheets embedded with 25 mm deep frustums above 30 sheets with 10 mm deep frustums. The frustums acted as miniature reservoirs. The sheets were alternately offset to allow the wastewater to flow horizontally along each sheet and vertically from sheet to sheet down through the reactor. Biofilms developed on the sheets and treated the wastewater. During the 212-d study, the total hydraulic loading rate based on the TPSA of the sheets was 35 l m(-2) d(-1). SWW was pumped for 10 min each hour, in a step feed arrangement at a rate of 23.33 l m(-2) d(-1) on to the top sheet during Phases 1 and 2, and 11.67 l m(-2) d(-1) onto Sheet 16 during Phase 1 (days 1-92) and onto Sheet 30 during Phase 2 (days 93-212). The substrate loading rate during Phases 1 and 2 was 94.8 g total chemical oxygen demand (COD) m(-2) d(-1) and 10.5 g total nitrogen (TN) m(-2) d(-1), based on the TPSA. At steady state in Phase 2, the unit achieved excellent carbon removal of 99.7% 5-day biochemical oxygen demand (BOD(5)) and 96.7% total COD, equivalent to TPSA removal rates of 67.5 g BOD(5)m(-2)d(-1) and 91.7 g COD m(-2) d(-1). The nitrogen removal percentages were 98.3% total ammonium-nitrogen (NH(4)-N(t)) and 72.8% TN, which equated to TPSA removal rates of 4.8 g NH(4)-N(t) m(-2) d(-1) and 7.6g TN m(-2) d(-1). No sloughing of solids or clogging of media occurred during the study. The unit was simple to construct and operate, with little maintenance.     

A paradigm of an integrated transboundary environmental education,training, and technology transfer project

The Rodopi mountain range is located between Greece and Bulgaria and constitutes a natural and political boundary whose crest delimits the frontier between the two countries. However, these two neighboring countries have significant differences: Greece is one of the oldest members of the European Union (EU) while Bulgaria has just recently entered the European family. As a result, the existing financial and political differences between the two nations are also reflected in issues concerning the environmental know-how, education, and training, since Greece seems to have a small lead in these fields. On the other hand, given that Bulgaria possesses exceptional scientific personnel, it has made significant progress in all aspects of environmental policy during the last decade by absorbing up-to-date knowledge and putting it into practice; thus, catching up with the other EU countries in environmental issues is just a matter of time. Taking these factors into account, the Department of Forestry and Natural Environment Management of the Technological Educational Institute of Kavala (Greece) and the Department of Geography-Ecology and Natural History (Bulgaria) prepared a joint proposal which was approved and financed by the European Union Initiative ΙNTERREG IIIΑ/PHARE CBC GREECE-BULGARIA. The proposal concerns the Rodopi mountains and focuses on integrated environmental education, technology exchange, and transfer between the two institutions. The Rodopi complex constitutes a very important ecosystem of particular ecological and biological interest for both countries. This paper reveals the cooperation possibilities on environmental education and know-how exchange with regard to the shared natural resources of these contiguous countries.     

Kinetic extractions to assess mobilization of Zn, Pb, Cu, and Cd in a metal-contaminated soil: EDTA vs. citrate

Kinetic EDTA and citrate extractions were used to mimic metal mobilization in a soil contaminated by metallurgical fallout. Modeling of metal removal rates vs. time distinguished two metal pools: readily labile (QM1) and less labile (QM2). In citrate extractions, total extractability (QM1+QM2) of Zn and Cd was proportionally higher than for Pb and Cu. Proportions of Pb and Cu extracted with EDTA were three times higher than when using citrate. We observed similar QM1/QM2 ratios for Zn and Cu regardless of the extractant, suggesting comparable binding energies to soil constituents. However, for Pb and Cd, more heterogeneous binding energies were hypothesized to explain different kinetic extraction behaviors. Proportions of citrate-labile metals were found consistent with their short-term, in-situ mobility assessed in the studied soil, i.e., metal amount released in the soil solution or extracted by cultivated plants. Kinetic EDTA extractions were hypothesized to be more predictive for long-term metal migration with depth.