The Properties of Poly(<Emphasis Type="SmallCaps">l</Emphasis>-Lactide) Prepared by Different Synthesis Procedure

Different synthesis methods were applied to determine optimal conditions for polymerization of (3S)-cis-3,6-dimethyl-1,4-dioxane-2,5-dione (l-lactide), in order to obtain poly(l-lactide) (PLLA). Bulk polymerizations (in vacuum sealed vessel, high pressure reactor and in microwave field) were performed with tin(II) 2-ethylhexanoate as the initiator. Synthesis in the vacuum sealed vessel was carried out at the temperature of 150 °C. To reduce the reaction time second polymerization process was carried out in the high pressure reactor at 100 °C and at the pressure of 138 kPa. The third type of rapid synthesis was done in the microwave reactor at 100 °C, using frequency of 2.45 GHz and power of 150 W at the temperature of 100 °C. The temperature in this method was controlled via infrared system for in-bulk measuring. The solution polymerization (with trifluoromethanesulfonic acid as initiator) was possible even at the temperature of 40 °C, yielding PLLA with narrow molecular weight distribution in a very short period of time (less than 6 h). The obtained polymers had the number-average molecular weights ranging from 43,000 to 178,000 g mol⁻¹ (polydispersity index ranging from 1 to 3) according to the gel permeation chromatography measurements. The polymer structure was characterized by Fourier transform infrared and NMR spectroscopy. Thermal properties of the obtained polymers were investigated using thermogravimetry and differential scanning calorimetry.     

Effect of feeding strategy and COD/sulfate ratio on the removal of sulfate in an AnSBBR with recirculation of the liquid phase

The objective of this work was to analyze the effect of the interaction between feeding strategy and COD/sulfate ratio on the removal efficiency of sulfate and organic matter from a synthetic wastewater. An anaerobic sequencing batch reactor with recirculation of the liquid phase and containing immobilized biomass on polyurethane foam (AnSBBR) was used. The AnSBBR with a total volume of 3.7 L, treated 2.0 L synthetic wastewater in 8-h cycles at 30 ± 1 °C and was inoculated with anaerobic biomass from a UASB. Two feeding strategies were assessed: (a) batch and (b) batch followed by fed-batch. In strategy (a) the reactor was fed in 10 min with 2 L wastewater containing sulfate and carbon sources. In strategy (b) 1.2 L wastewater (containing only the sulfate source) was fed during the first 10 min of the cycle and the remaining 0.8 L (containing only the carbon source) in 240 min. The COD/sulfate ratios assessed were 1 and 3. Based on these values and on the concentrations of organic matter (0.5–11.25 gCOD/L) and sulfate (0.5 and 2.5 gSO₄^2?/L), the sulfate and organic matter loading rates applied equaled 1.5 and 4.5 gSO₄^2?/L d for sulfate and 1.5, 4.5 and 13.5 gCOD/L d for organic matter. After stabilization of the system time profiles were run of monitored parameters (COD, sulfate, sulfide and sulfite). In general, the reactor showed to be robust for use in the anaerobic treatment of wastewaters containing sulfate. Gradual feeding (strategy b) of the carbon source favored sulfate reduction, resulting in sulfate removal efficiencies of 84–98% and organic matter removal efficiencies of 48–95%. The best results were observed under COD/sulfate ratio equal to 1 (loading rates of 1.5 and 4.5 gSO₄^2?/L d for sulfate, and 1.5 and 4.5 gCOD/L d for organic matter). When COD/sulfate ratio was 3 (loading rates of 1.5 and 4.5 gSO₄^2?/L d for sulfate, and 4.5 and 13.5 gCOD/L d for organic matter) the effect of feed mode became less significant. These results show that the strategy batch followed by fed-batch is more advantageous for COD/sulfate ratios near the stoichiometric value (0.67) and higher organic matter and sulfate concentrations.     

Physical Properties, Photo- and Bio-degradation of Baked Foams Based on Cassava Starch, Sugarcane Bagasse Fibers and Montmorillonite

The objectives of this work were to develop biodegradable trays from cassava starch, sugarcane fibers and Na-montmorillonite (Na-MMT) using a baking process and to study the effects of these components on the physical properties, photo- and bio-degradation of the trays. The sample F20 (produced with 20 g fiber/100 g formulation) showed the maximum yield production (100 %). All formulations resulted in well-shaped trays with densities between 0.1941 and 0.2966 g/cm³. The addition of fibers and Na-MMT resulted in less dense and less rigid trays compared to control samples (only starch). The studied processing conditions resulted in good nanoclay dispersion, leading to the formation of an exfoliated structure. The evaluation of the photo-degradation stability of the trays under UV exposure for 336 h showed that a sample produced with a specific combination of fiber and nanoclay (20 g fiber and 5 g nanoclay/100 g formulation) had the highest loss in stress at break (91 %). Biodegradation assays showed that Control trays (starch) and F20 (20 g fiber/100 g formulation) lost a greater percentage of their weight after 90 days of incubation in soil, with losses of up to 85.50 and 82.70 %, respectively.     

Influence of organic loading on an anaerobic sequencing biofilm batch reactor (ASBBR) as a function of cycle period and wastewater concentration

The effect of organic loading on the performance of a mechanically stirred anaerobic sequencing biofilm batch reactor (ASBBR) has been investigated, by varying influent concentration and cycle period. For microbial immobilization 1-cm polyurethane foam cubes were used. An agitation rate of 500 rpm and temperature of 30+/-2 degrees C were employed. Organic loading rates (OLR) of 1.5-6.0gCODl(-1)d(-1) were applied to the 6.3-l reactor treating 2.0 l synthetic wastewater in 8 and 12-h batches and at concentrations of 500-2000mgCODl(-1), making it possible to analyze the effect of these two operation variables for the same organic loading range. Microbial immobilization on inert support maintained approximately 60 gTVS in the reactor. Filtered sample organic COD removal efficiencies ranged from 73 to 88% for organic loading up to 5.4gCODl(-1)d(-1). For higher organic loading (influent concentration of 2000mgCODl(-1) and 8-h cycle) the system presented total volatile acids accumulation, which reduced organics removal efficiency down to 55%. In this way, ASBBR with immobilized biomass was shown to be efficient for organic removal at organic loading rates of up to 5.4gCODl(-1)d(-1) and to be more stable to organic loading variations for 12-h cycles. This reactor might be an alternative to intermittent systems as it possesses greater operational flexibility. It might also be an alternative to batch systems suspended with microorganisms since it eliminates both the uncertainties regarding granulation and the time necessary for biomass sedimentation, hence reducing the total cycle period.     

Fed-batch and batch operating mode analysis of a stirred anaerobic sequencing reactor with self-immobilized biomass treating low-strength wastewater

This work presents an analysis of a stirred anaerobic sequencing discontinuous reactor with different substrate feeding strategies resulting in batch, fed-batch/batch and fed-batch operating modes. The reactor, containing granulated biomass, was fed with approximately 2.0L of synthetic domestic wastewater with Chemical Oxygen Demand of nearly 500 mg/L per cycle and operated at 30 degrees C and 50 rpm. Three feeding strategies with a total cycle time of 6 h, including 30-min settling, were adopted: batch mode with a fill cycle of 6 min, a fed-batch/batch mode with fill cycles of 60, 120 and 240 min and fed-batch mode with a fill cycle of 320 min. The system attained average non-filtered and filtered substrate removal efficiency of 78 and 84%, respectively, for all operating conditions, presenting good stability, solid retention and no granule break-up. A first order kinetic model with a residual organic matter concentration was proposed to analyze the influence of the feeding strategy on the performance during a cycle and bicarbonate alkalinity and total volatile acids concentration profiles were also quantified in order to verify the transient stability behavior.     

PCB accumulation and tissue distribution in cave salamander (Proteus anguinus anguinus, Amphibia, Urodela) in the polluted karstic hinterland of the Krupa River, Slovenia

For over two decades, a manufacturer of electrical capacitors disposed of its waste within the karstic hinterland of the Krupa River (Slovenia) resulting in the surroundings becomming heavily polluted with PCB. Albeit the extent of the contamination has been known since 1983 and the Krupa River has become one of the most PCB polluted river in Europe, the effects on the cave fauna of the region remain unknown. The most famous cave dweller of the Krupa hinterland is the endemic cave salamander Proteus anguinus anguinus. In this study we determine the levels of PCB in the tissues of the Proteus and in river sediments. The total concentration of PCB in individual tissue samples from specimens of the Krupa spring was between 165.59 μg g⁻¹ and 1560.20 μg g⁻¹ dry wt, which is at least 28-times higher than those from an unpolluted site. The kidneys contained the lowest concentration, while the highest concentration was in subcutaneous fat and tissues with high lipid contents like visceral fat and liver. Total PCB concentrations in sediment samples from the Krupa River were between 5.47 and 59.20 μg g⁻¹ dry wt showing that a high burden of PCB still remains in the region. The most abundant PCB congeners in all analyzed samples were di-ortho substituted (PCB #101, #118, #138 and #158), but higher proportion of mono-ortho PCB was present in sediments. The ability of Proteus to survive a high PCB loading in its environment and especially in its tissues is remarkable. Its partial elimination of low chlorinated and mono-ortho substituted congeners is also reported.     

Interaction effects of organic load and cycle time in an AsBr applied to a personal care industry wastewater treatment

A mechanically stirred anaerobic sequencing batch reactor (ASBR) containing granular biomass was applied to the treatment of a wastewater simulating the effluent from a personal care industry. The ASBR was operated with cycle lengths (t_C) of 8, 12 and 24 h and applied volumetric organic loads (AVOL) of 0.75, 0.50 and 0.25 gCOD/L.d, treating 2.0 L liquid medium per cycle. Stirring frequency was 150 rpm and the reactor was kept in an isothermal chamber at 30 °C. Increase in t_C resulted in efficiency increase at constant AVOL, reaching 77% at t_C of 24 h versus 69% at t_C of 8 h. However, efficiency decreased when AVOL decreased as a function of increasing t_C, due to the lack of substrate in the reaction medium. Moreover, replacing part of the wastewater by a chemically balanced synthetic one did not yield the expected effect and system efficiency dropped.     

Does monensin in chicken manure from poultry farms pose a threat to soil invertebrates?

Monensin is a carboxylic polyether ionophore used in the poultry industry as a coccidiostat. It enters the environment via manure from broiler farms. In spite of its potential presence in the environment, information concerning monensin residues in manure and soil and its toxicity to soil organisms are insufficient. In the present study, two beneficial soil invertebrate species, earthworms (Eisenia andrei) and woodlice (Porcellio scaber), were used to assess the toxicity of monensin. Animals were exposed to a range of monensin concentrations via soil or food. Earthworm reproduction was found to be the most susceptible endpoint (NOEC=3.5 mg kg(-1) dry soil; EC(50)=12.7 mg kg(-1) dry soil), while no adverse effects were recorded in isopods (NOEC?849mgkg(-1) dry soil, NOEC?357mgkg(-1) dry food). The obtained toxicity data were compared with potential concentrations of monensin in soil. In view of this, manure from broiler chickens treated with monensin at a poultry farm was sampled. According to monensin and nitrogen concentrations in the chicken manure and the degradation time of monensin, the predicted environmental concentration (PEC) was calculated. PEC of monensin is around 0.013 mg kg(-1) soil if manure is used after 3 months of composting and 0.05 mg kg(-1) soil if used without storage. Data for earthworm reproduction was used to estimate the predicted no-effect concentration (PNEC). If fresh chicken manure is applied to terrestrial ecosystems, the risk quotient (PEC/PNEC ratio) is above 1, which indicates that monensin might pose an environmental risk under certain conditions. To prevent this, it is strongly recommended to compost chicken manure for several months before using it as fertiliser.