Moisture Sorption Characteristics of Chitosan/Polyethylene Oxide Blended Films

Studies on the moisture sorption characteristics of chitosan/polyethylene oxide (PEO) blended films have been carried out at 27 °C for water activity (a _w) from 0.1 to 0.9. The sorption data at different a _w were used to fit 12 different sorption isotherm models proposed in the literature. The model constants were determined by linear fitting of the sorption equations. The ranges of applicability of water activity for the isotherms reported in the article lie between 0.11 to 0.44 (monomolecular layer) for the BET model and between 0.11 to 0.86 (monolayer & multilayer’s) for Smith, Caurie, Bradley and Oswin. The water activity for Halsey and Chung & Pfost models lies between 0.44 to 0.86 (multilayer) and 0.33 to 0.86 for Henderson and Freundlich models and 0.11 to 0.65 for Kuhn, Linear and Iglesias & Chirife models. The high coefficient of determination R ² (ranges from 0.82 to 1) confirms the applicability of the equations employed. The study on the application of such water activity data of chitosan/PEO blended films on different model equations will be helpful in prediction of durability and functional behavior of moisture sensitive biopolymeric films     

Sorption of strontium on bentonite

Sorption of Sr on bentonite was studied using the batch technique. Distribution coefficients (K_d) were determined as a function of contact time, pH, sorbent and sorbate concentration and temperature. The data were interpreted in terms of Freundlich, Langmuir and Dubinin-Radushkevich isotherms. Thermodynamic parameters for the sorption system were determined at three different temperatures. The positive value of the heat of sorption, ΔH° = 30.62 kJ/mol at 298 K, shows that the sorption of strontium on bentonite is endothermic. The negative value of the free energy of sorption, ΔG° = −10.69 kJ/mol at 298 K, shows the spontaneity of the reaction. ΔG° becomes more negative with increasing temperature, which shows that the sorption process is more favorable at higher temperatures. The mean free energy for sorption, E 9 kJ/mol, suggests that ion exchange is the predominant mode of sorption in the Sr concentration range studied, i.e. 0.01 – 0.3 mol/dm³. The presence of complementary cations depresses the sorption of strontium on bentonite in the order Ca²⁺>Mg²⁺>K⁺>Na⁺. Some organic complexing agents and natural ligands also affect the sorption of strontium. The desorption studies with ground water at low strontium loadings on bentonite show that about 90% of Sr is irreversibly sorbed on the bentonite.     

Accumulation of Heavy Metals by in vitro cultures of plants

The aim of the project is to study heavy metals accumulation by the selected plants in both laboratory and field conditions. Within the experiments the aspen (Populus tremula × tremuloides), sunflower (Helianthus annuus) and corn (Zea mays) plants were studied. The reasons for this selection were: a fast growth of these plants, an accumulation capacity and an ability to survive in different types of soils. The study was carried out on the aspen plantlets grown in vitro. The plants were exposed to the aqueous solutions having concentrations 0.1 mM, 0.5 mM of Pb²⁺ or Ni²⁺, respectively. The accumulation capacityfor aspen, was about 70% of Pb²⁺ originally present in the solution. The starting concentration of Pb²⁺ (0.5 mM) exhibited no negative impact on the growth. Besides in vitro expositions, a pilot-scale phytoremediation experiment was carried out at the polluted industrial area (Zn – 75000 mg/kg), (Pb – 16000 mg/kg), (Cr – 590 mg/kg), (Cd – 90 mg/kg) and (Cu – 1700 mg/kg).     

Melt Processing of a New Biodegradable Synthetic Polymer in High-Speed Spinning and Underpressure Spunbonding Process

A new biodegradable synthetic polyesteramid (PEA) was characterized by means of thermogravimetry (TG) differential scanning calorimetry (DSC) and dynamic rheological measurements. Two glass transition ranges at about –33 and 38°C and a melting enthalpy of 33 J/g were measured, indicating that PEA is an immiscible blend of two components with a small crystalline part. The material was spun in a high-speed spinning process within the range of 2,000–6,000 M/min and an underpressure spunbonding process within the range of 3,600–7,700 M/min. The textile physical properties of the fibers were 100 MPa tenacity at an elongation at break of 30%, and an E-modulus of 0.5 GPa. The mass per unit area of the spunbonded nonwovens ranged from 70–159 g/M ². The strength of the spunbonded nonwovens was 28–51 N and 42–74 N in machine and cross direction, respectively. The air permeability of the nonwovens decreased at high air velocities and more fineness of the filaments from 1240–380 l/M ² s.     

Linking field experiments to long-term simulation of impacts of nitrogen deposition on heathlands and moorlands

The results from three long-term field manipulation studies of the impacts of increased nitrogen deposition (0–120 kg N ha^–1 yr^–1) on lowland and upland heathlands in the UK were compared, to test if common responses are observed. Consistent increases in Calluna foliar N content and decreases in litter C:N ratios were found across all sites, while increases in N leaching were not observed at any site over the range 0–80 kg ha^–1 yr^–1. However, the response of Calluna biomass did vary between sites, possibly reflecting site differences in nutrient status and management histories. Five versions of a simulation model of heathland responses to N were developed, each reflecting different assumptions about the fate and turnover of soil N. Model outputs supported the deduction from mass balance calculations at two of the field sites that N additions have resulted in an increase in immobilisation; the latter was needed to prevent the model overestimating measured N leaching. However, this version of the model significantly underestimated Calluna biomass. Model versions, which included uptake of organic N by Callunaand re-mobilisation of N from the soil organic store provided some improvement in the fit between modelled and field biomass data, but re-mobilisation also led to an overestimation of N leaching. Quantification of these processes and their response to increased N deposition are therefore critical to interpreting experimental data and predicting the long-term impacts of atmospheric deposition on heathlands and moorlands.     

Water transport in polylactic acid (PLA), PLA/ polycaprolactone copolymers, and PLA/polyethylene glycol blends

Polylactic acid (PLA) is a hydrolytically degradable aliphatic polyester, and water vapor permeability may have a significant influence on the rate of degradation. A method is devised to use bags prepared from PLA films and filled with molecular sieves to determine the water vapor permeability in the polymer, its copolymers with caprolactone, and blends with polyethylene glycol. The “solution-diffusion” model is used to determine the permeability parameters. These include the solubility coefficient,S, a measure of the equilibrium water concentration available for hydrolysis and the diffusion coefficient,D, which characterizes the rate of water vapor diffusion into the film under specific conditions. Values ofS andD at 50‡C and 90% relative humidity ranged from 400 × 10^-6 to 1000 × 10^-6 cm³ (STP)/(cm³ Pa) and 0.20 × 10^-6 to 1.0 × 10^-6 cm²/s, respectively. TheS andD coefficients were also measured at 20 and 40‡C and compared to those of other polymers. The degree of crystallinity was found to have little influence on the measured permeability parameters. The heat of sorption, δH_S, and the activation energy of diffusion, E_D, were used to show that the permeability process is best described by the “water cluster” model for hydrophobic polymers. Finally, the diffusion coefficient is used to compare the rate of water diffusion to the rate of water consumption by ester hydrolysis. Results indicate that hydrolytic degradation of PLA is reaction-controlled.     

Characterization of Environmentally Friendly Polymers by Inverse Gas Chromatography: I Amylopectin

Amylopectin, as a potato starch based polymer, with a molecular weight of six million gram/mol was characterized using the Inverse Gas Chromatography Method (IGC). DSC method was also used to measure the glass and melting temperatures. Both DSC and IGC agreed well on a T_g of 105°C and T_m of 160–166°C. Nineteen solutes (solvents) were injected onto a chromatographic column containing amylopectin. These solutes revealed the interaction of alkanes with AP, and the wettability and water intake of AP. Alkanes showed exothermic values of interaction parameters which were increased as the temperature increased and as the number of carbons in the alkane series decreased. Retention diagrams of these solutes in a temperature range of 80–200°C revealed two zones, crystalline and amorphous. T_g and T_m were measured using these zones which complimented the DSC values. The two zones were used to calculate the degree of crystallinity below the melting temperature which ranged from 85% at 104°C to 0% at 161°C. The dispersive component of the surface energy of amylopectin was measured using alkanes which ranged from 25.35 mJ/m² at 80°C to 8.47 mJ/m² at 200°C. This is attributed to the weak crystalline surface of AP at 80°C and when the surface melted at 160°C the surface energy decreased due to the thermal expansion of the surface.     

Protozooplankton in the Deep Oligotrophic Traunsee (Austria) Influenced by Discharges of Soda and Salt Industries

Traunsee is a deep oligotrophic lake in Austria characterised by an artificial enrichment of chloride in the hypolimnion (up to 170 mg L^-1) caused by waste disposal of soda and salt industries. Protists were collected monthly over one year, observed alive and after Quantitative Protargol Staining (ciliates) or via epifluorescence microscopy (heterotrophic flagellates). Three sites within the lake (0–40 m depths) were compared to deeper water layers from 60–160 m depths where chloride concentrations and conductivity were increased. In addition, we observed the protozooplankton of two neighbouring lakes, i.e. reference systems, during one sampling occasion. In Traunsee the abundance of ciliates was low (200–36 600 cells L^-1) in contrast to high species diversity (at least 60 different species; H_S = 2.6) throughout the year. The main pelagic species in terms of abundance were small oligotrichs and prostomatids like Rimostrombidium brachykinetum/hyalinum, Balanion planctonicum and Urotricha spp. throughout the investigation period. Among free-living heterotrophic flagellates, which occurred at densities of 40–2800 cells mL^-1, small morphotypes dominated in the pelagial. No differences at the community level between the three lakes could be observed and pelagic ciliates and flagellates seemed not to be affected by increased chloride concentrations or by enhanced conductivity.     

Assessment of the recycling potential of fresh concrete waste using a factorial design of experiments

Recycling of industrial wastes and by-products can help reduce the cost of waste treatment prior to disposal and eventually preserve natural resources and energy. To assess the recycling potential of a given waste, it is important to select a tool capable of giving clear indications either way, with the least time and work consumption, as is the case of modelling the system properties using the results obtained from statistical design of experiments. In this work, the aggregate reclaimed from the mud that results from washout and cleaning operations of fresh concrete mixer trucks (fresh concrete waste, FCW) was recycled into new concrete with various water/cement ratios, as replacement of natural fine aggregates. A 3² factorial design of experiments was used to model fresh concrete consistency index and hardened concrete water absorption and 7- and 28-day compressive strength, as functions of FCW content and water/cement ratio, and the resulting regression equations and contour plots were validated with confirmation experiments. The results showed that the fresh concrete workability worsened with the increase in FCW content but the water absorption (5–10 wt.%), 7-day compressive strength (26–36 MPa) and 28-day compressive strength (32–44 MPa) remained within the specified ranges, thus demonstrating that the aggregate reclaimed from FCW can be recycled into new concrete mixtures with lower natural aggregate content.     

An Automated Wet Deposition System to Compare the Effects of Reduced and Oxidised N on Ombrotrophic Bog Species: Practical Considerations

Critical N loads for ombrotrophic bogs, which often contain rare and N-sensitive plants (especially those in lower plant groups: lichens, mosses and liverworts), are based on very few experimental data from measured, low background N deposition areas. Additionally the relative effects of reduced versus oxidised N are largely unknown. This paper describes an automated field exposure system (30 km S. of Edinburgh, Scotland) for treating ombrotrophic bog vegetation with fine droplets of oxidised N (NaNO₃) and reduced N (NH₄Cl). Whim Moss exists in an area of low ambient N deposition (ca. 8 kg N ha^–1 y^–1), the sources and quantification of which are described. The wet N treatment system is run continuously, and is controlled/activated by wind speed and rainfall to provide a unique simulation of real world treatment patterns (no rain=no treatment). Simulated precipitation is supplied at ionic concentrations below4mMin rainwater collected on site. Treatments provide a replicated dose response to 16, 32 and 64 kg N ha^–1 y^–1 adjusted for ambient deposition (8 kg N ha^–1 y^–1). The 16 and 64 kg N ha^–1 y^–1 are duplicated with a P+K supplement. Baseline soil chemistry and foliar nutrient status was established for all 44 plots for Calluna vulgaris, Sphagnum capillifolium, Hypnum jutlandicum and Cladonia portentosa.     

Utilization of a leather industry waste

In the production of leather the main waste that remains after splitting of limed hides before tanning is the lowest layer of the skin together with the underlying fatty tissue (subcutis). It is characterized by a very high water content (up to 870 g kg⁻¹) and a balanced content of protein (40–60 g kg⁻¹ of the dry mass), fat (10–20 g kg⁻¹) of the dry mass) and carbohydrates. The object of this work was to elaborate a method to process this waste into useful products. The treatment proposed involves washing to remove the inorganic salts, separation of fat and extraction of collagen in hot water solution and additional extraction of protein from the insoluble residue after hydrolysis with alkaline proteinase. This results in the isolation of three fractions: fat—cattle tallow (4–12% of the total mass of the initial material), collagen hydrolysate—glue (5–10%) and protein concentrate for fodder (1–3% yield). Up to 95% of the protein in the initial material was extracted. Further purification of the collagen hydrolysate fraction into edible gelatin was achieved. The proposed method is applicable to every leather factory.     

A Conceptual Model of Spatially Heterogeneous Nitrogen Leaching from a Welsh Moorland Catchment

Soil- and stream-water data from the Plynlimon research area, mid-Wales, have been used to develop a conceptual model of spatial variations in nitrogen (N) leaching within moorland catchments. Extensive peats, in both hilltop and valley locations, are considered near-complete sinks for inorganic N, but leach the most dissolved organic nitrogen (DON). Peaty mineral soils on hillslopes also retain inorganic N within upper organic horizons, but a proportion percolates into mineral horizons as nitrate (NO ₃ ^– ), either through incomplete immobilisation in the organic layer, or in water bypassing the organic soil matrix via macropores. This NO ₃ ^– reaches the stream where mineral soilwaters discharge (via matrix throughflow or pipeflow) directly to the drainage network, or via small N-enriched flush wetlands. NO ₃ ^– in hillslope waters discharging into larger valley wetlands will be removed before reaching the stream. A concept of catchment nitrate leaching zones is proposed, whereby most stream NO ₃ ^– derives from localised areas of mineral soil hillslope draining directly to the stream; the extent of these zones within a catchment may thus determine its overall susceptibility to elevated surface water NO ₃ ^– concentrations.     

Effects of Temperature and Relative Humidity on Polylactic Acid Plastic Degradation

Three high molecular weight (120,000 to 200,000 g mol^–1) polylactic acid (PLA) plastic films from Chronopol (Ch-I) and Cargill Dow Polymers (GII and Ca-I) were analyzed for their degradation under various temperature and relative humidity (RH) conditions. Two sets of plastic films, each containing 11 samples, were randomly hung in a temperature/humidity-controlled chamber by means of plastic-coated paper clips. The tested conditions were 28, 40, and 55°C at 50 and 100% RH, respectively, and 55°C at 10% RH. The three tested PLA films started to lose their tensile properties when their weight-average molecular weight (M _w) was in the range of 50,000 to 75,000 g mol^–1. The average degradation rate of Ch-I, GII, and Ca-I was 28,931, 27,361, and 63,025 M _w/week, respectively. Hence, GII had a faster degradation rate than Ch-I and Ca-I under all tested conditions. The degradation rate of PLA plastics was enhanced by the increase in temperature and relative humidity. This trend was observed in all three PLA plastics (Ca-I, GII, and Ch-I). Of the three tested films, Ch-I was the first to lose its mechanical properties, whereas Ca-I demonstrated the slowest loss, with mechanical properties under all tested conditions.     

Air Pollution Zones and Harmful Pollution Levels of Alkaline Dust for Plants

For characterisation of landscapes in north-eastern Estoniaaffected by alkaline oil shale fly ash and cement dust the zonation-method based on average annual (C _y) and short-termconcentrations of pollutants in the air was used, as well as on deposition loads of dust and Ca²⁺. In the overground layer of atmosphere the zones with different air pollution loads were distinguished. A comparative analysis of pollution zones characteristics and biomonitoring data revealed that for sensitive lichen the dangerous level of alkaline dust in the air, introducingthe degradation of Sphagnum sp. at the level of C _y of dust 10–20 g m^-3 and at 0.5–1 hr maximums 100–150 g m^-3. For Scots pine (Pinus sylvestris L.) and Norway spruce (Picea abies (L.) Karst.) this limited concentration (decline of growth parameters) of cement dust is correspondingly following: 30–50 g m^-3 and 150–500 g m^-3, in case of fly ash the limit level of C _y amounting 100 g m^-3. Daily deposition load of Ca²⁺ should not exceed approximately 4.5–15 mg m^-2 for lichen; for conifers the harmful pollution load is higher – >22 mg m^-2.     

Early Effects of Atmospheric Ammonia Deposition on Calluna Vulgaris (L.) Hull Growing on an Ombrotrophic Peat Bog

This paper reports data from a field study investigating the impacts of elevated ammonia (NH₃) deposition on Calluna vulgaris growing on an ombrotrophic peat bog in S.E. Scotland. Shoot extension, foliar N concentrations, chlorophyll concentration and chlorophyll fluorescence were measured during the second growing season of exposure to a gradient of ammonia concentrations. Results indicate that NH₃ increases growth between 150–200 kg N ha^–1y^–1 cumulative deposition. Foliar N content increased significantly in response to NH₃ cumulative deposition up to 400 kg N ha^–1 y^–1 whereas chlorophyll a content significantly decreased. Measurements of Fv/Fm suggest that although NH₃ exposure altered the growth and reduced chlorophyll a, the efficiency of photosystem II was insensitive to NH₃-N deposition at this stage.     

Comparison of percolation to batch and sequential leaching tests: Theory and data

Leaching tests are becoming more relevant in assessing solid waste material, particularly with respect to groundwater risks. In the field, water infiltration is the dominant leaching mechanism, which is simulated in the lab with batch and column tests. In this study, we compared percolation, through analytical solutions of the advection–dispersion equation, to laboratory batch and sequential leaching tests. The analytical solutions are supported with comprehensive data from various field and laboratory leaching of different solutes from waste materials and soils collected in long-term joint research projects funded by the German Federal Ministry for Education and Research and the Federal Environment Agency. The comparison of theory and data is facilitated if concentrations and cumulative release are plotted versus the liquid–solid ratios (LS). Both theory and data indicate that leaching behaviour is independent of duration and physical dimensions of the leaching tests. This holds even if field lysimeters are compared to laboratory columns of different size, different flow velocities as well as different contact times. In general, laboratory batch tests over predict effluent concentrations (for LS < K_d). Leaching of solutes from solid samples of certain materials (e.g. chloride from incineration ashes or sulphate from demolition waste) in column and lysimeter tests compares very well and agrees with the analytical solutions. Overall, reproducibility and agreement with theory of column tests are better than batch tests, presumably because the latter are prone to artefacts (e.g. in liquid–solid separation steps). Theory and data fit surprisingly well, despite the fact that the theory is based on the local equilibrium assumption; non-linear sorption and chemical reactions in the solid waste materials are not considered.     

Petroliferous wastewaters treatment with water hyacinths (Raffinerie de Provence, France): Experimental statement

The production and purification abilities of the water hyacinth, Eichhornia crassipes (Mart.) Solms., were tested on petrochemical wastewaters at Raffinerie de Provence, Total (La Mède, France), in controlled and in situ experiments. The mean production obtained was of about 6.1 g (dry weight) day⁻¹ m⁻² (10-fold lower than those obtained on paper industry effluent), and can be explained by the high salinity and pH of the effluent, and the negative effect of hydrocarbons. In comparison with the control pond, the water hyacinth system induced a rapid settlement effect. Finally, the removal gains due to the water hyacinths system were about 26% for the suspended solids (i.e. 40.1 kg day⁻¹), 28% for the total hydrocarbons (i.e. 17.2 kg day⁻¹) and 18% for the total organic carbon (i.e. 27 kg day⁻¹).     

Controls on Leaching of N Species in Upland Moorland Catchments

Spatial and temporal changes in mobility of N species have been studied for three UK upland river networks, the Etherow in the South Pennines, the Nether Beck in the Lake District and the Dee in NE Scotland. The catchments are subject to N deposition at 35.1, 22.0 and 10.8–15.6 kg N ha^–1 yr^–1, respectively. TheNH ₄ ⁺ leaching appears to be predominantly regulated by flowpath in more polluted upland catchments. It is greatest where water draining acidified peaty soils contributes more to total discharge. Soluble organic matter may provide the dominant counter anion. In the Etherowand Dee catchments, which are dominated by acid mineral and organic soils, at high discharge NO ₃ ^– also appears to be associated with greater input of water from acidified soils. In contrast, for the Nether Beck, higher NO ₃ ^– concentrations are associated with tributaries draining soils contributingwater with higher alkalinity, suggesting nitrification is important. For the Etherow and Dee, dissolved organic N (DON) appears to originate predominantly from acidified, peaty soils. Spiking experiments with peat soil from the Etherow catchment confirmed the limited capacity of these soils to utilize inorganic N inputs, favouring equilibration with NH ₄ ⁺ inputs and leaching losses of inorganic N throughout the year.     

Carbon Sequestration: Do N Inputs and Elevated Atmospheric CO2 Alter Soil Solution Chemistry and Respiratory C Losses?

Soil respiration is a large C flux which is of primary importance in determining C sequestration. Here we ask how it is altered by atmospheric CO₂ concentration and N additions. Swards of Lolium perenne L. were grown in a Eutric cambisol under controlled conditions with and without the addition of 200 kg NO ₃ ^– –N ha^–1, at either 350 ppm or 700 ppm CO₂, for 3 months. Soil respiration and net canopy photosynthesis were both increased by added N and elevated CO₂, but soil respiration increased proportionately less than fixation by photosynthesis. Thus, both elevated CO₂ and N appeared to increase potential C sequestration, although adding N at elevated CO₂ reduced the C sequestered as a proportion of that fixed relative to elevated CO₂ alone. Across all treatments below-ground respiratory C losses were predicted by root biomass, but not by soil solution C and N concentrations. Specific root-dependent respiration was increased by elevated CO₂, such that belowg-round respiration per unit biomass and per unit plant N was increased.     

Investigation of the Thermosensitive Nanosphere Polymer in Removing Organophosphorus Pesticides from Water and Its Isotherm Study (Case Study: Diazinon)

In this research, a novel thermosensitive nanosphere polymer (TNP) was synthesized by copolymerization of N-isopropylacrylamide with 3-allyloxy-1,2-propanediol for the removal of diazinon from water. The characterization of the synthesized adsorbent has been performed by Fourier transform infrared spectrometer, scanning electron microscopy and elemental analysis. Batch adsorption method was performed to investigate the influences of various parameters like pH, temperature and contact time on the adsorption of diazinon. The equilibrium adsorption data of diazinon by TNP was studied by Langmuir, Freundlich, Temkin and Redlich–Peterson model. According to equilibrium adsorption results, the Langmuir, Freundlich and Temkin constants were evaluated to be 0.912 (L/mg), 7.916 (mg/g) (L/mg)^1/n and 2.494 respectively at pH 7 and room temperature. Based on Redlich–Peterson model analysis, the equilibrium data for the adsorption of diazinon was conformed well to the Langmuir isotherm model. This method was successfully applied for removal of diazinon from environmental samples. Moreover, in reusing of TNP, the sorption capacity was maintained without any significant change after 10 cycles of sorption–desorption process.