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.     

Moisture Sorption Characteristics of Microbially Produced Polysaccharide and Polyvinyl Alcohol Blends

Moisture sorption characteristics of microbial polysaccharide (Ps.C101) from Pseudomonas caryophilli and polyvinyl alcohol (PVA) blends have been carried out at 27°C for water activity from 0.1 to 0.9. The sorption data was used to fit six different sorption isotherm models proposed in literature. The model constants were determined by linear fitting of the sorption equations. The ranges of applicability of water activity for isotherm models reported in this paper lie in between 0.1 and 0.4 for Brunaur–Emmet–Teller (BET) model (monolayer), and in between 0.2 and 0.9 for other models. The value of the coefficient of determination (R² = 0.97 ± 0.02) confirms the applicability of the equations studied.     

Bisolute Equilibrium Studies for the Sorption of Basic Dyes on a GAC from Almond Shells: A Nonlinear Approach

Aqueous phase adsorption of three textile dyes onto a granular activated carbon produced from acid activation of almond shells is presented. Primarily, the sorption of three basic dyes, methylene blue, rhodamine b, and malachite green oxalate were studied. Four models, the Freundlich, the Langmuir, the Redlich-Peterson, and the Toth isotherms were compared for their quality of fit to the single-solute sorption data. Next, sorption of the three likely binary systems was examined. Four bi-solute models, the extended Langmuir with and without an interaction term, the extended Redlich-Peterson with an interaction term, and the empirical extended Freundlich model were used to predict sorption in the binary systems. Nonlinearly determined constants of the corresponding single-solute isotherms were used in the binary models to compare with experimental binary sorption data. For the single-solute system, the three-parameter models of the Redlich-Peterson and the Toth isotherms outperformed the Langmuir and Freundlich models. The empirical extended Freundlich model produced the closest comparison to the binary data in each system. In general, the nonlinear method provided a simple and computationally effective technique of producing optimal fitting parameters for the bi-solute sorption models.     

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.     

Biosorptive removal of Pb(II) and Cu(II) from wastewater using activated carbon from cassava peels

The ability of activated carbon from cassava peels to remove heavy metals like Cu(II) and Pb(II) from hospital wastewater was investigated. The study showed that a pH of 8 was the best for the sorption of both metal ions onto the biosorbent. The time-dependent experiments for the metal ions showed that the binding of the metal ions to the biomass was rapid and occurred within 20–120 min. Sorption efficiency increased with a rise in adsorbent dosage. It increased from 12 to 73 % for Pb(II) and 26 to 79 % for Cu(II) when the adsorbent dose increased from 2 to 12 g. An increase in temperature led to an increase in sorption for both metal ions. The Langmuir model showed that the biomass has a higher sorption capacity for Cu(II) than Pb(II), with q _m = 5.80 mg g^?1 for Pb(II) and 8.00 mg g^?1 for Cu(II). The Freundlich isotherm K _f was 1.4 for Pb(II) and 1.8 for Cu(II), indicating a preferential sorption of Cu(II) onto the biosorbent. Adsorption capacity was found to decrease with an increase in particle sizes. Sorption occurred by physical mechanisms and was mainly controlled by intraparticle diffusion.     

Integration of the Pesticide Impact Rating Index with a Geographic Information System for the Assessment of Pesticide Impact on Water Quality

The pesticide impact rating index (PIRI) has been integrated with a Geographic Information System (GIS) to enable regional assessment of pesticide impact on groundwater and surface water resources. The GIS version of PIRI (PIRI-GIS) was used to assess the impact of pre-planting atrazine use in the pine plantations on the Gnangara Mound, Western Australia. The impact on groundwater was found to be spatially variable, mainly dependent on soil type and depth to groundwater, because land use variables were spatially constant. Areas with the greatest impact on groundwater were those where the soil had a low sorption capacity for atrazine. Knowledge of the spatial distribution of the sorption coefficient based on organic carbon (K _oc) for atrazine was found to significantly improve the results from PIRI-GIS. Average values for K _oc (i.e. based on overseas data) were too low for most of the local soil types, resulting in a general overestimation of pesticide impact on groundwater resources, but an underestimation of impact in areas that should be of greatest concern (i.e. where the soil has a low sorption capacity for atrazine).     

Persistence of the De-Icing Additive Benzotriazole at an Abandoned Airport

The environmental fate of many of the additives in the deicing agents used at airports is poorly understood. One and two years after deicing activities ceased, soil and groundwater samples were taken at an abandoned airport. Benzotriazole (BT), a corrosion and flame inhibitor, was found in low concentrations in soils along runways (mean 0.33 mg/kg), at a snow disposal site (0.66 mg/kg), as well as in sediments of a drainage ditch (13 mg/kg). Locally, high BT concentrations were found in the groundwater below the deicing pad, the regeneration plant and the snow disposal site (1.2 to 1100 g/l). Methyl substituted triazoles or tolytriazoles (MeBT) were found in concentrations less than 10% of the BT concentration. Propylene glycol was not detected in soil samples and in only one of the groundwater samples. Microtox tests of the water samples revealed no acute toxic response, however a reduction in nitrification rate was observed (14–43%). The nitrification response could not be related directly to the BT concentration in the samples, although samples with a high BT concentration showed the largest reduction in nitrification rate. BT showed very little sorption in various soil matrices, only peat and compost with a high organic carbon content showed significant sorption. Sorption could be best described using a Freundlich isotherm. These results indicate a high mobility and possibly long persistence of BT in soil and groundwater, which may be attributed to the absence of microbial degradation of BT.     

Concentration Effects on Competitive Sorption of Trichloroethylene and Tetrachloroethylene to the Roots of Typha latifolia: Implications for Phytomonitoring

Uptake of organic contaminants by plant roots consists of two consecutive steps: sorption to plant roots and entrance into root xylem tissues through epidermal and endodermic membranes. Most research pertaining to phytoremediation assumed that sorption to plant roots is linear and non-competitive. A growing body of evidence, however, is suggesting that sorption to plant roots is nonlinear and competitive. The objective of this study was to examine the concentration effects of chemical constituents on the competitive sorption of trichloroethylene (TCE) and tetrachloroethylene (PCE) to the roots of Typha latifolia. Competitive sorption was clearly demonstrated by the reduced sorption of TCE and PCE in bi-solute systems than in single-solute systems. Concentration is an important factor affecting the extent of competition. In bi-solute systems, the PCE/TCE ratio on root surface approximately reflected the contaminant footprints in solution. The result was attributed to limited high energetically favorable sorption sites on the root surface and similar sorption mechanisms of TCE and PCE. The results hold significant importance for the application of phytomonitoring of organic contaminant mixtures.     

Effect of Sediment Humic Substances on Sorption of Selected Endocrine Disruptors

Characterizing sorption processes is essential to understand the environmental distribution and toxicity potential of endocrine disruptors in terrestrial and aquatic systems. The sorption behaviors of three endocrine disruptors (bisphenol A (BPA), 17β-estradiol (E2), and 17α-ethynylestradiol (EE2)) on sediments were investigated using batch techniques. Samples were taken from some representative reaches in several major Chinese rivers. More attention has been paid to the effect of sediment organic components on the sorption of BPA, E2, and EE2. The results show that the sediment organic carbon-normalized partition coefficients (K _oc (sed)) for three endocrine disruptors are in the order of EE2 > E2 > BPA, which corresponds to the octanol-water partitioning coefficients (logK _ow) of the compounds. Moreover, the K _oc values for humic substances (K _oc (hs)) are comparable with the K _oc (sed) values and highly dependent on the physico-chemical properties of humic substances in sediments. The UV absorptivity at 272 nm (A ₂₇₂), which suggests the abundance of aromatic rings in humic substance structure, correlates well with the K _oc (hs) values. In addition, the infrared spectra of the humic substances extracted from sediments show four strong bands centered at 3,400 cm⁻¹, 1,625 cm⁻¹, 1,390 cm⁻¹, and 1,025 cm⁻¹. The K _oc (hs) values have a positive linear relation with the peak area ratio for peak at 1,025 cm⁻¹ and a negative linear relation with the peak area ratio between peaks at 1,625 cm⁻¹ and 1,025 cm⁻¹. Hence, the hydrogen bonds play a critical role to the sorption of selected endocrine disruptors.     

Production and Consumption of NO in Forest and Pasture Soils from the Amazon Basin

NO production and the rate constant of NO consumptionin soil samples from Amazonian forest and pasturesites were determined in the laboratory. The purposewas to study NO production and consumption in soilsfrom both types of land use as functions of soiltemperature and soil moisture. NO productionincreased exponentially with soil temperature. Thedegree of increase depended on soil moisture,indicating that the response of NO production to achange in soil temperature is most pronounced at acertain intermediate soil moisture. NO productionpeaked at a soil moisture of 0.10 g g^-1, correspondingto 0.27 and 0.38 water-filled pore space for forestand pasture soils, respectively. The optimum soilmoisture for which maximum NO release was observedwas independent of soil temperature. NO consumptionwas most efficient at high soil temperatures andunder dry soil conditions. NO release wasapproximately 10 times larger for forest than pasturesoil. The difference may be related to the higherNO₃ ^- content in forest soil.     

Sensitivity of Water Quality Model Results for the Dutch Coastal Zone to the Distribution Coefficient of Cadmium

Results of a water quality model of the Dutch coastal zone appeared to be highly sensitive for the distribution coefficient particulate/dissolved (K_d) of cadmium.Field data of the Dutch coastal zone were used to calculate the annual and seasonal trend in the distribution coefficient of cadmium over the years 1983–88. A strong seasonal and spatial gradient in the distribution coefficient was found with relatively high values in summer and lower values in winter (K_d=3.0–7.0 log l/kg). Near the coast (2 km) the K_d was lower than more offshore (70 km from the coast). In addition, values for the distribution coefficient for cadmium were extracted from the literature (K_d=2.9–4.7 log l/kg).The range of K_d values obtained from the field data was used to perform model simulations for cadmium, in order to determine the sensitivity of the model to the distribution coefficient. The modelled yearly averaged concentrations of dissolved cadmium at one location 10 km from the coast, ranged from 0.005–0.035 μg/l, depending on the magnitude of the K_d used in the simulation. These concentrations are low compared to measured values (0.053 μg/l) due to an underestimation of the cadmium input to the North Sea, or possibly the occurrence of bottom-water exchange processes which the model does not include.     

Scaling methane oxidation: from laboratory incubation experiments to landfill cover field conditions

Evaluating field-scale methane oxidation in landfill cover soils using numerical models is gaining interest in the solid waste industry as research has made it clear that methane oxidation in the field is a complex function of climatic conditions, soil type, cover design, and incoming flux of landfill gas from the waste mass. Numerical models can account for these parameters as they change with time and space under field conditions. In this study, we developed temperature, and water content correction factors for methane oxidation parameters. We also introduced a possible correction to account for the different soil structure under field conditions. These parameters were defined in laboratory incubation experiments performed on homogenized soil specimens and were used to predict the actual methane oxidation rates to be expected under field conditions. Water content and temperature corrections factors were obtained for the methane oxidation rate parameter to be used when modeling methane oxidation in the field. To predict in situ measured rates of methane with the model it was necessary to set the half saturation constant of methane and oxygen, K_m, to 5%, approximately five times larger than laboratory measured values. We hypothesize that this discrepancy reflects differences in soil structure between homogenized soil conditions in the lab and actual aggregated soil structure in the field. When all of these correction factors were re-introduced into the oxidation module of our model, it was able to reproduce surface emissions (as measured by static flux chambers) and percent oxidation (as measured by stable isotope techniques) within the range measured in the field.     

Adsorption Efficiency of Polyaspartate-Montmorillonite Composite Towards the Removal of Pb(II) and Cd(II) from Aqueous Solution

The selective modification of sodium montmorillonite (Na⁺-Mt) surface with polyionene followed by poly (succinimde-co-aspartate) has been considered. Na⁺-Mt was allowed to react with well characterized polyionene in two fold excess. The resulting polyionene/Mt (IC) was further modified with poly (succinimide-co-aspartate) through an ion exchange process. The obtained polyaspartate/Mt (IPS) composite was characterized by elemental analysis, X-ray diffraction, FTIR spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and BET surface analyzer. The adsorption efficiency of IPS composite was investigated for the removal of Pb(II) and Cd(II) from aqueous solution under different experimental conditions including initial metal ions concentration, temperature and single and binary mixture systems of metal ions. The experimental data were analyzed by Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich models. Langmuir model reveals that the monolayer adsorption capacity of IPS was 92.59 and 67.57 mg/g for Pb(II) and Cd(II), respectively. The modification of parent Na⁺-Mt enhanced their adsorption capacity by about 87.91 and 29.84% for Pb(II) and Cd(II), respectively, due to inclusion of extra active sites of polyaspartate. The mean sorption energy, E calculated from Dubinin–Radushkevich isotherm were 2.75 and 1.98 kJ/mol for the adsorption of Pb(II) and Cd(II), respectively, indicating physical adsorption process. Also, The thermodynamic parameters were calculated and indicated that the adsorption was spontaneous and exothermic process. The mechanism of cation exchange and complexation of metal ions was suggested. IPS composite has a considerable potential for the removal of heavy metal ions from aqueous solution and wastewater stream.     

Monitoring of the Degradation Activities and the Diversity of the Microbial Community Degrading Refinery Waste Sludge

The biodegradation of n-alkanes and branched alkanes from waste sludge were observed in landfarming soils of Motor Oil Hellas (a petroleum refinery) and changes in the bacterial communities in the soils were monitored during the remediation. Bacterial 16S rRNA gene (rDNA)-based community fingerprint patterns were obtained from soil samples by terminal restriction fragment length polymorphism (T-RFLP) analysis. Changes in T-RFLP fingerprints, as well as in the petroleum contaminant composition of the polluted soil, correlated with degradation activities in field tests.     

Sorption and Recovery of Heavy Oils by Using Exfoliated Graphite

The behavior of sorption of heavy oils into exfoliated graphite samples with different bulk density was studied by using four grades of heavy oil with different viscosity. Maximum sorption capacity of exfoliated graphite was found to be 83 g of A-grade heavy oil per 1 g of the exfoliated graphite and also its sorption occurs very rapidly, within 1 min. Sorption capacity depended strongly on bulk density and total pore volume of exfoliated graphite. Time to reach maximum sorption, as well as sorption capacity, of an exfoliated graphite depended strongly on grade of heavy oil; a large amount of heavy oils with low viscosity was sorbed in a short time, but oils with high viscosity needed a long time although sorbed amount was relatively small.Heavy oils sorbed into exfoliated graphite could be recovered by a simple filtration under reduced pressure with the recovery ratio of about 70% and could not be differentiated from molecular weight values and the contents of various hydrocarbons. The exfoliated graphite packed into a bag was shown to give also high sorption capacity, if the material of the bag and the way of picking up from heavy oil were properly selected.     

Composition and Toxicity of Residual Bunker C Fuel Oil in Intertidal Sediments After 30 Years

In 1970, approximately 2000 m³ of Bunker C crude oil impacted 300 km of Nova Scotia’s coastline following the grounding of the tanker Arrow. Only 10% of the contaminated coast was subjected to cleanup, the remainder was left to cleanse naturally. To determine the long-term environmental impact of residual oil from this spill event, samples of sediment and interstitial water were recovered in 1993, 1997 and 2000 from a sheltered lagoon in Black Duck Cove. This heavily oiled site was intentionally left to recover on its own. Visual observations and chemical analysis confirmed that substantial quantities of the weathered cargo oil were still present within the sediments at this site. However, direct observations of benthic invertebrate abundance suggest that natural processes have reduced the impacts of the residual oil. To confirm this hypothesis, sediment and interstitial water samples from Black Duck Cove were assessed with a comprehensive set of biotests and chemical assays.Residual oil in the sediments had limited effect on hepatic CYP1A protein levels and mixed function oxygenase (MFO) induction in winter flounder (Pleuronectes americanus). No toxicity was detected with the Microtox solid phase test (Vibrio fischeri). Significant sediment toxicity was detected by the amphipod survival test (Eohaustorius estuarius) in four out of the eight contaminated sediments. Interstitial water samples were deemed non-toxic by the Microtox 100% test (Vibrio fischeri) and the echinoid fertilization test (Lytechinus pictus). Sediment elutriates were also found to be non-toxic in the grass shrimp embryo-larval toxicity (GSELTOX) test (Palaemonetes pugio).Recovery at this contaminated site is attributed to natural processes that mediated biodegradation and physical removal of oil from the sediments. In support of the latter mechanism, mineralization experiments showed that all test sediments had the capacity for hexadecane, octacosane and naphthalene degradation, while chemical analysis confirmed that the Bunker C oil from the Arrow had undergone substantial biodegradation.     

Levels and Characteristics of TOC in Throughfall, Forest Floor Leachate and Soil Solution in Undisturbed Boreal Forest Ecosystems

Total organic carbon (TOC) concentrations and fluxes in throughfall, forest floor leachate, soil solution (15 and 35 cm depths), and groundwater for coniferous forest sites in the boreal zone throughout Finland are described. Eight upland forest stands and one peatland forest stand are included in the study and the samples were collected during 1991–1997. Carbon (C) pools in the living tree biomass and soil compartments are presented, and the hydrophobic/hydrophilic and acidic components of dissolved organic carbon (DOC) in samples collected in autumn 1999 and spring 2000 from two of the sites are compared. Biomass (aboveground and belowground) pools of C averaged 88 Mg ha^-1 and soil (humus layer + 20 cm soil layer) averaged 55 Mg ha^-1. Stand throughfall TOC monthly mean concentrations ranged from 4.0 to 18.6 mg L^-1 and annual fluxes averaged 4.0 g m^-2 yr^-1. TOC concentrations in the water passing through the forest floor and soil decreased with depth. Plot mean concentrations at 35 cm depth values ranged from 4.1 to 21.2 mg L^-1 and fluxes averaged 3.7 g m^-2 yr^-1. Throughfall TOC concentrations were lowest during the winter, snowfall period and highest during the growing season. No monotonic trends in throughfall TOC concentrations over the 1991–1997 period were found. Soil solution TOC concentrations varied considerably, both within and between years. DOC in throughfall, forest floor, and soil solutions and in both autumn and spring seasons was dominated by hydrophobic fractions, particularly acids. Spruce canopies and litter appear to be important sources of soluble organic carbon, particularly acidic and hydrophobic compounds. Further studies on the nature and dynamics of organic carbon fluxing through coniferous, boreal forest ecosystems are needed.