Kinetics and thermodynamic studies of Methyl Orange removal by polyvinylidene fluoride-PEDOT mats

We report the preparation of poly(3,4-ethylene dioxythiophene) (PEDOT)-modified polyvinylidene fluoride electrospun fibers and their use as a novel adsorbent material for the removal of the anionic dye Methyl Orange (MO) from aqueous media. This novel adsorbent material can be used to selectively remove MO on a wide pH range (3.0–10.0), with a maximum capacity of 143.8 mg/g at pH 3.0. When used in a recirculating filtration system, the maximum absorption capacity was reached in a shorter time (20 min) than that observed for batch mode experiments (360 min). Based on the analyses of the kinetics and adsorption isotherm data, one can conclude that the predominant mechanism of interaction between the membrane and the dissolved dye molecules is electrostatic. Besides, considering the estimated values for the Gibbs energy, and entropy and enthalpy changes, it was established that the adsorption process is spontaneous and occurs in an endothermic manner. The good mechanical and environmental stability of these membranes allowed their use in at least 20 consecutive adsorption/desorption cycles, without significant loss of their characteristics. We suggest that the physical-chemical characteristics of PEDOT make these hybrid mats a promising adsorbent material for use in water remediation protocols and effluent treatment systems.     

Carbonization of waste PVC to develop porous carbon material without further activation

Efficient removal of chlorine from PVC achieved by two-stage heat-treatment (280 and 410 degrees C) provided chlorine-free isotropic pitch containing additive. The pitch was stabilized and carbonized into porous carbons with surface areas of approximately 300 m2/g. Resultant porous carbons showed three pore structures of supermicropore, micropore and mesopore. The generation of CO2 from the decomposition of the CaCO3 additive in waste PVC is responsible for the development of porous structures. The surface area of the carbonized product increased after the removal of CaO.     

The effect of sodium chloride on the dissolution of calcium silicate hydrate gels

The use of cement based materials will be widespread in the long-term management of radioactive materials in the United Kingdom. One of the applications could be the Nirex reference vault backfill (NRVB) as an engineered barrier within a deep geological repository. NRVB confers alkaline conditions, which would provide a robust chemical barrier through the control of the solubility of some key radionuclides, enhanced sorption and minimised corrosion of steel containers. An understanding of the dissolution of C-S-H gels in cement under the appropriate conditions (e.g., saline groundwaters) is necessary to demonstrate the expected evolution of the chemistry over time and to provide sufficient cement to buffer the porewater conditions for the required time. A programme of experimental work has been undertaken to investigate C-S-H gel dissolution behaviour in sodium chloride solutions and the effect of calcium/silicon ratio (C/S), temperature and cation type on this behaviour. Reductions in calcium concentration and pH values were observed with samples equilibrated at 45 degrees C compared to those prepared at 25 degrees C. The effect of salt cation type on salt-concentration dependence of the dissolution of C-S-H gels was investigated by the addition of lithium or potassium chloride in place of sodium chloride for gels with a C/S of 1.0 and 1.8. With a C/S of 1.0, similar increases in dissolved calcium concentration with increasing ionic strength were recorded for the different salts. However, at a C/S of 1.8, anomalously high calcium concentrations were observed in the presence of lithium.     

Mineralogical characterization of the Tournemire argillite after in situ interaction with concretes

This study aims to investigate, through mineralogical characterization (SEM, XRD) and mass-balance calculations, the effects of contact time, concrete types and presence of free water on the Tournemire argillite under in situ conditions. Three sampling zones from Excavation Disturbed Zone (EDZ) areas have been chosen: (1) dry contacts, collected at the tunnel masonry/argillite interface (contact time - 125 years), (2) wet contacts, taken close to drained areas below the tunnel roadbed in contact with the canal draining the Cernon fault water (contact time - 15 and 7 years) and at the tunnel masonry/argillite interface over 70 m from the Cernon fault (contact time - 125 years). This study shows that: in the absence of water, no significant modification of argillite is observed after 125 years, except for pyrite dissolution and gypsum precipitation; in the presence of water, precipitation of gypsum, recrystallization of mixed-layer clays, neoformation of zeolites and K-feldspars overgrowths are observed. At the concrete/argillite interface near the Cernon fault, important dolomite neoformation and leaching of chlorite and kaolinite occur. These processes are enhanced with contact time, low flow rate and the nature of the concrete (compound cement Portland CEM II 32.5). Evidence for oxidation processes linked to the EDZ (pyrite oxidation, Fe-oxy-hydroxide and gypsum precipitation) is observed.     

BR-319: Brazil’s Manaus-Porto Velho Highway and the Potential Impact of Linking the Arc of Deforestation to Central Amazonia

Brazil’s BR-319 Highway linked Manaus, in the state of Amazonas, to Porto Velho, Rondônia, until it became impassable in 1988. Now it is proposed for reconstruction and paving, which would facilitate migration from the “Arc of Deforestation” in the southern part of the Amazon region to new frontiers farther north. The purpose of the highway, which is to facilitate transport to São Paulo of products from factories in the Manaus Free Trade Zone, would be better served by sending the containers by ship to the port of Santos. The lack of a land connection to Manaus currently represents a significant barrier to migration to central and northern Amazonia. Discourse regarding the highway systematically overestimates the highway’s benefits and underestimates its impacts. A variety of changes would be needed prior to paving the highway if these potential impacts are to be attenuated. These include zoning, reserve creation, and increased governance in various forms, including deforestation licensing and control programs. More fundamental changes are also needed, especially the abandonment of the long-standing tradition in Brazil of granting squatters’ rights to those who invade public land. Organizing Amazonian occupation in such a way that road construction and improvement cease to lead to explosive and uncontrolled deforestation should be a prerequisite for approval of the BR-319 and other road projects for which major impacts are expected. These projects could provide the impetus that is needed to achieve the transition away from appropriation of public land by both small squatters and by grileiros (large-scale illegal claimants). A delay in reconstructing the highway is advisable until appropriate changes can be effected.     

Fish mercury increase in Lago Manso, a new hydroelectric reservoir in tropical Brazil

It has been frequently demonstrated that mercury (Hg) concentrations in fish rise in newly constructed hydroelectric reservoirs in the Northern Hemisphere. In the present work, we studied whether similar effects take place also in a tropical upland reservoir during impoundment and discuss possible causes and implications. Total Hg concentrations in fish and several soil and water parameters were determined before and after flooding at Rio Manso hydroelectric power plant in western Brazil. The Hg concentrations in soil and sediment were within the background levels in the region (22-35 ng g(-1) dry weight). There was a strong positive correlation between Hg and carbon and sulphur in sediment. Predatory fish had total Hg concentrations ranging between 70 and 210 ng g(-1) f.w. 7 years before flooding and between 72 and 755 ng g(-1) f.w. during flooding, but increased to between 216 and 938 ng g(-1) f.w. in the piscivorous and carnivorous species Pseudoplatystoma fasciatum, cachara, and Salminus brasiliensis, dourado, 3 years after flooding. At the same time, concentrations of organic carbon in the water increased and oxygen concentrations decreased, indicating increased decomposition and anoxia as contributing to the increased Hg concentrations in fish. The present fish Hg concentrations in commonly consumed piscivorous species are a threat to the health of the population dependent on fishing in the dam and downstream river for sustenance. Mercury exposure can be reduced by following fish consumption recommendations until fish Hg concentrations decrease to a safe level.     

Using Relative Risk to Compare the Effects of Aquatic Stressors at a Regional Scale

The regional-scale importance of an aquatic stressor depends both on its regional extent (i.e., how widespread it is) and on the severity of its effects in ecosystems where it is found. Sample surveys, such as those developed by the U.S. Environmental Protection Agency’s Environmental Monitoring and Assessment Program (EMAP), are designed to estimate and compare the extents, throughout a large region, of elevated conditions for various aquatic stressors. In this article, we propose relative risk as a complementary measure of the severity of each stressor’s effect on a response variable that characterizes aquatic ecological condition. Specifically, relative risk measures the strength of association between stressor and response variables that can be classified as either “good” (i.e., reference) or “poor” (i.e., different from reference). We present formulae for estimating relative risk and its confidence interval, adapted for the unequal sample inclusion probabilities employed in EMAP surveys. For a recent EMAP survey of streams in five Mid-Atlantic states, we estimated the relative extents of eight stressors as well as their relative risks to aquatic macroinvertebrate assemblages, with assemblage condition measured by an index of biotic integrity (IBI). For example, a measure of excess sedimentation had a relative risk of 1.60 for macroinvertebrate IBI, with the meaning that poor IBI conditions were 1.6 times more likely to be found in streams having poor conditions of sedimentation than in streams having good sedimentation conditions. We show how stressor extent and relative risk estimates, viewed together, offer a compact and comprehensive assessment of the relative importances of multiple stressors.     

Effect of Cadmium on Microbial Activity and a Ryegrass Crop in Two Semiarid Soils

Soil pollution with Cd is an environmental problem common in the world, and it is necessary to establish what Cd concentrations in soil could be dangerous to its fertility from toxicity effects and the risk of transference of this element to plants and other organisms of the food chain. In this study, we assessed Cd toxicity on soil microorganisms and plants in two semiarid soils (uncultivated and cultivated). Soil ATP content, dehydrogenase activity, and plant growth were measured in the two soils spiked with concentrations ranging from 3 to 8000 mg Cd/kg soil and incubated for 3 h, 20 days, and 60 days. The Cd concentrations that produced 5%; 10%;, and 50%; inhibition of each of the two soil microbiological parameter studied (ecological dose, ED, values) were calculated using two different mathematical models. Also, the effect of Cd concentration on plant growth of ryegrass (Lolium perenne, L.) was studied in the two soils. The Cd ED values calculated for soil dehydrogenase activity and ATP content were higher in the agricultural soils than in the bare soil. For ATP inhibition, higher ED values were calculated than for dehydrogenase activity inhibition. The average yields of ryegrass were reduced from 5.03 to 3.56 g in abandoned soil and from 4.21 to 1.15 g in agricultural soil with increasing concentrations of Cd in the soil. Plant growth was totally inhibited in abandoned and agricultural soils at Cd concentrations above 2000 and 5000 mg/kg soil, respectively. There was a positive correlation between the concentration of Cd in the plants and the total or DTPA-extractable concentrations of Cd in the soil.     

Use of Artificial Roost Structures by Bats at the Indianapolis International Airport

From 1992–1996, 3204 artificial roosts of 9 types were placed in woodlots near Indianapolis International Airport in an effort to provide habitat for the federally-endangered Indiana myotis (Myotis sodalis) and to determine the feasibility of using these structures to manage bats in a rapidly developing suburban area. We surveyed these structures at least annually during 1992–1999 and found only northern myotis (Myotis septentrionalis) regularly using the structures. Four other species were occasionally found using structures including big brown bats (Eptesicus fuscus, n = 14 individuals), little brown myotis (Myotis lucifugus, n = 2), Indiana myotis (Myotis sodalis, n = 2), and one silver-haired bat (Lasionycteris noctivagans). Single, triple, and Missouri-style batboxes were almost always used, rather than the six other types of experimental roosts that had been in place. However, after 10 years in place, it appears that Indiana bats are acclimated to boxes, as 6 of them were being used rather regularly by Indiana myotis. Bat boxes can provide roosting habitat for some species under conditions where few suitable roosts exist, but assuring an abundance of natural habitats is usually more desirable for conservation of tree-roosting bats.