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.     

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.     

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.     

Assessing the Effects of Alternative Setback Channel Constraint Scenarios Employing a River Meander Migration Model

River channel migration and cutoff events within large river riparian corridors create heterogeneous and biologically diverse landscapes. However, channel stabilization (riprap and levees) impede the formation and maintenance of riparian areas. These impacts can be mitigated by setting channel constraints away from the channel. Using a meander migration model to measure land affected, we examined the relationship between setback distance and riparian and off-channel aquatic habitat formation on a 28-km reach of the Sacramento River, California, USA. We simulated 100 years of channel migration and cutoff events using 11 setback scenarios: 1 with existing riprap and 10 assuming setback constraints from about 0.5 to 4 bankfull channel widths (bankfull width: 235 m) from the channel. The percentage of land reworked by the river in 100 years relative to current (riprap) conditions ranged from 172% for the 100-m constraint setback scenario to 790% for the 800-m scenario. Three basic patterns occur as the setback distance increases due to different migration and cutoff dynamics: complete restriction of cutoffs, partial restriction of cutoffs, and no restriction of cutoffs. Complete cutoff restriction occurred at distances less than about one bankfull channel width (235 m), and no cutoff restriction occurred at distances greater than about three bankfull widths (∼700 m). Managing for point bars alone allows the setbacks to be narrower than managing for cutoffs and aquatic habitat. Results suggest that site-specific “restriction of cutoff” thresholds can be identified to optimize habitat benefits versus cost of acquired land along rivers affected by migration processes.     

Nitrate and sediment fluxes from a California rangeland watershed

Long-term water quality records for assessing natural variability, impact of management, and that guide regulatory processes to safeguard water resources are rare for California oak woodland rangelands. This study presents a 20-yr record (1981-2000) of nitrate-nitrogen (NO(3)-N) and suspended sediment export from a typical, grazed oak woodland watershed (103 ha) in the northern Sierra Nevada foothills of California. Mean annual precipitation over the 20-yr period was 734 mm yr(-1) (range 366-1205 mm yr(-1)). Mean annual stream flow was 353 mm y(-1) (range 87-848 mm yr(-1)). Average annual stream flow was 48.1 +/- 16% of precipitation. Mean annual NO(3)-N export was 1.6 kg ha(-1) yr(-1) (range 0.18-3.6 kg ha(-1) yr(-1)). Annual NO(3)-N export significantly (P < 0.05) increased with increasing annual stream flow and precipitation. Mean daily NO(3)-N export was 0.004 kg ha(-1) d(-1) (range 10(-5) to 0.55 kg ha(-1) d(-1)). Mean annual suspended sediment export was 198 kg ha(-1) yr(-1) (range 23-479 kg ha(-1) yr(-1)). There was a positive relationship (P < 0.05) between annual suspended sediment export, annual stream flow and precipitation. Mean daily suspended sediment export was 0.54 kg ha(-1) d(-1) (range 10(-4) to 155 kg ha(-1) d(-1)). Virtually no sediment was exported during the dry season. The large variation in daily and annual fluxes highlights the necessity of using long-term records to establish quantitative water quality targets for rangelands and demonstrates the difficulty of designing a water quality monitoring program for these ecosystems.     

Persistence of fermentative process to phenolic toxicity in groundwater

The fermentation process is an important component in the biodegradation of organic compounds in natural and contaminated systems. Comparing with terminal electron-accepting processes (TEAPs), however, research on fermentation processes has to some extent been ignored in the past decades, particularly on the persistence of fermentation process in the presence of toxic organic pollutants. Both field and laboratory studies, presented here, showed that microbial processes in a groundwater-based system exhibited a differential inhibitory response to toxicity of phenolic compounds from coal tar distillation, thus resulting in the accumulation of volatile fatty acids (VFAs) and hydrogen. This indicated that fermentation processes could be more resistant to phenol toxicity than the subsequent TEAPs such as methanogenesis and sulfate reduction, thus providing us with more options for enhancing bioremediation processes.     

Nitrogen and phosphorus status of soils and trophic state of lakes associated with forage-based beef cattle operations in Florida

Forage-based livestock systems have been implicated as major contributors to deteriorating water quality, particularly for phosphorus (P) from commercial fertilizers and manures affecting surface and ground water quality. Little information exists regarding possible magnitudes of nutrient losses from pastures that are managed for both grazing and hay production and how these might impact adjacent bodies of water. We examined the changes that have occurred in soil fertility levels of rhizoma peanut (Arachis glabrata Benth.)-based beef cattle pastures (n = 4) in Florida from 1988 to 2002. These pastures were managed for grazing in spring followed by haying in late summer and were fertilized annually with P (39 kg P2O5 ha(-1)) and K (68 kg K2O ha(-1)). Additionally, we investigated trends in water quality parameters and trophic state index (TSI) of lakes (n = 3) associated with beef cattle operations from 1993 to 2002. Overall, there was no spatial or temporal buildup of soil P and other crop nutrients despite the annual application of fertilizers and daily in-field loading of animal waste. In fact, soil fertility levels showed a declining trend for crop nutrient levels, especially soil P (y = 146.57 - 8.14 x year; r2= 0.75), even though the fields had a history of P fertilization and the cattle were rotated into the legume fields. Our results indicate that when nutrients are not applied in excess, cow-calf systems are slight exporters of P, K, Ca, and Mg through removal of cut hay. Water quality in lakes associated with cattle production was "good" (30-46 TSI) based on the Florida Water Quality Standard. These findings indicate that properly managed livestock operations may not be major contributors to excess loads of nutrients (especially P) in surface water.