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.     

Pilot project of mechanical-biological treatment of waste in Brazil

By mechanical-biological treatment (MBT) of residual municipal solid waste the behaviour of landfills can be significantly improved. After MBT the organic content (COD and BOD5), total organic carbon, and total nitrogen in the leachate, as well as the gas production rate, are reduced to values lower than 90% of the fresh untreated waste. The volume of the stabilized material to be disposed on landfills decreases enormously, by up to 70%. The monitoring effort for a landfill constructed under these conditions is reduced to a minimum and the stabilized material can be used in other ways, as material for reforestation, for cover material or for thermal utilization to produce energy. Environmental conditions are important in MBT, as well as waste characteristics. This paper describes the results of a pilot project of MBT performed in Rio de Janeiro, Brazil. The results have shown that this technology can be used successfully in developing countries, with economy for the society and important results for the environment.     

Estimation of odor emission rate from landfill areas using the sniffing team method

The monitoring of the odor annoyance generated by a landfill area is difficult, since it is a multi-area-sources problem, with a discontinuous odor emission. This paper proposes an adaptation of the method of sniffing team campaigns to the particular case of fresh waste odors. The method is based on the field determination of odor perception points, followed by data processing with a bi-Gaussian-type model, adapted to handle the odors. In a first step, field observers delineate the region in which odor impact is experienced and then the emission rate is manipulated in a dispersion model until the predicted size of the impact zone matches that observed in the field. In a second step the adjusted emission rate is entered into the model to calculate the percentiles corresponding to the average annoyance zone. The originality of the proposed method is the introduction of all observation points and of all recorded meteorological data into the model. The paper discusses the method limitations and the errors induced on the results, i.e. the odor emission rate and the percentile lines (or iso-concentration lines) which are used to describe the odor concentrations on a map of the surroundings of the plant. The proposed method proves to be reliable for diffuse sources, such as landfill areas. The obtained results are coherent with other results found in the literature with other techniques.     

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.     

Cement/clay interactions-- a review: experiments, natural analogues, and modeling

The concept of storing radioactive waste in geological formations calls for large quantities of concrete that will be in contact with the clay material of the engineered barriers as well as with the geological formation. France, Switzerland and Belgium are studying the option of clayey geological formations. The clay and cement media have very contrasted chemistries that will interact and lead to a degradation of both types of material. The purpose of this review is to establish an exhaustive list of laboratory experiments so as to identify the reaction sequences in the evolution of both the clay minerals and accessory minerals during their alteration in an alkaline environment. We review the data on clay dissolution kinetics in this environment, and include an invaluable study of natural analogues that allow one to correlate the phenomena in time. The available data and experiments make it possible to construct predictive numerical models. However, as the quality of the data is inhomogeneous, we recommend a continuation of the thermodynamic and kinetic data acquisition. It is obvious that the numerical modeling of the alkaline disturbance will be more relevant if it can combine the advantages of the different detailed models: mineralogical completeness, combined modeling of the clay and cement media, evolution of the porosity, consideration of the pCO2 and all the surface reactions.     

用HPLC 分离和鉴定大气中的羰基化合物

大气中的挥发性羰基化合物可以通过2,4-二硝基苯肼(DNPH)原位衍生化而被捕集.采用反相HPLC 可以洗脱和分析这些羰基衍生物.本文采用该方法监测了美国佛蒙特州大气样品中的痕量甲醛、乙醛和丙酮.     

Environmental assessment of mercury dispersion, transformation and bioavailability in the Lake Victoria Goldfields, Tanzania

Environmental dispersion and transformation of mercury discharged from gold mining operations has been investigated in field and laboratory studies in order to provide better understanding of the degree of mercury (Hg) pollution and bioavailability in the Lake Victoria goldfields (LVGF) ecosystems. This paper reviews results already published elsewhere and presents additional data on Hg dynamics in the LVGF. Studies conducted at the Mugusu and Rwamagaza artisanal mines indicated different degrees of Hg contamination and dispersion in environmental matrices. Mercury concentration in contaminated river sediments near the Mugusu mine varied from 6.0 to 0.5 mg/kg on a dry weight basis. The highest Hg contamination levels (165-232 mg/kg) were associated with mine tailings at the Rwamagaza mine. Mercury concentrations in fish representing different dietary habits on the southwestern shore of Lake Victoria at the Nungwe Bay were very low (2-35 microg/kg) and thought to represent background levels. These and other results suggested that the use of Hg in gold extraction in the LVGF has not caused high Hg levels in lake fish. The study of Hg in lichens showed Parmelia lichen to be an effective bioindicator for atmospheric Hg contamination due to Hg emissions from gold-amalgam firing and purification operations. The Hg levels in the lichens around the Mugusu mine ranged from 3.1 to 0.1 microg/g; the highest levels were recorded in the lichens sampled close to gold-amalgam processing sites. The regional background level in the Parmelia lichen was 0.05-0.10 microg/g, with a mean level of 0.07 microg/g. Studies of Hg transformation in the mine tailings revealed unexpectedly high methylmercury (MeHg) levels in the tailings (629-710 ng/g), which indicated that oxidation and methylation of metallic Hg in the tailings occurred at significant levels under tropical conditions. Re-equilibration of the tailings with freshwater (FW) indicated the MeHg was firmly bound in the tailings and therefore very little MeHg was released to the water column (0.2-1.5 ng/L). The methylation of Hg in tropical loamy clay soil contaminated with HgCl(2) (5 mg Hg/kg) yielded MeHg concentrations of 11 and 14 ng/g when inundated with seawater and FW, respectively, for 4 weeks. Little MeHg was transferred from the soil to the equilibrated water (< or = 0.4 ng/L). Atmospheric exposure of the soil pre-inundated with FW resulted in net degradation of MeHg during the 1st week of exposure, followed by net production and accumulation of MeHg in the soil (up to 15.5 ng/g) during atmospheric desiccation. Mercury uptake by fish from the Hg(0)-contaminated aquatic sediment-tailings system in the aquarium experiment was found to be low, suggesting the low availability of MeHg for bioaccumulation in the system. These and other results provide useful insights into Hg transformation, mobility and bioavailability in tropical aquatic systems affected by Hg pollution from gold mining operations.     

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.     

Changes in soil characteristics and plant species composition along a moisture gradient in a Mediterranean pasture

Soil physicochemical characteristics, total aboveground biomass, number of species and relative abundance of groups and individual species were measured along a moisture gradient in a pasture, flooded in part during winter through early summer, adjacent to Pamvotis lake in Ioannina, Greece. Soil and vegetation measurements were conducted in 39 quadrats arranged in four zones perpendicular to the moisture gradient. The zone closest to the lake, recently separated from the lake, became part of the pasture and its soil texture was quite different from that of the other zones with a substrate containing 91% sand. Except for pH, this zone had the lowest values in the other five soil physicochemical characteristics measured (organic matter, total and extracted inorganic nitrogen, Olsen extracted phosphorus and extractable potassium); in the other zones organic matter, total nitrogen, phosphorus and potassium tended to increase from the driest to the wettest zone. Total aboveground biomass, ranging from 280 to 840 gm-2, is high for herbaceous pastures in the conditions of Mediterranean climate and it was not related to distance from the lake's shoreline, although the highest values were measured at intermediate distances, or to any of the various soil characteristics measured. Also, the number of species/0.25 m2 was not related to any of the various soil characteristics, but it was highest at the intermediate distances from the lake's shoreline. Species composition varied along the moisture gradient. Forbs as well as annual grasses and legumes declined in abundance from the driest to the wettest places; the reverse was the case for sedges and perennial grasses and legumes. These results indicate that the soil moisture gradient was the principal factor affecting soil characteristics and plant species composition. Since most species were recorded in all the four zones of the pasture, indicating that these can tolerate all variations in abiotic conditions of pasture, the vegetation zonation seems to be influenced by competition. Each functional group of species tends to dominate in a particular range of the soil moisture gradient where it is better suited and tends to exclude competitively other species. Management practices (mowing and grazing) affect the kinds of processes which maintain the observed community structure either by preventing the establishment of later successional species, like reeds and woody species, or by moderating the shoot competition, especially in the wetter zones, and thus permitting the creeping species to grow successfully.