Waste polyvinylchloride derived pitch as a precursor to develop carbon fibers and activated carbon fibers

Polyvinylchloride (PVC) was successfully recycled through the solvent extraction from waste pipe with an extraction yield of ca. 86%. The extracted PVC was pyrolyzed by a two-stage process (260 and 410 degrees C) to obtain free-chlorine PVC based pitch through an effective removal of chlorine from PVC during the heat-treatment. As-prepared pitch (softening point: 220 degrees C) was spun, stabilized, carbonized into carbon fibers (CFs), and further activated into activated carbon fibers (ACFs) in a flow of CO2. As-prepared CFs show comparable mechanical properties to commercial CFs, whose maximum tensile strength and modulus are 862 MPa and 62 GPa, respectively. The resultant ACFs exhibit a high surface area of 1200 m2/g, narrow pore size distribution and a low oxygen content of 3%. The study provides an effective insight to recycle PVC from waste PVC and develop a carbon precursor for high performance carbon materials such as CFs and ACFs.     

Modeling Acidification Recovery on Threatened Ecosystems: Application to the Evaluation of the Gothenburg Protocol in France

To evaluate the acid deposition reduction negotiated for 2010 within the UNECE LRTAP Gothenburg Protocol, sulphur and nitrogen deposition time-series (1880–2100) were compared to critical loads of acidity on five French ecosystems: Massif Central basalt (site 1) and granite (2); Paris Bassin tertiary sands (3); Vosges mountains sandstone (4) and Landes eolian sands (5). The SAFE model was used to estimate the response of soil solution pH and ratio to the deposition scenario. Among the five sites, critical loads were exceeded in the past at sites 3, 4 and 5. Sites 3 and 4 were still expected to exceed in 2010, the Protocol year. Further reduction of atmospheric deposition, mainly nitrogen, would be needed to achieve recovery on these ecosystems. At sites 3, 4 and 5, the delay between the critical load exceedance and the violation of the critical chemical criterion was estimated to be 10 to 30 years in the top soil and 50 to 90 years in the deeper soil. At site 5, a recovery was expected in the top soil in 2010 with a time lag of 10 years. Unexpectedly, soil pH continued to decrease after 1980 in the deeper soil at sites 2 and 5. This time lag indicated that acidification moved down the soil profile as a consequence of slow base cation depletion by ion exchange. This delayed response of the soil solution was the result of the combination of weathering rates and vegetation uptake but also of the relative ratio between base cation deposition and acid compounds.     

Effects of environmental methylmercury on the health of wild birds, mammals, and fish

Wild piscivorous fish, mammals, and birds may be at risk for elevated dietary methylmercury intake and toxicity. In controlled feeding studies, the consumption of diets that contained Hg (as methylmercury) at environmentally realistic concentrations resulted in a range of toxic effects in fish, birds, and mammals, including behavioral, neurochemical, hormonal, and reproductive changes. Limited field-based studies, especially with certain wild piscivorous bird species, e.g., the common loon, corroborated laboratory-based results, demonstrating significant relations between methylmercury exposure and various indicators of methylmercury toxicity, including reproductive impairment. Potential population effects in fish and wildlife resulting from dietary methylmercury exposure are expected to vary as a function of species life history, as well as regional differences in fish-Hg concentrations, which, in turn, are influenced by differences in Hg deposition and environmental methylation rates. However, population modeling suggests that reductions in Hg emissions could have substantial benefits for some common loon populations that are currently experiencing elevated methylmercury exposure. Predicted benefits would be mediated primarily through improved hatching success and development of hatchlings to maturity as Hg concentrations in prey fish decline. Other piscivorous species may also benefit from decreased Hg exposure but have not been as extensively studied as the common loon.     

Risk assessment of trace elements in the stomach contents of Indo-Pacific Humpback Dolphins and Finless Porpoises in Hong Kong waters

The potential health risks due to inorganic substances, mainly metals, was evaluated for the two resident marine mammals in Hong Kong, the Indo-Pacific Humpback Dolphin (Sousa chinensis) and the Finless Porpoise (Neophocaena phocaenoides). The stomachs from the carcasses of twelve stranded dolphins and fifteen stranded porpoises were collected and the contents examined. Concentrations of thirteen trace elements (Ag, As, Cd, Co, Cr, Cs, Cu, Hg, Mn, Ni, Se, V and Zn) were determined by inductively coupled plasma mass spectrometer (ICP-MS). An assessment of risks of adverse effects was undertaken using two toxicity guideline values, namely the Reference Dose (RfD), commonly used in human health risk assessment, and the Toxicity Reference Value (TRV), based on terrestrial mammal data. The levels of trace metals in stomach contents of dolphins and porpoises were found to be similar. Risk quotients (RQ) calculated for the trace elements showed that risks to the dolphins and porpoises were generally low and within safe limits using the values based on the TRV, which are less conservative than those based on the RfD values. Using the RfD-based values the risks associated with arsenic, cadmium, chromium, copper, nickel and mercury were comparatively higher. The highest RQ was associated with arsenic, however, most of the arsenic in marine organisms should be in the non-toxic organic form, and thus the calculated risk is likely to be overestimated.     

Pteris umbrosa R. Br. as an arsenic hyperaccumulator: accumulation, partitioning and comparison with the established As hyperaccumulator Pteris vittata

The capacity of the Australian native fern Pteris umbrosa to function as an arsenic (As) hyperaccumulator (shoot:soil As concentration >1) was examined by growing plants under glasshouse conditions in an inert medium supplemented with As. Arsenic preferentially accumulated in the fronds, a trait of a hyperaccumulator. The As concentration of fronds decreased with age, being particularly high in the croziers and low in the senesced fronds. Below ground, rhizomes accumulated more As than adventitious roots. Uptake from a range of solution concentrations followed Michaelis Menten kinetics up to a soil solution As concentration of 400mgl(-1). The K(m) for As uptake by roots suggested the operation of a low-affinity carrier. The predicted Nernst membrane potential indicated that uptake was against the electrochemical gradient of As. At 600mgl(-1), the rate of As uptake increased and phytotoxic effects were indicated by a significant decline in biomass. Arsenic uptake and translocation in P. umbrosa and Pteris vittata were similar at low exposure to As. At higher exposure, As uptake and translocation by P. vittata increased more than in P. umbrosa. The growth rate of both ferns was similar, whereas the biomass distribution was not, with P. vittata having a much larger root mass. This suggests that As uptake by P. umbrosa roots was very efficient and may be improved by stimulating root growth to enhance its potential.     

Aerobic degradation of di- and trichlorobenzenes by two bacteria isolated from polluted tropical soils

Two polychlorinated biphenyl (PCBs)-degrading bacteria were isolated by traditional enrichment technique from electrical transformer fluid (Askarel)-contaminated soils in Lagos, Nigeria. They were classified and identified as Enterobacter sp. SA-2 and Pseudomonas sp. SA-6 on the basis of 16S rRNA gene analysis, in addition to standard cultural and biochemical techniques. The strains were able to grow extensively on dichloro- and trichlorobenzenes. Although they failed to grow on tetrachlorobenzenes, monochloro- and dichlorobenzoic acids, they were able to utilize all monochlorobiphenyls, and some dichlorobiphenyls as sole sources of carbon and energy. The effect of incubation with axenic cultures on the degradation of 0.9 mM 1,4-dichlorobenzene, 0.44 mM 1,2,3- and 0.43 mM 1,3,5-trichlorobenzene in mineral salts medium was studied. Approximately, 80-90% of these xenobiotics were degraded in 200 h, concomitant with cell increase of up to three orders of magnitude, while generation times ranged significantly (P<0.05) from 17-32 h. Catechol 1,2-dioxygenase and catechol 2,3-dioxygenase activities were detected in crude cell-free extracts of cultures pre-grown with benzoate, with the latter enzyme exhibiting a slightly higher activity (0.15-0.17 micromolmin(-1) mg of protein(-1)) with catechol, suggesting that the meta-cleavage pathway is the most readily available catabolic route in the SA strains. The wider substrate specificity of these tropical isolates may help in assessing natural detoxification processes and in designing bioremediation and bioaugmentation methods.     

Photolytic degradation of triclosan in freshwater and seawater

A 12-days photolysis experiment of triclosan, a widely used bactericide, was performed in freshwater and seawater under a low intensity artificial white light source. Photodegradation of triclosan was observed in both the freshwater and seawater samples. Assuming a first-order reaction, half-lives of triclosan in the freshwater and seawater were approximately 8 and 4 days, respectively. 2,8-Dichlorodibenzo-p-dioxin (DCDD) was detected in both the freshwater and seawater samples after 3 days of irradiation. The photodegradation of triclosan and the production of DCDD suggest that triclosan could be less stable and DCDD might be more stable in seawater than freshwater. As a result, DCDD produced from triclosan survives for a longer time in seawater.     

Removal of added nitrate in the single, binary, and ternary systems of cotton burr compost, zerovalent iron, and sediment: Implications for groundwater nitrate remediation using permeable reactive barriers

Recent research has shown that carbonaceous solid materials and zerovalent iron (Fe(0)) may potentially be used as media in permeable reactive barriers (PRBs) to degrade groundwater nitrate via heterotrophic denitrification in the solid carbon system, and via abiotic reduction and autotrophic denitrification in the Fe(0) system. Questions arise as whether the more expensive Fe(0) is more effective than the less expensive carbonaceous solid materials for groundwater nitrate remediation, and whether there is any synergistic effect of mixing the two different types of materials. We carried out batch tests to study the nature and rates of removal of added nitrate in the suspensions of single, binary, and ternary systems of cotton burr compost, Peerless Fe(0), and a sediment low in organic carbon. Cotton burr compost acted as both organic carbon source and supporting material for the growth of indigenous denitrifiers. Batch tests showed that cotton burr compost alone removed added nitrate at a greater rate than did Peerless Fe(0) alone on an equal mass basis with a pseudo-first-order rate constant k=0.0830+/-0.0031 h(-1) for cotton burr compost and a k=0.00223+/-0.00022 h(-1) for Peerless Fe(0); cotton burr compost also removed added nitrate at a faster rate than did cotton burr compost mixed with Peerless Fe(0) and/or the sediment. Furthermore, there was no substantial accumulation of ammonium ions in the cotton burr compost system, in contrast to the systems containing Peerless Fe(0) in which ammonium ions persisted as major products of nitrate reduction. It is concluded that cotton burr compost alone may be used as an excellent denitrification medium in a PRB for groundwater nitrate removal. Further study is needed to evaluate performance of its field applications.     

Androgenic and antiandrogenic activities in water and sediment samples from the river Lambro, Italy, detected by yeast androgen screen and chemical analyses

The river Lambro is the most polluted tributary of the river Po in North Italy and was chosen as a representative water course discharging industrialized areas. Water and sediment samples of the river Lambro were investigated regarding the presence of endocrine disrupting compounds. A combined procedure was used consisting of solid-phase extraction and HPLC based fractionation of samples, of screening for (anti)androgenic activity using the yeast androgen screen (YAS) and of chemical analysis using HPLC-MS/MS and GC-MS. Androgenic and antiandrogenic activities were found in specific fractions of the water and sediment while the total extracts showed antiandrogenic activity only. The chemical analysis of the fractions and total extracts with antiandrogenic activities revealed the presence of compounds with suspected antiandrogenic potency such as bisphenol A, iprodione, nonylphenol, p,p'-DDE and tert-octylphenol but other unknown compounds contributed mainly to the observed antiandrogenic activities. The antiandrogenic load of the river Lambro ranged between 1.34 and 17.1 microM flutamide-equivalents and may pose a risk to aquatic environments. Future screenings for EDC in the environment that have the potential to interfere with reproduction of aquatic organisms should be extended to different modes of actions including (anti)androgenic ones.     

Preliminary evidence of a decline in perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) concentrations in American Red Cross blood donors

The purpose of this pilot study was to determine whether perfluorooctanesulfonate (PFOS,C(8)F(17)SO(3)(-)) and perfluorooctanoate (PFOA,C(7)F(15)CO(2)(-)) concentrations in American Red Cross blood donors from Minneapolis-St. Paul, Minnesota have declined after the 2000-2002 phase-out of perfluorooctanesulfonyl-fluoride (POSF, C(8)F(17)SO(2)F)-based materials by the primary global manufacturer, 3M Company. Forty donor plasma samples, categorized by age and sex, were collected in 2005, and PFOS and PFOA concentrations were compared to 100 (non-paired) donor serum samples collected in 2000 from the same general population that were analyzed at the time using ion-pair extraction methods with tetrahydroperfluorooctanesulfonate as an internal standard. Eleven of the 100 samples originally collected were reanalyzed with present study methods that involved (13)C- labeled PFOA spiked into the donor samples, original samples, control human plasma, and the calibration curve prior to extraction, and was used as a surrogate to monitor extraction efficiency. Quantification was performed by high performance liquid chromatography tandem mass spectrometry methods. Among the 100 serum samples analyzed for PFOS, the geometric mean was 33.1 ng ml(-1) (95% CI 29.8-36.7) in 2000 compared to 15.1 ng ml(-1) (95% CI 13.3-17.1) in 2005 (p<0.0001) for the 40 donor plasma samples. The geometric mean concentration for PFOA was 4.5 ng ml(-1) (95% CI 4.1-5.0) in 2000 compared to 2.2 ng ml(-1) (95% CI 1.9-2.6) in 2005 (p<0.0001). The decrease was consistent across donors' age and sex. To confirm these preliminary findings, additional sub-sets of year 2000 samples will be analyzed, and a much larger biomonitoring study of other locations is planned.