Kinetic and chemical assessment of the UV/H2O2 treatment of antiepileptic drug carbamazepine

The UV/H2O2-induced degradation of carbamazepine, a worldwide used antiepileptic drug, recently found as contaminant in many municipal sewage treatment plant (STP) effluents and other aquatic environments, is investigated. The oxidation treatment caused an effective removal of the drug. At complete abatement of the substrate after 4 min treatment, a 35% value of removed total organic carbon (TOC) was obtained. A kinetic constant of (2.05+/-0.14) x 10(9) lmol(-1)s(-1) was determined for OH radical attack to carbamazepine in the UV/H2O2 process. Preparative TLC of the reaction mixture led to the isolation of acridine-9-carboxaldehyde as a reaction intermediate. HPLC and GC/MS analysis indicated formation of small amounts of acridine, salicylic acid, catechol and anthranilic acid among the reaction products. Under the same reaction conditions, synthetically prepared 10,11-epoxycarbamazepine was easily degraded to acridine as main product, suggesting that this epoxide is a likely intermediate in the oxidative conversion of carbamazepine to acridine. Under sunlight irradiation, carbamazepine in water underwent slow degradation to afford likewise acridine as main product. In view of the mutagenic properties of acridine, these results would raise important issues concerning the possible environmental impact of carbamazepine release through domestic wastewaters and support the importance of prolonged oxidation treatments to ensure complete degradation of aromatic intermediates.     

Photodegradation of organic pollutants on the spruce needle wax surface under laboratory conditions

The photochemistry of selected organic compounds, including common pollutants, on the paraffin (as a model matrix) and spruce wax surfaces was studied under laboratory conditions. Two model transformations were evaluated: (1) intramolecular rearrangements of valerophenone and 2-nitrobenzaldehyde, and (2) hydrogen abstraction between an excited benzophenone and the hydrocarbon paraffin/wax chains. The steric or polar influence of the solid matrix on conformational and translational motion, its optical properties, hydrogen abstraction probabilities, and consequences of the guest-molecule segregation are discussed in this work. Furthermore, the photochemical reactivity of some common anthropogenic pollutants, such as chlorinated biphenyls (4-chlorobiphenyl, 2,4-dichlorobiphenyl, and 4,4'-dichlorobiphenyl), 4-chlorophenol, and DDT, was evaluated. The surface of spruce wax is presented as probable reaction medium for photochemical transformations. Although the matrix presents certain restrictions for bimolecular reactions, common photodegradations should be generally feasible in nature. In addition, paraffin was found to be a suitable model matrix for the studies of possible photochemical transformations that can occur on natural plant surfaces.     

Impact of sublethal doses of 2,4-D, simulating drift, on tomato yield

Tomato is considered one of the most sensitive crops regarding 2,4-D drift. In many cases, such susceptibility has led to important restrictions in the use of 2,4-D based products. Field experiments were carried out for two consecutive years in tomato, by applying sublethal doses of 2,4-D (ranging from 0.42 to 13.44 g a.i. ha(-1)) directly to plants, at different stages of growth, as a simulation of eventual drifts to the crop. The range of rates was based on the assumption of a 0.0625-2.0% drift level of a 1 L ha(-1) of the most common formulated herbicides. For this crop, the range of rates between 0.42 and 13.44 g a.i ha(-1) applied at the beginning of flowering caused a linear crop reduction. On the other hand, rates < or = 13.44 g a.i. ha(-1) applied after full development of fourth truss stage or latter had no effect on crop yield or development. For tomato, tolerance to 2,4-D strongly increases with plant age.     

The influence of climate and soil properties on calcium nutrition and vitality of silver fir (Abies alba Mill.)

As a part of a broader research into the nutrition of silver fir (Abies alba Mill.), the variation of calcium concentrations was investigated in needles and soil in two subsequent, climatologically diverse years. Statistically significant differences between plots were determined in Ca concentrations in soils. Concentrations of Ca in needles were statistically different regarding plot, defoliation class, sampling date within the same year and also between years. Fir trees on acid-rock based soils had lower, often inadequate concentrations of Ca in needles; the opposite was true for trees growing on Ca-rich soils. Trees of lower vitality generally exhibited poor Ca nutrition. Drought in the second year of research caused poor absorption of Ca on all plots and in all defoliation classes, but the combined influence of climate and soil properties affected especially trees of low vitality on acid-rock based soils.     

A model of area fidelity,nomadism, and distribution patterns of loggerhead sea turtles (<Emphasis Type="Italic">Caretta caretta</Emphasis>) in the Mediterranean Sea

Sea turtle tagging carried out in Italy in the period 1981–2006 resulted in 125 re-encounters of loggerhead turtles (Caretta caretta) after a mean of 2.5 years, from different marine areas in the Mediterranean. At first finding, turtles ranged 25–83 cm of curved carapace length. Data were analyzed according to size, area, habitat type, season, in order to provide indication of movement patterns. When integrated with other information, results indicate that: (1) a part of turtles in the oceanic stage show a nomad behavior with movements among different oceanic areas; (2) another part show fidelity to an oceanic area; (3) turtles in the neritic stage show fidelity to neritic areas, and once settled to one area, change to other neritic areas is unlikely; (4) nomad oceanic turtles are significantly larger than sedentary ones, and also larger than turtles found in neritic areas; it is hypothesized that these could be Atlantic turtles that eventually leave the Mediterranean; (5) ecological transition from oceanic to neritic habitats occurs at a wide range of sizes, and some turtles may have a very brief oceanic stage; (6) turtles in the oceanic stage are more likely to recruit to neritic areas close to their oceanic areas than to distant ones; (7) part of turtles from some Mediterranean nesting beaches might frequent a relatively limited area range, including both oceanic and neritic areas; (8) in most of the Mediterranean, latitudinal seasonal migrations are unlikely. A general model of movement patterns of loggerhead turtles in the Mediterranean is proposed.     

Caribbean mangroves and seagrass beds as daytime feeding habitats for juvenile French grunts, Haemulon flavolineatum

Caribbean seagrass beds are important feeding habitats for so-called nocturnally active zoobenthivorous fish, but the extent to which these fishes use mangroves and seagrass beds as feeding habitats during daytime remains unclear. We hypothesised three feeding strategies: (1) fishes feed opportunistically in mangroves or seagrass beds throughout the day and feed predominantly in seagrass beds during night-time; (2) fishes start feeding in mangroves or seagrass beds during daytime just prior to nocturnal feeding in seagrass beds; (3) after nocturnal feeding in seagrass beds, fishes complete feeding in mangroves or seagrass beds during the morning. We studied the effect of habitat type, fish size, social mode and time of day on resting and feeding behaviour of large juvenile (5–10 cm) and sub-adult (10–15 cm) Haemulon flavolineatum in mangroves and seagrass beds during daytime. Sub-adults occurred in mangroves only, spent most time on resting, and showed rare opportunistic feeding events (concordant with strategy 1), regardless of their social mode (solitary or schooling). In contrast, large juveniles were present in both habitat types and solitary fishes mainly foraged, while schooling fishes mainly rested. Exceptions were small juveniles (±5 cm) in seagrass beds which foraged intensively while schooling. Large juveniles showed more feeding activity in seagrass beds than in mangroves. In both habitat types, they showed benthic feeding, whereas pelagic feeding was observed almost exclusively in the seagrass beds. In both habitat types, their feeding activity was highest during 8:00–10:30 hours (concordant with strategy 3), and for seagrass fishes, it was also high during 17:30–18:30 hours (concordant with strategy 2). The study shows that both mangroves and seagrass beds provide daytime feeding habitats for some life-stages of H. flavolineatum, which is generally considered a nocturnal feeder.     

Humerus and femur length in fetuses with down syndrome

The aim of the study was to assess the value of sonographic measurement of fetal humerus and femur lengths in the second trimester as a screening tool for Down syndrome (DS). We reviewed retrospectively fetal sonographic biometry made at the time of amniocentesis between 15 and 19 weeks. The study group consisted of 27 DS fetuses. The control group comprised 500 normal fetuses chosen randomly. The expected humeral and femoral lengths for a given biparietal diameter were estimated by linear regression equations from the 500 normal fetuses. Receiver operating characteristic curve analysis was performed to evaluate both the detection rate and the false-positive rate of different cut-off values of measured to expected lengths ratios. The median femur and humeral lengths in DS fetuses were 0·91 times the expected values. No significant differences in the detection rate and false-positive rate were found between the humerus and femur lengths. When the humeral and femoral lengths were combined, we observed a remarkable reduction in the false-positive rate. A measured to expected length ratio of 0·91 detected 44·4 per cent of DS fetuses with 7·6 per cent false positives. These results suggest that the combination of femoral and humeral lengths may permit a more efficient use of ultrasound in screening for Down syndrome than the use of either alone.     

Ozonation of refractory chemicals in leachate with hydrogen peroxide

Nearly 97% of organic chemicals in Hong Kong leachate could be effectively removed by the UASB( upflow anaerobic sludge blanket) process followed by the fenton coagulation. The COD of leachate was lowered from an average of 12900 mg/L to 1440 mg/L after the UASB treatment, and was further lowered to 394 mg/L after the fenton coagulation. The remaining refractory residues could be further removed by ozonation with the addition of H2Oz. The ozonation for the supernatant of the fenton coagulation was most effective at pH 7-8, with the addition of 300 mg/L of H202, and 30 min of reaction. The final effluent contained only 85 mg/L of COD and 10 mg/L of BOD5. On the other hand, direct ozonation of UASB effluent lowered the COD to 905 mg/L and BOD5 to 103 mg/L. Ozonation improved the biodegradability of the organic residues, and also converted oart of oruanic-N in the leachate into NH3-N and NO3^- -N.     

Global Biomass Energy Potential

The intensive use of renewable energy is one of the options to stabilize CO₂atmospheric concentration at levels of 350 to 550ppm. A recent evaluation of the global potential of primary renewable energy carried out by Intergovernmental Panel on Climate Change (IPCC) sets a value of at least 2800EJ/yr, which is more than the most energy-intensive SRES scenario forecast for the world energy requirement up to the year 2100. Nevertheless, what is really important to quantify is the amount of final energy since the use of renewable sources may involve conversion efficiencies, from primary to final energy, different from the ones of conventional energy sources. In reality, IPCC does not provide a complete account of the final energy from renewables, but the text claims that using several available options to mitigate climate change, and renewables is only one of them, it is possible to stabilize atmospheric carbon dioxide (CO₂) concentration at a low level. In this paper, we evaluate in detail biomass primary and final energy using sugarcane crop as a proxy, since it is one of the highest energy density forms of biomass, and through afforestation/reforestation using a model presented in IPCC Second Assessment Report (SAR). The conclusion is that the primary-energy potential for biomass has been under-evaluated by many authors and by IPCC, and this under-evaluation is even larger for final energy since sugarcane allows co-production of electricity and liquid fuel. Regarding forests we reproduce IPCC results for primary energy and calculate final energy. Sugarcane is a tropical crop and cannot be grown in all the land area forecasted for biomass energy plantation in the IPCC/TAR evaluation (i.e. 1280Mha). Nevertheless, there are large expanses of unexploited land, mainly in Latin America and Africa that are subject to warm weather and convenient rainfall. With the use of 143Mha of these lands it is possible to produce 164EJ/yr (1147GJ/hayr or 3.6W/m²on average) of primary energy and 90EJ/yr of final energy in the form of liquid fuel (alcohol) and electricity, using agricultural productivities near the best ones already achievable and biomass gasification technology. More remarkable is that these results can be obtained with the operation of 4,000 production units with unitary capacity similar to the largest currently in operation. These units should be spread over the tropical land area yielding a plantation density similar to the one presently observed in the state of São Paulo, Brazil, where alcohol and electricity have been commercialized in a cost-effective way for several years. Such an amount of final energy would be sufficiently large to fulfill all the expected global increase in oil demand, as well as in electricity consumption by 2030, assuming the energy demand of such sources continues to grow at the same pace observed over the last two decades. When sugarcane crops are combined with afforestation/reforestation it is possible to show that carbon emissions decline for some IPCC SRES scenarios by 2030, 2040 and 2050. Such energy alternatives significantly reduce CO₂emissions by displacing fossil fuels and promote sustainable development through the creation of millions of direct and indirect jobs. Also, it opens an opportunity for negative CO₂emissions when coupled with carbon dioxide capture and storage.