Kinetics of scrap tyre pyrolysis under vacuum conditions

Scrap tyre pyrolysis under vacuum is attractive because it allows easier product condensation and control of composition (gas, liquid and solid). With the aim of determining the effect of vacuum on the pyrolysis kinetics, a study has been carried out in thermobalance. Two data analysis methods have been used in the kinetic study: (i) the treatment of experimental data of weight loss and (ii) the deconvolution of DTG (differential thermogravimetry) curve. The former allows for distinguishing the pyrolysis of the three main components (volatile components, natural rubber and styrene–butadiene rubber) according to three successive steps. The latter method identifies the kinetics for the pyrolysis of individual components by means of DTG curve deconvolution. The effect of vacuum in the process is significant. The values of activation energy for the pyrolysis of individual components of easier devolatilization (volatiles and NR) are lower for pyrolysis under vacuum with a reduction of 12 K in the reaction starting temperature. The kinetic constant at 503 K for devolatilization of volatile additives at 0.25 atm is 1.7 times higher than that at 1 atm, and that corresponding to styrene–butadiene rubber at 723 K is 2.8 times higher. Vacuum enhances the volatilization and internal diffusion of products in the pyrolysis process, which contributes to attenuating the secondary reactions of the repolymerization and carbonization of these products on the surface of the char (carbon black). The higher quality of carbon black is interesting for process viability.The large-scale implementation of this process in continuous mode requires a comparison to be made between the economic advantages of using a vacuum and the energy costs, which will be lower when the technologies used for pyrolysis require a lower ratio between reactor volume and scrap tyre flow rate.     

Organotins in the sediments of the Zuari estuary, west coast of India

Industrial use of organotins such as butyltins and phenyltins has increased several folds during the last two decades. Butyltins and phenyltins are synthetic, multipurpose chemicals, which have been extensively used in marine antifouling paints. They have been known to be extremely poisonous to mollusc fishery resources (oysters, clams, etc.). Contamination of Zuari estuary sediments was assessed by quantitative determination of butyltins and phenyltins by using GC-MS using the electron ionization mode. Butyltins predominated in the whole area over phenyltins. Butyltins contributed about 70-90% of the organotins in general. The concentration of butyltins in sediments ranged from 20 to 7621 ng Sn/g. The concentration of phenyltins in sediments ranged from 0 to 46 ng Sn/g. Degradation indices for butyltins and phenyltins were calculated. The Butyltin degradation index (BDI) for the Zuari sediments ranged from 0 to 2.7 indicating a lot of fresh input of butyltins in the estuary and a lower degradation rate. The phenyltin degradation index (PhDI) ranged from 1 to 10 implying that different processes were prevalent at different stations. The observed organotin levels in the Zuari estuary indicate some highly localized areas of contamination which are severe enough to cause harmful effects on marine flora and fauna. Therefore, there is a need to regulate the use of butyltins and phenyltins as biocides in marine antifouling paints.     

Heat stress and crop yields in the Mediterranean basin: impact on expected insurance payouts

Insurance programmes have been indicated as a tool to reduce the economic risk associated with climate change, and crop growth simulation models can be used effectively to assess future trends in crop insurance payouts. This paper assesses the economic role of increasing weather extremes under future climate change on the expected insurance payouts for durum wheat (Triticum turgidum L. spp. durum) over the Mediterranean basin, focusing attention on the effects of heat stresses (HSs). A crop growth simulation, Sirius Quality version 2 (SQ2), calibrated for three varieties (long, medium and short growth cycle) was applied on seven sites under present (1975–1990) and future climate conditions (2030–2050) obtained from five regional circulation models under SRES scenario A1b. The intensity of HSs at anthesis was included as reducing factor of yield originally simulated by SQ2 calculated according to a specific empirical model. Simulated yields were then fitted to the most appropriate distribution, which was used to calculate the expected payouts according to the probability of yields being below a guaranteed level. We found that the simulated crop yields were, in general, negatively skewed and that Weibull probability density function (PDF), admitting negative skewing, provided the best performances in their fitting. The simulation of HSs modified the original shape of the Weibull PDF by increasing the skewness of the distribution. The results of the insurance model indicated that the modification of crop PDFs induced by HSs led to a general increase in payouts with respect to unstressed conditions, with a marked difference between present (+11 %, on average for the selected sites) and future periods (+25 %). When compared to the present, a general decrease in payouts (?1.1 %) was observed when HSs were not included in the simulations. Conversely, HSs impact resulted in a general increase in payouts (+10.3 %) where the highest increase was detected for the long growth cycle variety (+16.6 %) and the lowest for that with short growth cycle (?1.6 %). These results emphasize the importance of the appropriate characterization of crop yield distribution, the economic implications of HSs in a risk management context and a possible strategy to cope with climate change and variability.     

The importance of achieving a high customer satisfaction with recycling services in communities

Some studies show that there are external, infrastructural, and economic factors that enable individuals and communities to act ecologically. A variable associated with sustainable behavior is the level of satisfaction with infrastructural and economic factors, which in turn relates to recycling behavior. The main aim of this study was to assess the reliability and validity of the customer satisfaction with recycling scale and to analyze its relationship with sociodemographic variables (age and gender), house location (in the center or the suburbs, population size of), and psychological variables (self-reported individual recycling behaviors, general satisfaction with recycling service companies, and the perception of costs and the quality of service). A total of 1498 individuals responded to the in-home questionnaire related to these variables. Exploratory and confirmatory factorial analyses confirm a good fit for a four-dimensional model: assurance, tangibles, empathy, and communication. Results show that those individuals who live in town centers tend to self-report higher levels of satisfaction with tangibles than those living in the suburbs. Population sizes correlate significantly and negatively with the four dimensions of service satisfaction, while age seems to relate significantly and negatively to all the studied variables. Finally, we discuss the implications regarding the importance of customer satisfaction in facilitating the environmentally responsible behavior.     

Toxicity of mixtures of perfluorooctane sulphonic acid with chlorinated chemicals and lipid regulators

The toxicological interaction of perfluorooctane sulphonic acid (PFOS) with the chlorinated pollutants triclosan and 2,4,6-trichlorophenol and the lipid regulators gemfibrozil and bezafibrate was evaluated using the combination index-isobologram equation. The endpoint for bioassays was the growth rate inhibition of the green alga Pseudokirchneriella subcapitata. The results showed that most of the binary combinations assayed exhibited antagonism at all effect levels. The addition of a third component induced a less antagonistic or even synergistic behaviour. This was particularly marked for the ternary mixture of triclosan and 2,4,6-trichlorophenol with PFOS, for which synergism was very strong at all effect levels, with a combination index as low as 0.034 ± 0.002 at EC₅₀ for the mixture. The results obtained indicate that the evaluation of mixture toxicity from single component data using the concentration addition approach could severely underestimate combined toxicity.     

Characterization of Atrazine-Loaded Biodegradable Poly(Hydroxybutyrate-Co-Hydroxyvalerate) Microspheres

Polyhydroxybutyrate-co-hydroxyvalerate microspheres (PHBV-MS) were prepared as a delivery system for the herbicide atrazine (ATZ). Characterization of the system included investigation of in vitro release properties and genotoxicity. ATZ − PHBV-MS particle diameters showed a size distribution range of 1–13 μm. Differential scanning calorimetry analyses indicated that ATZ was associated with the PHBV microparticles. The release profiles showed a different release behavior for the pure herbicide in solution, as compared with that containing ATZ-loaded PHBV-MS. Korsmeyer–Peppas model analyses showed that atrazine release from the microparticles occurred by a combination of diffusion through the matrix and partial diffusion through water-filled pores of the PHBV microparticles. A Lactuca sativa test result showed that the genotoxicity of ATZ-loaded PHBV-MP was decreased in relation to ATZ alone. The results demonstrate a viable biodegradable herbicide release system using atrazine for agrochemical purposes.     

Pedestrian crossing behavior,an observational study in the city of Ushuaia,Argentina

Objectives: Pedestrian crashes are a critical problem in Latin American countries. However, little research has been published about pedestrians and even less about their behaviors in a naturalistic context. The objective of the present research was to explore risky pedestrian crossing behaviors in traffic intersections in an argentine city (Ushuaia). It is focused in different stages of the crossing process, traffic code violations, and other potentially risky behaviors such as distractions. A high frequency of risky behaviors among pedestrians was expected. Moreover, according to previous findings, it was hypothesized that men and younger pedestrians would show riskier behaviors.

Methods: Participants were 802 pedestrians (53.9% females) observed at several intersections (with and without traffic lights) in the city of Ushuaia. Behaviors were codified following a standardized observation protocol. Observers documented information on behavior previous to, during, and after crossing. Gender and age were also registered. Data were gathered through video recording. Frequency analyses of observed behaviors were conducted for the total sample, as well as by gender and by age group. A general crossing risk index was calculated to facilitate comparisons between the genders and age groups. We conducted an analysis of variance to evaluate gender and age differences for this index.

Results: A high proportion of risky behaviors were observed among pedestrians. The majority of pedestrian waited in the street (as opposed to on the sidewalk) before crossing, did not comply with traffic lights, or crossed outside the crosswalk. A large number of pedestrians were distracted while crossing. Men presented higher scores on risky behaviors than women. No differences were observed by age group.

Conclusions: The high level of risk behaviors during the different stages of street crossing is worrisome and reinforces the idea that pedestrians are responsible for many of the conflicts with motorists. Many of the risky behaviors seem to be associated with gender, which is in line with the previous literature showing more risk behaviors among men than among women. No differences were found for age group. Findings are interpreted considering some features of the Argentine road culture.     

Distribution of potentially harmful elements in soils around a large coal-fired power plant

An understanding of the spatial distribution and contribution of a power plant to local soil contamination is important for the planning of soil use and prioritizing remedial actions for public safety. Consequently, the aim of this study was to map the spatial distribution of potentially hazardous elements (PHEs; Cu, Pb, Zn, Ni, Cr, Fe, Mn, Cd, As, and Se) in soils around a large (796 MW) coal-fired power plant in Brazil. For the purpose, 33 soil samples were collected in the area within a radius of approximately 17.5 km from the plant and subsequently analyzed for PHEs. The frequency and direction of winds were also obtained from a meteorological station in the region. The sampling area was divided into four quadrants (northwest: N-NW; northeast: N-NE; southeast: S-SE; southwest: S-SW), and there were significant negative correlations between the distance and the concentrations of Se in the S-SE quadrant and As in the S-SW and S-SE quadrants. There were positive correlations between distance from the plant and the concentration of Mn in the N-NE quadrant and the concentration of Cd in the S-SW quadrant. The dominant direction of the winds was N-NE. The indexes used in this study showed low-to-moderate enrichment factor, but detailed analysis of the dominant quadrant of the winds showed a correlation with higher concentrations in the soils closer to the power plant for at least seven of the PHEs analyzed, especially with regard to As. Therefore, we conclude that the distribution of the metalloid As can be used as a marker of the spatial distribution of contamination from the thermoelectric plant, but the dynamics of the other elements suggests that the presence of other sources of contamination may also compromise the quality of local soils.