Pyrolysis of permethrin and formation of precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) under non-oxidative conditions

This article reports the computational and experimental results of the thermal decomposition of permethrin, a potential source of dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). We have performed a quantum chemical analysis by applying density functional theory to obtain the decomposition pathways of permethrin and the formation mechanism of dibenzofuran. We have conducted the pyrolysis experiments in a tubular reactor and identified the pyrolysis products to demonstrate the agreement between the experimental measurements and quantum chemical calculations. The initiation of the decomposition of permethrin involves principally the aromatisation of permethrin into 3-phenoxyphenylacetic acid, 2-methylphenyl ester (J) and concomitant loss of 2HCl. This rearrangement is followed by the rupture of the O–CH₂ linkage in J, with a rate constant derived from the quantum chemical results of 1 × 10¹⁵ exp(−68 kcal/mol/RT) s⁻¹ for temperatures between 700 and 1300 K. This is confirmed by finding that the rate constant for unimolecular rearrangement of permethrin into J is 1.2 × 10¹² exp(−53 kcal/mol/RT) s⁻¹ over the same range of temperatures and exceeds the direct fission rate constant at all temperatures up to 850 ± 120 °C as well as by the experimental detection of J prior to the detection of the initial products incorporating diphenyl ether, 1-methyl-3-phenoxybenzene, 3-phenoxybenzaldehyde and 1-chloromethyl-3-phenoxybenzene. As the temperature increases, we observe a rise in secondary products formed directly or indirectly (via phenol/phenoxy) including aromatics (naphthalene), biphenyls (biphenyl, 4-methyl-1,1′-biphenyl) and dibenzofuran (DF). In particular, we discover by means of quantum chemistry a direct route from 2-phenoxyphenoxy to naphthalene. We detect no polychlorinated dibenzo-p-dioxins and dibenzofurans. Unlike the case of oxidative pyrolysis [Tame, N.W., Dlugogorski, B.Z., Kennedy, E.M., 2007b. Formation of dioxins in fires of arsenic-free treated wood: Role of organic preservatives. Environ. Sci. Technol. 41, 6425–6432] where significant yields of both PCDD and PCDF were obtained, under non-oxidative conditions the thermal decomposition of permethrin does not form appreciable amounts of PCDD or PCDF and the presence of oxygen (and/or a sizable radical pool) appears necessary for the formation of dibenzo-p-dioxin itself or PCDD/F from phenol/phenoxy.     

A global assessment of chromium pollution using sperm whales (Physeter macrocephalus) as an indicator species

Chromium (Cr) is a well-known human carcinogen and a potential reproductive toxicant, but its contribution to ocean pollution is poorly understood. The aim of this study was to provide a global baseline for Cr as a marine pollutant using the sperm whale (Physeter macrocephalus) as an indicator species. Biopsies were collected from free-ranging whales around the globe during the voyage of the research vessel The Odyssey. Total Cr levels were measured in 361 sperm whales collected from 16 regions around the globe detectable levels ranged from 0.9 to 122.6 μg Cr g tissue⁻¹ with a global mean of 8.8 ± 0.9 μg g⁻¹. Two whales had undetectable levels. The highest levels were found in sperm whales sampled in the waters near the Islands of Kiribati in the Pacific (mean = 44.3 ± 14.4) and the Seychelles in the Indian Ocean (mean = 19.5 ± 5.4 μg g⁻¹). The lowest mean levels were found in whales near the Canary Islands (mean = 3.7 ± 0.8 μg g⁻¹) and off of the coast of Sri Lanka (mean = 3.3 ± 0.4 μg g⁻¹). The global mean Cr level in whale skin was 28-times higher than mean Cr skin levels in humans without occupational exposure. The whale levels were more similar to levels only observed previously in human lung tissue from workers who died of Cr-induced lung cancer. We conclude that Cr pollution in the marine environment is significant and that further study is urgently needed.     

Influence of titanium dioxide nanoparticles on speciation and bioavailability of arsenite

In this study, the influence of the co-existence of TiO₂ nanoparticles on the speciation of arsenite [As(III)] was studied by observing its adsorption and valence changing. Moreover, the influence of TiO₂ nanoparticles on the bioavailability of As(III) was examined by bioaccumulation test using carp (Cyprinus carpio). The results showed that TiO₂ nanoparticles have a significant adsorption capacity for As (III). Equilibrium was established within 30 min, with about 30% of the initial As (III) being adsorbed onto TiO₂ nanoparticles. Most of aqueous As (III) was oxidized to As(V) in the presence of TiO₂ nanoparticles under sunlight. The carp accumulated considerably more As in the presence of TiO₂ nanoparticles than in the absence of TiO₂ nanoparticles, and after 25-day exposure, As concentration in carp increased by 44%. Accumulation of As in viscera, gills and muscle of the carp was significantly enhanced by the presence of TiO₂ nanoparticles.     

Effects of environmental illiteracy and environmental awareness among middle school students on environmental behavior

This study proposes and employs a structural model to examine the effects of environmental literacy, environmental awareness, environmental attitudes, and environmental behavior among middle school students in Eski?ehir on their purchase of environmentally friendly products. In the proposed structural model, environmental illiteracy and environmental awareness were the exogenous latent variables, while pro-environmental attitude, pro-environmental behavior, and the purchase of environmentally friendly products were the endogenous latent variables. The latent variable of environmental illiteracy did not have a statistically significant effect on environmental attitudes and purchase of environmentally friendly products, whereas environmental awareness had a positive effect on pro-environmental attitudes and the purchase of environmentally friendly products. These findings indicate that students with environmental awareness also develop positive attitudes toward the environment, and the presence of a positive attitude toward the environment leads them to display pro-environmental behaviors and adopt a positive attitude toward environmentally friendly products.     

Investigating soils retention ratios and modelling geochemical factors affecting heavy metals retention in soils in a tropical urban watershed

This study aimed at investigating the retention of Pb and Cd in soils and the geochemical factors influencing the adsorption of these pollutants. Soil samples were air-dried and ground to pass through a 2-mm sieve, and different soil extracts were prepared for chemical analysis (organic matter, cation exchange capacity and pH). Total Pb and Cd were extracted with diacid using digestion method and determined by atomic adsorption spectrophotometer (AAS) after filtration. Results revealed that the heavy metals retention ratio (RR) of the Rhodic ferralsol, Xanthic ferralsol and Mollic gleysol (2) were very high for Cd (>80 %) and was relatively low (generally < 60 %) for Pb. In contrast, RRs for the Plinthic gleysol and the Mollic gleysol (1) were relatively low (<60 %), regardless of the heavy metal concerned. Multiple regression equations indicated for Pb and Cd concentrations different linear relationships over simple linear regression, when pH, organic matter, clay percentage and cation exchange capacity (CEC) were used as independent variables. Results indicate that organic matter exerts major influences on the retention of Pb and Cd in soils, while CEC, clay content and pH have a minor influence in this process in the Ntem watershed. From these observations, the application of soil organic matter could be a solution in protecting shallow aquifers from heavy metal pollution and thus insuring that they are not a hazard to public health.     

2014, The “year without a summer” in Italy: news media coverage and implications for the climate change debate

In 2014, there was virtually no summer in northern and central-southern Italy. Storm after storm battered the peninsula, triggering floods and landslides from Veneto to Puglia. We studied the coverage of “the year without a summer” in Italy by analyzing the content of 171 news articles from two influential online newspapers. Our software-based analysis enabled us to observe that the two newspapers hardly ever mentioned climate change in their coverage of the weather anomaly that affected Italy in the summer of 2014. This type of coverage is in line with climate science, according to which there is no evidence of a climate change-related influence on summer precipitation patterns in Southern Europe—whereas such influence has been documented for northern Europe. We compared our results with a recent paper, which documented that the same online dailies chose to represent the particularly hot summer of 2012 in Italy as a direct consequence of climate change. We corroborated this comparison also on the basis of a preliminary analysis we performed on the media coverage of the exceptionally hot and arid summer of 2015 in Italy.     

The impacts of the waterfront development in Iskandar Malaysia

The increasing number of waterfront projects shows that the concept of waterfront development has contributed to the advancement of the Malaysian construction industry. This study seeks to assess the impacts of the implementation of waterfront development in Iskandar Malaysia eliciting the perceived relative importance of these impacts. A comprehensive literature review has been conducted to collate the potential impacts of the waterfront development. A total of 363 sets of questionnaires were distributed to the contractors and developers registered under G7 category of the Construction Industry Development Board in Malaysia. Results show that the most significant influence of the waterfront development is related to economic benefits, while environmental impacts are not considered as a priority for this category of stakeholders. In addition, this study also indicates that the implementation of the waterfront projects has generated numerous job opportunities within the developed region. Moreover, exchanging knowledge in the planning and managing of the waterfront development is imperative to the development of the waterfront projects. Nevertheless, the shortcomings of these developments, such as the negative environmental impact on natural beaches and the coastline (i.e. pollution) as well as human-related issues (i.e. excessive human settlement), should not be taken lightly. This research confirms that the reclamation of land for waterfront development is closely correlated with the destruction of these natural structures.     

Dynamics of leaf litter and soil respiration in a complex multistrata agroforestry system,Pernambuco, Brazil

High litter inputs in agroforestry systems contribute to soil microbial activity, soil fertility and productivity. Considering that the cycling of organic matter is essential to the maintenance of physical–chemical and microbiological properties of the soil, the aims of this work were to estimate the production, accumulation and decomposition of litter, and assess soil microbial respiration in a complex multistrata agroforestry system located in the north-east of Brazil. This agroforestry system has three strata formed by forest and fruit trees and species of multiple uses. During 3 years (2011–2013), leaf litter was sampled monthly to account for litterfall and quarterly to account for litter accumulation. The rates of litter decomposition were estimated using the ratio produced-to-accumulated litter, and the correlation between litter fall and rainfall was calculated. Precipitation data were provided by the water and climate agency of Pernambuco (APAC). Soil samples (0–15 cm) were also taken quarterly, simultaneously with the litter accumulation samples, and soil microbial respiration was assessed using the capture, by a KOH solution, of the evolved CO₂. The annual production of leaf litter was stable in the 3 years of study in this agroforestry system, and the monthly input of litter to the soil was influenced by rainfall, being higher in the dry seasons. The accumulated litter on the ground was constant, as was microbial activity (respiration) through time. The estimated litter decomposition rates were 1.49 (first year), 1.33 (second year) and 1.42 (third year), being considered rapid rates of decomposition. This guarantees (to the farmer) that this system is capable of maintaining soil fertility and eliminates the need for chemical fertilizers.