Linear and non-linear relationships mapping the Henry’s law parameters of organic pesticides

This work aims to predict the air to water partitioning for 96 organic pesticides by means of the Quantitative Structure–Property Relationships Theory. After performing structural feature selection with Genetics Algorithms and Replacement Method linear approaches, it is found that among the most important molecular features appears the Moriguchi octanol–water partition coefficient, and higher lipophilicities would lead to compounds having higher Henry’s law constants. We also compare the statistical performance achieved by four fully-connected Feed-Forward Multilayer Perceptrons Artificial Neural Networks. The statistical results found reveal that the best performing model uses the Levenberg–Marquardt with Bayesian regularization (BR) weighting function for achieving the most accurate predictions.     

Kinetic study of the OH reaction with some hydrochloroethers under simulated atmospheric conditions

Using the relative rate technique, rate constants for the gas-phase reactions of hydroxyl radicals with 2-chloroethyl methyl ether (k₁), 2-chloroethyl ethyl ether (k₂) and bis(2-chloroethyl) ether (k₃) have been measured. Experiments were carried out at (298 ± 2) K and atmospheric pressure using synthetic air as bath gas. Using n-pentane and n-heptane as reference compounds, the following rate constants were derived: k₁ = (5.2 ± 1.2) × 10^?12, k₂ = (8.3 ± 1.9) × 10^?12 and k₃ = (7.6 ± 1.9) × 10^?12, in units of cm³ molecule^?1 s^?1. This is the first experimental determination of k₂ and k₃ under atmospheric pressure. The rate constants obtained are compared with previous literature data and the observed trends in the relative rates of reaction of hydroxyl radicals with the ethers studied are discussed. The atmospheric implications of the results are considered in terms of lifetimes and fates of the hydrochloroethers studied.     

High efficiencies in the electrochemical oxidation of an anthraquinonic dye with conductive-diamond anodes

Oxidation of anthraquinonic dye Acid Blue 62 by electrolysis with conductive-diamond electrodes is studied in this work. COD, TOC, and color have been selected to monitor the degradation of the molecule as a function of several operating inputs (current density, pH, temperature, and NaCl concentration). Results show that the electrochemical oxidation of this model of large molecules follows a first order kinetics in all the conditions assessed, and it does not depend on the pH and temperature. The occurrence of chloride ions in wastewaters increases the rate of color and COD removal as a consequence of the mediated oxidation promoted by the chlorinated oxidizing species. However, chloride occurrence does not have an influence on the mineralization rate. First-order kinetic-constants for color depletion (attack to chromophores groups), oxidation (COD removal), and mineralization (TOC removal) were found to depend on the current density and to increase significantly with its value. A single model was proposed to explain these changes in terms of the mediated oxidation processes. Rate of mineralization remained very close to that expected for a purely mass transfer-controlled process. This was explained assuming that mediated oxidation does not have a significant influence on the mineralization in spite it has some effect on intermediate oxidation stages. The efficiency of the oxidation was found to depend mainly on the concentration of COD being negligible the effect of the other inputs assessed except for the occurrence of chloride ions. Opposite, the efficiency of mineralization depends on concentration of TOC and current density and it did not depend on the chloride occurrence. This observation was found to have an important influence on the power required to remove a given percentage of the initial TOC or COD. To decrease COD efficiently, the occurrence of chloride in the solution is very important, while to remove TOC efficiently, it is more important to work at low current densities and chloride effect is negligible. Energy consumption could be decreased by folds using the proper conditions.     

Risk of laryngeal and nasopharyngeal cancer associated with arsenic and cadmium in the Tunisian population

Chronic exposure to heavy metals has long been recognized as being capable of increasing head and neck cancer (HNC) incidence, such as laryngeal (LC) and nasopharyngeal (NPC), among exposed human populations. The aim of the present study was to evaluate the concentrations of arsenic (As) and cadmium (Cd) in the blood of 145 patients (LC and NPC) and 351 controls in order to establish a potential relationship between these factors and the occurrence of LC and NPC. Mean blood levels of As and Cd in patients (5.67 and 3.51 μg/L, respectively) were significantly higher than those of controls (1.57 and 0.74 μg/L, respectively). The blood levels of As and Cd were mostly significantly higher than those of controls (p?<?0.05) after controlling the other risk factors of HNC including tobacco smoking and chewing, and alcohol drinking. Cd levels in blood increase significantly with the number of occupational exposure years for patients (p?<?0.05). However, seafood was not found to be contributing as an exposure source. Among these risk factors, smoking (>30 pack years) and occupational exposure (>20 years) presented the most significant association with HNC (OR?=?10.22 and 10.38, respectively, p?<?0.001). Cd level in blood sample of cases that are occupationally exposed/tobacco users (smokers and chewers) were higher than that of non-occupationally exposed/nontobacco users (p?<?0.001). The logistic regression model illustrated that HNC (LC?+?NPC) was significantly associated with blood levels of As (OR?=?2.41, p?<?0.001) and Cd (OR?=?4.95, p?<?0.001).     

Factors Influencing the Emissions of Nitrated-Polynuclear Aromatic Hydrocarbons(Nitro-PAH) from Diesel Engines

The potential problem of 1-nitropyrene (1-NP) formation during filter sampling of diesel emissions from dilution tubes is assessed. Rates of formation are calculated using data generated from several independent filter exposure studies. A portion of the 1-NP (12% average) found in participates collected from light-duty (LDD) and heavy-duty diesels (HOD) was found to be due to formation on the filter under average sampling conditions of 10-15/1 dilution at 44°C with 3 ppm NO₂ for 23 min. On the average, the concentration of 1-NP in participates emitted from HDD is 16 times less than that found in LDD run under similiar transient conditions. The average emission rate of 1-NP generated from the LDD and HDD was 4.7 μg/km and 1.5 μg/km, respectively for the vehicles operating under Federal Test Procedure (FTP)-transient conditions. Under operating conditions which increase exhaust temperature (increased speed and load), the concentration of nitro-PAH is significantly reduced with a concurrent increase in the concentration of partially oxidized nitro-PAH and dinitro-PAH. The concentration of 1-NP in the particulates measured from HDD in these dilution tube studies (0.33-0.95 ppm, depending upon engine load) is comparable to that measured in highway tunnel experiments (0.54 ppm average).     

Ecosystem services and hydroelectricity in Central America: modelling service flows with fuzzy logic and expert knowledge

Because ecosystem services are generally not produced and used in the same place, their assessment should consider the flows of services from ecosystems to users. These flows depend on the characteristics and spatial distribution of ecosystems and users, the spatial relationships between them, and the presence of filters or barriers between ecosystems and users. The objective of this paper is to map the ecosystem services provided to the Costa Rican and Nicaraguan hydroelectric sectors, which are crucial sectors for national sustainable development and depend directly on hydrological ecosystem services. The paper presents an approach for modelling the flows of multiple services from diverse ecosystems to diverse users through different kinds of filters in a landscape. The approach uses expert knowledge and fuzzy numbers to handle uncertainties. The analyses for Costa Rica and Nicaragua show how the approach helps identify priority areas for the conservation and restoration of forests for the services they provide to the hydroelectric sector. As such, it is a useful tool for defining spatially targeted policies for the conservation of ecosystem services and for involving the users of ecosystem services in ecosystem management.     

Climate engineering and human rights

ABSTRACT

In this Forum, three scholars discuss how climate engineering will pose novel human rights challenges, and may well force reconsideration of how human rights are applied as a guide to action. Following a short introduction, the first section introduces three competing approaches to human rights, arguing views which emphasize fairness or attempt to maximize satisfaction are more promising than one viewing human rights as inviolable ‘side-constraints’. The second section draws lessons from climate migration that are relevant for climate engineering in terms of incorporating a human rights approach to duties, rights, and participation. The final section compares the ‘needs-based’ and ‘rights-based’ approaches to humanitarian work in the face of climate change and climate engineering, raising concerns for duty-bearers and right-holders. The Forum’s conclusion draws together points of overlap and suggests a path forward for policy and research on this topic.     

Quantifying road dust resuspension in urban environment by Multilinear Engine: A comparison with PMF2

Atmospheric PM pollution from traffic comprises not only direct emissions but also non-exhaust emissions because resuspension of road dust that can produce high human exposure to heavy metals, metalloids, and mineral matter. A key task for establishing mitigation or preventive measures is estimating the contribution of road dust resuspension to the atmospheric PM mixture. Several source apportionment studies, applying receptor modeling at urban background sites, have shown the difficulty in identifying a road dust source separately from other mineral sources or vehicular exhausts. The Multilinear Engine (ME-2) is a computer program that can solve the Positive Matrix Factorization (PMF) problem. ME-2 uses a programming language permitting the solution to be guided toward some possible targets that can be derived from a priori knowledge of sources (chemical profile, ratios, etc.). This feature makes it especially suitable for source apportionment studies where partial knowledge of the sources is available.In the present study ME-2 was applied to data from an urban background site of Barcelona (Spain) to quantify the contribution of road dust resuspension to PM₁₀ and PM_2.5 concentrations. Given that recently the emission profile of local resuspended road dust was obtained (Amato, F., Pandolfi, M., Viana, M., Querol, X., Alastuey, A., Moreno, T., 2009. Spatial and chemical patterns of PM₁₀ in road dust deposited in urban environment. Atmospheric Environment 43 (9), 1650–1659), such a priori information was introduced in the model as auxiliary terms of the object function to be minimized by the implementation of the so-called “pulling equations”.ME-2 permitted to enhance the basic PMF solution (obtained by PMF2) identifying, beside the seven sources of PMF2, the road dust source which accounted for 6.9 μg m^?3 (17%) in PM₁₀, 2.2 μg m^?3 (8%) of PM_2.5 and 0.3 μg m^?3 (2%) of PM₁. This reveals that resuspension was responsible of the 37%, 15% and 3% of total traffic emissions respectively in PM₁₀, PM_2.5 and PM₁. Therefore the overall traffic contribution resulted in 18 μg m^?3 (46%) in PM₁₀, 14 μg m^?3 (51%) in PM_2.5 and 8 μg m^?3 (48%) in PM₁. In PMF2 this mass explained by road dust resuspension was redistributed among the rest of sources, increasing mostly the mineral, secondary nitrate and aged sea salt contributions.