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.     

Economic potential for conversion to organic farming: a net present value analysis in the East Mau Catchment,Nakuru, Kenya

This paper discusses the economic potential in terms of income changes that may result from conversion to low-external-input agriculture (LEIA) organic farming in a Kenya’s catchment area. A spreadsheet model applying the gross margin and net present value analysis was developed to estimate economic returns to labour and land of alternative smallholder cropping systems in the East Mau Catchment. The income and costs over a 10-year horizon associated with current cropping practices of a typical farm household cultivating 1.12 hectares of maize–bean intercrop, Irish potato, carrots, tomatoes, cabbages and kales mix were characterized based on field work conducted in 2008–2010. An “average” smallholder LEIA organic farm was simulated based on the conventional one, and its income discounted. A comparison was then made of the two farm types. Results indicate annual net present value returns to cropped land average Ksh 21,878/ha ($ 267/ha) and Kshs 22,561/ha (€ 275/ha) in 2010 values for conventional and prototype LEIA organic farming systems, respectively. Net returns are particularly sensitive to crop yields and price and cost of fertilizers and seeds. Further efforts should be made to provide an economic analysis of other LEIA organic farming practices such as composting, double digging and agroforestry in terms of additional labour costs resultant. The model can be extended to build more scenarios on the role of price premiums. Additionally, further research should be done to exploit the socio-demographic factors affecting the adoption of low-external-input systems.     

Natural resource abundance in Nigeria: From dependence to development

There are several strategies open to an economy in its attempt to attain sustainable economic development depending on its historical background and resource endowment. One of such is the resource-led strategy. Nigeria is superabundantly rich in crude oil and has reaped billions of petrodollars. However, the country seems to be facing the problem of successfully translating this huge oil wealth into sustainable development. This paper employs the vector error-correction methodology in examining the long-run impact of the huge oil wealth accruing to Nigeria on its economic development. Indicators such as per capita GDP (PGDP), household consumption, infrastructural development (electricity), and agricultural and manufacturing output growth rates are examined. The results suggest a significant positive long-run impact of per capita oil revenue on per capita household consumption and electricity generation, while a negative relationship is established for GDP, agriculture and manufacturing. Even for those variables with negative relationship at current period, there exist positive relationships at subsequent lags. Thus, oil revenue, if properly managed and invested, could be effectively used to induce oil-led development in Nigeria provided the current inhibitions of corruption, lack of transparency, accountability and fairness in its use and distribution are removed.     

Efficient microwave degradation of humic acids in water using persulfate and activated carbon

Environmental Chemistry Letters - Humic acids are complex mixtures of organic molecules of different sizes, molecular weights and functional groups such as phenols, carboxyls, quinones and amino...     

Restored Riparian Buffers as Tools for Ecosystem Restoration in the MAIA; Processes, Endpoints, and Measures of Success for Water, Soil, Flora, and Fauna

Riparian buffer restorations are used as management tools to produce favorable water quality impacts, moreover among the many benefits riparian buffers may provide, their application as instruments for water quality restoration rests on a relatively firm foundation of research. However, the extent to which buffers can restore riparian ecosystems; their functionality and species composition, are essentially unknown. In light of the foregoing, two broad areas of research are indicated. First, data are needed to document the relative effectiveness of riparian buffers that differ according to width, length, and plant species composition. These questions, of managing buffer dimension and species composition for functionality, are of central importance even when attenuation of nutrient and sediment loads alone are considered. Second, where ecosystem restoration is the goal, effects to in-stream and terrestrial riparian biota need to be considered. Relatedly, the effects of the restoration on the landscape need to be considered. Particularly, at what rate do the effects of the riparian buffer on in-stream water quality, biota, and habitat diminish downstream from restored sites? Answers to these important questions are needed, for streams and watersheds of different size and for areas of differing soil type within watersheds. U.S. EPA-NRMRL has initiated as research project that will document the potential for buffers to restore riparian ecosystems; focusing on water quality effects, but also, importantly, documenting effects on biota. While substantial riparian buffer management initiatives are already underway, the extent of landscapes that influence riparian ecosystems in the eastern United States is large; leaving ample opportunity for this suggested research to provide improved buffer designs in the future. The ultimate goal of research projects developed under this paradigm of ecosystem restoration is to develop data that are needed to implement riparian buffer restorations in the mid-Atlantic and elsewhere, especially the eastern United States.     

Mapping afforestation and deforestation from 1974 to 2012 using Landsat time-series stacks in Yulin District, a key region of the Three-North Shelter region, China

The Three-North Shelter Forest Program is the largest afforestation reconstruction project in the world. Remote sensing is a crucial tool to map land use and land cover change, but it is still challenging to accurately quantify the change in forest extent from time-series satellite images. In this paper, 30 Landsat MSS/TM/ETM+ epochs from 1974 to 2012 were collected, and the high-quality ground surface reflectance (GSR) time-series images were processed by integrating the 6S atmosphere transfer model and a relative reflectance normalization algorithm. Subsequently, we developed a vegetation change tracking method to reconstruct the forest change history (afforestation and deforestation) from the time-series Landsat GSR images based on the integrated forest z-score (IFZ) model by Huang et al. (2009a), which was improved by multi-phenological IFZ models and the smoothing processing of IFZ data for afforestation mapping. The mapping result showed a large increase in the extent of forest, from 380,394 ha (14.8 % of total district area) in 1974 to 1,128,380 ha (43.9 %) in 2010. Finally, the land cover and forest change map was validated with an overall accuracy of 89.1 % and a kappa coefficient of 0.858. The forest change time was also successfully retrieved, with 22.2 % and 86.5 % of the change pixels attributed to the correct epoch and within three epochs, respectively. The results confirmed a great achievement of the ecological revegetation projects in Yulin district over the last 40 years and also illustrated the potential of the time-series of Landsat images for detecting forest changes and estimating tree age for the artificial forest in a semi-arid zone strongly influenced by human activities.     

How effective has the Clean Water Act been at reducing pollutant mass emissions to the Southern California Bight over the past 35 years?

The Clean Water Act (CWA) has regulated discharges of contaminants since 1972. However, evaluations of the CWA's effectiveness at improving regional water quality are lacking, primarily because integration of monitoring data from multiple dischargers to assess cumulative effects is not required. A rare opportunity exists to assess CWA effectiveness by integrating mass emissions data from all major sources of contaminants to the Southern California Bight from 1971 to 2000. While the coastal population grew by 56% and total effluent volume increased 31% since 1971, mass emissions of nearly all constituents decreased since passage of the CWA, most by greater than 65%. Publicly owned treatment works were the dominant point source of many contaminants, but also accounted for the greatest reductions in pollutant discharge since 1971. As point source treatment has improved, the relative contribution of non-point sources, such as storm water runoff has increased. Despite the increased importance of storm water discharges, regional monitoring and data compilation of this source is lacking, making it difficult to accurately assess trends in non-point source discharge.     

Fetoscopic tracheal occlusion for treatment of non-isolated congenital diaphragmatic hernia

Fetoscopic endotracheal occlusion (FETO) is a prenatal treatment that may increase survival in severe congenital diaphragmatic hernia (CDH). In the USA, FETO is offered for isolated severe left-sided CDH in the context of an FDA-approved feasibility study. FETO in non-isolated cases of severe CDH is only performed with a compassionate use exemption from US regulatory bodies. Anomalies frequently associated with CDH include congenital cystic lesions of the lung and cardiac defects. We describe two cases of non-isolated severe left-sided CDH that underwent prenatal FETO, survived after birth and underwent postnatal surgical repair. The potential benefit of FETO in this setting is discussed. © 2017 John Wiley & Sons, Ltd.