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.     

National Emission Standards Introduction

A feature of the 63rd annual meeting of the Air Pollution Control Association, held June 14–18, 1970 in St. Louis, was a plenary session on national emission standards. Presided over by John S. Lagarias, APCA past president, the session explored the theme for both motor vehicles and stationary sources through the presentations of Delbert S. Barth and Arthur C. Stern and the discussions of John A. Maga and Robert L. Harris, Jr. The essence of their remarks appears on the following pages.     

Effects of Fluoride on Agriculture

The effects of atmospheric fluorides on plants are summarized with respect to the level of biological organization at which they occur. The factors that determine the occurrence and degree of these effects are reviewed briefly. A series of economic effects on agriculture is postulated and its possible relationship to the botanical effects of fluorides is discussed.     

Rotary Kiln Incineration IV. An Indepth Study— Kiln Exit,Transition and Afterburner Sampling During Liquid CCl4 Processing

Detailed temperature and stable species concentration data are presented from the kiln exit, transition section and afterburner of a full-scale incinerator facility firing natural gas/carbon tetrachloride/air. The data are collected as part of a cooperative program involving university, industry and government participation. The overall goal of the program is to develop an understanding and predictive capability for rotary kiln and afterburner performance as influenced by basic design and operational parameters. The data demonstrate that nonuniformities in stable species and temperature exist, under certain operating conditions, at the kiln exit in the vertical direction only. Measurements from the transition section indicate that non-uniformities may exist within this region under certain operating conditions. Flow perturbations from within the kiln can persist into the afterburner, although the degree of nonuniformity is substantially reduced compared to either the kiln or transition sections. High destruction and removal efficiencies were achieved under all operating conditions of these tests through a combination of kiln and secondary combustion processing.     

Multi-step approach for comparing the local air pollution contributions of conventional and innovative MSW thermo-chemical treatments

In the sector of municipal solid waste management the debate on the performances of conventional and novel thermo-chemical technologies is still relevant. When a plant must be constructed, decision makers often select a technology prior to analyzing the local environmental impact of the available options, as this type of study is generally developed when the design of the plant has been carried out. Additionally, in the literature there is a lack of comparative analyses of the contributions to local air pollution from different technologies. The present study offers a multi-step approach, based on pollutant emission factors and atmospheric dilution coefficients, for a local comparative analysis. With this approach it is possible to check if some assumptions related to the advantages of the novel thermochemical technologies, in terms of local direct impact on air quality, can be applied to municipal solid waste treatment. The selected processes concern combustion, gasification and pyrolysis, alone or in combination. The pollutants considered are both carcinogenic and non-carcinogenic. A case study is presented concerning the location of a plant in an alpine region and its contribution to the local air pollution. Results show that differences among technologies are less than expected. Performances of each technology are discussed in details.     

Linking Climate Trends to Population Dynamics in the Baltic Ringed Seal: Impacts of Historical and Future Winter Temperatures

A global trend of a warming climate may seriously affect species dependent on sea ice. We investigated the impact of climate on the Baltic ringed seals (Phoca hispida botnica), using historical and future climatological time series. Availability of suitable breeding ice is known to affect pup survival. We used detailed information on how winter temperatures affect the extent of breeding ice and a climatological model (RCA3) to project the expected effects on the Baltic ringed seal population. The population comprises of three sub-populations, and our simulations suggest that all of them will experience severely hampered growth rates during the coming 90 years. The projected 30 730 seals at the end of the twenty-first century constitutes only 16 % of the historical population size, and thus reduced ice cover alone will severely limit their growth rate. This adds burden to a species already haunted by other anthropogenic impacts.