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.     

IFTCIP: An Integrated Optimization Model for Environmental Management under Uncertainty

In this study, an interval-fuzzy two-stage chance-constrained integer programming (IFTCIP) method is developed for supporting environmental management under uncertainty. The IFTCIP improves upon the existing interval, fuzzy, and two-stage programming approaches by allowing uncertainties expressed as probability distributions, fuzzy sets, and discrete intervals to be directly incorporated within a general mixed integer linear programming framework. It has advantages in uncertainty reflection, policy investigation, risk assessment, and capacity-expansion analysis in comparison to the other optimization methods. Moreover, it can help examine the risk of violating system constraints and the associated consequences. The developed method is applied to the planning for facility expansion and waste-flow allocation within a municipal solid waste management system. Violations of capacity constraints are allowed under a range of significance levels, which reflects tradeoffs between the system cost and the constraint-violation risk. The results indicate that reasonable solutions for both binary and continuous variables have been generated under different risk levels. They are useful for generating desired decision alternatives with minimized system cost and constraint-violation risk under various environmental, economic, and system-reliability conditions. Generally, willingness to take a higher risk of constraint violation will guarantee a lower system cost; a strong desire to acquire a lower risk will run into a higher system cost.     

Thermodynamics of interaction of lindane on silty loam and silty clay loam Indian soils

Abstract

Interaction of lindane with silty loam and silty clay loam soils was studied in batch tests at 23, 30 and 37° C. Sorption experiments were carried out at four concentrations and for varying time of contact upto 72 hours. This was followed by desorption studies. No desorption was observed. The sorption data was analysed using sorption equations and evaluating the thermodynamic parameters. The sorption was found to be predominantly entropic in nature and a combined effect of adsorption and chemisorption. The effect of organic matter and other chemical and mineralogical constituents of soils has also been discussed. The sorption with single application of lindane with the two soil types indicates that the insecticide is less likely to reach groundwater.     

Biomass and nutrient concentration of sweet corn roots and shoots under organic amendments application

Two field experiments were conducted at the Waimanalo research station on the island of O'ahu, Hawaii to study the effect of chicken (CM) and dairy (DM) manures on biomass and nutrient concentration in sweet corn roots and shoots. Sweet corn (super sweet 10, Zea Mays L. subsp. mays) was grown for two consecutive growing seasons under four rates of application (0, 168, 337, and 672 kg ha^{? 1} total N equivalent) and one time (OTA) or two time (TTA) applications of organic manure types and rates. There were significant effects of types, rates, and number of manure applications on dry biomass and macro- and micro-nutrient concentration in roots and shoots tissues. Results of root tissue indicated a significant accumulation of N and C under CM and DM treatments compared with the control treatment. Manure application rates significantly increased the accumulation of N and C in root tissue. Dry weight of roots and shoots and both macro- and micro-nutrient contents in the plant tissues significantly increased under TTA treatment compared with OTA treatment. There was a significant correlation (r² = 0.46 to 0.81) between root biomass, macro-, and micro-nutrient contents during both growing seasons. The results of the study indicates that amending soils with CM at the highest application rate provided the best crop performance in terms of root and shoot biomass, crop N, C, and other macro- and micro-nutrients.     

Molecular composition of recycled organic wastes,as determined by solid-state 13C NMR and elemental analyses

Using solid state ¹³C NMR data and elemental composition in a molecular mixing model, we estimated the molecular components of the organic matter in 16 recycled organic (RO) wastes representative of the major materials generated in the Sydney basin area. Close correspondence was found between the measured NMR signal intensities and those predicted by the model for all RO wastes except for poultry manure char. Molecular nature of the organic matter differed widely between the RO wastes. As a proportion of organic C, carbohydrate C ranged from 0.07 to 0.63, protein C from <0.01 to 0.66, lignin C from <0.01 to 0.31, aliphatic C from 0.09 to 0.73, carbonyl C from 0.02 to 0.23, and char C from 0 to 0.45. This method is considered preferable to techniques involving imprecise extraction methods for RO wastes. Molecular composition data has great potential as a predictor of RO waste soil carbon and nutrient outcomes.     

Ambient TSP concentration and dustfall in major cities of China: Spatial distribution and temporal variability

Based on environmental monitoring data in 93 major cities and meteorological records at 398 weather stations in China from 1981 to 2007, total suspended particle (TSP) concentration, the intensity of dustfall, and sand and dust storm frequency (F_d) were analysed. During the past 27 years, the annual average TSP concentration (C_TSP) in 93 cities was 402 μg m^?3. Annual average C_TSP decreased from the north to the south and from inland to the coast areas with a peak value of 628.8 μg m^?3 in Lanzhou. In the 1980s, 1990s and 2000s, annual average C_TSP was 628.7, 319.2, and 250.1 μg m^?3, respectively. Annual average intensity of dustfall (I_d) was 240.5 t km^?2 a^?1, decreased from northern to southern China and from inland to the coast areas with the maximum value of 717.2 t km^?2 a^?1 in Baotou. In the 1980s, 1990s and 2000s, annual average I_d was 334.8, 220.9, 146 t km^?2 a^?1 respectively. Annual average I_d in the Loess Plateau region was commonly higher than 200 t km^?2 a^?1. The annual average F_d decreased from arid regions in northwestern China to humid areas in southeastern China with two sand and sand storm centers existing in Xinjiang Taklamakan Desert and western Inner Mongolia. The annual average F_d in the 1980s, 1990s, 2000s was 16, 8, 6 days respectively, decreased steadily from 18 days in 1981–5 days in 2007. Annual average I_d had a positive linear relation to annual average C_TSP (R² = 0.96). Annual average F_d had a positive relation with annual average C_TSP (R² = 0.97) as well as annual average I_d (R² = 0.94). TSP was the chief pollutant influencing Air Pollution Index (API) in northern China in spring and winter seasons. Sand and dust storm might be a major factor affecting the temporal variability and spatial distribution of TSP and dustfall in China.     

Novel synthesis of multicomponent porous nano-hybrid composite,theoretical investigation using DFT and dye adsorption applications: disposing of waste with waste

Environmental Science and Pollution Research - Extensive studies have shown that doping can enhance the properties of graphene, but the application to real industrial wastewater treatment and...     

Are either sod and catalase or the polyamines involved in the paraquat resistance of Conyza canadensis ?

Abstract

Paraquat/atrazine coresistant (PqAR) and paraquat resistant (PqR) horseweed (Conyza canadensis /L./ Cronq.) plants showed ‐ in the first hour after 0.5 mM paraquat spraying ‐ a decreased catalase activity followed by a slight increase. However, the enzyme activity remained always below the initial value. Sensitive plants showed a significant increase of catalase activity in the first 4 hour after spraying. The transient character of paraquat inhibition, the recovery of photosyn‐thetic activity of the PqAR Conyza plants (characterized by variable fluorescence) after spraying remained unaffected by the Superoxide dismutase (SOD) inhibitor, diethyldithiocarbamate. This indicates that SOD is not involved in the resistance mechanism. Untreated resistant biotypes showed about 2.5 times higher total polyamine and putrescine level than the sensitive one. 100 μM of exogenously added putrescine was observed as having a protecting effect against paraquat in floated leaves of the sensitive biotype only. The resistant leaves were unaffected probably on account of their higher endogenous polyamine level. It is concluded that polyamines may play a role in the paraquat resistance of Conyza canadensis.     

Inexact fuzzy-stochastic constraint-softened programming – A case study for waste management

In this study, an inexact fuzzy-stochastic constraint-softened programming method is developed for municipal solid waste (MSW) management under uncertainty. The developed method can deal with multiple uncertainties presented in terms of fuzzy sets, interval values and random variables. Moreover, a number of violation levels for the system constraints are allowed. This is realized through introduction of violation variables to soften system constraints, such that the model’s decision space can be expanded under demanding conditions. This can help generate a range of decision alternatives under various conditions, allowing in-depth analyses of tradeoffs among economic objective, satisfaction degree, and constraint-violation risk. The developed method is applied to a case study of planning a MSW management system. The uncertain and dynamic information can be incorporated within a multi-layer scenario tree; revised decisions are permitted in each time period based on the realized values of uncertain events. Solutions associated with different satisfaction degree levels have been generated, corresponding to different constraint-violation risks. They are useful for supporting decisions of waste flow allocation and system-capacity expansion within a multistage context.     

Fire Regime Changes in La Michilía Biosphere Reserve, Durango, Mexico

Abstract: The ability of reserves to maintain natural ecosystem processes such as fire disturbance regimes is central to long-term conservation. Fire-scarred tree samples were used to reconstruct fire regimes at five study sites totaling approximately 230 ha in pine (   Pinus spp.) and oak ( Quercus spp.) forests of La Michilía Biosphere Reserve on the dry east slope of the Sierra Madre Occidental, Durango, Mexico. Study sites covered a 20-km environmental gradient of elevation, topography, and human land uses. Plant communities ranged from oak-pine to mixed conifer forests. Fires were frequent at all sites prior to 1930, when large-scale grazing of domestic livestock was initiated. Widespread fires have been excluded from four of the five sites since 1945, with an essentially uninterrupted regime of frequent fires continuing only in the reserve core. Xeric sites had many, smaller fires, whereas mesic sites had fewer but larger fires. On a reserve-wide scale, a fire burned on at least one site nearly every year, usually in the dry spring or early summer season, but fire years were rarely synchronous among the sites. Fire occurrence was weakly related to the Southern Oscillation climate pattern; major reserve-wide fire years almost never coincided with wet Southern Oscillation extremes but only occasionally matched dry extremes. Maintenance of the long-term frequent-fire regime in the reserve core is one indicator that the biosphere reserve model has been successful in conserving natural processes, but the protected area is small ( 7000 ha). Because of the key role of frequent-fire regimes in regulating ecosystem structure and function, restoration of the ecological role of fire disturbance is a desirable conservation strategy.