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.     

Choice of parameters for passive shielding of power-frequency magnetic fields

Epidemiological studies suggesting the possibility of harmful effects on human (specifically children’s leukaemia) due to long-term exposure to magnetic fields of extremely low frequency (e.g. 50/60 Hz) and relatively low values (i.e. over the microtesla range) have stirred high activity in the topic of magnetic field mitigation. To reduce these fields, it is common to use passive metal screens (e.g. plates made of aluminium or steel). To design them, effective and fast numerical computations are highly desirable. In this article, a method is presented, which computes various parameters of screens in a given shielding problem and yields magnetic field distribution and shielding factors. The method takes into consideration the 3D field distribution and is able to solve systems with large aspect ratios (thin thickness in comparison with its other dimensions); this is a common problem where other methods such as finite elements often experience difficulties. The presented method computes separately the field inside and outside the screens. Afterwards, the solutions are “stitched” together along the border of the subregions. Two practical examples are given of the developed numerical method.     

Removal of an anionic dye (Acid Blue 92) by coagulation–flocculation using chitosan

Chitosan (a biopolymer) is an aminopolysaccharide that can be used for the treatment of colored solutions by coagulation–flocculation (as an alternative to more conventional processes such as sorption). Acid Blue 92 (a sulfonic dye) was selected as a model dye for verifying chitosan's ability to treat textile wastewater. A preliminary experiment demonstrated that chitosan was more efficient at color removal in tap water than in demineralized water, and that a substantially lower concentration of chitosan could be used with tap water. Dye removal reached up to 99% under optimum concentration; i.e., in terms of the acidic solutions and the stoichiometric ratio between the amine groups of the biopolymer and the sulfonic groups in the dye. The flocs were recovered and the dye was efficiently removed using alkaline solutions (0.001–1 M NaOH solutions) and the biopolymer, re-dissolved in acetic acid solution, was reused in a further treatment cycle.     

Age and lost working days as a result of an occupational accident: A study in a shiftwork rotation system

The present work analyzed the relationship of age and tenure with occupational accident severity of 156 male shiftworkers at an industrial plant. Based on past research, negative binomial regression analyses were performed to examine the association of age and tenure with the lost working days due to medically certified occupational accidents (LWDI). The main effects of age and tenure and the contribution of age by tenure interaction and age squared terms were examined. Regression results indicated a significant association of age by tenure interaction with LWDI. However, this relationship was non-significant when considering an age squared term in the regression equation, suggesting a non-linear association of age with LWDI. The findings are discussed in regard to the specific preventative measures of occupational accidents in shiftwork systems that could be addressed to different age groups.     

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.     

Long-Term Relationship between Phosphorus Inputs and Wetland Phosphorus Concentrations in a Northern Everglades Marsh

Assessments of long-term relationships between changes innutrient inputs and wetland nutrient concentrations can becomplicated by fluctuations in other environmental factors aswell as by problems typical of long-term monitoring data.Consequently, statistical analysisof these types of data sets requirescareful consideration of environmental covariates, potentialbiases in the monitoring design, and irregularities caused bychanges in field sampling protocols. We evaluated therelationship between anthropogenic phosphorus (P) inputs andwater-column total P (TP) concentrations in a northernEverglades marsh by statistically analyzing available datacollected from several sampling programs over the past 20 years(1978–1997). Canal inputs of agricultural runoff contributemost of the P to the marsh and have produced a zone ofenrichment within the marsh during the past few decades.Regression analyses showed that both canal and marsh TPconcentrations increased during the 1980s and then decreased inthe 1990s. However, the statistical relationship between canal Pinputs and marsh TP, while significant, generally was weakexcept for marsh locations adjacent to the canal. Strongerrelationships existed between marsh TP and hydrologic parameterssuch as marsh water depth, which is controlled by changes inweather patterns and marsh management. In particular, dryconditions during the 1980s may have contributed to observedincreases in marsh P concentrations and the movement of a P`front' further into the marsh. Higher rainfall and water depthsand agricultural best management programs initiated during the1990s have been associated with reduced P concentrations incanal waters entering the marsh. While it is anticipated thatthis reduction eventually will result in lower marsh TPconcentrations, this effect is not yet evident, possibly due tointernal loading of P from enriched marsh soils. Our findingsillustrate some of the environmental factors that can complicateattempts to develop empirical relationships between P inputs andwetland P concentrations and to use such relationships to forecast changesin marsh concentrations based on past monitoring data alone.     

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.     

The hydrochemistry of groundwater in the Densu River Basin, Ghana

Hydrochemical analyses of groundwater samples were used to establish the hydrochemistry of groundwater in the Densu River Basin. The groundwater was weakly acidic, moderately mineralized, fresh to brackish with conductivity ranging from of 96.6 μS cm^???1 in the North to 10,070 μS cm^???1 in the South. Densu River basin have special economic significance, representing the countries greatest hydrostructure with freshwater. Chemical constituents are generally low in the North and high in the South. The order of relative abundance of major cations in the groundwater is Na^?+??> Ca^2?+??> Mg^2?+??> K^?+? while that of anions is Cl^????> HCO $_{3}^{-} >$ SO $_{4}^{2-} >$ NO $_{3}^{-}$ . Four main chemical water types were delineated in the Basin. These include Ca–Mg–HCO₃, Mg–Ca–Cl, Na–Cl, and mixed waters in which neither a particular cation nor anion dominates. Silicate weathering and ion exchange are probably the main processes through which major ions enter the groundwater system. Anthropogenic activities were found to have greatly impacted negatively on the quality of the groundwater.     

Minimax regret optimization analysis for a regional solid waste management system

Solid waste management (SWM) facilities are crucial for environmental management and public health in urban regions. Due to the waste management hierarchy, one of the greatest challenges that organizations face today is to figure out how to diversify the treatment options, increase the reliability of infrastructure systems, and leverage the redistribution of waste streams among incineration, compost, recycling, and other facilities to their competitive advantage region wide. Systems analysis plays an important role for regionalization assessment of integrated SWM systems, leading to provide decision makers with break-through insights and risk-informed strategies. This paper aims to apply a minimax regret optimization analysis for improving SWM strategies in the Lower Rio Grande Valley (LRGV), an economically fast growing region in the US. Based on different environmental, economic, legal, and social conditions, event-based simulation in the first stage links estimated waste streams in major cities in LRGV with possible solid waste management alternatives. The optimization analysis in the second stage emphasizes the trade-offs and associated regret evaluation with respect to predetermined scenarios. Such optimization analyses with multiple criteria have featured notable successes, either by public or private efforts, in diverting recyclables, green waste, yard waste, and biosolids from the municipal solid waste streams to upcoming waste-to-energy, composting, and recycling facilities. Model outputs may link prescribed regret scenarios in decision making with various scales of regionalization policies. The insights drawn from the system-oriented, forward-looking, and preventative study can eventually help decision-makers and stakeholders gain a scientific understanding of the consequences of short-term and long-term decisions relating to sustainable SWM in the fast-growing US-Mexico borderland.