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.     

Micromorphology and chemistry of airborne particles in Brussels during agriculture working periods in surrounding region

The main objective of our research was to compare the airborne particle micromorphology and chemistry in the Brussels environment during agriculture working periods in the surrounding farming region. We used specific methods and instrumentation that are adapted to the climate peculiarities of the Brussels region, the period of investigations (12 months) and the proposed objectives. For the agricultural works we defined the following six periods: before sowing, sowing, after sowing, before harvest, harvest and after harvest. The results indicate a possible temporal correlation between agricultural work periods and airborne particle concentration, micromorphology and chemistry in the Brabant-Brussels region. For wheat and corn plant-growth periods, the average particle size, defined as the area obtained by a planar projection of the particulate, showed important variations in time. For sugar beet and endive, the average area size variations are less important. The roughness and sphericity parameters for the growth periods of the four different plants also showed significant differences. Many of the larger particulates (> 10 microm) are aggregates of even finer particles coated with many still finer ones. The airborne particle chemistry averages (atomic percentage At%), showed that three constituents (Si, S and Fe) dominate all the samples (except for particles 3-10 microm in size, which contain a relatively large percentage of Al). Applying similar investigation methods to study the correlations between airborne particle dynamics in urban zones and the agriculture working periods in their surrounding regions could be of interest to better understand the complexity of the PM problematic.     

Calculating losses of crops in Denmark caused by high ozone levels

In order to help guide air pollution legislation at the European level, harmful air pollution effects on agriculture crops and the consequent economic implications for policy have been studied for more than a decade. Ozone has been labeled as the most serious of the damaging air pollutants to agriculture, where growth rates and consequently yields are dramatically reduced. Quantifying the effects has formed a key factor in policymaking. Based on the widely held view that AOT40 (Accumulated exposure Over Threshold of 40 ppb) is a good indicator of ozone-induced damage, the Danish Eulerian Model (DEM) was used to compute reduced agriculture yields on a 50 km×50 km grid over Europe. In one set of scenarios, a ten year meteorological time series was combined with realistic emission inventories. In another, various idealized emission reduction scenarios are applied to the same meteorological time series. The results show substantial inter-annual variability in economic losses, due in most part to meteorological conditions which varied much more substantially than the emissions during the same period. It is further shown that, taking all uncertainties into account, estimates of ozone-induced economic losses require that a long meteorological record is included in the analysis, for statistical significance to be improved to acceptable levels for use in policy analysis. In this study, calculations were made for Europe as a whole, though this paper presents results relevant for Denmark.     

A comprehensive method for aeolian particle granulometry and micromorphology analyses

The aim of this study was to use a new approach to investigate aeolian particle granulometry and micromorphology. Taking total aeolian deposition into account, we used parameters such as, particle area, perimeter, shape analysis for particle roughness (area/perimeter) and elongation (long/short axis). These parameters were analyzed on temporal and spatial scales at four study sites in the eastern Negev Desert, Israel. The total collection of particles was sorted into three size groups based on particle area to facilitate comparison. The classic definition of particle size (equating particle length with particle diameter) produced relatively small variations among the three size classes (25-38.6%). Our proposed comprehensive method demonstrated significant variation among the three size classes (13.9-60.8%), e.g. the classic method placed 36.4% of the particles in size class two while the new method placed 60.8% of the particles in this size class; the differences were even more significant regarding size class 3 (38.6% vs. 13.9%, respectively). The classic method did not facilitate investigation of particle roughness and elongation. With this new approach, it was possible to clearly define the particles by size class, based on these characteristics. With roughness, the variation among size classes 2 and 3 was about 27%. With elongation, the variation among size classes two and three was about 21%. Applying similar investigation method to study the aeolian particle granulometry and micromorphology can better facilitate more detailed calculation of particle size distribution, roughness and elongation.     

Risk assessment and distribution of soil Pb in Guangdong, China

In this study, the spatial distributions of soil lead (Pb) concentration in three horizontal soils in Guangdong, China, were surveyed and analyzed using geostatistics and geography information systems (GIS). Findings indicated that the Pb geometric mean concentration of 23.3 mg/kg in surface soils was found to be higher than those in global soils, which ranged from 2.3–235 mg/kg. In addition, the Pb geometric mean concentrations from A- to C-horizon were found to be 23.3, 27.2, and 28.6 mg/kg, respectively. The classification of a soil Pb environmental risk in an area was likewise presented based on the different levels of environmental quality of Pb and was done by GIS technology. Accordingly, there is a higher local concentration of Pb in the surrounding areas of Guangzhou where there is higher population density and in the north of Guangdong, which is a historic mining area. The results obtained by the environmental risk assessment reveal that about 46% of total surveyed area was above the background value, that is, 2.7% of the total area was at risk of pollution.     

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.     

Hydrogeochemical data as a tool for exploration and mapping: a case study from part of Afikpo Basin southeastern Nigeria

Fourteen (14) characters from six (6) water samples collected from springs, ponds, and streams located in Lower Cretaceous sedimentary area of Afikpo Basin have been analyzed. These include pH, turbidity, conductivity, total dissolved solid, hardness, Fe²⁺, Ca²⁺, Mg²⁺, K⁺, NO₃ ^?, Cl^?, SO₄ ^2?, and Na⁺. These sediments, which are Turonian and Coniacian in age, are subdivided into two by a basic rock dyke. Results of the analyses show clearly that the Turonian sediments, intruded by dolerite, have net Fe²⁺, HCO₃ ^?, Ca²⁺, Mg²⁺, Mn²⁺, Cl^?, and SO₄ ^2? concentration while those from the younger Coniacian sediment have net higher amounts of K⁺, Na⁺, and Mn²⁺. The overriding mafic minerals in the basic intrusive rock possibly led to higher leaching into ground water system near it. On the other hand, the presence of feldsparthic to kaolinitic sands of the younger Coniacian units led to higher K⁺ and Na⁺ matter in the water from these zones. The formations dip away from the older sediments. Concentrations of these characters are within acceptable drinking water standards by World Health Organization but noticeable anomalous zones for Fe²⁺, Mg²⁺, and Ca²⁺ are zones of basic rock suites. Areas with greater Na⁺ and K⁺ are traceable to sandy units. It is thus concluded that more analysis of surface, subsurface, and pond water samples can be utilized for minerals search and geological mapping. At this stage, it forms a veritable reconnaissance tool.     

Effects of pH, organic acids, and competitive cations on mercury desorption in soils

The effects of pH, organic acids, and competitive cations on Hg(2+) desorption were studied. Three representative soils for rice production in China, locally referred to as a yellowish red soil (YRS), purplish clayey soil (PCS), and silty loam soil (SLS) and classified as Gleyi-Stagnic Anthrosols in FAO/UNESCO nomenclature, were, respectively, collected from Jiaxin County, Deqing County, and Xiasha District of Hangzhou City, Zhejiang Province. Most of the added Hg(2+) was adsorbed at low initial concentrations (<2 mg l(-1)). Desorption of the adsorbed Hg(2+) in 0.01M KCl (simulating soil solution) was minimal, but was significantly enhanced by the change of pH, and the presence of organic acids or competitive cations. The desorption of Hg(2+) in the soils decreased with pH from 3.0 to 5.0, leveled off at pH 5.0-8.0, but increased with pH from 7.0 to 9.0. The presence of organic ligands enhanced Hg(2+) desorption in the soils except for YRS, in which the addition of tartaric, malic, or oxalic acid reduced Hg(2+) desorption at low concentrations (<10(-4)M), but Hg(2+) desorption generally increased with organic acid concentration. Citric acid was most effective in increasing Hg(2+) desorption, followed by tartaric acid and malic acid; and oxalic acid was the least effective. Desorption of adsorbed Hg(2+) increased with increasing concentrations of added Cu(2+) or Zn(2+). Applied Cu(2+) increased Hg(2+) desorption more than Zn(2+) at the same loading rate. CAPSULE: The effects of organic acids and competitive cations on Hg desorption in soil-water system are related to their concentrations, basic chemical properties, and soil properties.     

Simultaneous conversion of CHClF(2) and CH(3)Br to CH(2)CF(2)

Gas phase reaction of CHClF(2) with CH(3)Br in an alumina tube reactor at 773-1123 K as a function of various input ratios of CH(3)Br to CHClF(2) is presented. The major products detected include C(2)F(4), CH(2)CF(2), and CH(4). Minor products include CH(3)Cl, CHF(3), C(2)H(4), C(2)H(2), CH(2)CF-CF(3), and C(2)H(3)F. The reaction produces a high yield of CH(2)CF(2) (53% based on CHClF(2) feed) at 1123 K and an input molar ratio of CH(3)Br to CHClF(2) of 1.8, suggesting that the reaction potentially can be developed as a process to convert two ozone depleting substances (CHClF(2) and CH(3)Br) to a highly valuable chemical, CH(2)CF(2). The reaction of CHClF(2) with CH(3)Cl and CH(3)I was also investigated under similar reaction conditions, to assist in understanding the reaction chemistry involved in the reaction of CHClF(2) with CH(3)Br.     

Spatial and temporal variations and possible sources of dichlorodiphenyltrichloroethane (DDT) and its metabolites in rivers in Tianjin, China

Water, suspended solid (SS) and sediment samples were collected from nine water courses in Tianjin, China and analyzed for dichlorodiphenyltrichloroethane (DDT) and its metabolites (DDXs, including o,p'-,p,p'-DDT, DDD and DDE). The average DDX concentrations in water, SS and sediment were 59+/-30 ng l(-1), 2690+/-1940 ng g(-1)dry wt. and 340+/-930 ng g(-1)dry wt., respectively. Due to the termination of the extensive agricultural application and industrial manufacture, DDXs in river sediment decreased by one order of magnitude since 1970's and low DDT fractions in these sediments were observed. Still, DDXs in the sediments near the outlets of the major manufacturers remained relatively high attributed to the historic input. DDXs in sediment were also positively correlated with organic matter content. Spatial distributions of DDXs in SS and water was different from that in sediment. For SS, a negative correlation between DDX concentration and SS content indicated a dilution effect in many rivers. Dissolved organic carbon content was the major factor affecting DDX concentrations in water phase. Wastewater discharged from dicofol manufacturers and likely illegal agricultural application were the primary reasons causing high DDT (DDE+DDD) ratios in SS and water.