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.     

Impact of water saturation level on arsenic and metal mobility in the Fe-amended soil

The impact of water saturation level (oxidizing-reducing environment) on As and metal solubility in chromium, copper, arsenic (CCA)-contaminated soil amended with Fe-containing materials was studied. The soil was mixed with 0.1 and 1 wt% of iron grit (Fe(0)) and 1, 7 and 15 wt% of oxygen scarfing granulate (OSG, a by-product of steel processing). Solubility of As and metals was evaluated by a batch leaching test and analysis of soil pore water. Soil saturation with water greatly increased As solubility in the untreated as well as in the Fe-amended soil. This was related to the reductive dissolution of Fe oxides and increased concentration of As(III) species. Fe amendments showed As reducing capacity under both oxic and anoxic conditions. The cytotoxicity of the soil pore water correlated with the concentration of As(III). The Fe-treatments as well as water saturation of soil were less significant for the solubility of Cu, Cr and Zn than for As. The batch leaching test used for waste characterization substantially underestimated As solubility that could occur under water-saturated (anaerobic) conditions. In the case of soil landfilling, other techniques than Fe-stabilization of As containing soil should be considered.     

Development of a Quantitative Pasture Phosphorus Management Tool Using the SWAT Model1

Abstract: Assessment tools to evaluate phosphorus loss from agricultural lands allow conservation planners to evaluate the impact of management decisions on water quality. Available tools to predict phosphorus loss from agricultural fields are either: (1) qualitative indices with limited applicability to address offsite water quality standards, or (2) models which are prohibitively complex for application by most conservation planners. The purpose of this research was to develop a simple interface for a comprehensive hydrologic/water quality model to allow its usage by farmers and conservation planners. The Pasture Phosphorus Management (PPM) Calculator was developed to predict average annual phosphorus (P) losses from pastures under a variety of field conditions and management options. PPM Calculator is a vastly simplified interface for the Soil and Water Assessment Tool (SWAT) model that requires no knowledge of SWAT by the user. PPM Calculator was validated using 33 months of data on four pasture fields in northwestern Arkansas. This tool has been extensively applied in the Lake Eucha/Spavinaw Basin in northeastern Oklahoma and northwestern Arkansas. PPM Calculator allows conservation planners to take advantage of the predictive capacity of a comprehensive hydrologic water quality model typically reserved for use by hydrologists and engineers. This research demonstrates the applicability of existing water quality models in the development of user friendly P management tools.     

On the influence of environmental factors on harvest: the French Guiana shrimp fishery paradox

Environmental Economics and Policy Studies - The purpose of this paper is to investigate the environmental nature of the French Guiana shrimp fishery dynamics through an empirical analysis. To do...     

Health risk assessment of potentially harmful elements and dietary minerals from vegetables irrigated with untreated wastewater,Pakistan

In the developing world, vegetables are commonly grown in suburban areas irrigated with untreated wastewater containing potentially harmful elements (PHEs). In Pakistan, there is no published work on the bioaccessibility aspect of PHEs and dietary minerals (DMs) in sewage-irrigated soil or the vegetables grown on such soils in Pakistan. Several industrial districts of Pakistan were selected for assessment of the risk associated with the ingestion of vegetables grown over sewage-irrigated soils. Both the total and bioaccessible fraction of PHEs (Cd, Co, Cr, Ni, and Pb) and DMs (Fe, Cu, Mn, Zn, Ca, Mg, and I) in soils and vegetable samples were measured. The concentrations of these PHEs and DMs in sewage-irrigated and control soils were below published upper threshold limits. However, compared to control soils, sewage irrigation over the years decreased soil pH (7.7 vs 8.1) and enhanced dissolved organic carbon (1.8 vs 0.8 %), which could enhance the phyto-availability of PHEs and DMs to crops. Of the PHEs and DMs, the highest transfer factor (soil to plant) was noted for Cd and Ca, respectively. Concentrations of PHEs in most of the sewage-irrigated vegetables were below the published upper threshold limits, except for Cd in the fruiting portion of eggplant and bell pepper (0.06–0.08 mg/kg Cd, dry weight) at three locations in Gujarat and Kasur districts. The bioaccessible fraction of PHEs can reduce the context of dietary intake measurements compared to total concentrations, but differences between both measurements were not significant for Cd. Since the soils of the sampled districts are not overly contaminated compared to control sites, vegetables grown over sewage-irrigated soils would provide an opportunity to harvest mineral-rich vegetables potentially providing consumers 62, 60, 12, 104, and 63 % higher dietary intake of Cu, Mn, Zn, Ca, and Mg, respectively. Based on Fe and vanadium correlations in vegetables, it is inferred that a significant proportion of total dietary Fe intake could be contributed by soil particles adhered to the consumable portion of vegetables. Faecal sterol ratios were used to identify and distinguish the source of faecal contamination in soils from Gujranwala, Gujarat, and Lahore districts, confirming the presence of human-derived sewage biomarkers at different stages of environmental alteration. A strong correlation of some metals with soil organic matter concentration was observed, but none with sewage biomarkers.     

Atrazine contamination in agricultural soils from the Yangtze River Delta of China and associated health risks

Atrazine is one of the most widely applied and persistent herbicides in the world. In view of limited information on the regional contamination of atrazine in soils in China, this study investigated the spatial distribution and environmental impacts of atrazine in agricultural soils collected from the Yangtze River Delta (YRD) as an illustrative analysis of rapidly developing regions in the country. The results showed that the concentrations of atrazine in the YRD agricultural soils ranged from <1.0 to 113 ng/g dry weight, with a mean of 5.7 ng/g, and a detection rate of 57.7 % in soils. Pesticide factory might be a major source for the elevated levels of atrazine in Zhejiang Province. The contamination of atrazine was closely associated with land use types. The concentrations and detection rates of atrazine were higher in corn fields and mulberry fields than in rice paddy fields. There was no significant difference in compositions of soil microbial phospholipids fatty acids among the areas with different atrazine levels. Positive relationship (R = 0.417, p < 0.05, n = 30) was observed between atrazine and total microbial biomass. However, other factors, such as soil type and land management practice, might have stronger influences on soil microbial communities. Human health risks via exposure to atrazine in soils were estimated according to the methods recommended by the US EPA. Atrazine by itself in all the soil samples imposed very low carcinogenic risks (<10^?6) and minimal non-cancer risks (hazard index <1) to adults and children.     

Triclocarban: UV photolysis,wastewater disinfection,and ecotoxicity assessment using molecular biomarkers

Triclocarban (TCC) is an antibacterial agent found in pharmaceuticals and personal care products (PPCP). It is potentially bioaccumulative and an endocrine disruptor, being classified as a contaminant of emerging concern (CEC). In normal uses, approximately 96% of the used TCC can be washed down the drain going into the sewer system and eventually enter in the aquatic environment. UV photolysis can be used to photodegrade TCC and ecotoxicity assays could indicate the photodegradation efficiency, since the enormous structural diversity of photoproducts and their low concentrations do not always allow to identify and quantify them. In this work, the TCC was efficiently degraded by UVC direct photolysis and the ecotoxicity of the UV-treated mixtures was investigated. Bioassays indicates that Daphnia similis (48 h EC₅₀ = 0.044 μM) was more sensitive to TCC than Pseudokirchneriella subcapitata (72 h IC₅₀ = 1.01 μM). TCC and its photoproducts caused significant effects on Eisenia andrei biochemical responses (catalase and glutathione-S-transferase); 48 h was a critical exposure time, since GST reached the highest activity values. UVC reduced the TCC toxic effect after 120 min. Furthermore, TCC was photodegraded in domestic wastewater which was simultaneously disinfected for total coliform bacterial (TCB) (360 min) and Escherichia coli (60 min).

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Graphical abstract TCC degradation and ecotoxicological assessment

     

Evaluation of the sensitivity spectrum of a video tracking system with zebrafish (<Emphasis Type="Italic">Danio rerio</Emphasis>) exposed to five different toxicants

The aim of this study was to develop a biological early warning system for the detection of aquatic toxicity and test it with five toxicants with distinct chemical nature. This was done in order to verify the spectrum of sensitivities of the proposed system, as well as the potential identification capability of the tested contaminants, using only the analysis of zebrafish’s behavior. Six experimental conditions were tested: negative control and five toxicants (bleach, lindane, tributyltin, mercury, and formaldehyde). The exposure time was 45 min, and the concentrations used corresponded to 9% of LC₅₀’s-96 h for the tested compounds, to ensure ecologically relevant results. A total of 108 fish were used, with each individual experimental condition being tested 18 times. A statistical model of diagnosis was used, combining self-organizing map and correspondence analysis. The values of sensitivity, specificity, accuracy, false positive, false negative, positive predictive value (PPV), and negative predictive value (NPV) were calculated. The objectives of the work were accomplished and the system showed a good overall diagnostic performance with 79% in accuracy, 77% in sensitivity, and 88% in specificity. The lowest result of the predictive values was 78% (lindane and mercury), in the case of the NPV, and 86% (bleach and lindane), in the case of the PPV. The best result of the predictive values was 100% (bleach and tributyltin), for the NPV, and 89% (tributyltin), for the PPV. Regarding the five tested toxicants, the system was able to correctly identify the agent responsible for the contamination in 40% of the positive diagnoses.     

Dental enamel as biomarker for environmental contaminants in relevant industrialized estuary areas in São Paulo,Brazil

Heavy metal contamination is a long-standing and very well-known public health problem, and its exposure can cause damage to several organs of human body, especially on the central nervous system of young children and teenagers. The aim of this article is to evaluate lead, cadmium, and manganese contamination in 125 children from 6 to 13 years old living in contaminated areas during the period from 2006 to 2009 (São Vicente, Cubatão Downtown, Bertioga and Cubatão Pilões/Água Fria). This estuary area is the most important example of environmental degradation by chemicals from industrial sources. This is a cross-sectional study through clinical examinations and dental enamel tests. All mothers from these children lived in the area since before the pregnancy. Lead, cadmium, and manganese levels (μg/g) were measured on dental enamel samples through graphite furnace atomic absorption spectrometry, searching for the occurrence of heavy metals. The mean lead concentrations were 139.48 μg/g in Cubatão Pilões/Água Fria, 170.45 μg/g in Cubatão Downtown, 213.52 μg/g in São Vicente, and 151.89 μg/g in Bertioga. The mean cadmium concentrations were 10.83 μg/g in Cubatão Pilões/Água Fria, 12.58 μg/g in Cubatão Downtown, 10.92 μg/g in São Vicente, and 14.57 μg/g in Bertioga. The mean manganese concentrations were 23.49 μg/g in Cubatão Pilões/Água Fria, 30.90 μg/g in Cubatão Downtown, 41.46 μg/g in São Vicente, and 42.00 μg/g in Bertioga. Dental surface enamel may be used as an efficient biomarker of past environmental exposure to lead, manganese, and cadmium which are associated to well-known sources of heavy metal contamination. The results suggest that the evaluated children were exposed to sources of lead, cadmium, and manganese since before their conceptions. Although Bertioga initially was chosen as a control area of this study, it was also was verified to have heavy metal contamination on examined children.