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.     

Influence of titanium dioxide nanoparticles on speciation and bioavailability of arsenite

In this study, the influence of the co-existence of TiO₂ nanoparticles on the speciation of arsenite [As(III)] was studied by observing its adsorption and valence changing. Moreover, the influence of TiO₂ nanoparticles on the bioavailability of As(III) was examined by bioaccumulation test using carp (Cyprinus carpio). The results showed that TiO₂ nanoparticles have a significant adsorption capacity for As (III). Equilibrium was established within 30 min, with about 30% of the initial As (III) being adsorbed onto TiO₂ nanoparticles. Most of aqueous As (III) was oxidized to As(V) in the presence of TiO₂ nanoparticles under sunlight. The carp accumulated considerably more As in the presence of TiO₂ nanoparticles than in the absence of TiO₂ nanoparticles, and after 25-day exposure, As concentration in carp increased by 44%. Accumulation of As in viscera, gills and muscle of the carp was significantly enhanced by the presence of TiO₂ nanoparticles.     

Screening analysis of volatile organic contaminants in commercial inorganic coagulants used for drinking water treatment

A method for quality screening is suggested to detect volatile impurities in inorganic coagulants that are used for drinking water treatment. Static headspace gas chromatography with mass spectrometry detection (HS–GCMS) is sensitive and selective to detect volatiles in low concentrations. This study has discovered that volatile organic impurities are detectable in ferric and aluminium-based coagulants which are used for drinking water treatment. For ferric chloride, 2-propanol was detected at a level of 17–24 μg ml⁻¹, acetone at 0.7–1.7 μg ml⁻¹, 1,1,1-trichloroacetone at 0.02–0.04 μg ml⁻¹, trichloromethane at 0.01–0.02 μg ml⁻¹ and toluene at 0.01–0.12 μg ml⁻¹. For ferric chloride sulfate, acetone was detected at a level of 0.12 μg ml⁻¹, 1,1,1-trichloroacetone at 0.06–0.08 μg ml⁻¹, trichloromethane at 0.13–0.23 μg ml⁻¹, bromodichloromethane at 0.04–0.06 μg ml⁻¹ and dibromochloromethane at 0.04–0.05 μg ml⁻¹. For aluminium hydroxide chloride, only trichloromethane was detectable, but below the method detection limits (MDL). Although the concentrations of these impurities in commercial coagulants are low, this observation is important and should have impact on water industries for them to pay attention to the chemicals they are using for drinking water production.     

Physical Modeling of Emissions from Naturally Ventilated Underground Parking Garages

The dispersion of pollutants from naturally ventilated underground parking garages has been studied in a boundary layer wind tunnel. Two idealized model setups have been analysed, one was simulating pollutant dispersion around an isolated rectangular building and one was representing dispersion in a finite array of idealized building blocks. Flow and dispersion close to modelled ground level emission sources was measured. The results illustrate the complexity of the flow around buildings and provide insight in pollutant transport from ground level sources located directly on building surfaces. As a result, areas critical with respect to high pollutant concentrations could be visualized. Particularly, the results show high concentration gradients on the surface of the buildings equipped with modelled emission sources. Inside the boundary layers on the building walls, a significant amount of pollutants is transported to upwind locations on the surface of the building. The paper documents the potential of physical modelling to be used for the simulation and measurement of dispersion close to emission sources and within complex building arrangements.     

Development of an integrated sensor to measure odors

Odorous air samples collected from several sources were presented to an olfactometer, an electronic nose, a hydrogen sulfide (H(2)S) detector and an ammonia (NH(3)) detector. The olfactometry measurements were used as the expected values while measurements from the other instrumentation values became input variables. Five hypotheses were established to relate the input variables and the expected values. Both linear regression and artificial neural network analyses were used to test the hypotheses. Principal component analysis was utilized to reduce the dimensionality of the electronic nose measurements from 33 to 3 without significant loss of information. The electronic nose or the H(2)S detector can individually predict odor concentration measurements with similar accuracy (R (2) = 0.46 and 0.50, respectively). Although the NH(3) detector alone has a very poor relationship with odor concentration measurements, combining the H(2)S and NH(3) detectors can predict odor concentrations more accurately (R (2) = 0.58) than either individual instrument. Data from the integration of the electronic nose, H(2)S, and NH(3) detectors produce the best prediction of odor concentrations (R (2) = 0.75). With this accuracy, odor concentration measurements can be confidently represented by integrating an electronic nose, and H(2)S and NH(3) detectors.     

Quantitative arsenic speciation in two species of earthworms from a former mine site

The relationship between the total arsenic concentration and the chemical speciation of arsenic in two species of earthworm (Lumbricus rubellus and Dendrodrilus rubidus) in relation to the host soil, was investigated for 13 sites of varying arsenic content, including a background level garden soil and a former mine site at the Devon Great Consols, UK. Earthworms were collected with the host soil (As soil concentration range 16-12, 466 mg kg(-1) dry weight) and measured for their total arsenic (concentration range 7-595 mg kg(-1) dry weight) using inductively coupled plasma mass spectrometry (ICP-MS). A methanol-water mixture was used to extract arsenic species from the earthworms prior to determination of the individual arsenic species by a combination of anion and cation exchange high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). A gradient elution anion exchange method is presented whereby nine arsenic species could be measured in one sample injection. Arsenic species were identified by comparison of retention times and sample spiking with known standards and a fully characterised seaweed extract. Arsenic was generally present in the earthworm as arsenate (As(V)) or arsenite (As(III)) and arsenobetaine (AB). Methylarsonate (MA), dimethylarsinate (DMA) and three arsenosugars (glycerol, phosphate, sulfate) were present as minor constituents. These results are discussed in relation to the mechanisms for coping with exposure to soil bound arsenic.     

Critical technical elements of state bioassessment programs: a process to evaluate program rigor and comparability

We developed a systematic process to evaluate state/tribal bioassessment programs to provide information about the rigor of the technical approach. This is accomplished via on-site interviews to produce an evaluation that assigns one of four levels of rigor as an outcome. Level 4 is the most rigorous and reflects a technical capacity to accurately determine incremental condition and support management programs. The remaining three levels are less able to assess incremental condition and are appropriate for only some management support needs. Accurately determining impairment and diagnosing pollution-specific stressors are fundamental tasks that states/tribes must accomplish to provide management support. This goal is fulfilled to varying degrees by most states/tribes. The evaluation employs a checklist and a sliding scale of rigor for 13 technical elements. Feedback is provided to each state/tribe via a technical memorandum that describes the technical components of the monitoring program, highlights strengths, and recommends improvements for specific technical issues. This can be used to refine the bioassessment and monitoring programs to better support management programs. The results of 14 state/tribal evaluations are included here. The majority (nine states, one tribe) revealed that most operate at level 2 with developmental activities that will elevate the level of program rigor already underway. Two states operate level 4 programs and each have numeric biocriteria and refined designated uses in their water quality standards. This is the ultimate goal of the process of engaging states in the development of bioassessment programs in the U.S.     

Assessment and significance of phytoplankton species composition within Chesapeake Bay and Virginia tributaries through a long-term monitoring program

Phytoplankton and water quality long term trends are presented from a 20-year monitoring program of Chesapeake Bay and several of its major tributaries. Increasing phytoplankton biomass and abundance are ongoing within this estuarine complex, with diatoms the dominant component, along with chlorophytes and cyanobacteria as sub-dominant contributors in the tidal freshwater and oligohaline regions. Diatoms, dinoflagellates, and cryptomonads are among the major flora downstream in the tributaries and within the Chesapeake Bay. Water quality conditions within the three tributaries have remained rather stable over this time period; while there are long term trends of reduced nutrients, increasing bottom oxygen, and decreasing water clarity for the lower Chesapeake Bay. Of note is an increasing trend of cyanobacteria biomass at 12 of the 13 stations monitored at tributary and Chesapeake Bay stations, plus the presence of 37 potentially harmful taxa reported for these waters. However, the overall status of the phytoplankton populations is presently favorable, in that it is mainly represented and dominated by taxa suitable as a major food and oxygen source within this ecosystem. Although potentially harmful taxa are present, they have not at this time exerted profound impact to the region, or replaced the diatom populations in overall dominance.