Ferrate(VI) enhanced photocatalytic oxidation of pollutants in aqueous TiO<Subscript>2</Subscript> suspensions

Background, aim and scope  

Photocatalytic oxidation using UV irradiation of TiO₂ has been studied extensively and has many potential industrial applications, including the degradation of recalcitrant contaminants in water and wastewater treatment. A limiting factor in the oxidation process is the recombination of conduction band electrons (e ⁻ _cb) with electron holes (h_vb⁺) on the irradiated TiO₂ surface; thus, in aqueous conditions, the presence of an effective electron scavenger will be beneficial to the efficiency of the oxidation process. Ferrate (FeO₄²⁻) has received much recent attention as a water treatment chemical since it behaves simultaneously as an oxidant and coagulant. The combination of ferrate [Fe(VI)] with UV/TiO₂ photocatalysis offers an oxidation synergism arising from the Fe(VI) scavenging of e ⁻ _cb and the corresponding beneficial formation of Fe(V) from the Fe(VI) reduction. This paper reviews recent studies concerning the photocatalytic oxidation of problematic pollutants with and without ferrate.     

Biological Assessment to Support Ecological Recovery of a Degraded Headwater System

An assessment of the benthic macroinvertebrate community was conducted to characterize the ecological recovery of a channelized main stem and two small tributaries at the Watershed Research and Education Center (WREC, Arkansas, USA). Three other headwater streams in the same basin were also sampled as controls and for biological reference information. A principal components analysis produced stream groupings along an overall gradient of physical habitat integrity, with degraded reaches showing lower RBP habitat scores, reduced flow velocities, smaller substrate sizes, greater conductivity, and higher percentages of sand and silt substrate. The benthic macroinvertebrate assemblage at WREC was dominated by fast-reproducing dipteran larvae (midge and mosquito larvae) and physid snails, which comprised 71.3% of the total macroinvertebrate abundance over three sampling periods. Several macroinvertebrate assemblage metrics should provide effective targets for monitoring overall improvements in the invertebrate assemblage including recovery towards a more complex food web (e.g., total number of taxa, number of EPT taxa, percent 2 dominant taxa). However, current habitat conditions and the extent of existing degradation, system isolation and surrounding urban or agricultural land-uses might affect the level of positive change to the system. We therefore suggest a preliminary restoration strategy involving the addition of pool habitats in the system. At one pool we collected a total of 29 taxa (dominated by water beetle predators), which was 59% of total number of taxa collected at WREC. Maintaining water-retentive pools to collect flows and maintain water permanence focuses on enhancing known biology and habitat, thus reducing the effects of abiotic filters on macroinvertebrate assemblage recovery. Furthermore, biological assessment prior to restoration supports a strategy primarily focused on improving the existing macroinvertebrate community in the current context of the system, thereby reducing costs associated with active channel restoration. Monitoring future biological recovery and determining the contribution of changing assemblages to specific ecological processes would provide a critical underpinning for adaptive management and ecologically-effective restoration.     

Development of Thixotropic Coatings Using Dimerized Soybean Oil Fatty Acids: The Case of Polyamide of 1,2-Phenylene Diamine

Soybean oil (SBO) was dimerized and the crude dimer acid product reacted with 1,2-phenylene diamine at 210 ± 5 °C under inert atmosphere to obtain fatty polyamide (FPA). The FPA was used to modify a commercial alkyd resin by reacting a mixture of the alkyd resin with 5 wt% of FPA at 120 °C for 80 min under inert atmosphere. The FTIR spectrum of the FPA modified resin showed evidence of higher degree of H-bonding than was found for the unmodified alkyd. White gloss coatings of 15, 20, 25, and 30% solids were formulated from the modified and unmodified resins and examined for performance with respect to: leveling, sag resistance, drying time, pigment settling, skinning tendency and film hardness. Results showed that the unmodified alkyd coatings exhibited good leveling but poor sag resistance at all solid contents. In contrast, FPA modified alkyd coatings combined good leveling with high sag resistance indicating their thixotropic nature. A strong tendency to pigment settling was observed for unmodified alkyd coatings but was not observed in the FPA modified alkyd coatings. The modified alkyd coatings showed skinning while the unmodified alkyd coatings did not skin. A 30% solids coating formulation of the FPA modified resin showed shorter surface dry time but longer hard dry time than the unmodified alkyd resin coating.     

How life history contributes to stress response in the Manila clam <Emphasis Type="Italic">Ruditapes philippinarum</Emphasis>

Introduction  

Within the last decade, numerous studies have investigated the role of environmental history on tolerance to stress of many organisms. This study aims to assess if Manila clams Ruditapes philippinarum may react differently to cadmium exposure and trematode parasite infection (Himasthla elongata) depending on their origin and environmental history in Arcachon Bay (France).     

Characteristics of springtime profiles and sources of ozone in the low troposphere over northern Taiwan

To quantify the possible sources of the high ambient ozone concentration in the low troposphere over Taiwan, ozone sounding data from a two-year intensive field measurement program conducted in April and early May of 2004 and 2005 in northern Taiwan has been examined. We found that the vertical ozone distributions and occurrence of enhanced ozone in the lower troposphere (below 6 km) mainly resulted from (1)Type NE: the long-range transport of ozone controlled by the prevailing northeasterly winds below 2 km, (2)Type LO: the local photochemical ozone production process, and (3)Type SW: the strong southwest/westerly winds aloft (2–6 km). In the boundary layer (BL), where Asian continental outflow prevails, the average profile for type NE is characterized by a peak ozone concentration of nearly 65 ppb at about 1500 m altitude. For type LO, high ozone concentration with an average ozone concentration greater than 80 ppb was also found in the BL in the case of stagnant atmospheric and sunny weather conditions dominated. For type SW, significant ozone enhancement with average ozone concentration of 70–85 ppb was found at around 4 km altitude. It is about 10 ppb greater than that of the types NE and LO at the same troposphere layer owing to the contribution of the biomass burning over Indochina. Due to Taiwan's unique geographic location, the complex interaction of these ozone features in the BL and aloft, especially features associated with northeasterly and south/southwesterly winds, have resulted in complex characteristics of ozone distributions in the lower troposphere over northern Taiwan.     

Establishing ozone flux–response relationships for winter wheat: Analysis of uncertainties based on data for UK and Polish genotypes

The work outlined in this paper had three objectives. The first was to explore the effects of ozone pollution on grain yield and quality of commercially-grown winter wheat cultivars. The second was to derive a stomatal ozone flux model for winter wheat and compare with those already developed for spring wheat. The third was to evaluate exposure- versus flux–response approaches from a risk assessment perspective, and explore the implications of genetic variation in modelled ozone flux.Fifteen winter wheat cultivars were grown in open-top chambers where they were exposed to four levels of ozone. During fumigation, stomatal conductance measurements were made over the lifespan of the flag leaf across a range of environmental conditions. Although significant intra-specific variation in ‘ozone sensitivity’ (in terms of impacts on yield) was identified, yield was inversely related (R² = 0.63, P < 0.001) to the accumulated hourly averaged ozone exposure above 40 ppb during daylight hours (AOT40) across the dataset. The adverse effect of ozone on yield was principally due to a decline in seed weight. Algorithms defining the influence of environmental variables on stomatal uptake were subtly different from those currently in use, based on data for spring wheat, to map ozone impacts on pan-European cereal yield. Considerable intra-specific variation in phenological effects was identified. This meant that an ‘average behaviour’ had to be derived which reduced the predictive capability of the derived stomatal flux model (R² = 0.49, P < 0.001, 15 cultivars included). Indeed, given the intra-specific variability encountered, the flux model that was derived from the full dataset was no better in predicting O₃ impacts on wheat yield than was the AOT40 index. The study highlights the need to use ozone risk assessment tools appropriate to specific vegetation types when modelling and mapping ozone impacts at the regional level.     

Comparison of land-use regression models between Great Britain and the Netherlands

Land-use regression models have increasingly been applied for air pollution mapping at typically the city level. Though models generally predict spatial variability well, the structure of models differs widely between studies. The observed differences in the models may be due to artefacts of data and methodology or underlying differences in source or dispersion characteristics. If the former, more standardised methods using common data sets could be beneficial. We compared land-use regression models for NO₂ and PM_10, developed with a consistent protocol in Great Britain (GB) and the Netherlands (NL).Models were constructed on the basis of 2001 annual mean concentrations from the national air quality networks. Predictor variables used for modelling related to traffic, population, land use and topography. Four sets of models were developed for each country. First, predictor variables derived from data sets common to both countries were used in a pooled analysis, including an indicator for country and interaction terms between country and the identified predictor variables. Second, the common data sets were used to develop individual baseline models for each country. Third, the country-specific baseline models were applied after calibration in the other country to explore transferability. The fourth model was developed using the best possible predictor variables for each country.A common model for GB and NL explained NO₂ concentrations well (adjusted R² 0.64), with no significant differences in intercept and slopes between the two countries. The country-specific model developed on common variables for NL but not GB improved the prediction.The performance of models based upon common data was only slightly worse than models optimised with local data. Models transferred to the other country performed substantially worse than the country-specific models. In conclusion, care is needed both in transferring models across different study areas, and in developing large inter-regional LUR models.     

Kinetic study of the OH reaction with some hydrochloroethers under simulated atmospheric conditions

Using the relative rate technique, rate constants for the gas-phase reactions of hydroxyl radicals with 2-chloroethyl methyl ether (k₁), 2-chloroethyl ethyl ether (k₂) and bis(2-chloroethyl) ether (k₃) have been measured. Experiments were carried out at (298 ± 2) K and atmospheric pressure using synthetic air as bath gas. Using n-pentane and n-heptane as reference compounds, the following rate constants were derived: k₁ = (5.2 ± 1.2) × 10^?12, k₂ = (8.3 ± 1.9) × 10^?12 and k₃ = (7.6 ± 1.9) × 10^?12, in units of cm³ molecule^?1 s^?1. This is the first experimental determination of k₂ and k₃ under atmospheric pressure. The rate constants obtained are compared with previous literature data and the observed trends in the relative rates of reaction of hydroxyl radicals with the ethers studied are discussed. The atmospheric implications of the results are considered in terms of lifetimes and fates of the hydrochloroethers studied.     

Using a reduced Common Representative Intermediates (CRIv2-R5) mechanism to simulate tropospheric ozone in a 3-D Lagrangian chemistry transport model

A reduced chemical scheme (CRIv2-R5) which describes ozone formation from the tropospheric degradation of methane and 22 emitted non-methane hydrocarbons and oxygenated volatile organic compounds has been applied in a global-3D chemistry transport model (STOCHEM). The scheme, which contains 220 species in 609 reactions, has been used to simulate ozone and its precursors for the meteorological year of 1998 and the results have been compared with those from STOCHEM runs with its original chemistry. Compared with the original chemistry scheme, the degradation of a larger number of more reactive VOCs in the CRI scheme results in the formation (and their consequent transportation) of more NO_x active reservoirs thus leading to formation of more ozone away from land-based sources. Conversely, the more reactive VOCs also lead to greater removal of OH in continental areas and greater formation of OH in marine environments. STOCHEM run with the CRI scheme simulates more ozone (by up to 10 ppb), which results in better agreement with observed vertical ozone profiles. The CRI scheme transforms the globally and annually integrated ozone budget for the considered year in STOCHEM from a net loss of ?55 Tg yr^?1 to a net gain of +50 Tg yr^?1.     

Improved land cover and emission factors for modeling biogenic volatile organic compounds emissions from Hong Kong

This paper describes a study of local biogenic volatile organic compounds (BVOC) emissions from the Hong Kong Special Administrative Region (HKSAR). An improved land cover and emission factor database was developed to estimate Hong Kong emissions using MEGAN, a BVOC emission model developed by Guenther et al. (2006). Field surveys of plant species composition and laboratory measurements of emission factors were combined with other data to improve existing land cover and emission factor data. The BVOC emissions from Hong Kong were calculated for 12 consecutive years from 1995 to 2006. For the year 2006, the total annual BVOC emissions were determined to be 12,400 metric tons or 9.82 × 10⁹ g C (BVOC carbon). Isoprene emission accounts for 72%, monoterpene emissions account for 8%, and other VOCs emissions account for the remaining 20%. As expected, seasonal variation results in a higher emission in the summer and a lower emission in the winter, with emission predominantly in day time. A high emission of isoprene occurs for regions, such as Lowest Forest-NT North, dominated by broadleaf trees. The spatial variation of total BVOC is similar to the isoprene spatial variation due to its high contribution. The year to year variability in emissions due to weather was small over the twelve-year period (?1.4%, 2006 to 1995 trendline), but an increasing trend in the annual variation due to an increase in forest land cover can be observed (+7%, 2006 to 1995 trendline). The results of this study demonstrate the importance of accurate land cover inputs for biogenic emission models and indicate that land cover change should be considered for these models.