The effect of nitroaromatics' composition on their toxicity in vivo: novel, efficient non-additive 1D QSAR analysis

Novel 1D QSAR approach that allows analysis of non-additive effects of molecular fragments on toxicity has been proposed. Twenty-eight nitroaromatic compounds including some well-known explosives have been chosen for this study. The 50% lethal dose concentration for rats (LD50) was used as the estimation of toxicity in vivo to develop 1D QSAR models on the framework of Simplex representation of molecular structure. The results of 1D QSAR analysis show that even the information about the composition of molecules provides the main trends of toxicity changes. The necessity of consideration of substituents' mutual impacts for the development of adequate QSAR models of nitroaromatics' toxicity was demonstrated. Statistic characteristics for all the developed partial least squares QSAR models, except the additive ones are quite satisfactory (R2=0.81-0.92; Q2=0.64-0.83; R2 test=0.84-0.87). A successful performance of such models is due to their non-additivity i.e. possibility of taking into account the mutual influence of substituents in benzene ring which plays the governing role for toxicity change and could be mediated through the different C-H fragments of the ring. The correspondence between observed and predicted by these models toxicity values is good. This allowing combine advantages of such approaches and develop adequate consensus model that can be used as a toxicity virtual screening tool.     

Changes in sewage sludge carbon forms along a treatment stream

The behaviour and fate of macronutrients and pollutants in sewage sludge applied to the land are affected by the chemical composition of the sludge organic matter, which in turn is influenced by both sewage source and by sewage treatment processes. In this study, (13)C nuclear magnetic resonance (NMR) spectroscopy was used to characterise the organic matter of sludges collected at three different points along the treatment stream of a municipal sewage works with a domestic catchment. Sludge at the first point, an undigested liquid (UL) sludge, had a substantially different composition to the anaerobically digested (AD) and dewatered sludge cake (DC) materials, which were similar to each other. In particular, the UL sludge contained more alkyl C than the AD or DC sludges. All three sludges were found to contain mobile alkyl C that is poorly observed using the cross polarisation (CP) technique, necessitating the use of the less sensitive, but more quantitatively reliable direct polarisation (DP) technique to obtain accurate distributions of C types.     

Synthesis and analytical follow-up of the mineralization of a new fluorosurfactant prototype

Fluorinated surfactants have become essential in numerous technical applications due to their unparalleled effectiveness and efficiency. The environmental persistence of the non-biodegradable perfluorinated alkyl moiety has become a matter of concern. Therefore, it was searched for new molecules with chemically stable fluorinated end groups which can be microbially transformed into labile fluorinated substances. One prototype substance, 10-(trifluoromethoxy)decane-1-sulfonate, has shown biomineralization. Monitoring the formation of metabolites over time elucidated the mechanism of biotransformation. Analysis was performed utilizing liquid chromatography-single quadrupole mass spectrometry (LC-MS) and quadrupole-time of flight tandem mass spectrometry (QqTOF-MS). It was possible to distinguish between two major degradation pathways of the fluorinated alkylsulfonate derivative: (i) a desulfonation and subsequent oxidation and degradation of the alkyl chain being predominant and (ii) an insertion of oxygen with a subsequent cleavage and degradation of the molecule. The utilized trifluoromethoxy-endgroup resulted in instable trifluoromethanol after degradation of the alkyl chain, which led to a high degree of mineralization of the molecule.     

Dairy washwater treatment using a horizontal flow biofilm system

In Ireland, dairy farmyard washwater commonly comprises farmyard run-off and dairy parlour washings. Land-spreading is the most widely used method for treating this wastewater. However, this method can be labour intensive and can cause, in some cases, the degradation of surface and ground waters, mainly due to nitrogen contamination. In this study, a horizontal flow biofilm reactor (HFBR) with step-feed was constructed and tested in the laboratory, to remove organic carbon and nitrogen from a agricultural strength synthetic washwater (SWW). The HFBR had an average top plan surface area (TPSA) of 0.1002 m(2) and consisted of a stack of 45 polystyrene horizontal sheets--15 sheets embedded with 25 mm deep frustums above 30 sheets with 10 mm deep frustums. The frustums acted as miniature reservoirs. The sheets were alternately offset to allow the wastewater to flow horizontally along each sheet and vertically from sheet to sheet down through the reactor. Biofilms developed on the sheets and treated the wastewater. During the 212-d study, the total hydraulic loading rate based on the TPSA of the sheets was 35 l m(-2) d(-1). SWW was pumped for 10 min each hour, in a step feed arrangement at a rate of 23.33 l m(-2) d(-1) on to the top sheet during Phases 1 and 2, and 11.67 l m(-2) d(-1) onto Sheet 16 during Phase 1 (days 1-92) and onto Sheet 30 during Phase 2 (days 93-212). The substrate loading rate during Phases 1 and 2 was 94.8 g total chemical oxygen demand (COD) m(-2) d(-1) and 10.5 g total nitrogen (TN) m(-2) d(-1), based on the TPSA. At steady state in Phase 2, the unit achieved excellent carbon removal of 99.7% 5-day biochemical oxygen demand (BOD(5)) and 96.7% total COD, equivalent to TPSA removal rates of 67.5 g BOD(5)m(-2)d(-1) and 91.7 g COD m(-2) d(-1). The nitrogen removal percentages were 98.3% total ammonium-nitrogen (NH(4)-N(t)) and 72.8% TN, which equated to TPSA removal rates of 4.8 g NH(4)-N(t) m(-2) d(-1) and 7.6g TN m(-2) d(-1). No sloughing of solids or clogging of media occurred during the study. The unit was simple to construct and operate, with little maintenance.     

Relationships between street characteristics and perceived attractiveness for walking reported by elderly people

Walking is important for the health of elderly people. Previous studies have found a relationship between neighbourhood characteristics, physical activity and related health aspects. The multivariate linear regression model presented here describes the relationships between the perceived attractiveness of streets for walking along and (physical) street characteristics. Two hundred and eighty-eight independently living elderly people (between 55 and 80 years old) participated in the study. Street characteristics were assessed along homogeneous street subsections defined as ‘links’. Positively related to perceived attractiveness of links were the following street characteristics: slopes and/or stairs, zebra crossings, trees along the route, front gardens, bus and tram stops, shops, business buildings, catering establishments, passing through parks or the city centre, and traffic volume. Litter on the street, high-rise buildings, and neighbourhood density of dwellings were negatively related to perceived link attractiveness. Overall, the results suggest that three main aspects affect perceived attractiveness of streets for walking, namely tidiness of the street, its scenic value and the presence of activity or other people along the street. The results are discussed within the context of these three aspects.     

Effect of spatial variation on salinity tolerance of macroinvertebrates in Eastern Australia and implications for ecosystem protection trigger values

Salinisation of freshwater has been identified as a serious environmental issue in Australia and around the world. Protective concentrations (trigger values) for salinity can be used to manage salinity impacts, though require locally relevant salinity tolerance information. 72-h acute salinity tolerance values were determined for 102 macroinvertebrates collected from 11 locations in four biologically distinct freshwater bio-regions in Northeast Australia and compared with sensitivities observed in Southeast Australia. The salinity tolerance of individual taxa was consistent across Northeast Australia and between Northeast and Southeast Australia. However, two distinct communities were identified in Northeast Australia using distributions of the acute tolerance values and a calculated index of salinity sensitivity. Salinity trigger values should therefore be representative of local or regionally relevant communities and may be adequately calculated using sensitivity values from throughout Eastern Australia. The results presented provide a basis for assessing salinity risk and determining trigger values for salinity in freshwater ecosystems at local and regional scales in Eastern Australia.     

Particle fluxes above forests: observations, methodological considerations and method comparisons

This paper reports a study designed to test, evaluate and compare micro-meteorological methods for determining the particle number flux above forest canopies. Half-hour average particle number fluxes above a representative broad-leaved forest in Denmark derived using eddy covariance range from -7x10(7) m(-2) s(-1) (1st percentile) to 5x10(7) m(-2) s(-1) (99th percentile), and have a median value of -1.6x10(6) m(-2) s(-1). The statistical uncertainties associated with the particle number flux estimates are larger than those for momentum fluxes and imply that in this data set approximately half of the particle number fluxes are not statistically different to zero. Particle number fluxes from relaxed eddy accumulation (REA) and eddy covariance are highly correlated and of almost identical magnitude. Flux estimates from the co-spectral and dissipation methods are also correlated with those from eddy covariance but exhibit higher absolute magnitude of fluxes.     

Plant and Soil System Responses to Ozone After 3 Years in a Lysimeter Study with Juvenile Beech (Fagus sylvatica L.)

A lysimeter study was performed to monitor effects of elevated ozone on juvenile trees of Fagus sylvatica L. as well as on the plant–soil system. During a fumigation period over almost three growing seasons, parameters related to plant growth, phenological development and physiology as well as soil functions were studied. The data analyses identified elevated ozone to delay leaf phenology at early and to accelerate it at late developmental stages, to reduce growth, some leaf nutrients (Ca, K) as well as some soluble phenolics (hydroxycinnamic acid derivatives, total flavonol glycosides). No or very weak ozone effects were found in mobile carbon pools of leaves (starch, sucrose), and other phenolic compounds (flavans). Altered gene expression related to stress and carbon cycling corresponded well with findings from leaf phenology and chemical composition analyses indicating earlier senescence and oxidative stress in leaves under elevated ozone. Conversely in the soil system, no effects of ozone were detected on soil enzyme activities, rates of litter degradation and lysimeter water balances. Despite the fact that the three reported years 2003–2005 were climatically very contrasting including a hot and dry as well as an extremely wet summer, and also mild as well as cold winters, the influence of ozone on a number of plant parameters is remarkably consistent, further underlining the phytotoxic potential of elevated tropospheric ozone levels.     

A framework for valuing the health benefits of improved bathing water quality in the River Irvine catchment

A simple model predicting bathing water concentrations of Escherichia coli from livestock in the Irvine catchment in SW Scotland has been adapted for intestinal enterococci (IE). This has been used to predict risk of bather illness by extrapolation of published data on bather IE exposure vs incidence of gastro-enteritis. Simulated reduction in the risk of illness by reduced faecal loading was multiplied by a willingness to pay for risk reduction to estimate the annual benefits of mitigation. Health benefits of reducing loading by 75% at Irvine Beach were estimated by a willingness to pay method to be about pound 276k pa. Estimated annualised costs of diffuse pollution mitigation measures across the catchment were higher (> pound 1m), and it is very unlikely that 75% mitigation is achievable with current stocking rates. Further work should explore the influence of uncertainty of model parameters, and use emerging epidemiological information on specific zoonotic pathogens such as E. coli O157 and Cryptosporidium. Other components of the value of clean water should also be included to obtain a complete estimate of the cost:benefit of mitigation.     

Influence of Na2S on the degradation kinetics of CCl4 in the presence of very pure iron

This paper presents the results of kinetic studies to investigate the effect of FeS film formation on the degradation rate of CCl(4) by 99.99% pure metallic iron. The film was formed by submersing metallic iron grains in an oxygen free HCO(3)(-)/CO(3)(2-) electrolyte solution. When the grains had reached a quasi steady-state value of the corrosion potential, Na(2)S((aq)) was injected. Upon injection, a microm thick poorly crystalline FeS film formed immediately on the iron surface. Over time, the iron became strongly corroded and both the FeS film and the metallic iron grains began to crack leading to exposure of bare metallic iron to the solution. The effect of the surface film on the degradation rate of CCl(4) was investigated following four periods of aging, 1, 10, 30, and 60 days. Relative to the controls, the 1-day sulfide-aged iron showed a substantial decrease in rate of degradation of CCl(4.) However, over time, the rate of degradation increased and surpassed the degradation rate obtained in the controls. It has been proposed that CCl(4) is reduced to HCCl(3) by metallic iron by electron transfer. The FeS film is substantially less conducting than the bulk iron metal or non-stoichiometric magnetite and from the results of this study, greatly decreases the rate of CCl(4) degradation relative to iron that has not been exposed to Na(2)S. However, continued aging of the FeS film results in breakdown and stress-induced cracking of the film, followed by dissolution and cracking of the iron itself. The cracking of the bulk iron is believed to be a consequence of hydrogen embrittlement, which is promoted by sulfide. The increase in CCl(4) degradation rate, as the FeS films age, suggests that the process of hydrogen cracking increases the surface area available for charge transfer.