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The effects of initial dye concentration and disc rotation speed were studied on the performance of a continuously operated rotating biological contactor RBC reactor in decolourising an azo dye containing synthetic wastewater, employing the statistically planned 2k full factorial design of experiments. While the initial dye concentration in the study varied between 50 mg&47;l and 100 mg&47;l, the disc rotation speed ranged from 5 rpm to 11 rpm. The RBC with a hydraulic retention time of two days showed steady state dye decolourisation efficiency of more than 92&37; in all the experimental runs. Statistical analyses in the form of Analysis of Variance ANOVA and significance test of factors revealed that the main effects of both the factors were highly significant P &60; 0.05 on the performance of the RBC and the effect of initial dye concentration was, however, negative and more compared to that of the disc rotation speed. � 2009 Inderscience Enterprises Ltd.

Large-scale use of leaded gasoline was an important source of the neurotoxin lead in the European environment. After a sequence of regulations on the allowed gasoline lead content and, eventually, a ban on the use of lead additives in gasoline, road transport was no longer considered a source of atmospheric lead. Currently a discrepancy exists between measured atmospheric lead concentrations and model-predicted concentrations, suggesting that lead emissions to the atmosphere may be underestimated. Recently it was suggested that lead emission from unleaded gasoline combustion is still an important source and may (partly) fill the gap between modelled and observed atmospheric lead concentrations. In this paper we assess the plausibility of the latter suggestion by following various emission estimation methodologies. The uncertainty of lead emissions from road transport is further reduced by chemical analysis of fuel samples. The result of our assessment is that lead from road transport fuel combustion is not the missing lead source needed to fill the gap between modelled and observed lead concentrations. Road transport is still a source of lead through brake wear and a small contribution from exhaust emissions but this contributes no more than 5-8% of the EU25 total emission. © 2009 Elsevier B.V. All rights reserved.

The presence of parts per billion (ppb) levels of chlorpyrifos (O, O-Diethyl-O-(3,5,6-trichloro-2-pyridyl) phosphorothioate) and malathion (S-1,2-bis(ethoxycarbonyl) ethyl O, O-dimethyl phosphorodithioate), two common pesticides found in the surface waters of developing countries, have been visually detected using gold nanoparticles. Visual detection of the presence of pesticide is possible when the color change occurring by the adsorption of pesticides on gold nanoparticles is enhanced by sodium sulfate. The method presented here is simple and there is no need of sample preparation or preconcentration. The response occurs within seconds and the color change is very clear. The detection is possible if chlorpyrifos and malathion are present up to a concentration of 20 and 100 ppb, respectively. Themethod shows great potential for on-site pesticide monitoring. The method is also applicable as a qualitative technique for the performance evaluation of various household water filters, which claim pesticide removal. � Taylor & Francis Group, LLC.

A separation/preconcentration procedure, based on the coprecipitation of Cr(3+), Fe(3+), Pb(2+) and Zn(2+) ions using a new organic coprecipitant, 3-phenly-4-o-hydroxybenzylidenamino-4,5-dihydro-1,2,4-triazole, 5-one (POHBAT) without adding any carrier element has been developed The method thus has been.,, called carrier element-free coprecipitation (CEFC). The resultant concentrated elements were determined by flame atomic absorption spectrometric determinations. The influences of some analytical parameters including pH of the solution, amount of the coprecipitant, standing time, centrifugation rate and time, sample volume and diverse ions were investigated on the quantitative recoveries of analyte ions. The validation of the present preconcentration procedure was performed by the analysis of two certified reference materials. The recoveries of understudy analytes were found in the range of 93-98%, while the detection limits were calculated in the range of 0.3-2.0 mu g L(-1). The precision of the method evaluated as relative standard deviation (R.S.D.), was in the range of 3-7% depend on the analytes. The proposed method was successfully applied to environmental samples for the determination of the analytes. (C) 2008 Elsevier B.V. All rights reserved.

Biomarkers are widely used to measure environmental impacts on marine species. For many biomarkers, it is not clear how the signal levels relate to effects on the whole organism. This paper shows how species sensitivity distributions (SSDs) can be applied to evaluate multiple biomarker responses in species assemblages. To our knowledge, the present study compared for the first time SSDs based on biomarker response levels for marine species to a SSD for whole-organism responses. The comparison indicates that for exposure to dispersed oil in the marine environment, the selected biomarkers were, on average, 35- to 50-fold more sensitive than the whole-organism effect. At the 5% hazardous concentration derived from the SSD for whole-organism effects, which is a conservative threshold level, the potentially affected fraction of species showing biomarker response corresponds to approximately 80%. Variation in species sensitivity, expressed either as biomarker or as whole-organism response levels, were similar. Although uncertainties exist, the link between biomarkers and risk assessment presented here provides a preliminary guideline for deciding when biomarker responses likely are hazardous and, therefore, require further investigation. © 2009 SETAC.

Large-scale use of leaded gasoline was an important source of the neurotoxin lead in the European environment. After a sequence of regulations on the allowed gasoline lead content and, eventually, a ban on the use of lead additives in gasoline, road transport was no longer considered a source of atmospheric lead. Currently a discrepancy exists between measured atmospheric lead concentrations and model-predicted concentrations, suggesting that lead emissions to the atmosphere may be underestimated. Recently it was suggested that lead emission from unleaded gasoline combustion is still an important source and may (partly) fill the gap between modelled and observed atmospheric lead concentrations. In this paper we assess the plausibility of the latter suggestion by following various emission estimation methodologies. The uncertainty of lead emissions from road transport is further reduced by chemical analysis of fuel samples. The result of our assessment is that lead from road transport fuel combustion is not the missing lead source needed to fill the gap between modelled and observed lead concentrations. Road transport is still a source of lead through brake wear and a small contribution from exhaust emissions but this contributes no more than 5-8% of the EU25 total emission. © 2009 Elsevier B.V. All rights reserved.

We present a case study of the development of Sacrower See, a stratified, eutrophic lake in northeastern Germany, over the past 13,000 years. Total epilimnetic phosphorus (TP) concentrations were reconstructed quantitatively using a diatom-TP transfer function. Fossil chironomid assemblages were used to support the trophic reconstruction and helped assessing past hypolimnetic oxygen availability. The results indicate eutrophic and anoxic conditions during the Younger Dryas cold period (∼12,700-11,600 cal. BP) preceding the present interglacial. Throughout the early and mid-Holocene (∼11,600-4000 cal. BP) stable oligo- to mesotrophic conditions with diatom-inferred TP values of ∼20 μg L-1 prevailed. First evidence of increasing Holocene TP is recorded at ∼3500 cal. BP associated with Bronze Age human impact and for the past 900 years diatoms indicate increasing TP values of 30-60 μg L-1. During the early Holocene and the past two millennia chironomids indicated anoxic hypolimnetic conditions. The chironomid fauna is considered typical of oligo- to mesotrophic lakes. As a consequence of strongly increased primary production the hypolimnion of Sacrower See became anoxic again during the past 140 years. Our results indicate that highly productive eutrophic conditions can exist prior to cultural eutrophication. At Sacrower See the shift from eutrophic conditions in the Lateglacial to oligo-mesotrophic conditions in the early and mid-Holocene was associated with the climatic warming at the Younger Dryas/Holocene transition. The high productive state during the cold Younger Dryas is associated with changes in seasonality: the prolonged winters caused longer ice cover, stronger stratification, anoxia in the hypolimnion, and consequent internal phosphorus loading. During the warm Holocene, however, hypolimnetic anoxia and internal phosphorus loading decreased significantly, resulting in a substantially lower productivity.

Total concentration is not a reliable indicator of metal phytoavailability in soils. There is a dearth of single universal multielement methods with critical value. Therefore, this study was implemented to select appropriate methods for evaluation of phytoavailable metal status in peaches grown in alkaline alluvial soils. Component plant parts (leaf and fruit flesh and peel) and soil samples were collected from 21 orchards. Fourteen extraction methods were applied to the soils to determine the phytoavailable metal content of the soils. Metal [iron (Fe), manganese (Mn), zinc (Zn), copper (Cu), chromium (Cr), nickel (Ni), cobalt (Co), lead (Pb), and cadmium (Cd)] concentrations in leaf, flesh, and peel samples were assayed, and the relationship was investigated among metals in component parts of the plant. Metals were assayed by various methods to select the most representative method. The methods of aqua regia, Morgan extraction solution, ammonium acetate (NH4OAc; pH4.8), 0.01M disodium ethylenediamine-di-o-hydroxyphenylacetic acid (Na2EDDHA), and sodium acetate (NaOAc) + diethylenetriaminepentaacetic acid (DTPA) for Fe and DTPA + triethanolamine (TEA) + calcium chloride (CaCl2), 0.05 N hydrochloric acid (HCl) + 0.025 N sulfuric acid (H2SO4), NH4OAc (pH4.8), 0.05M ethylenediaminetetraacetic acid (EDTA; pH7.0), 0.01M Na2EDDHA, and 1M ammonium bicarbonate (NH4HCO3) + 0.005M DTPA for Ni were well correlated to Fe and Ni in the leaves, respectively. The main factors affecting Fe and Ni availability in the soils were compared with the other methods. Therefore, based on this study, 0.01M Na2EDDHA should be used for determination of phytoavailable Fe and Ni status in peaches grown on alkaline alluvial soils. Poor correlation was found among the rest of the metals assayed by the methods, concentrations of these metals in component parts of the peach trees, and the examined soil properties. Metal content of the flesh had low correlation coefficients with the examined properties.

Biomarkers are widely used to measure environmental impacts on marine species. For many biomarkers, it is not clear how the signal levels relate to effects on the whole organism. This paper shows how species sensitivity distributions (SSDs) can be applied to evaluate multiple biomarker responses in species assemblages. To our knowledge, the present study compared for the first time SSDs based on biomarker response levels for marine species to a SSD for whole-organism responses. The comparison indicates that for exposure to dispersed oil in the marine environment, the selected biomarkers were, on average, 35- to 50-fold more sensitive than the whole-organism effect. At the 5% hazardous concentration derived from the SSD for whole-organism effects, which is a conservative threshold level, the potentially affected fraction of species showing biomarker response corresponds to approximately 80%. Variation in species sensitivity, expressed either as biomarker or as whole-organism response levels, were similar. Although uncertainties exist, the link between biomarkers and risk assessment presented here provides a preliminary guideline for deciding when biomarker responses likely are hazardous and, therefore, require further investigation. © 2009 SETAC.

We present a case study of the development of Sacrower See, a stratified, eutrophic lake in northeastern Germany, over the past 13,000 years. Total epilimnetic phosphorus (TP) concentrations were reconstructed quantitatively using a diatom-TP transfer function. Fossil chironomid assemblages were used to support the trophic reconstruction and helped assessing past hypolimnetic oxygen availability. The results indicate eutrophic and anoxic conditions during the Younger Dryas cold period (∼12,700-11,600 cal. BP) preceding the present interglacial. Throughout the early and mid-Holocene (∼11,600-4000 cal. BP) stable oligo- to mesotrophic conditions with diatom-inferred TP values of ∼20 μg L-1 prevailed. First evidence of increasing Holocene TP is recorded at ∼3500 cal. BP associated with Bronze Age human impact and for the past 900 years diatoms indicate increasing TP values of 30-60 μg L-1. During the early Holocene and the past two millennia chironomids indicated anoxic hypolimnetic conditions. The chironomid fauna is considered typical of oligo- to mesotrophic lakes. As a consequence of strongly increased primary production the hypolimnion of Sacrower See became anoxic again during the past 140 years. Our results indicate that highly productive eutrophic conditions can exist prior to cultural eutrophication. At Sacrower See the shift from eutrophic conditions in the Lateglacial to oligo-mesotrophic conditions in the early and mid-Holocene was associated with the climatic warming at the Younger Dryas/Holocene transition. The high productive state during the cold Younger Dryas is associated with changes in seasonality: the prolonged winters caused longer ice cover, stronger stratification, anoxia in the hypolimnion, and consequent internal phosphorus loading. During the warm Holocene, however, hypolimnetic anoxia and internal phosphorus loading decreased significantly, resulting in a substantially lower productivity.

Atmospheric transport and dispersion were investigated during the CAPITOUL campaign using measurements of sulphur hexafluoride (SF6) tracer. Six releases of SF6 tracer were performed (March 9-11 and July 1-3, 2004) in the same suburban area of Toulouse conurbation, during the Intensive Observing Periods (IOP) of CAPITOUL. Concentration data were collected both at ground-level along axes perpendicular to the wind direction (at distances ranging between 280 m and 5000 m from the release point), and above the ground at 100 m and 200 m height using aircraft flights. Meteorological conditions were all associated with daytime anticyclonic conditions with weak winds and convective clear and cloudy boundary layers. A meso-scale dispersion modelling system, PERLE, developed at Meteo-France for environmental emergencies in case of atmospheric accidental release, was evaluated in terms of meteorology and dispersion, for the different tracer experiments, in its operational configuration. PERLE is based on the combination of the non-hydrostatic meso-scale MESO-NH model, running at 2 km horizontal resolution, and the Lagrangian particle model SPRAY. The statistical meteorological evaluation includes two sets of simulations with initialisation from ECMWF or ALADIN. The meteorological day-to-day error statistics show fairly good Meso-NH predictions, in terms of wind speed, wind direction and near-surface temperature. A strong sensitivity to initial fields concerns the surface fluxes, crucial for dispersion, with an excessive drying of the convective boundary layer with ALADIN initial fields, leading to an overprediction of surface sensible heat fluxes. A parameterization of dry and shallow convection according to the Eddy-Diffusivity-Mass-Flux (EDMF) approach (Pergaud et al. 2008) allows an efficient mixing in the Convective Boundary Layer (CBL) and improves significantly the wind fields. A statistical evaluation of the dispersion prediction was then performed and shows a realistic behaviour of the system, with a good location of the concentration maxima. But the lateral spread of the plumes is quasi-systematically underestimated, mainly in July, even when meteorological conditions are well reproduced. In the same way, higher integrated concentration values are slightly overestimated. The remove of the EDMF scheme in Meso-NH artificially improves the horizontal dispersion, underlying compensating errors. Sensitivity tests performed on the Lagrangian time scales in the coupling Meso-NH-SPRAY have been conducted. But they don't solve the shortcoming and lead to the conclusion that SPRAY could have some difficulties to correctly reproduce the mixing for daytime thermal convection. © Springer-Verlag 2008.

The conventional treatment of dark coloured textile wastewater using chemical coagulation generates large volume of sludge, which requires further treatment and disposal. In the present investigation, a systematic optimization study of the important variables influencing the decolorization of Reactive Orange-16 (RO-16) and Reactive Red-35 (RR-35) dyes by the white-rot fungus (Trametes versicolor) was carried out. A full factorial central composite design was employed for experimental design and optimization of results. The effect of concentrations of dye, glucose and ammonium chloride on decolorization was studied and optimized using Response Surface Methodology (RSM). Maximum decolorization of 94.5% and 90.7% for RO-16 and RR-35 was obtained at optimum concentrations of dye, glucose and ammonium chloride i.e., 0.66, 17.50 and 2.69 g/L for RO-16 and 0.68, 16.67 and 2.13 g/L for RR-35, respectively. � 2008 Elsevier B.V. All rights reserved.

Seasonal and interannual variability in atmospheric carbon dioxide (CO2) concentrations was simulated using fluxes from fossil fuel, ocean and terrestrial biogeochemical models, and a tracer transport model with time-varying winds. The atmospheric CO2 variability resulting from these surface fluxes was compared to observations from 89 GLOBALVIEW monitoring stations. At northern hemisphere stations, the model simulations captured most of the observed seasonal cycle in atmospheric CO2, with the land tracer accounting for the majority of the signal. The ocean tracer was 3–6 months out of phase with the observed cycle at these stations and had a seasonal amplitude only ∼10% on average of observed. Model and observed interannual CO2 growth anomalies were only moderately well correlated in the northern hemisphere (R ∼ 0.4–0.8), and more poorly correlated in the southern hemisphere (R < 0.6). Land dominated the interannual variability (IAV) in the northern hemisphere, and biomass burning in particular accounted for much of the strong positive CO2 growth anomaly observed during the 1997–1998 El Niño event. The signals in atmospheric CO2 from the terrestrial biosphere extended throughout the southern hemisphere, but oceanic fluxes also exerted a strong influence there, accounting for roughly half of the IAV at many extratropical stations. However, the modeled ocean tracer was generally uncorrelated with observations in either hemisphere from 1979–2004, except during the weak El Niño/post-Pinatubo period of the early 1990s. During that time, model results suggested that the ocean may have accounted for 20–25% of the observed slowdown in the atmospheric CO2 growth rate

The influence of aerosols on cloud properties is an important modulator of the climate system. Traditional Köhler theory predicts the equilibrium concentration of cloud condensation nuclei (CCN); however, it is not known to what extent particles exist in the atmosphere that may be prevented from acting as CCN by kinetic limitations. We measured the rate of cloud droplet formation on atmospheric particles sampled at four sites across the United States during the summer of 2006: Great Smoky Mountain National Park, TN; Bondville, IL; Houston, TX; and the Atmospheric Radiation Measurement Program Southern Great Plains site near Lamont, OK. We express droplet growth rates with the mass accommodation coefficient (α), and report values of α measured in the field normalized to the mean α measured for lab-generated ammonium sulfate (AS) particles (i.e., α'=α/αAS). Overall, 59% of ambient CCN grew at a rate similar to AS. We report the fraction of CCN that were "low-α' " (α'−1, corresponding to α−2). Of the 16 days during which these measurements were made, 8 had relatively few low-α' CCN (82% during at least one ~30 min period). Day to day variability was greatest in Tennessee and Illinois, and low-α' particles were most prevalent on days when back trajectories suggested that air was arriving from aloft. The highest fractions of low-α' CCN in Houston and Illinois occurred around local noon, and decreased later in the day. These results suggest that for some air masses, accurate quantification of CCN concentrations may need to account for kinetic limitations.

During last decades, a number of projects have been launched to validate models for predicting the behaviour of radioactive substances in the environment. The project of the "Aquatic" working group of the project EMRAS (Environmental Modelling for Radiation Safety) organised by the International Atomic Energy Agency (IAEA) was based on the validation and assessment of models for predicting the behaviour of radionuclides in the aquatic ecosystems. The present paper describes a blind test of models aimed at assessing the dispersion of tritium releases in the Loire River (France), on a large domain (∼350 km) and on a period of six months, by comparing the results obtained by operational-to-experimental values of tritium concentration at Angers, a city along the Loire River. The common conclusion is that the models used by the different participants namely 1D models and models based on a schematic hydraulic (box models) are reliable tools for tritium transport modelling. Nevertheless, the importance of proper and detailed hydrological data for the appropriate prediction of pollutant migration in water is demonstrated by the example provided during this study. © 2007 Elsevier Ltd. All rights reserved.

Interannual variability (IAV) in tropospheric species concentrations can be driven by variability in emissions, chemistry, transport and UV radiation. In a 3D CTM study we have found good agreement between the IAV of NO2 columns observed by the GOME satellite instrument and model simulations over Western Europe from 1996 to 2000. We find that meteorological variability is an important factor during this period. Averaged 10 m wind speeds from the European Centre for Medium-Range Weather Forecasts (ECMWF) operational analysis are a good proxy for the overall meteorology driving the IAV during the studied period of 1996-2000. Copyright © 2008 Royal Meteorological Society.

The absence of species in polluted sediments does not necessarily imply exclusion due to toxicity. Other factors, like for instance food availability and oxygen content, could also partly cause their absence. Hence, knowledge of the (combinations of) factors acting on individual organisms is essential in order to understand how populations can persist in polluted sediments. In this study species-specific responses of two benthic invertebrate species, the mayfly Ephoron virgo and the midge Chironomus riparius, to environmental variables were compared. It was assessed how these responses determine the distribution of these species in polluted sediments. Subsequently, it was discussed how these results can assist in the formulation and implementation of policies with respect to the ecological risks of pollution to benthic invertebrates. The present study showed that sediment pollution is likely to act only occasionally as a single selective force reducing the persistence of sensitive species. Yet, it was shown in our studies that the pollution level in some tested sediments limits the persistence of insects with the sensitivity of E. virgo. In other cases, however, a combination of conditions is likely to determine their persistence. As shown here for C. riparius, sediment pollution drives this species close to intoxication, but a high availability of food enables them to persist very well. The present study provides evidence that pollution levels exceeding current Dutch Negligible Concentrations may pose a detectable ecological effect at least for sensitive benthic invertebrates. © 2008 Elsevier B.V. All rights reserved.

Groundwater quality management relies more and more on models in recent years. These models are used to predict the risk of groundwater contamination for various land uses. This paper presents an assessment of uncertainties and sensitivities to input parameters for a regional model. The model had been set up to improve and facilitate the decision-making process between stakeholders and in a groundwater quality conflict. The stochastic uncertainty and sensitivity analysis comprised a Monte Carlo simulation technique in combination with a Latin hypercube sampling procedure. The uncertainty of the calculated concentrations of nitrate leached into groundwater was assessed for the various combinations of land use, soil type, and depth of the groundwater table in a vulnerable, sandy region in The Netherlands. The uncertainties in the shallow groundwater were used to assess the uncertainty of the nitrate concentration in the abstracted groundwater. The confidence intervals of the calculated nitrate concentrations in shallow groundwater for agricultural land use functions did not overlap with those of non-agricultural land use such as nature, indicating significantly different nitrate leaching in these areas. The model results were sensitive for almost all input parameters analyzed. However, the NSS is considered pretty robust because no shifts in uncertainty between factors occurred between factors towards systematic changes in fertilizer and manure inputs of the scenarios. In view of these results, there is no need to collect more data to allow science based decision-making in this planning process. © 2008 Elsevier B.V. All rights reserved.

Historic emissions from ore smelters typically cause regional soil contamination. We developed a modelling approach to assess the impact of such contamination on groundwater and surface water load, coupling unsaturated zone leaching modelling with 3D groundwater transport modelling. Both historic and predictive modelling were performed, using a mass balance approach for three different catchments in the vicinity of three smelters. The catchments differ in their hydrology and geochemistry. The historic modelling results indicate that leaching to groundwater is spatially very heterogeneous due to variation in soil characteristics, in particular soil pH. In the saturated zone, cadmium is becoming strongly retarded due to strong sorption at neutral pH, even though the reactivity of the sandy sediments is low. A comparison between two datasets (from 1990 to 2002) on shallow groundwater and modelled concentrations provided a useful verification on the level of statistics of "homogeneous areas" (areas with comparable land use, soil type and geohydrological situation) instead of comparison at individual locations. While at individual locations observations and the model varies up to two orders of magnitude, for homogeneous areas, medians and ranges of measured concentrations and the model results are similar. A sensitivity analysis on metal input loads, groundwater composition and sediment geochemistry reveals that the best available information scenario based on the median value of input parameters for the model predicts the range in observed concentrations very well. However, the model results are sensitive to the sediment contents of the reactive components (organic matter, clay minerals and iron oxides). Uncertainty in metal input loads and groundwater chemistry are of lesser importance. Predictive modelling reveals a remarkable difference in geochemical and hydrological controls on subsurface metal transport at catchment-scale. Whether the surface water load will peak within a few decades or continue to increase until after 2050 depends on the dominant land use functions in the areas, their hydrology and geochemical build-up. © 2007 Elsevier B.V. All rights reserved.

Groundwater quality management relies more and more on models in recent years. These models are used to predict the risk of groundwater contamination for various land uses. This paper presents an assessment of uncertainties and sensitivities to input parameters for a regional model. The model had been set up to improve and facilitate the decision-making process between stakeholders and in a groundwater quality conflict. The stochastic uncertainty and sensitivity analysis comprised a Monte Carlo simulation technique in combination with a Latin hypercube sampling procedure. The uncertainty of the calculated concentrations of nitrate leached into groundwater was assessed for the various combinations of land use, soil type, and depth of the groundwater table in a vulnerable, sandy region in The Netherlands. The uncertainties in the shallow groundwater were used to assess the uncertainty of the nitrate concentration in the abstracted groundwater. The confidence intervals of the calculated nitrate concentrations in shallow groundwater for agricultural land use functions did not overlap with those of non-agricultural land use such as nature, indicating significantly different nitrate leaching in these areas. The model results were sensitive for almost all input parameters analyzed. However, the NSS is considered pretty robust because no shifts in uncertainty between factors occurred between factors towards systematic changes in fertilizer and manure inputs of the scenarios. In view of these results, there is no need to collect more data to allow science based decision-making in this planning process. © 2008 Elsevier B.V. All rights reserved.

The electro-optical properties of thin films of electron donor-acceptor blends of a fluorene copolymer (PF10TBT) and a fullerene derivative (PCBM) were studied. Transmission electron microscopy shows that in these films nanocrystalline PCBM clusters are formed at high PCBM content. For all concentrations, a charge transfer (CT) transition is observed with absorption spectroscopy, photoluminescence, and electroluminescence. The CT emission is used as a probe to investigate the dissociation of CT excited states at the donor-acceptor interface in photovoltaic devices, as a function of an applied external electric field and PCBM concentration. We find that the maximum of the CT emission shifts to lower energy and decreases in intensity with higher PCBM content. We explain the red shift of the emission and the lowering of the open-circuit voltage (VOC) of photovoltaic devices prepared from these blends with the higher relative permittivity of PCBM (εr = 4.0) compared to that of the polymer (εr = 3.4), stabilizing the energy (ECT) of CT states and of the free charge carriers in blends with higher PCBM concentration. We show that the CT state has a short decay time (τ = ca. 4 ns) that is reduced by the application of an external electric field or with increasing PCBM content. The field-induced quenching can be explained quantitatively with the Onsager-Braun model for the dissociation of the CT states when including a high electron mobility in nanocrystalline PCBM clusters. Furthermore, photoinduced absorption spectroscopy shows that increasing the PCBM concentration reduces the yield of neutral triplet excitons forming via electron-hole recombination, and increases the lifetime of radical cations. The presence of nanocrystalline domains with high local carrier mobility of at least one of the two components in an organic heterojunction may explain efficient dissociation of CT states into free charge carriers. © 2008 American Chemical Society.

Historic emissions from ore smelters typically cause regional soil contamination. We developed a modelling approach to assess the impact of such contamination on groundwater and surface water load, coupling unsaturated zone leaching modelling with 3D groundwater transport modelling. Both historic and predictive modelling were performed, using a mass balance approach for three different catchments in the vicinity of three smelters. The catchments differ in their hydrology and geochemistry. The historic modelling results indicate that leaching to groundwater is spatially very heterogeneous due to variation in soil characteristics, in particular soil pH. In the saturated zone, cadmium is becoming strongly retarded due to strong sorption at neutral pH, even though the reactivity of the sandy sediments is low. A comparison between two datasets (from 1990 to 2002) on shallow groundwater and modelled concentrations provided a useful verification on the level of statistics of "homogeneous areas" (areas with comparable land use, soil type and geohydrological situation) instead of comparison at individual locations. While at individual locations observations and the model varies up to two orders of magnitude, for homogeneous areas, medians and ranges of measured concentrations and the model results are similar. A sensitivity analysis on metal input loads, groundwater composition and sediment geochemistry reveals that the best available information scenario based on the median value of input parameters for the model predicts the range in observed concentrations very well. However, the model results are sensitive to the sediment contents of the reactive components (organic matter, clay minerals and iron oxides). Uncertainty in metal input loads and groundwater chemistry are of lesser importance. Predictive modelling reveals a remarkable difference in geochemical and hydrological controls on subsurface metal transport at catchment-scale. Whether the surface water load will peak within a few decades or continue to increase until after 2050 depends on the dominant land use functions in the areas, their hydrology and geochemical build-up. © 2007 Elsevier B.V. All rights reserved.

A group of Roman glass objects from the Bocholtz burial in the SW of Limburg (The Netherlands) was found to have been subject to varying degrees of degradation. Many of the 25 colourless glass objects were fragmented to pieces

17a-Ethinyl estradiol (EE2) is a synthetic estrogen widely used in combination with othersteroid hormones in oral contraceptives and in the contraceptive patch. EE2 has been detected in sewage treatment plant effluents in the low nanogram -per-liter range and occasionally in surface waters in the U.S., U.K., Canada, Brazil, Germany, and elsewhere. The mode of action is receptor-mediated, and estrogen receptors exist in mammals and other vertebrates. A large number of studies on the effects of EE2 on aquatic organisms exist. One hundred English language studies published between 1994 and 2007, one as yet unpublished study, and findings published in conference proceedings (in German) were compared to published data quality criteria to identify the most relevant studies for deriving a predicted no-effect concentration (PNEC). Reproduction in fish was identified as the most sensitive end point in aquatic species. A species sensitivity distribution was constructed using no observed effect concentrations (NOECs) for reproductive effects from 39 papers in 26 species, resulting in a median hazardous concentration at which 5% of the species tested are affected (HC5,50) of 0.35 ng/L. After comparing this HC5,50 to all of the laboratory and field-derived toxicity information available for EE2, we recommend using 0.35 ng/L as the PNEC for EE2 in surface water. This PNEC is below 95% of the existing NOECs for effects on reproduction and is also below virtually all of the NOECs for vitellogenin induction in the key fish reproduction studies.

Dry deposition fluxes and total (gas+particle) concentrations of polychlorinated biphenyls (PCBs) were measured between August 2004 and May 2005. Samples were collected from an urban-industrial site of Bursa, Turkey. A stainless steel pot and a high volume air sampler (HVAS) were employed to collect deposition and ambient air samples, respectively. The dry deposition fluxes of PCBs ranged from 3,600 to 56,000 pg m(-2) d(-1) while the total PCB concentrations collected simultaneously were between 35 and 348 pg m(-3). The average dry deposition flux value was in line with the previously reported values. Possible variations in PCB fluxes were likely due to PCB and total suspended particle (TSP) concentrations, and meteorological conditions. No seasonal trends were observed for the bulk deposition samples. The 3- and 4- chlorobiphenyls (CBs) were abundant homolog groups in bulk and concentration samples with ratios of 67% and 90%, respectively. Apparent bulk deposition velocities were calculated by dividing the dry deposition flux value by particle phase air concentration values of PCBs measured with HVAS. The calculated apparent dry deposition velocities ranged from 0.23 cm s(-1) to 3.09 cm s(-1) (aver +/- SD, 0.74 +/- 0.23 cm s(-1)).

The effect of the matrix composition (main constituents) on the concentration and chemical behavior of uranium in phosphogypsum stack solutions and leachates has been investigated. Solid and aqueous samples were taken from three different sub-areas of a phosphogypsum stack at a coastal area in Vasilikos (Cyprus). The sub-areas are characterized whether by their acidity (e.g. "aged" and "non-aged" phosphogypsum) or by their salt content, originating from pulping water during wet stacking or (after deposition) from the adjacent sea. Measurements in stack solutions and leachates showed that phosphogypsum characteristics affect both, the concentration and the chemical behavior of uranium in solution. Uranium concentration in solutions of increased salinity is up to three orders of magnitude higher than in solutions of low salinity and this is attributed to the effect of ionic strength on the solubility of phosphogypsum. Modelling showed that uranium in stack solutions is predominantly present in the form of uranium(VI) phosphate complexes (e.g. UO2(H2PO4)2, UO2HPO4), whereas in leachates uranium(VI) fluoro complexes (e.g. UO2F2, UO2F3-) are predominant in solution. The latter indicates that elution of uranium from phosphogypsum takes places most probably in the form of fluoro complexes. Both, effective elution by saline water and direct migration of uranium to the sea, where it forms very stable uranium(VI) carbonato complexes, indicate that the adjacent sea will be the final receptor of uranium released from Vasilikos phosphogypsum. © 2007 Elsevier Ltd. All rights reserved. 99 2 359 366 Cited By :15

Purified alkali stable xylanase from Aspergillus fischeri was immobilized on polystyrene beads using diazotization method. An expanded bed bioreactor was developed with these immobilized beads to biobleach the paper pulp in continuous mode. Response surface methodology was applied to optimize the biobleaching conditions. Temperature (�C), flow rate of pulp (ml/min) and concentration of the pulp (%) were selected as variables in this study. Optimal conditions for biobleaching process were reaction temperature 60 �C, flow rate of 2 ml/min and 5% (w/v) of pulp. The kappa number reduced from 66 in the unbleached pulp to 20 (reduction of 87%). This system proves to be a better option for the conventional chlorine based pulp bleaching. � 2008 Elsevier Ltd. All rights reserved.

This study focuses on the importance of solute dissolution kinetics for cloud droplet formation. To comprehensively account for the kinetics, a numerical model of the process was developed. Simulations of cloud droplet growth were performed for solute diffusivity, droplet growth rates, dry particle and droplet diameters relevant for ambient conditions. Simulations suggest that high ambient supersaturations and low solute diffusivity are major contributors to significant decreases in effective solute surface concentrations during droplet growth. The numerical simulations were incorporated into Köhler theory to assess the impact of dissolution kinetics on the droplet equilibrium vapor pressure. The modified Köhler theory implies that only CCN with slowly dissolving solute could have a "dynamical" equilibrium saturation ratio that is appreciably different from that obtained using thermodynamic equilibrium arguments alone. Copyright 2007 by the American Geophysical Union.