Photodegradation of bisphenol A in simulated lake water containing algae, humic acid and ferric ions

The photodegradation of bisphenol A (BPA), a suspected endocrine disruptor (ED), in simulated lake water containing algae, humic acid and Fe3+ ions was investigated. Algae, humic acid and Fe3+ ions enhanced the photodegradation of BPA. Photodegradation efficiency of BPA was 36% after 4h irradiation in the presence of 6.5 x 10(9) cells L(-1) raw Chlorella vulgaris, 4 mg L(-1) humic acid and 20 micromol L(-1) Fe3+. The photodegradation efficiency of BPA was higher in the presence of algae treated with ultrasonic than that without ultrasonic. The photodegradation efficiency of BPA in the water only containing algae treated with ultrasonic was 37% after 4h irradiation. The algae treated with heating can also enhance the photodegradation of BPA. This work helps environmental scientists to understand the photochemical behavior of BPA in lake water.     

Perfluorinated Surfactants in Surface and Drinking Waters (9 pp)

Background, Aim and Scope In this paper recent results are provided of an investigation on the discovery of 12 perfluorinated surfactants (PS) in different surface and drinking waters (Skutlarek et al. 2006 a, Skutlarek et al. 2006 b). In the last years, many studies have reported ubiquitous distribution of this group of perfluorinated chemicals, especially perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in the environment, particularly in wildlife animal and human samples (Giesy and Kannan 2001, Houde et al. 2006, Prevedouros et al. 2006). Perfluorinated surfactants (e.g. PFOS and PFOA) have shown different potentials for reproductory interference and carcinogenity in animal experiments as well as partly long half-lives in humans (Guruge et al. 2006, FSA UK 2006a, FSA UK 2006b, 3M 2005, OECD 2002, Yao and Zhong 2005). They possess compound-dependent extreme recalcitrance against microbiological and chemical degradation and, in addition, they show variable potentials for bioaccumulation in animals and humans (Houde et al. 2006). Materials and Methods: Surface and drinking water samples were collected from different sampling sites: - Surface waters: samples taken from the rivers Rhine, Ruhr, Moehne and some of their tributaries. Further samples were taken from the Rhine-Herne-Canal and the Wesel-Datteln-Canal. - Drinking waters: samples taken in public buildings of the Rhine-Ruhr area. After sample clean-up and concentration by solid-phase extraction, the perfluorinated surfactants were determined using HPLC-MS/MS. Results: All measured concentrations (sum of seven mainly detected components) in the Rhine river and its main tributaries (mouths) were determined below 100 ng/L. The Ruhr river (tributary of the Rhine) showed the highest concentration (94 ng/L), but with a completely different pattern of components (PFOA as major component), as compared with the other tributaries and the Rhine river. Further investigations along the Ruhr river showed remarkably high concentrations of PS in the upper reaches of the Ruhr river and the Moehne river (tributary of the Ruhr) (Ruhr: up to 446 ng/L, Moehne: up to 4385 ng/L). The maximum concentration of all drinking water samples taken in the Rhine-Ruhr area was determined at 598 ng/L with the major component PFOA (519 ng/L). Discussion: The surface water contaminations most likely stem from contaminated inorganic and organic waste materials (so-called 'Abfallgemisch'). This waste material was legally applied to several agricultural areas on the upper reaches of the Moehne. Perfluorinated surfactants could be detected in some suchlike soil samples. They contaminated the river and the reservoir belonging to it, likely by superficial run-off over several months or probably years. Downstream, dilution effects are held responsible for decreasing concentrations of PS in surface waters of the Moehne and the Ruhr river. In analogy to the surface water samples, PS (major component PFOA) can be determined in many drinking water samples of the Rhine-Ruhr area where the water supplies are mainly based on bank filtration and artificial recharge. Conclusions: The concentrations found in drinking waters decreased with the concentrations of the corresponding raw water samples along the flow direction of the Ruhr river (from east to west) and were not significantly different from surface water concentrations. This indicates that perfluorinated surfactants are at present not successfully removed by water treatment steps. Recommendations and Perspectives: Because of their different problematic properties (persistence, mobility, toxicity, bioaccumulation), the concentrations of specific perfluorinated surfactants and their precursors in drinking waters and food have to be minimised. Therefore, it is of utmost importance to take the initiative to establish suitable legal regulations (limitations/ban) concerning the production and use of these surfactants and their precursors. Furthermore, it is indispensable to protect water resources from these compounds. A discussion on appropriate limit values in drinking water and foodstuffs is urgently needed. Concerning the assumed soil contamination, the corresponding regulation (Bioabfall-Verordnung 1998 – Regulation on Organic Waste 1998) should be extended to allow the control of relevant organic pollutants.     

Sorption and desorption behavior of chloroanilines and chlorophenols on montmorillonite and kaolinite

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.0 g of clay were equilibrated with 100.0 mL solutions of each chemical at concentrations ranging from 10.0 to 200.0 mg/L. The uptake of the compounds was deduced from the results of HPLC-UV-Vis analysis. The lipophilic species were best retained by both clay materials. The most lipophilic chemical used in the study, 2,4,6-trichloroaniline, was also the most strongly retained, with sorption of up to 8 mg/g. In desorption experiments, which also relied on HPLC-UV-Vis technique, 2,4,6-trichloroaniline was the least desorbed from montmorillonite. However, on kaolinite all of the compounds under study were irreversibly retained. The experimental data have been modelled according to the Langmuir and Freundlich isotherms. A hypothesis is proposed concerning the sorption mechanism and potential applications of the findings in remediation strategies have been suggested.     

Quantitation of Hydroxyl Radicals from Photolysis of Fe(III)-Citrate Complexes in Aerobic Water (5 pp)

Background For their high photoreactivity, Fe(III)-carboxylate complexes are important sources of H2O2 for some atmospheric and surface waters. Citrate is one kind of carboxylate, which can form complexes with Fe(III). In our previous study, we have applied Fe(III)-citrate complexes to degrade and decolorize dyes in aqueous solutions both under UV light and sunlight. Results have shown that carboxylic acids can promote the photodegradation efficiency. It is indicated that the photolysis of Fe(III)-citrate complexes may cause the formation of some reactive species (e. g. H2O2 and ·OH). This work is attempted to quantify hydroxyl radicals generated in the aqueous solution containing Fe(III)-citrate complexes and to interpret the photoreactivity of Fe(III)-citrate complexes for degrading organic compounds. Methods By using benzene as the scavenger to produce phenol, the photogeneration of ·OH in the aqueous solution containing Fe (III)-citrate complexes was determined by HPLC. Results and Discussion In the aqueous solution containing 60.0/30.0 mM Fe(III)/citrate and 7.0 mM benzene at pH 3.0, 96.66 mM ·OH was produced after irradiation by a 250W metal halide light (l ≥ 313 nm) for 160 minutes. Effects of initial pH value and concentrations of Fe(III) and citrate on ·OH radical generation were all examined. The results show that the greatest photoproduction of ·OH in the aqueous solution (pH ranged from 3.0 to 7.0) was at pH 3.0. The photoproduction of ·OH increased with increasing Fe(III) or citrate concentrations. Conclusion In the aqueous solutions containing Fe(III)-citrate complexes, ·OH radicals were produced after irradiation by a 250W metal halide light. It can be concluded that Fe(III)-citrate complexes are important sources of ·OH radicals for some atmospheric and surface waters. Recommendations and Outlook It is believed that the photolysis of Fe(III)-citrate complexes in the presence of oxygen play an important role in producing ·OH both in atmospheric waters and surface water where high concentrations of ferric ions and citrate ions exist. The photoproduction of ·OH has a high oxidizing potential for the degradation of a wide variety of natural and anthropogenic organic and inorganic substances. We can use this method for toxic organic pollutants such as organic dyes and pesticides.     

Real-world vehicle emissions: A summary of the 15th coordinating research council on-road vehicle emissions workshop

The Coordinating Research Council held its 15th workshop in April 2005, with nearly 90 presentations describing the most recent mobile source-related emissions research. In this paper, the authors summarize the presentations from researchers who are engaged in improving our understanding of the contribution of mobile sources to air quality. Participants in the workshop discussed emission models and emission inventories, results from gas- and particle-phase emissions studies from spark-ignition and diesel-powered vehicles (with an emphasis in this workshop on particle emissions), effects of fuels on emissions, evaluation of in-use emissions control programs, and efforts to improve our capabilities in performing on-board emissions measurements, as well as topics for future research.     

Conceptual approaches for the development of dynamic specific activity models of 14C transfer from surface water to humans

Carbon-14 is a particularly interesting radionuclide from the perspective of dose estimation. Many nuclear facilities, including power reactors, release 14C into the environment, and much of this is as 14CO2. This mixes readily with stable CO2, and hence enters the food chain as fundamental biomolecules. This isotopic mixing is often used as the basis for dose assessment models. The present model was developed for the situation of 14C releases to surface waters, where there are distinct changes in the water 14C activity concentrations throughout the year. Complete isotopic mixing (equilibrium) cannot be assumed. The model computes the specific activity (activity of 14C per mass of total C) in water, phytoplankton, fish, crops, meat, milk and air, following a typical irrigation-based food-chain scenario. For most of the biotic compartments, the specific activity is a function of the specific activity in the previous time step, the specific activity of the substrate media, and the C turnover rate in the tissue. The turnover rate is taken to include biochemical turnover, growth dilution and mortality, recognizing that it is turnover of C in the population, not a tissue or an individual, that is relevant. Attention is paid to the incorporation of 14C into the surface water biota and the loss of any remaining 14CO2 from the surface water-air interface under its own activity concentration gradient. For certain pathways, variants in the conceptual model are presented, in order to fully discuss the possibilities. As an example, a new model of the soil-to-plant specific activity relationship is proposed, where the degassing of both 14C and stable C from the soil is considered. Selection of parameter values to represent the turnover rates as modeled is important, and is dealt with in a companion paper.     

Radiological Dispersion Devices: are we prepared?

Already before the events of September 11th 2001 concern was raised about the spread of orphan sources and their potential use in Radiological Dispersion Devices by terrorist groups. Although most of the simulated scenarios foresee a rather limited direct health impact on the population, the affected region would suffer from the indirect consequences such as social disruption, cleanup requirements and economic costs. The nature of such a radiological attack would anyway be different compared to conventional radiological accidents, basically because it can happen anywhere at any time. Part of the response resides in a general preparedness scheme incorporating attacks with Radiological Dispersion Devices. Training of different potential intervention teams is essential. The response would consist of a prioritised list of actions adapted to the circumstances. As the psychosocial dimension of the crisis could be worse than the purely radiological one, an adapted communication strategy with the public aspect would be a key issue.     

Levels and congener pattern of polychlorinated biphenyl and organochlorine pesticide residues in bluefin tuna (Thunnus thynnus) from the Straits of Messina (Sicily, Italy)

The aim of this study is to assess the accumulation of OCs and PCBs in Thunnus thynnus and to elucidate the suitability of this species as a bioindicator for monitoring contaminations of these compounds in the marine ecosystems of the Straits of Messina. This investigation was conducted on fat, liver and muscle samples of 14 T. thynnus collected during April 2004. Quantitative determination of OCs and PCBs in the various samples examined has been carried out using GC-ECD and GC-MS. The results obtained show the presence of low concentrations of p,p'-DDE and PCB congeners (138, 153 and 180) in all fat, liver and muscle samples caught in the Straits of Messina. Concentrations of p,p'-DDE and PCB congeners (138, 153 and 180) in all the samples examined were below MRLs (CE n. 97/41, 1999/65 and 1999/71).     

Diffusion of (226)Ra and (40)K radionuclides reproduced in underwater sedimentary columns in laboratory

The potential radiological impact of the increase of radioactive substances in the environment makes interesting the study of the migration of the contaminant radionuclides in soils and sediments, which are the last receiver system of these substances. By using a battery of sedimentary columns controlled in the laboratory, the diffusion of the (226)Ra and (40)K radionuclides has been studied, assessing their respective effective diffusion coefficients in a similar sedimentary medium. A decreasing temporal evolution is obtained, associated to the progressive 'fixation' of the radionuclides by the clay minerals of the sediment, followed by a constant tendency. A timescale of the 'fixation' by the sediment is determined, being of the order of days for (226)Ra and of the order of months for (40)K, so the progressive 'fixation' of (40)K by the clay minerals of the sediments is slower than in the case of (226)Ra.     

A dynamic model for assessing radiological consequences of tritium routinely released in rivers. Application to the Loire River

A dynamic model for assessing the transfer of tritium in a food chain was applied to the Loire River, where 14 nuclear power plants situated on five different sites operate. The model considers several potential exposure pathways in the aquatic and terrestrial ecosystems: transfer of tritium through the aquatic food chain (especially fish); use of river water for agricultural purposes (irrigation) and transfer of radionuclides through the terrestrial food chain (vegetables, meat, milk); subsequent internal exposure of humans due to ingestion of contaminated foodstuffs. For biological environmental compartments, the transfer of tritium to organic matter (i.e. OBT) was simulated. For each of the parameters introduced in this model, a probability density function, allowing further uncertainty and sensitivity analyses, was proposed. Uncertainty/sensitivity analyses were performed to determine a confidence interval for the mean annual dose to critical groups and to identify the parameters responsible for the uncertainty and subsequent research priorities.