Background, aims, and scope Since toxaphene (polychlorocamphene, polychloropinene, or strobane) mixtures were applied for massive insecticide use in the 1960s to replace the use of DDT, some of their congeners have been found at high latitudes far away from the usage areas. Especially polychlorinated bornanes have demonstrated dominating congeners transported by air up to the Arctic areas. Environmental fate modeling has been applied to monitor this phenomenon using parallel zones of atmosphere around the globe as interconnected environments. These zones, shown in many meteorological maps, however, may not be the best way to configure atmospheric transport in air trajectories. The latter could also be covered by connecting a chain of simple model boxes. We aim to study this alternative approach by modeling the trajectory chain using catchment boxes of our FATEMOD model. Polychlorobornanes analyzed in biota of the Barents Sea offered one case to study this modeling alternative, while toxaphene has been and partly still is used massively at southern East Europe and around rivers flowing to the Aral Sea. Materials and methods Pure model substances of three polychlorobornanes (toxaphene congeners P26, P50, and P62) were synthesized, their environmentally important thermal properties measured by differential scanning calorimetry, as evaluated from literature data, and their temperature dependences estimated by the QSPR programs VPLEST, WATSOLU, and TDLKOW. The evaluated property parameters were used to model their atmospheric long-range transport from toxaphene heavy usage areas in Ukraine and Aral/SyrDarja/AmuDarja region areas, through East Europe and Northern Norway (Finnmarken) to the Barents Sea. The time period used for the emission model was June 1997. Usual weather conditions in June were applied in the model, which was constructed by chaining FATEMOD model boxes of the catchment's areas along assumed maximal air flow trajectories. Analysis of the three chlorobornanes in toxaphene mixtures function as a basis for the estimates of emission levels caused by its usage. High estimate (A) was taken from contents in a Western product chlorocamphene and low estimate (B) from mean contents in Russian polychloroterpene products to achieve modeled water concentrations. Bioaccumulation to analyzed lipid of aquatic biota at the target region was estimated by using statistical calculation for persistent organic pollutants in literature. Results The results from model runs A and B (high and low emission estimate) for levels in sea biota were compared to analysis results of samples taken in August 1997 at Barents Sea. The model results (ng g⁻¹ lw): 4-95 in lipid of planktovores and 7-150 in lipid of piscivores, were in fair agreement with the analysis results from August 1997: 21-31 in Themisto libellula (chatka), 26-42 in Boreocadus saida (Polar cod), and 5-27 in Gadus morhua (cod) liver. Discussion The modeling results indicate that the application of chained simple multimedia catchment boxes on predicted trajectory is a useful method for estimation of volatile airborne persistent chemical exposures to biota in remote areas. For hazard assessment of these pollutants, their properties, especially temperature dependences, must be estimated by a reasonable accuracy. That can be achieved by using measurements in laboratory with pure model compounds and estimation of properties by thermodynamic QSPR methods. The property parameters can be validated by comparing their values at an environmental temperature range with measured or QSPR-estimated values derived by independent methods. The chained box method used for long-range air transport modeling can be more suitable than global parallel zones modeling used earlier, provided that the main airflow trajectories and properties of transported pollutants are predictable enough. Conclusions Long-range air transport modeling of persistent, especially photo-resistant organic compounds using a chain of joint simple boxes of catchment's environments is a feasible method to predict concentrations of pollutants at the target area. This is justified from model results compared with analytical measurements in Barents Sea biota in August 1997: three of six modeled values were high and the other three low compared to the analysis results. The order of magnitude level was similar in both modeled (planktovore and piscivore) and observed (chatka and polar cod) values of lipid samples. The obtained results were too limited to firm validation but are sufficient to justify feasibility of the method, which prompts one to perform more studies on this modeling system. Recommendations and perspectives For assessment of the risk of environmental damages, chemical fate determination is an essential tool for chemical control, e.g., for EU following the REACH rules. The present conclusion of applicability of the chained single-box multimedia modeling can be validated by further studies using analyses of emissions and target biota in various other cases. To achieve useful results, fate models built with databases having automatic steps for most calculations and outputs accessible to all chemical control professionals are essential. Our FATEMOD program catchments at environments and compound properties listed in the database represent a feasible tool for local, regional, and, according our present test results, for global exposure predictions. As an extended use of model, emission estimates can be achieved by reversed modeling from analysis results of samples corresponding to the target area.

Background, aim, and scope The need for global and integrated approaches to water resources management, both from the quantitative and the qualitative point of view, has long been recognized. Water quality management is a major issue for sustainable development and a mandatory task with respect to the implementation of the European Water Framework Directive as well as the Swiss legislation. However, data modelling to develop relational databases and subsequent geographic information system (GIS)-based water management instruments are a rather recent and not that widespread trend. The publication of overall guidelines for data modelling along with the EU Water Framework Directive is an important milestone in this area. Improving overall water quality requires better and more easily accessible data, but also the possibility to link data to simulation models. Models are to be used to derive indicators that will in turn support decision-making processes. For this whole chain to become effective at a river basin scale, all its components have to become part of the current daily practice of the local water administration. Any system, tool, or instrument that is not designed to meet, first of all, the fundamental needs of its primary end-users has almost no chance to be successful in the longer term. Materials and methods Although based on a pre-existing water resources management system developed in Switzerland, the methodological approach applied to develop a GIS-based water quality management system adapted to the Romanian context followed a set of well-defined steps: the first and very important step is the assessment of needs (on the basis of a careful analysis of the various activities and missions of the water administration and other relevant stakeholders in water management related issues). On that basis, a conceptual data model (CDM) can be developed, to be later on turned into a physical database. Finally, the specifically requested additional functionalities (i.e. functionalities not provided by classical commercial GIS software), also identified during the assessment of needs, are developed. This methodology was applied, on an experimental basin, in the Ialomita River basin. Results The results obtained from this action-research project consist of a set of tangible elements, among which (1) a conceptual data model adapted to the Romanian specificities regarding water resources management (needs, data availability, etc.), (2) a related spatial relational database (objects and attributes in tables, links, etc.), that can be used to store the data collected, among others, by the water administration, and later on exploited with geographical information systems, (3) a toolbar (in the ESRI environment) offering the requested data processing and visualizing functionalities. Lessons learned from this whole process can be considered as additional, although less tangible, results. Discussion The applied methodology is fairly classical and did not come up with revolutionary results. Actually, the interesting aspects of this work are, on the one hand, and obviously, the fact that it produced tools matching the needs of the local (if not national) water administration (i.e. with a good chance of being effectively used in the day-to-day practice), and, on the other hand, the adaptations and adjustments that were needed both at the staff level and in technical terms. Conclusions This research showed that a GIS-based water management system needs to be backed by some basic data management tools that form the necessary support upon which a GIS can be deployed. The main lesson gained is that technology transfer has to pay much attention to the differences in existing situations and backgrounds in general, and therefore must be able to show much flexibility. The fact that the original objectives could be adapted to meet the real needs of the local end-users is considered as a major aspect in achieving a successful adaptation and development of water resources management tools. Time needed to setup things in real life was probably the most underestimated aspect in this technology transfer process. Recommendations and perspectives The whole material produced (conceptual data model, database and GIS tools) was disseminated among all river basin authorities in Romania on the behalf of the national water administration (ANAR). The fact that further developments, for example, to address water quantity issues more precisely, as envisaged by ANAR, can be seen as an indication that this project succeeded in providing an appropriate input to improve water quality in Romania on the long term.

Background, aim, and scope Pharmaceuticals and their metabolites are detected in the aquatic environment and our drinking water supplies. The need for high quality drinking water is one of the most challenging problems of our times, but still only little knowledge exists on the impact of these compounds on ecosystems, animals, and man. Biological waste water treatment in constructed wetlands is an effective and low-cost alternative, especially for the treatment of non-industrial, municipal waste water. In this situation, plants get in contact with pharmaceutical compounds and have to tackle their detoxification. The mechanisms for the detoxification of xenobiotics in plants are closely related to the mammalian system. An activation reaction (phase I) is followed by a conjugation (phase II) with hydrophilic molecules like glutathione or glucose. Phase III reactions can be summarized as storage, degradation, and transport of the xenobiotic conjugate. Until now, there is no information available on the fate of pharmaceuticals in plants. In this study, we want to investigate the fate and metabolism of N-acetyl-4-aminophenol (paracetamol) in plant tissues using the cell culture of Armoracia rusticana L. as a model system. Materials and methods A hairy root culture of A. rusticana was treated with acetaminophen in a liquid culture. The formation and identification of metabolites over time were analyzed using HPLC-DAD and LC-MSn techniques. Results With LC-MS technique, we were able to detect paracetamol and identify three of its metabolites in root cells of A. rusticana. Six hours after incubation with 1 mM of acetaminophen, the distribution of acetaminophen and related metabolites in the cells resulted in 18% paracetamol, 64% paracetamol-glucoside, 17% paracetamol glutathione, and 1% of the corresponding cysteine conjugate. Discussion The formation of two independently formed metabolites in plant root cells again revealed strong similarities between plant and mammalian detoxification systems. The detoxification mechanism of glucuronization in mammals is mirrored by glucosidation of xenobiotics in plants. Furthermore, in both systems, a glutathione conjugate is formed. Due to the existence of P450 enzymes in plants, the formation of the highly reactive NAPQI intermediate is possible. Conclusions In this study, we introduce the hairy root cell culture of A. rusticana L. as a suitable model system to study the fate of acetaminophen in plant tissues. Our first results point to the direction of plants being able to take up and detoxify the model substrate paracetamol. These first findings underline the great potential of using plants for waste water treatments in constructed wetlands. Recommendations and perspectives This very first study on the detoxification of a widely used antipyretic agent in plant tissues again shows the flexibility of plant detoxification systems and their potential in waste water treatment facilities. This study covers only the very first steps of acetaminophen detoxification in plants; still, there is no data on long-term exposure as well as the possible impact of pharmaceuticals on the plant health and stress defense. Long-term experiments need to be performed to follow the fate of acetaminophen in root and leaf cells in a whole plant system, and to evaluate possible usage of plants for the remediation of acetaminophen from waste water.

Background, aim and scope One of the problems to affect Portland cement matrices is low resistance to aggressive agents, due principally to the presence of a high content of portlandite in the hydrated cements. Pozzolanic materials have played an important role in the improving the durability of cement-based materials for decades. This work studies the behaviour of cement mortar matrices blended with 10% calcined paper sludge (source for metakaolinite) and exposed to different environmental conditions (saline and non-saline environments) after 6 and 12 months of exposure. Materials and methods Two cements were studied: an ordinary Portland cement (CEM 1, 42.5R), acting as reference cement, and a blended cement formulated by mixing 90% (by mass) of CEM 1, 42.5R with 10% (by mass) of paper sludge calcined at 700°C for 2 h. The specimens were exposed 1 year to saline and non-saline environments. All the mineralogy samples were studied through X-ray diffraction and scanning electron microscopy (SEM) equipped with an energy dispersive X-ray analyser. The in-depth study on ionic mobility was performed on samples subjected to natural exposure (coast and tableland) for 6 and 12 months. Results Portland cement was composed of quartz, calcite, calcium hydroxide and tobermorite gels. The pozzolanic cement (10% calcined paper sludge) is of the same composition but a high calcite concentration and barium carbonate. SEM analysis from coastline show deposits of variable composition. The deposits are identified on the surface of different mineral components. The minerals from tableland are much fractured, i.e. calcite and feldspars. Inside the fractures, the deposits and the ions are located and trapped superficially. Discussion SEM analysis of control cement Portland and 10% calcined paper sludge shows deposits on quartz and calcite with a very high concentration of Pb, Zn, Cl and barium sulphate. A very porous aspect is due to the presence of the different aggregate types. This porous configuration permits retention of the ion environment. The pozzolanic cement in environments subject to the saline mist favours the retention and transport of ions observed. Something similar also happens with the increase in exposure to outdoor weather. Non-saline samples show temperature changes (ice or thaw cycles). Barium retention is kept on the surface in fracture lines by the gelification processes. In general, it may be inferred that an increase in exposure time increases the diffusion of ions towards test piece interiors. The chemical composition profiles show that the ions present different penetration speeds. Conclusions The results indicate the better vulnerability of pozzolanic cements from calcined paper sludge in saline and non-saline environments. The cements with a 10% addition of calcined paper sludge favour retention and transport of ion has been observed. Recommendations and perspectives Today, projects are centred on a new recycling line for industrial waste of this kind, with special attention on its incorporation in cement manufacture as a pozzolanic material, setting the most appropriate activation conditions of the mineralogical compound in this waste (kaolinite and metakaolinite) and taking them as a starting point for this project. The use of pozzolanic cement with 10% addition of calcined paper sludge is a system which favours ionic retention.

Background, aim, and scope The success of phytoextraction depends upon the identification of suitable plant species that hyperaccumulate heavy metals and produce large amounts of biomass using established agricultural techniques. In this study, the Mediterranean saltbush Atriplex halimus L., which is a C4 perennial native shrub of Mediterranean basin with an excellent tolerance to drought and salinity, is investigated with the main aim to assess its phytoremediation potential for Pb and Cd removal from contaminated soils. In particular, the influence of soil salinity in metal accumulation has been studied as there is notable evidence that salinity changes the bioavailability of metals in soil and is a key factor in the translocation of metals from roots to the aerial parts of the plant. Materials and methods Three pot experiments were conducted under greenhouse conditions for a 10-week period with A. halimus grown in soil artificially polluted with 20 ppm of Cd and/or 800 ppm of Pb and irrigated with three different salt solutions (0.0%, 0.5%, and 3.0% NaCl). Soil measurements for soil characterization were performed with the expiration of the first week of plant exposure to metals and NaCl, and at the end of the experimental period, chlorophyll content, leaf protein content, leaf specific activity of guaiacol peroxidase (EC 1.11.1.7), shoot water content, biomass, and Cd and Pb content in the plant tissues were determined. Additionally, any symptoms of metal or salt toxicity exhibited by the plants were visually noted during the whole experimental period. Results The experimental data suggest that increasing salinity increases cadmium uptake by A. halimus L. while in the case of lead there was not a clear effect of the presence of salt on lead accumulation in plant tissues. A. halimus developed no visible signs of metal toxicity; only salt toxicity symptoms were observed in plants irrigated with 3% NaCl solutions. Chlorophyll content, leaf protein content, shoot water content, and biomass were not negatively affected by the metals; instead, there was even an increase in the amount of photosynthetic pigments in plants treated with both metals and salinity. The specific activity of guaiacol peroxidase seems to have a general tendency for increase in plants treated with the metals in comparison with the respective controls but a statistically significant difference exists only in plants treated with the metal mixture and saline conditions. Discussion The data revealed that lead and cadmium accumulation in plant tissues was kept generally at low levels. Salinity was found to have a positive effect on cadmium uptake by the plant and this may be related to a higher bioavailability of the metal in soil due to decreased Cd sorption on soil particles. On the other hand, salinity did not influence in a clear way the uptake of Pb by the plant probably because of lead's limited mobility in soils and plant tissues. Cd and Pd usually decrease the chlorophyll content and biomass and change water relations in plants; however, A. halimus was found not to be affected indicating that it is a Cd- and Pb-tolerant plant. Guaiacol peroxidase activity as one of the parameters expressing oxidative damage and extent of stress in plants was not generally found to be significantly affected under the presence of metals in most plants suggesting that the extent of stress in plants was minimal, while only for plants treated with the metal mixture and low salinity the enzyme activity was elevated confirming that this enzyme serves as an antioxidative tool against the reactive oxygen species produced by the metals. Conclusions Atriplex halimus L. is a Pb- and Cd-tolerant plant but metal concentrations achieved in plant tissues were kept generally at low levels; however, metal accumulation in shoots, especially for Cd, considered together with its high biomass production, rapid growth, and deep root system able to cope with poor structure and xeric characteristics of several polluted soils suggest that this plant deserves further investigation. Recommendations and perspectives Phytoextraction by halophytes is a promising alternative for the remediation of heavy metal contaminated sites affected by salinity since saline depressions often indicate sites of industrial effluents accumulation, contaminated by heavy metals, including Pb and Cd. Halophytes are also promising candidates for the removal of heavy metals from non-saline soils. Furthermore, the use of such plants can be potentially viewed as an alternative method for soil desalination where salt is removed from the soil instead of being washed downwards by water or other solutions.

Background, aim, and scope It can be learned from the Pistacia spp. germplasm collection (http://www.bgu.ac.il/pistacia) that the growth of Salsola inermis is inhibited in the vicinity of the evergreen Pistacia lentiscus, but not in the surroundings of the deciduous Pistacia atlantica and Pistacia chinensis. Irrigation of trees during the summer months increases soil salinity around the trees. It was therefore hypothesized that inhibition of S. inermis around P. lentiscus is related to depletion of salt in the vicinity of the latter species. Materials and methods A multi-approach experimental scheme was carried out which included soil edaphic characterization and germination tests. To test salt tolerance of P. lentiscus, plants were grown in a hydroponic system for a month in medium containing NaCl, while physiological and growth parameters were measured. Results Conductivity measurements in summer, during the growth season of S. inermis, indicated that soil salinity beneath deciduous Pistacia trees was significantly higher than that below P. lentiscus. Germination of S. inermis seeds on filter paper moistened with P. lentiscus low-conductivity soil filtrate was twice as high as that of the deciduous trees high-conductivity soil filtrates. Nevertheless, fresh and dry weights of mature S. inermis growing next to P. atlantica and P. chinensis were 2.9 to 4.8 times higher than those of plants growing in the vicinity of P. lentiscus. In a hydroponic system, no significant differences were found in growth parameters and stomatal conductance between P. lentiscus growing in control and salt treatments. It was therefore proposed that salt depletion in the vicinity of P. lentiscus inhibits the growth, but not germination, of S. inermis thus confirming the halophylic characteristics of this plant. Discussion The nature of Salsola-Pistacia interactions cannot be explained by allelopathic effects; hence, plausible salt-driven interactions were considered. Our data showed that S. inermis accumulated salt and has halophytic characteristics. Interestingly, germination of S. inermis was inhibited in medium containing salt, but the salt was obligatory for further growth, development, and fast biomass production. These results explained the observation of large biomass accumulation in the more saline soil around the deciduous P. atlantica and P. chinensis and the lack of development in the salt-depleted soil around the salt-tolerant accumulator P. lentiscus. Conclusions Soil salinity around Pistacia trees critically affects the growth of S. inermis. Inhibition of S. inermis growth, but not germination, around the evergreen P. lentiscus, stems from the latter's ability to deplete salt from its surroundings. The results indicated that P. lentiscus is able to tolerate and accumulate salt, which we assume contributes to its wide distribution along the Mediterranean coast in Israel. Recommendations and perspectives While the phytoremediation potential of Salsola spp. has been explored to some extent, this of P. lentiscus has not been tested and proven before. The results suggest that the evergreen perennial salt-tolerant P. lentiscus can be recommended for horticulture purposes and soil stabilization in relatively saline environments.

Background, aim, and scope The reclamation of nonferrous metal-polluted soil by phytoremediation requires an overall and permanent plant cover. To select the most suitable plant species, it is necessary to study metal effects on plants over the time, thereby checking that metals remain stored in root systems and not transferred to aerial parts. In this purpose, the seasonal and annual variations of metal bioaccumulation, transfer, and phytotoxicity in Trifolium repens and Lolium perenne grown in a Cd-, Pb-, and Zn-contaminated soil were also studied. Materials and methods The experimental site was located near a closed smelter. In spring 2004, two areas were sown with T. repens and L. perenne, respectively. Thereafter, the samplings of plant roots and shoots and surrounding soils were realized in autumn 2004 and spring and autumn 2005. The soil agronomic characteristics, the Cd, Pb, and Zn concentrations in the surrounded soils and plant organs, as well as the oxidative alterations (superoxide dismutase [SOD], malondialdehyde [MDA], and 8-hydroxy-2'-deoxyguanosine [8-OHdG]) in plant organs were carried out. Results Whatever the sampling period, metal concentrations in soils and plants were higher than background values. Contrary to the soils, the fluctuations of metal concentrations were observed in plant organs over the time. Bioaccumulation and transfer factors confirmed that metals were preferentially accumulated in the roots as follows: Cd>Zn>Pb, and their transfer to shoots was limited. Foliar metal deposition was also observed. The results showed that there were seasonal and annual variations of metal accumulation in the two studied plant species. These variations differed according to the organs and followed nearly the same pattern for the two species. Oxidative alterations were observed in plant organs with regard to SOD antioxidant activities, MDA, and 8-OHdG concentrations. These alterations vary according to the temporal variations of metal concentrations. Discussion Metal concentrations in surrounded soils and plant organs showed the effective contamination by industrial dust emissions. Metals absorbed by plants were mainly stored in the roots. With regard to this storage, the plants seemed to limit the metal transfer to their aerial parts over the time, thereby indicating their availability for metal phytostabilization. Aerial deposition was another source of plant exposure to nonferrous metals. Despite the occurrence of metal-induced oxidative alterations in plant organs, both plant species seemed to tolerate a high metal concentration in soils. Conclusions Taken together, these results indicated that T. repens and L. perenne were able to form a plant cover on highly Cd-, Pb-, and Zn-polluted soils, to limit the metal transfer to their aerial parts and were relatively metal-tolerant. All these characteristics made them suitable for phytostabilization on metal-contaminated soils. These findings also highlighted the necessity to take into account seasonal and annual variations for a future phytomanagement. Recommendations and perspectives In this work, the behavior of plant species grown in metal-polluted soil has been studied during 2 years. Obviously, this time is too short to ensure that metals remain accumulated in the root system and few are transferred in aerial parts over the time. It is why regular monitoring should be achieved during more than a decade after the settlement of the plant cover. This work will be completed by the study of the T. repens and L. perenne effects on mobility of metals in order to evaluate the quantities of pollutants which could be absorbed by the biota and transferred to groundwater. Bioaccessibility tests could be also realized on polluted soils in order to evaluate the phytostabilization impacts on the exposition risks for humans.

Background, aim and scope Estrogenic and non-estrogenic chemicals typically co-occur in the environment. Interference by non-estrogenic chemicals may confound the assessment of the actual estrogenic activity of complex environmental samples. The aim of the present study was to investigate whether, in which way and how seriously the estrogenic activity of single estrogens and the observed and predicted joint action of estrogenic mixtures is influenced by toxic masking and synergistic modulation caused by non-estrogenic chemical confounders. Materials and methods The yeast estrogen screen (YES) was adapted so that toxicity and estrogenicity could be quantified simultaneously in one experimental run. Mercury, two organic solvents (dimethyl sulfoxide (DMSO) and 2,4-dinitroaniline), a surfactant (LAS-12) and the antibiotic cycloheximide were selected as toxic but non-estrogenic test chemicals. The confounding impact of selected concentrations of these toxicants on the estrogenic activity of the hormone 17ß-estradiol was determined by co-incubation experiments. In a second step, the impact of toxic masking and synergistic modulation on the predictability of the joint action of 17ß-estradiol, estrone and estriol mixtures by concentration addition was analysed. Results Each of the non-estrogenic chemicals reduced the apparent estrogenicity of both single estrogens and their mixtures if applied at high, toxic concentrations. Besides this common pattern, a highly substance- and concentration-dependent impact of the non-estrogenic toxicants was observable. The activity of 17ß-estradiol was still reduced in the presence of only low or non-toxic concentrations of 2,4-dinitroaniline and cycloheximide, which was not the case for mercury and DMSO. A clear synergistic modulation, i.e. an enhanced estrogenic activity, was induced by the presence of slightly toxic concentrations of LAS-12. The joint estrogenic activity of the mixture of estrogens was affected by toxic masking and synergistic modulation in direct proportion to the single estrogens, which allowed for an adequate adaptation of concentration addition and thus unaffected predictability of the joint estrogenicity in the presence of non-estrogenic confounders. Discussion The modified YES proved to be a reliable system for the simultaneous quantification of yeast toxicity and estrogen receptor activation. Experimental results substantiate the available evidence for toxic masking as a relevant phenomenon in estrogenicity assessment of complex environmental samples. Synergistic modulation of estrogenic activity by non-estrogenic confounders might be of lower importance. The concept of concentration addition is discussed as a valuable tool for estrogenicity assessment of complex mixtures, with deviations of the measured joint estrogenicity from predictions indicating the need for refined analyses. Conclusions Two major challenges are to be considered simultaneously for a reliable analysis of the estrogenic activity of complex mixtures: the identification of known and suspected estrogenic compounds in the sample as well as the substance- and effect-level-dependent confounding impact of non-estrogenic toxicants. Recommendations and perspectives The application of screening assays such as the YES to complex mixtures should be accompanied by measures that safeguard against false negative results which may be caused by non-estrogenic but toxic confounders. Simultaneous assessments of estrogenicity and toxicity are generally advisable.

Background, aim and scope Each year, large quantities of pharmaceuticals are consumed worldwide for the treatment and prevention of human and animal diseases. Although the drugs and the metabolites observed in the wastewaters and in the environment are present at concentrations several orders of magnitude lower than the concentrations required to exert their effects in humans or animals, their long-term impact on the environment is commonly not known. In this study, the occurrence of six antihistamines, which are used for the relief of allergic reactions such as hay fever, was determined in sewage treatment plants wastewaters and in recipient river waters. Materials and methods The occurrence of the antihistamines cetirizine, acrivastine, fexofenadine, loratadine, desloratadine and ebastine in sewage treatment plants wastewaters and in recipient river waters was studied. The analytical procedure consisted of solid-phase extraction of the water samples followed by liquid chromatography separation and detection by a triple-quadrupole mass spectrometer in the multiple reaction mode. Results Cetirizine, acrivastine and fexofenadine were detected in both influent and effluent wastewater samples at concentration levels ranging from about 80 to 220 ng/L, while loratadine, desloratadine and ebastine could not be detected in any samples. During sewage treatment, the concentration of the antihistamines dropped by an average of 16-36%. Furthermore, elevated concentrations of antihistamines were observed in samples collected during the season of most intensive plant pollen production, i.e. in May. In the river water samples, the relative pattern of occurrence of cetirizine, acrivastine and fexofenadine was similar to that in the wastewater samples; although the concentration of the compounds was substantially lower (4-11 ng/L). The highest concentrations of the studied drugs were observed near the discharging point of the sewage treatment plant. Discussion The highest concentrations of antihistamines in STP wastewaters correlate with the outbreak of allergic reaction caused by high amounts of plant pollens in the air. The analysis results of the river water samples show that the antihistamines are carried far away from the effluent discharge points. They may account for a part of the mix of pharmaceuticals and of pharmaceutical metabolites that occur downstream of STPs. Conclusions Antihistamines are poorly degraded/eliminated under the biological treatment processes applied in the wastewater treatment plants and, consequently, they are continuously being discharged along with other drugs to the aquatic environment. Recommendations and perspectives As a huge quantity and variety of drugs and their metabolites are continuously discharged to rivers and the sea, the compounds should be considered as contaminants that may possess risks to the aquatic ecosystem. Further studies are urgently needed on the environmental fate of the antihistamines and other pharmaceuticals in the aquatic environment. These studies should be concerned with the stability of the compounds, their transformation reactions and the identity of the transformation products, the distribution of drugs and their uptake and effects in organisms. On the basis of these studies, the possible environmental hazards of pharmaceuticals may be assessed.

Background, aim, and scope In 1875, the geoscientist Walter Suess introduced several spheres, such as the lithosphere and the atmosphere to promote a comprehensive understanding of the system earth. Since then, this idea became the dominating concept for the understanding of the distribution of chemical elements in the system earth. Meanwhile, due to the importance of human beings on global element fluxes, the term anthroposphere was introduced. Nevertheless, in face of the ongoing urbanization of the earth, this concept is not any more adequate enough to develop a comprehensive understanding of global element fluxes in and between solid, liquid, and gaseous phases. This article discusses a new concept integrating urbanization into the geoscientific concept of spheres. Main features No geological exogenic force has altered the earth's surface during the last centuries in such an extent as human activity. Humans have altered the morphology and element balances of the earth by establishing agrosystems first and urban systems later. Currently, urban systems happen to become the main regulators for fluxes of many elements on a global scale due to ongoing industrial and economic development and a growing number of inhabitants. Additionally, urban systems are constantly expanding and cover more and more former natural and agricultural areas. For nature, urban systems are new phenomena, which never existed in previous geological eras. The process of the globe's urbanization concurrently is active with the global climate change. In fact, urban systems are a major emitter for climate active gases. Thus, beside the global changes in economy and society, urbanization is an important factor within the global change of nature as is already accepted for climate, ecosystems, and biodiversity. Results Due to the fact that urbanization has become a global process shaping the earth and that the urban systems are globally cross-linked among each other, a new geoscientific sphere has to be introduced: the astysphere. This sphere comprises the parts of the earth influenced by urban systems. Accepting urbanization as global ongoing process forming the astysphere comprehensively copes with the growing importance of urbanization on the creation of present geologic formations. Discussion Anthropogenic activities occur mainly in rural and urban environments. For long lasting periods of human history, human activities mainly were focused on hunting and agriculture, but since industrialization, urbanized areas became increasingly important for the material and energy fluxes of earth. Thus, it seems appropriate to classify the anthroposphere into an agriculturally and an urban-dominated sphere, which are the agrosphere (Krishna 2003) and the astysphere (introduced by Norra 2007). Conclusions We have to realize that urban systems are deposits, consumers, and transformers of resources interacting among each other and forming a network around the globe. Since the future of human mankind depends on the sustainable use of available resources, only a global and holistic view of the cross-linked urban systems forming together the astysphere provide the necessary geoscientific background understanding for global urban material and energy fluxes. If we want to ensure worth-living conditions for future generations of mankind, we have to develop global models of the future needs for resources by the global metasystem of urban systems, called astysphere. Perspectives The final vision for geoscientific research on the astysphere must be to design models describing the global process of urbanization of the earth and the development of the astysphere with respect to fluxes of materials, elements, and energy as well as with respect to the forming of the earth's face. Besides that, just from the viewpoint of fundamental research, the geoscientific concept of spheres has to be complemented by the astysphere if this concept shall fully represent the system earth.