A mass balance model for mercury based on the fugacity concept is applied to Lake Superior, Lake Michigan, Onondaga Lake and Little Rock Lake to evaluate model performance, analyze cycling of three mercury species groups (elemental, divalent and methyl mercury), and identify important processes that determine the source-to-concentration relationship of the three mercury species groups in these lakes. This model application to four disparate ecosystems is an extension of previous applications of fugacity-based models describing mercury cycling. The model performs satisfactorily following site-specific parameterization, and provides an estimate of minimum rates of species interconversion that compare well with literature. Volatilization and sediment burial are the main processes removing mercury from the lakes, and uncertainty analyses indicate that air-water exchange of elemental mercury and water–sediment exchange of divalent mercury attached to particles are influential in governing mercury concentrations in water. Any new model application or field campaign to quantify mercury cycling in a lake should consider these processes as important.

Antibiotics are among the most successful drugs used for human therapy. However, since they can challenge microbial populations, they must be considered as important pollutants as well. Besides being used for human therapy, antibiotics are extensively used for animal farming and for agricultural purposes. Residues from human environments and from farms may contain antibiotics and antibiotic resistance genes that can contaminate natural environments. The clearest consequence of antibiotic release in natural environments is the selection of resistant bacteria. The same resistance genes found at clinical settings are currently disseminated among pristine ecosystems without any record of antibiotic contamination. Nevertheless, the effect of antibiotics on the biosphere is wider than this and can impact the structure and activity of environmental microbiota. Along the article, we review the impact that pollution by antibiotics or by antibiotic resistance genes may have for both human health and for the evolution of environmental microbial populations. The article reviews the current knowledge on the effects that pollution by antibiotics and antibiotic resistance genes may have for the microbiosphere.

Among air pollutants, ozone is the most important stressor to vegetation, which undergoes damage and biomass reduction after penetration of ozone molecules into the leaf tissues through the stomata. Stomatal ozone fluxes are considered the governing factor needed to assess risk to plant health due to ozone. Although this parameter may be calculated by modeling, direct measurements are scarce. Moreover, southern European situations, especially regarding Italy, require special attention due to the decoupling between ozone concentrations and fluxes. This work reviews ozone flux measurements made during the last 15 years through Italy. The dependence of ozone fluxes on environmental factors such as water supply is stronger than the dependence on the surface covering species.

Background, aim, and scope The project was set to construct an extensive wetland in the southernmost region of Israel at Kibbutz Neot Smadar (30°02′45″ N and 35°01′19″ E). The results of the first period of monitoring, summary, and perspectives are presented. The constructed wetland (CW) was built and the subsequent monitoring performed in the framework of the Southern Arava Sustainable Waste Management Plan, funded by the EU LIFE Fund. The specific aims were: (1) To end current sewage disposal and pollution of the ground, the aquifer, and the dry river bed (wadi) paths by biologically treating the sewage as part of the creation of a sustainable wetland ecosystem. (2) Serve as an example of CW in the Negev highlands and the Arava Valley climates for neighboring communities and as a test ground for plants and building methods appropriate to hyper arid climate. (3) Serve as an educational resource and tourist attraction for groups to learn about water reuse, recycling, local wildlife and migrating birds, including serving the heart of a planned Ecological-Educational Bird Park. This report is intended to allow others who are planning similar systems in hyper arid climates to learn from our experience. Materials and methods The project is located in an extreme arid desert with less than 40 mm of rain annually and temperature ranges of −5°C to +42°C. The site receives 165-185 m³ of municipal and agricultural wastes daily, including cowshed and goat wastes and winery outflow. Results The CW establishment at Neot Smadar was completed in October 2006. For 8 months, clean water flowed through the system while the plants were taking root. In June 2007, the wetland was connected to the oxidation pond and full operation began. Because of seepage and evaporation, during the first several months, the water level was not high enough to allow free flow from one bed to the next. To bed A, the water was pumped periodically from the oxidation pond (Fig. 1) and from there flowed by gravitation through the rest of the system. The initial results of the monitoring are promising. In nearly all measurements, the system succeeded as expected to reduce levels of contaminants at least to the level acceptable for irrigating fruit trees and often to the level of unlimited irrigation. The introduction of the plants in the system and their physiological performance were evaluated and were found to correlate well to the quality of water in the various beds. Discussion It should be said at the outset that evaluation of the performance of a CW system is a long-term process. Thus, the main aim of this report is to present the problems, difficulties, preliminary results, and concepts concerned with the first stage of establishment of CW in an extremely dry region. Conclusions The CW system was designed to dispose of municipal and agricultural wastes in a way that not merely reduces pollution, but adds to environmental quality by creating accessible parkland for local residents and tourists. Several factors affected the performance of the system at the initial stages of operation: ecological balance between microbes and plants, big seasonal variations, seepage and evaporation reduced the flow in the initial operation of the system. Despite the initial difficulties, the quality of water coming out the system is acceptable for irrigation. Recommendations and perspectives The CW can function well under extreme dryland conditions. The oxidation pond was the major source of evaporation and bad odors. Therefore, alternatives to the oxidation pond are needed. Cost effectiveness of the system still has to be evaluated systematically.

Background Due to the requirements of the EU Water Framework Directive and other legal regulations (e.g., national laws like the German Federal Soil Protection Act), but also due to the implementation of the new EU chemicals management system REACH, environmental monitoring will gain increasing importance for the surveillance of environmental quality as well as for the assessment of chemicals. Against this background, the Work Group on 'Environmental Monitoring' of the Division of 'Environmental Chemistry and Ecotoxicology' within the German Chemical Society has compiled a position paper on substance-related environmental monitoring. Scope Core elements of this position paper are the definitions of important terms like monitoring, exposure monitoring, effect monitoring, and integrated monitoring. Moreover, temporal and spatial aspects (monitoring of spatial distributions, trend monitoring, and retrospective monitoring) and their applications are discussed. The main focus of this position paper is the coverage of aspects which have to be observed for the preparation and implementation of a monitoring program. Essential is the clear specification of the targets of the monitoring which determine the development of the monitoring concept and its realization, e.g., if environmental media (compartments) or organisms are most appropriate as samples for the aim of the study. Of course, also the properties of the target substances are important (e.g., lipophilicity/bioaccumulation as pre-requisite for an exposure monitoring with organisms). Finally, the monitoring phases of sample planning, sampling, storage and transport of samples, selection of analytical methods, quality assurance measures as well as reporting are discussed. Perspectives An important issue for the future is to link the quantification of chemicals in environmental compartments (exposure and pollution monitoring) more closely to the study of biological effects (effect monitoring) than has been the case up to now. Furthermore, by inclusion of a spatial differentiation, a comprehensive evaluation of the state of an ecosystem can be obtained and the relevance of the results improved. Practical examples of monitoring studies which illustrate various aspects covered in this position paper will be presented in a series of publications by members of the Work Group in the following issues of this journal.

Background, aim, and scope At tropical latitudes, and especially on the semi-arid coasts of the Brazilian Northeast, the rainfall regime governs the water quality of estuaries due to the pronounced difference between the rainy and dry seasons. These changes may be responsible for seasonal changes in bioavailability of mercury (Hg) and other pollutants to the estuarine and coastal biota. Mercury bioaccumulates along estuarine-marine food chains usually result in higher concentrations in tissues of top predators and posing a risk to both marine mammals and humans alike. The Goiana River Estuary (7.5° S) is a typical estuary of the semi-arid tropical regions and supports traditional communities with fisheries (mollusks, fish, and crustacean). It is also responsible for an important part of the biological production of the adjacent coastal waters. Materials and methods Trichiurus lepturus (Actinopterygii: Perciformes) is a pscivorous marine straggler. Fish from this species (n = 104) were captured in a trapping barrier used by the local traditional population and using an otter trawl net along the main channel of the low estuary during two dry seasons (D1 = November, December 2005, January 2006; D2 = November, December 2006, January 2007) and the end of a rainy season (R = August, September, October 2006). Fish muscle samples were preserved cold and then freeze-dried prior to analysis of its total mercury (Hg-T) contents. Total mercury was determined by cold vapor atomic absorption spectrometry (CV-AAS) with sodium borohydride as a reducing agent. Results The studied individuals (n = 104) were sub-adult (30-70 cm, 71 ind.) and adult fish (>70 cm, 33 ind.). Weight (W) (204.1 ± 97.9 g, total biomass = 21,229.7 g) and total length (TL) (63.1 ± 10.1 cm, range 29.5-89.0 cm) presented a significant (p < 0.05) correlation. Two-way ANOVA (n = 81) showed that TL and W had significant differences (p < 0.05) among seasons, being higher in D1 than in D2 and R, respectively. Moreover, season vs. month interaction were detected for the variables length and weight. For the variable weight was detected significant difference for the factor month (p < 0.05). It suggests that the fish enter the estuary at the end of the rainy season and increase in length and weight during the time they spend in the estuary. Fish from this estuary are shown to be fit for human consumption (125.3 ± 61.9 μgHg-T kg⁻¹ w.wt.; n = 104). Fish mercury contents increased with size and weight. Correlations between TL and Hg-T (r = 0.37286) and between W and Hg-T (r = 0.38212) were significant (p < 0.05). Dryer months showed higher mercury concentrations in fish (D1 773.4 ± 207.5 μgHg-T kg⁻¹ d.wt., n = 27; D2 370.1 ± 78.8 μgHg-T kg⁻¹ d.wt., n = 27; R 331.2 ± 138.5 μgHg-T kg⁻¹ d.wt., n = 27). The variable mercury concentration showed differences in relation to the factor season (p < 0.05), where fish captured during the first dry season showed the highest concentration of mercury. The correlation between Hg-T and rainfall (Rf) showed a negative correlation (r = -0.56; p < 0.05). Discussion The main likely source of mercury to this estuary is diffuse continental run off, including urban and industrial effluents. Since concentration of mercury in fish tissue is negatively correlated to rainfall, but positively correlated with fish length and weight, it suggests that fish growth in this estuary results in mercury uptake and concentration on the fish tissue. In the dry season of 2005-2006, when rainfall remained below the historic average, fish bioaccumulated significantly more mercury than in the dry season 2006-2007, when rainfall was within the predictable historic average. It is suggested that less rainfall, and consequently less particulate matter and less primary production in the estuary, make mercury more available to the higher levels of the estuarine food chain. In the case of higher rainfall, when river flow increases and water quality in the estuary is reduced, mercury probably is quickly exported associated to the particulate matter to the adjacent coastal waters where it then disperses. This species is a potential routine bioindicator for mercury contamination of the biota, but so far was used only with a limited number of individuals and contexts. Conclusions Fish from the Goiana River estuary can still be safely consumed by the local population. However, any further contamination of this resource might lead to total mercury levels above the recommended limits for pregnant women and small children. The proposed heavy dependency of total mercury levels in fish on water quality indicates that land use and water quality standards must be more closely watched in order to guarantee that best possible practices are in place to prevent bioaccumulation of mercury and its transfer along the food chain. Human interventions and climatic events which affect river water flow are also playing a role in the mercury cycle at tropical semi-arid estuaries. Recommendations and perspectives T. lepturus is largely consumed by coastal populations of tropical and sub-tropical countries all over the world. It is also consumed by a number of marine mammals over which we have a strong conservation interest. This species is also a link among different ecosystems along the estuarine ecocline. Therefore, knowledge of its degree of contamination might contribute to public health issues as well as marine conservation actions. Studies on mercury and other contaminants using this species as bioindicator (cosmopolitan, readily available) could help elucidating mechanisms through which pollutants are being transferred not only through the food chain, but also from estuarine-coastal-open waters. In addition, using the same species in marine pollution studies, especially as part of a mosaic of species, allows for wide range comparisons of marine food chain contamination.

Background, aim, and scope Dissolved organic matter, measured as dissolved organic carbon (DOC), is an important component of aquatic ecosystems and of the global carbon cycle. It is known that changes in DOC quality and quantity are likely to have ecological repercussions. This review has four goals: (1) to discuss potential mechanisms responsible for recent changes in aquatic DOC concentrations; (2) to provide a comprehensive overview of the interactions between DOC, nutrients, and trace metals in mainly boreal environments; (3) to explore the impact of climate change on DOC and the subsequent effects on nutrients and trace metals; and (4) to explore the potential impact of DOC cycling on climate change. Main features We review recent research on the mechanisms responsible for recent changes in aquatic DOC concentrations, DOC interactions with trace metals, N, and P, and on the possible impacts of climate change on DOC in mainly boreal lakes. We then speculate on how climate change may affect DOC export and in-lake processing and how these changes might alter nutrient and metal export and processing. Furthermore, the potential impacts of changing DOC cycling patterns on climate change are examined. Results It has been noted that DOC concentrations in lake and stream waters have increased during the last 30 years across much of Europe and North America. The potential reasons for this increase include increasing atmospheric CO₂ concentration, climate warming, continued N deposition, decreased sulfate deposition, and hydrological changes due to increased precipitation, droughts, and land use changes. Any change in DOC concentrations and properties in lakes and streams will also impact the acid-base chemistry of these waters and, presumably, the biological, chemical, and photochemical reactions taking place. For example, the interaction of trace metals with DOC may be significantly altered by climate change as organically complexed metals such as Cu, Fe, and Al are released during photo-oxidation of DOC. The production and loss of DOC as CO₂ from boreal lakes may also be affected by changing climate. Climate change is unlikely to be uniform spatially with some regions becoming wetter while others become drier. As a result, rates of change in DOC export and concentrations will vary regionally and the changes may be non-linear. Discussion Climate change models predict that higher temperatures are likely to occur over most of the boreal forests in North America, Europe, and Asia over the next century. Climate change is also expected to affect the severity and frequency of storm and drought events. Two general climate scenarios emerge with which to examine possible DOC trends: warmer and wetter or warmer and drier. Increasing temperature and hydrological changes (specifically, runoff) are likely to lead to changes in the quality and quantity of DOC export from terrestrial sources to rivers and lakes as well as changes in DOC processing rates in lakes. This will alter the quality and concentrations of DOC and its constituents as well as its interactions with trace metals and the availability of nutrients. In addition, export rates of nutrients and metals will also change in response to changing runoff. Processing of DOC within lakes may impact climate depending on the extent to which DOC is mineralized to dissolved inorganic carbon (DIC) and evaded to the atmosphere or settles as particulate organic carbon (POC) to bottom sediments and thereby remaining in the lake. The partitioning of DOC between sediments and the atmosphere is a function of pH. Decreased DOC concentrations may also limit the burial of sulfate, as FeS, in lake sediments, thereby contributing acidity to the water by increasing the formation of H₂S. Under a warmer and drier scenario, if lake water levels fall, previously stored organic sediments may be exposed to greater aeration which would lead to greater CO₂ evasion to the atmosphere. The interaction of trace metals with DOC may be significantly altered by climate change. Iron enhances the formation of POC during irradiation of lake water with UV light and therefore may be an important pathway for transfer of allochthonous DOC to the sediments. Therefore, changing Fe/DOC ratios could affect POC formation rates. If climate change results in altered DOC chemistry (e.g., fewer and/or weaker binding sites) more trace metals could be present in their toxic and bioavailable forms. The availability of nutrients may be significantly altered by climate change. Decreased DOC concentrations in lakes may result in increased Fe colloid formation and co-incident loss of adsorbable P from the water column. Conclusions Climate change expressed as changes in runoff and temperature will likely result in changes in aquatic DOC quality and concentration with concomitant effects on trace metals and nutrients. Changes in the quality and concentration of DOC have implications for acid-base chemistry and for the speciation and bioavailability of certain trace metals and nutrients. Moreover, changes in DOC, metals, and nutrients are likely to drive changes in rates of C evasion and storage in lake sediments. Recommendations and perspectives The key controls on allochthonous DOC quality, quantity, and catchment export in response to climate change are still not fully understood. More detailed knowledge of these processes is required so that changes in DOC and its interactions with nutrients and trace metals can be better predicted based on changes caused by changing climate. More studies are needed concerning the effects of trace metals on DOC, the effects of changing DOC quality and quantity on trace metals and nutrients, and how runoff and temperature-related changes in DOC export affect metal and nutrient export to rivers and lakes.

Background, aim, and scope Catch decline of freshwater fish has been recorded in several countries. Among the possible causes, habitat change is discussed. This article focuses on potentially increased levels of fine sediments going to rivers and their effects on gravel-spawning brown trout. Indications of increased erosion rates are evident from land-use change in agriculture, changes in forest management practices, and from climate change. The latter induces an increase in air and river water temperatures, reduction in permafrost, changes in snow dynamics and an increase in heavy rain events. As a result, an increase in river sediment is likely. Suspended sediment may affect fish health and behaviour directly. Furthermore, sediment loads may clog gravel beds impeding fish such as brown trout from spawning and reducing recruitment rates. To assess the potential impact on fine sediments, knowledge of brown trout reproductive needs and the effects of sediment on brown trout health were evaluated. Approach We critically reviewed the literature and included results from ongoing studies to answer the following questions, focusing on recent decades and rivers in alpine countries. Have climate change and land-use change increased erosion and sediment loads in rivers? Do we have indications of an increase in riverbed clogging? Are there indications of direct or indirect effects on brown trout from increased suspended sediment concentrations in rivers or from an increase in riverbed clogging? Results Rising air temperatures have led to more intensive precipitation in winter months, earlier snow melt in spring, and rising snow lines and hence to increased erosion. Intensification of land use has supported erosion in lowland and pre-alpine areas in the second half of the twentieth century. In the Alps, however, reforestation of abandoned land at high altitudes might reduce the erosion risk while intensification on the lower, more easily accessible slopes increases erosion risk. Data from laboratory experiments show that suspended sediments affect the health and behaviour of fish when available in high amounts. Point measurements in large rivers indicate no common lethal threat and suspended sediment is rarely measured continuously in small rivers. However, effects on fish can be expected under environmentally relevant conditions. River bed clogging impairs the reproductive performance of gravel-spawning fish. Discussion Overall, higher erosion and increased levels of fine sediment going into rivers are expected in future. Additionally, sediment loads in rivers are suspected to have considerably impaired gravel bed structure and brown trout spawning is impeded. Timing of discharge is put forward and is now more likely to affect brown trout spawning than in previous decades. Conclusions Reports on riverbed clogging from changes in erosion and fine sediment deposition patterns, caused by climate change and land-use change are rare. This review identifies both a risk of increases in climate erosive forces and fine sediment loads in rivers of alpine countries. Increased river discharge and sediment loads in winter and early spring could be especially harmful for brown trout reproduction and development of young life stages. Recently published studies indicate a decline in trout reproduction from riverbed clogging in many rivers in lowlands and alpine regions. However, the multitude of factors in natural complex ecosystems makes it difficult to address a single causative factor. Recommendations and perspectives Further investigations into the consequences of climate change and land-use change on river systems are needed. Small rivers, of high importance for the recruitment of gravel-spawning fish, are often neglected. Studies on river bed clogging are rare and the few existing studies are not comparable. Thus, there is a strong need for the development of methods to assess sediment input and river bed clogging. As well, studies on the effects to fish from suspended sediments and consequences of gravel beds clogging under natural conditions are urgently needed.

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 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.