Fate of β-blockers in aquifer material under nitrate reducing conditions: Batch experiments

The fate of the three environmentally relevant β-blockers atenolol, metoprolol and propranolol has been studied in batch experiments involving aquifer material and nitrate reducing conditions. Results from the about 90 d long tests indicate that abiotic processes, most likely sorption, jointly with biotransformation to atenololic acid were responsible for the 65% overall removal observed for atenolol. Zero order kinetics, typical of enzyme-limited reactions, controlled the transformation of this beta blocker to its corresponding carboxylic acid. The mass balance evidences that no mineralization of atenolol occurs in the biotic experiment and that atenololic acid is more stable than its parent compound under the studied conditions. This finding stresses the importance of considering atenololic acid as target compound in the environmental studies on the fate of atenolol. For metoprolol and propranolol the results from the experiment suggest a slower sorption to be the dominant removal process, which led to final decreases in concentrations of 25-30% and 40-45%, respectively. Overall, the removals observed in the experiments suggest that subsurface processes potentially constitute an alternative water treatment for the target beta-blockers, when compared to the removals reported for conventional wastewater treatment plants.     

Trihalomethane formation during water disinfection in four water supplies in the Somes river basin in Romania

Background, aim and scope

After the discovery of chloroform in drinking water, an extensive amount of work has been dedicated to the factors influencing the formation of halogenated disinfections by-products (DBPs). The disinfection practice can vary significantly from one country to another. Whereas no disinfectant is added to many water supplies in Switzerland or no disinfectant residual is maintained in the distribution system, high disinfectant doses are applied together with high residual concentrations in the distribution system in other countries such as the USA or some southern European countries and Romania. In the present study, several treatment plants in the Somes river basin in Romania were investigated with regard to chlorine practice and DBP formation (trihalomethanes (THMs)). Laboratory kinetic studies were also performed to investigate whether there is a relationship between raw water dissolved organic matter, residual chlorine, water temperature and THM formation.

Materials and methods

Drinking water samples were collected from different sampling points in the water treatment plant (WTP) from Gilau and the corresponding distribution system in Cluj-Napoca and also from Beclean, Dej and Jibou WTPs. The water samples were collected once a month from July 2006 to November 2007 and stored in 40-mL vials closed with Teflon lined screw caps. Water samples were preserved at 4°C until analysis after sodium thiosulfate (Na₂S₂O₃) had been added to quench residual chlorine. All samples were analysed for THMs using headspace GC-ECD between 1 and 7 days after sampling. The sample (10 mL) was filled into 20-mL headspace vials and closed with a Teflon-lined screw cap. Thereafter, the samples were equilibrated in an oven at 60°C for 45 min. The headspace (1 mL) was then injected into the GC (Cyanopropylphenyl Polysiloxane column, 30 m × 53 mm, 3 μm film thickness, Thermo Finnigan, USA). The MDLs for THMs were determined from the standard deviation of eight standards at 1 μg/L. The MDLs for CHCl₃, CHBrCl₂, CHBr₂Cl and CHBr₃ were 0.3, 0.2, 0.3 and 0.6 μg/L, respectively. All kinetic laboratory studies were carried out only with water from the WTP Gilau. The experiments were conducted under two conditions: baseline conditions (pH 7, 21°C, 2.5 mg/L Cl₂) to gain information about the change of the organic matter in the raw water and seasonally variable conditions to simulate the actual process at the treatment plant and the distribution system.

Results and discussion

This study shows that the current chlorination practice in the investigated plants complies with the THM drinking water standards of the EU. The THM concentrations in all samples taken in the four treatment plants and distributions systems were below the EU drinking water standard for TTHMs of 100 μg/L. Due to the low bromide levels in the raw waters, the main THM formed in the investigated plants is chloroform. It could also be seen that the THM levels were typically lower in water supplies with groundwater as their water resource. In one plant (Dej) with a pre-ozonation step, a significantly lower (50%) THM formation during post-chlorination was observed. Laboratory chlorination experiments revealed a good correlation between chloroform formation and the consumed chlorine dose. Also, these experiments allowed a semi-quantative prediction of the chloroform formation in the distribution system of Cluj-Napoca.

Conclusions

CHCl₃ was the most important trihalomethane species observed after the chlorination of water in all of the sampled months. However, TTHM concentrations did not exceed the maximum permissible value of 100 μg/L (EU). The THM formation rates in the distribution system of Cluj-Napoca have a high seasonal variability. Kinetic laboratory experiments could be used to predict chloroform formation in the Cluj-Napoca distribution system. Furthermore, an empirical model allowed an estimation of the chloroform formation in the Gilau water treatment plant.

     

Adaptivity of wayfinding strategies in a multi-building ensemble: The effects of spatial structure, task requirements, and metric information

This study investigates the adaptivity of wayfinding strategies in a real-world setting of a multi-building ensemble. Familiarity with the environment, map usage and verbal vs. visual task instructions were systematically varied. Measures included path choices, wayfinding performance and information usage. Thirty-two participants had to find eight goals in a multi-level building ensemble consisting of two distinctive building parts. It was tested whether the standard wall-mounted floor maps found in the majority of public buildings can help navigation in a complex unknown environment. Unfamiliar users tried to make use of these plans more frequently, but were not able to compensate for spatial knowledge deficits compared to participants familiar with the setting. Two strategies of multi-level wayfinding were compared with respect to a region-based hierarchical planning approach. Strategy selection could be shown to be highly adaptive to spatial properties of the environment as well as characteristics of the task instruction, i.e., spatial precision of target information. Overall, the strategy of moving horizontally into the target building prior to vertical travel was shown to be more effective in this multi-building setting.     

Solid fuels in chemical-looping combustion

The feasibility of using a number of different solid fuels in chemical-looping combustion (CLC) has been investigated. A laboratory fluidized bed reactor system for solid fuel, simulating a chemical-looping combustion system by exposing the sample to alternating reducing and oxidizing conditions, was used. In each reducing phase 0.2 g of fuel in the size range 180–250 μm was added to the reactor containing 40 g oxygen carrier of size 125–180 μm. Two different oxygen carriers were tested, a synthetic particle of 60% active material of Fe₂O₃ and 40% MgAl₂O₄ and a particle consisting of the natural mineral ilmenite. Effect of steam content in the fluidizing gas of the reactor was investigated as well as effect of temperature. A number of experiments were also made to investigate the rate of conversion of the different fuels in a CLC system. A high dependency on steam content in the fluidizing gas as well as temperature was shown. The fraction of volatiles in the fuel was also found to be important. Furthermore the presence of an oxygen carrier was shown to enhance the conversion rate of the intermediate gasification reaction. At 950 °C and with 50% steam the time needed to achieve 95% conversion of fuel particles with a diameter of 0.125–0.18 mm ranged between 4 and 15 min depending on the fuel, while 80% conversion was reached within 2–10 min. In almost all cases the synthetic Fe₂O₃ particle with 40% MgAl₂O₄ and the mineral ilmenite showed similar results with the different fuels.     

A comparative assessment of land cover dynamics of three protected forest areas in tropical eastern Africa

Processes of deforestation, known to threaten tropical forest biodiversity, have not yet been studied sufficiently in East Africa. To shed light on the patterns and causes of human influences on protected forest ecosystems, comparisons of different study areas regarding land cover dynamics and potential drivers are needed. We analyze the development of land cover since the early 1970s for three protected East African rainforests and their surrounding farmlands and assess the relationship between the observed changes in the context of the protection status of the forests. Processing of Landsat satellite imagery of eight or seven time steps in regular intervals results in 12 land cover classes for the Kakamega–Nandi forests (Kenya) and Budongo Forest (Uganda) whereas ten are distinguished for Mabira Forest (Uganda). The overall classification accuracy assessed for the year 2001 or 2003 is similarly high for all three study areas (81% to 85%). The time series reveal that, despite their protection status, Kakamega–Nandi forests and Mabira Forest experienced major forest decrease, the first a continuous forest loss of 31% between 1972/1973 and 2001, the latter an abrupt loss of 24% in the late 1970s/early 1980s. For both forests, the temporally dense time series show short-term fluctuations in forest classes (e.g., areas of forest regrowth since the 1980s or exotic secondary bushland species from the 1990s onwards). Although selectively logged, Budongo Forest shows a much more stable forest cover extent. A visual overlay with population distribution for all three regions clearly indicates a relationship between forest loss and areas of high population density, suggesting population pressure as a main driver of deforestation. The revealed forest losses due to local and commercial exploitation further demonstrate that weak management impedes effective forest protection in East Africa.     

Acid mine drainage in the Iberian Pyrite Belt: 2. Lessons learned from recent passive remediation experiences

The Iberian Pyrite Belt (IPB), SW Spain and Portugal, contains about 100 abandoned mine wastes and galleries that release acid mine drainages (AMD) to the Tinto and Odiel rivers. In situ passive remediation technologies are especially suitable to remediate the drainages of these orphan sites. However, traditional remediation systems, designed for coal mines, have been demonstrated inefficient to treat the IPB mine waters. Due to their high acidity and metal loads, large amount of solids precipitate and fast clogging of porosity or passivation (coating) of the reactive grains occurs. To overcome these problems, the dispersed alkaline substrate (DAS) a mixture of fine-grained limestone sand and a coarse inert matrix (e.g., wood shavings) was developed. The small grains provide a large reactive surface and dissolve almost completely before the growing layer of precipitates passivates the substrate. The high porosity retards clogging. However, calcite dissolution only raises pH to values around 6.5, at which the hydroxides of trivalent metals (Al and Fe) precipitate, but it is not high enough to remove divalent metals. Caustic magnesia (MgO) buffers the solution pH between 8.5 and 10. A DAS system replacing limestone with caustic magnesia has been tested to be very efficient to remove divalent metals (Zn, Cd, Mn, Cu, Co, Ni, and Pb) from the water previously treated with calcite.     

Identification of a phytotoxic photo-transformation product of diclofenac using effect-directed analysis

The pharmaceutical diclofenac (DCF) is released in considerably high amounts to the aquatic environment. Photo-transformation of DCF was reported as the main degradation pathway in surface waters and was found to produce metabolites with enhanced toxicity to the green algae Scenedesmus vacuolatus. We identified and subsequently confirmed 2-[2-(chlorophenyl)amino]benzaldehyde (CPAB) as a transformation product with enhanced toxicity using effect-directed analysis. The EC₅₀ of CPAB (4.8 mg/L) was a factor of 10 lower than that for DCF (48.1 mg/L), due to the higher hydrophobicity of CPAB (log K_ow = 3.62) compared with DCF (log D_ow = 2.04) at pH 7.0.     

Large-scale spatial pollution patterns around the North Sea indicated by coastal bird eggs within an EcoQO programme

To categorize the marine environmental health status, the Oslo and Paris commissions have recently formulated Ecological Quality Objectives (EcoQOs) for many ecological features including the contamination of coastal bird eggs with mercury and organochlorines. In this study, we describe spatial and temporal patterns of egg contamination around the North Sea and compared them to the EcoQOs. Concentrations of mercury, polychlorinated biphenyl (??PCB) congeners, dichlorodiphenyltrichloroethane (??DDT) and derivatives, hexachlorobenzene (HCB) and hexachlorocyclohexane (??HCH) isomers were analysed in two tern species (Sterna hirundo and Sterna paradisaea) and Oystercatcher (Haematopus ostralegus) eggs collected between 2008 and 2010 in a total of 21 sites in seven countries surrounding the North Sea. Hg, ??PCB and HCB were highest in the southern sites, while ??DDT and ??HCH concentrations were greatest in eggs from the western North Sea and the Elbe estuary. There were rarely any consistent decreases over time for any compounds. In the terns, Hg, HCB and ??HCH increased at most sites, ??PCB and ??DDT in Sweden and Norway. In the Oystercatcher, HCB and ??HCH increased at more than the half of the sites, ??PCB, ??DDT and Hg at several German sites. In the terns, Hg, ??PCB and ??DDT exceeded the EcoQO in all, HCB in most years and sites. At most sites, ??HCH fulfilled the EcoQO in some study years. In the Oystercatcher, Hg, ??PCB and ??DDT exceeded the EcoQO in all or most years and sites. HCB and ??HCH fulfilled the EcoQO in some or all years at most sites. The EcoQO was exceeded most frequently in estuaries. We conclude that EcoQOs are suitable for drawing contamination patterns of the coastal North Sea in an easily understandable manner, offering the opportunity to harmonize the EcoQOs with coordinated environmental monitoring programmes.     

Long term remediation of highly polluted acid mine drainage: a sustainable approach to restore the environmental quality of the Odiel river basin

During 20 months of proper operation the full scale passive treatment in Mina Esperanza (SW Spain) produced around 100 mg/L of ferric iron in the aeration cascades, removing an average net acidity up to 1500 mg/L as CaCO₃ and not having any significant clogging problem. Complete Al, As, Cd, Cr, Cu, Ti and V removal from the water was accomplished through almost the entire operation time while Fe removal ranged between 170 and 620 mg/L. The system operated at a mean inflow rate of 43 m³/day achieving an acid load reduction of 597 g·(m² day)⁻¹, more than 10 times higher than the generally accepted 40 g·(m² day)⁻¹ value commonly used as a passive treatment system designing criteria. The high performance achieved by the passive treatment system at Mina Esperanza demonstrates that this innovative treatment design is a simple, efficient and long lasting remediation option to treat highly polluted acid mine drainage.     

Land-use legacies in the forest structure of silvopastoral oak woodlands in the Eastern Mediterranean

Eastern Mediterranean silvopastoral oak woodlands have been greatly damaged through forest conversion, illegal lumbering, overgrazing, and forest fires. The aim of this study was to assess land-use changes and the legacies that they have imprinted on the forest structure of Quercus macrolepis and accompanying Quercus pubescens and Quercus cerris woodlands on Lesvos Island, Greece. The size structures of adult oak populations were analyzed as indicators of long-term oak regeneration, while short-term recruitment was determined by counting oak seedlings and saplings. The size structure of the adult Q. macrolepis population was similar to the inverse J-shaped distribution typical for natural Mediterranean oak forests, indicating continuous recruitment with a constant mortality rate of mature individuals. Seedling and sapling densities were highly variable, but generally low in relation to adult oak densities. Recruitment of oak seedlings and saplings was positively related to determinants such as forest cover, adult oak density and basal area, woody plant richness, and litter cover. Both seedling and sapling occurrence were negatively associated with dung frequency, which suggests that sheep grazing imposes a barrier to oak recruitment. The study outlines a comprehensive land-use transition from the 1950 to 1970s, during which a complex and multifunctional agrosilvopastoral land-use system was simplified to an intensive grazing system. The discrepancy between the successful long-term regeneration and the less successful short-term recruitment of oaks illustrates that intensified livestock grazing has been a major driver of vegetation change. Grazing impact is likely to interact with increasing drought conditions, which may trigger a negative feedback cycle that undermines the capacity of woodlands to sustain ecosystem services.