Four years of continuous monitoring of the Meirama end-pit lake and its impact in the definition of future uses

Following the technical closure of the brown lignite Meirama mine (NW Spain) in April 2008, the reclamation of the mined area is being accomplished with the controlled flooding of its large pit. During the first 7 months of flooding, the sequential arrest of the ground water dewatering system led to the growth of an acidic water body of about 2 hm³. Since October 2008, the surface waters from some local streams have been diverted towards the pit so that these have become the major water input in the flooding process. Surface water has promoted a major change in the chemical composition of the lake water so that, at present, its surface has a circum neutral pH, net alkalinity, and low conductivity. At present, the lake has slightly more than one half of its final volume, and it is expected the overflow in 3 to 3.5 years. The lake is meromictic, with a sharp chemocline separating the acidic monimolimnion (pH?≈?3.2, acidity?≈?150 mg CaCO₃/L, κ ₂₅?≈?2.4 mS/cm) from the main water body (pH?≈?6.5, alkalinity?≈?15 mg CaCO₃/L, κ ₂₅?≈?0.3 mS/cm). Oxygen is being depleted at the bottom of the lake so that the monimolimnion became anoxic in January 2011. Above the chemocline, the composition of the lake is similar, but not identical, to that of the flooding stream waters. Close to the surface, some constituents (pH, metals) show strong seasonal variations in coincidence with the phytoplankton growing periods. Those parameters whose limits are legally prescribed comply with the corresponding water quality standards, and they are also consistent with the forecasting results obtained in early modeling. At present, a project considering the construction of an uptake tunnel to exploit the lake is being developed for the emergency water supply of the metropolitan area of A Coruña.     

Utilization of nSiO2, fly ash, and nSiO2/fly ash composite for the remediation of triphenyltin (TPT) from contaminated seawater

The removal of triphenyltin chloride from contaminated simulated seawater with adsorption method was discussed. The adsorbents used are fly ash, nSiO₂, and nSiO₂/fly ash composite. The results showed that the adsorption of the adsorbents increases with increase in the adsorbent dose, contact time, pH, stirring speed, initial TPT concentration, and decreased with increase in temperature. The adsorption fitted well with the Freundlich isotherm, showing that the adsorbent and TPT combined with function groups and the adsorption kinetics followed the pseudo-second-order kinetic model. The thermodynamic parameters were also evaluated. Optimal conditions for the adsorption of TPT from simulated seawater were applied to TPT removal from natural seawater. A higher removal efficiency of TPT (>99 %) was obtained for the nSiO₂/fly ash composite but not for fly ash and nSiO₂.     

How Resilient Are Europe’s Inshore Fishing Communities to Change? Differences Between the North and the South

One would hypothesize that the Common Fisheries Policy, as the umbrella framework for fisheries management in the EU would have the greatest impact on fishers’ communities across Europe. There are, however, biological, economic, social, and political factors, which vary among fishing communities that can affect how these communities react to changes. This paper explores the links between institutional arrangements and ecological dynamics in two European inshore fisheries socio-ecological systems, using a resilience framework. The Mediterranean small-scale fishers do not seem to have been particularly affected by the Common Fisheries Policy regulations but appear affected by competition with the politically strong recreational fishers and the invasion of the rabbit fish population. The inshore fishers along the East coast of Scotland believe that their interests are not as sufficiently protected as the interests of their offshore counterpart. Decisions and initiatives at global, EU, and sometimes national level, tend to take into account those fisheries sectors which have a national economic importance. A socio-ecological analysis can shift the focus from biological and economic aspects to more sustainable long-term delivery of environmental benefits linked to human wellbeing.     

Effects of nitrogen application rate and a nitrification inhibitor dicyandiamide on methanotroph abundance and methane uptake in a grazed pasture soil

Methane-oxidizing bacteria (methanotrophs) in the soil are a unique group of methylotrophic bacteria that utilize methane (CH₄) as their sole source of carbon and energy which limit the flux of methane to the atmosphere from soils and consume atmospheric methane. A field experiment was conducted to determine the effect of nitrogen application rates and the nitrification inhibitor dicyandiamide (DCD) on the abundance of methanotrophs and on methane flux in a grazed pasture soil. Nitrogen (N) was applied at four different rates, with urea applied at 50 and 100 kg N ha^?1 and animal urine at 300 and 600 kg N ha^?1. DCD was applied at 10 kg ha^?1. The results showed that both the DNA and selected mRNA copy numbers of the methanotroph pmoA gene were not affected by the application of urea, urine or DCD. The methanotroph DNA and mRNA pmoA gene copy numbers were low in this soil, below 7.13?×?10³ g^?1 soil and 3.75?×?10³ μg^?1 RNA, respectively. Daily CH₄ flux varied slightly among different treatments during the experimental period, ranging from ?12.89 g CH₄ ha^?1 day^?1 to ?0.83 g CH₄ ha^?1 day^?1, but no significant treatment effect was found. This study suggests that the application of urea fertilizer, animal urine returns and the use of the nitrification inhibitor DCD do not significantly affect soil methanotroph abundance or daily CH₄ fluxes in grazed grassland soils.     

Activated sludge systems removal efficiency of veterinary pharmaceuticals from slaughterhouse wastewater

The knowledge on the efficiency of wastewater treatment plants (WWTPs) from animal food production industry for the removal of both hormones and antibiotics of veterinary application is still very limited. These compounds have already been reported in different environmental compartments at levels that could have potential impacts on the ecosystems. This work aimed to evaluate the role of activated sludge in the removal of commonly used veterinary drugs, enrofloxacin (ENR), tetracycline (TET), and ceftiofur, from wastewater during a conventional treatment process. For that, a series of laboratory-controlled experiments using activated sludge were carried out in batch reactors. Sludge reactors with 100 μg/L initial drug charge presented removal rates of 68 % for ENR and 77 % for TET from the aqueous phase. Results indicated that sorption to sludge and to the wastewater organic matter was responsible for a significant percentage of drugs removal. Nevertheless, these removal rates still result in considerable concentrations in the aqueous phase that will pass through the WWTP to the receiving environment. Measuring only the dissolved fraction of pharmaceuticals in the WWTP effluents may underestimate the loading and risks to the aquatic environment.     

Phenol depletion by thermally activated peroxydisulfate at 70°C

The ability of thermal activated peroxydisulfate (PS) of mineralizing phenol at 70 °C from contaminated waters is investigated. Phenol in concentrations of 10⁻⁴ to 5 × 10⁻⁴ M is quantitatively depleted by 5 × 10⁻³ to 10⁻² M activated PS in 15 min of reaction. However, mineralization of the organic carbon is not observed. Instead, an insoluble phenol polymer-type product is formed. A reaction mechanism including the formation of phenoxyl radicals and validated by computer simulations is proposed. High molecular weight phenolic products are formed by phenoxyl radical H-abstraction reactions. This is not the case for the room temperature degradation of phenol by sulfate radicals where sulfate addition to the aromatic ring mainly leads to the generation of hydroxycyclohexadienyl radicals leading to hydroxybenzenes and oxidized open chain products. Therefore, a change in the reaction mechanism is observed with increasing temperature, and thermal activation of PS at 70 °C does not lead to the mineralization of phenol. Thus PS activation at 70 °C may be considered a potential method to reduce the load of phenol in polluted waters by polymerization.     

Estrogen receptor mediated activity in bankside groundwater, with flood suspended particulate matter and floodplain soil - an approach combining tracer substance, bioassay and target analysis

Bankside groundwater is widely used as drinking water resource and, therefore, contamination has to be avoided. In the European Union groundwater protection is explicit subject to Water Framework Directive. While groundwater pollution may originate from different sources, this study investigated on impacts via flood events.Groundwater was sampled with increasing distance to the river Rhine near Karlsruhe, Germany. Samples were HPLC-MS-MS analyzed for the river contaminant carbamazepine to indicate river water infiltration, giving permanent presence in 250 m distance to the river (14-47 μg L⁻¹). Following a flood event, concentrations of about 16-20 μg L⁻¹ could also be detected in a distance of 750 m to the river. Furthermore, estrogenic activity as determined with the Yeast Estrogen Screen assay was determined to increase up to a 17β-ethinylestradiol equivalent concentration (E-EQ) = 2.9 ng L⁻¹ near the river, while activity was initially measured following the flood with up to E-EQ = 2.6 ng L⁻¹ in 750 m distance. Detections were delayed with increasing distance to the river indicating river water expansion into the aquifer.Flood suspended matter and floodplain soil were fractionated and analyzed for estrogenic activity in parallel giving up to 1.4 ng g⁻¹ and up to 0.7 ng g⁻¹, respectively. Target analysis focusing on known estrogenic active substances only explained <1% of measured activities.Nevertheless, river water infiltration was shown deep into bankside groundwater, thus, impacting groundwater quality. Therefore, flood events have to be in the focus when aiming for groundwater and drinking water protection as well as for implementation of Water Framework Directive.     

Ecotoxicity evaluation of selected sulfonamides

Sulfonamides (SAs) are a group of antibiotic drugs widely used in veterinary medicine. The contamination of the environment by these pharmaceuticals has raised concern in recent years. However, knowledge of their (eco)toxicity is still very basic and is restricted to just a few of these substances. Even though their toxicological analysis has been thoroughly performed and ecotoxicological data are available in the literature, a systematic analysis of their ecotoxicological potential has yet to be carried out. To fill this gap, 12 different SAs were chosen for detailed analysis with the focus on different bacteria as well as non-target organisms (algae and plants). A flexible (eco)toxicological test battery was used, including enzymes (acetylcholinesterase and glutathione reductase), luminescent marine bacteria (Vibrio fischeri), soil bacteria (Arthrobacter globiformis), limnic unicellular green algae (Scenedesmus vacuolatus) and duckweed (Lemna minor), in order to take into account both the aquatic and terrestrial compartments of the environment, as well as different trophic levels. It was found that SAs are not only toxic towards green algae (EC₅₀ = 1.54-32.25 mg L⁻¹) but have even stronger adverse effect on duckweed (EC₅₀ = 0.02-4.89 mg L⁻¹) than atrazine - herbicide (EC₅₀ = 2.59 mg L⁻¹).     

Assessing inter-laboratory comparability and limits of determination for the analysis of cyclic volatile methyl siloxanes in whole Rainbow Trout (Oncorhynchus mykiss)

Cyclic volatile methyl siloxanes (cVMS) are high volume production chemicals used in a wide range of industrial and consumer products. Three cVMS compounds (D4, D5, and D6) have and are undergoing environmental risk evaluations in several countries and have been proposed for legal regulation in Canada. As interest in monitoring concentrations of these chemicals in the environment increase, there is a need to evaluate the analytical procedures for cVMS in biological matrices in order to assess the quality of data produced. The purpose of this study was to determine laboratory testing performance for measuring residues of D4, D5, and D6 in a standard set of fish homogenate samples and to estimate limits of determination for each substance. The samples sent to each laboratory consisted of homogenized whole body tissues of hatchery raised rainbow trout which were fed food fortified with D4, D5, and D6 (dosed) and trout that were fed standard food rations (control). The participants analyzed each sample using their analytical method of choice using their own standards and procedures for quantification and quality control. With a few exceptions, participating laboratories generated comparable results for D4, D5, and D6 in both the dosed and control samples having z-scores between 2 and −2. Method detection limits for the whole fish matrix were on average 2.4 ng g⁻¹ ww for D4, 2.3 ng g⁻¹ ww for D5, and 1.8 ng g⁻¹ ww for D6.     

Bromination of selected pharmaceuticals in water matrices

The bromination of five selected pharmaceuticals (metoprolol, naproxen, amoxicillin, phenacetin, and hydrochlorothiazide) was studied with these compounds individually dissolved in ultra-pure water. The apparent rate constants for the bromination reaction were determined as a function of the pH, obtaining the sequence amoxicillin > naproxen ? hydrochlorothiazide ≈ phenacetin ≈ metoprolol. A kinetic mechanism specifying the dissociation reactions and the species formed for each compound according to its pK_a value and the pH allowed the intrinsic rate constants to be determined for each elementary reaction. There was fairly good agreement between the experimental and calculated values of the apparent rate constants, confirming the goodness of the proposed reaction mechanism.In a second stage, the bromination of the selected pharmaceuticals simultaneously dissolved in three water matrices (a groundwater, a surface water from a public reservoir, and a secondary effluent from a WWTP) was investigated. The pharmaceutical elimination trend agreed with the previously determined rate constants. The influence of the main operating conditions (pH, initial bromine dose, and characteristics of the water matrix) on the degradation of the pharmaceuticals was established. An elimination concentration profile for each pharmaceutical in the water matrices was proposed based on the use of the previously evaluated apparent rate constants, and the theoretical results agreed satisfactorily with experiment. Finally, chlorination experiments performed in the presence of bromide showed that low bromide concentrations slightly accelerate the oxidation of the selected pharmaceuticals during chlorine disinfection.