Investigation of pharmaceutical metabolites in environmental waters by LC-MS/MS

Pharmaceuticals, once ingested, are commonly metabolized in the body into more polar and soluble forms. These compounds might not be completely removed in the wastewater treatment plants and consequently being discharged into the aquatic ecosystem. In this work, a multi-class sensitive method for the analysis of 21 compounds, including 7 widely consumed pharmaceuticals and 14 relevant metabolites, has been developed based on the use of UHPLC-MS/MS in selected reaction monitoring (SRM) mode. The method was validated in six surface waters (SW) and six effluent wastewaters (EWW) at realistic concentration levels that can be found in waters. The optimized method was applied to the analysis of different types of water samples (rivers, lakes and effluent wastewater), detecting nearly all the parent compounds and metabolites investigated in this work. This fact illustrates that not only pharmaceuticals but also their metabolites are commonly present in these types of waters. Analytical research and monitoring programs should be directed not only towards parent pharmaceuticals but also towards relevant metabolites to have a realistic overview of the impact of pharmaceuticals in the aquatic environment.     

Differential blood counting in fish as a non-destructive biomarker of water contamination exposure

Differential white blood cell counting was performed on blood from the fish species Oreochromis niloticus and was used as an in situ indicator of the species’ exposure to contamination. Ten young fish were collected in an area influenced by the discharge of effluents and from a fish farm (control group). The fish were anesthetized and caudal puncture was used to collect the blood. Differential white blood cell counting was performed, as well as the counting of total leukocytes and thrombocytes (in 2000 cells). Physicochemical parameters of the water from both sites were analyzed. The water from the polluted area was found to have high conductivity and low levels of dissolved oxygen, factors that indicate poor environmental quality. Fish collected from the polluted site presented higher percentages of eosinophils and monocytes and fewer thrombocytes because of exposure to pollution and hypoxic conditions. The differential white blood cell count represents a suitable biomarker of environmental health and provides a tool for biomonitoring water quality.     

Differences in the Spatial Distribution and Chemical Composition of PM10 Between the UK and Poland

The Fine Resolution Atmospheric Multi-pollutant Exchange Model was used to calculate the spatial distribution and chemical composition of PM₁₀ concentrations for two geographically remote countries in Europe—the UK and Poland—for the year 2007. These countries are diverse in terms of pollutant emissions as well as climate conditions. Information on the contribution of natural and anthropogenic as well as national and imported particles in total PM₁₀ concentrations in both countries is presented. The paper shows that the modelled national annual average PM₁₀ concentrations, calculated for the entire country area, are similar for the UK and Poland and close to 12 μg m^?3. Secondary inorganic aerosols dominate the total PM₁₀ concentrations in Poland. Primary particulate matter has the greatest contribution to total PM₁₀ in the UK, with large contribution of base cations. Anthropogenic sources predominate (81 %) in total PM₁₀ concentrations in Poland, whereas natural prevail in the UK—hence, the future reduction of PM₁₀ air concentrations by emissions reduction could be more difficult in the UK than in Poland.     

Effects of payments for ecosystem services on wildlife habitat recovery

Conflicts between local people's livelihoods and conservation have led to many unsuccessful conservation efforts and have stimulated debates on policies that might simultaneously promote sustainable management of protected areas and improve the living conditions of local people. Many government‐sponsored payments‐for‐ecosystem‐services (PES) schemes have been implemented around the world. However, few empirical assessments of their effectiveness have been conducted, and even fewer assessments have directly measured their effects on ecosystem services. We conducted an empirical and spatially explicit assessment of the conservation effectiveness of one of the world's largest PES programs through the use of a long‐term empirical data set, a satellite‐based habitat model, and spatial autoregressive analyses on direct measures of change in an ecosystem service (i.e., the provision of wildlife species habitat). Giant panda (Ailuropoda melanoleuca) habitat improved in Wolong Nature Reserve of China after the implementation of the Natural Forest Conservation Program. The improvement was more pronounced in areas monitored by local residents than those monitored by the local government, but only when a higher payment was provided. Our results suggest that the effectiveness of a PES program depends on who receives the payment and on whether the payment provides sufficient incentives. As engagement of local residents has not been incorporated in many conservation strategies elsewhere in China or around the world, our results also suggest that using an incentive‐based strategy as a complement to command‐and‐control, community‐ and norm‐based strategies may help achieve greater conservation effectiveness and provide a potential solution for the park versus people conflict.     

Characterization of As and trace metals embedded in PM10 particles in Puebla City, México

Forty-eight air-filter samples (PM₁₀) were analysed to identify the concentration level of partially leached metals (PLMs; As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and V) from Puebla City, México. Samples were collected during 2008 from four monitoring sites: (1) Tecnológico (TEC), (2) Ninfas (NIN), (3) Hermanos Serdán (HS) and (4) Agua Santa (AS). The results indicate that in TEC, As (avg. 424 ng m^?3), V (avg. 19.2 ng m^?3), Fe (avg. 1,202 ng m^?3), Cu (avg. 86.6 ng m^?3), Cr (41.9 ng m^?3) and Ni (18.6 ng m^?3) are on the higher side than other populated regions around the world. The enrichment of PLMs is due to the industrial complexes generating huge dust particles involving various operations. The results are supported by the correlation of metals (Mn, Cd and Co) with Fe indicating its anthropogenic origin and likewise, As with Cd, Co, Fe, Mn, Pb and V. The separate cluster of As, Fe and Mn clearly signifies that it is due to continuous eruption of fumaroles from the active volcano Popocatépetl in the region.     

Assessment of soils contamination with veterinary antibiotic residues in Northern Poland using developed MAE-SPE-LC/MS/MS methods

Among the wide range of compounds reaching the soil are the veterinary antimicrobials. Since no regulations regarding acceptable levels of drug concentrations in the environment exist, monitoring tests, particularly concerning soils, are carried out very rarely. This study presents a preliminary assessment of the contamination of agricultural soils in Northern Poland with seven antimicrobial veterinary medicines which has never been carried out before. Veterinary drugs were detected in 54% of the examined soil samples; the most commonly detected drugs were sulfonamides and trimethoprim. The highest indicated concentrations refer to enrofloxacin (57.0 μg kg^?1) and trimethoprim (47.8 μg kg^?1). The presence of these target drugs in the soil environment confirms the need for further monitoring studies. The analytical methods developed in this study are an excellent tool to achieve this goal and allow an estimation of the risk connected with the presence of veterinary antimicrobials in soils.

     

Sand as a relevant fraction in geochemical studies in intertidal environments

Soil and sediment samples from several intertidal environment exposed to different types of contamination were studied to investigate the importance of grain size in relation to the capacity of the substrates to retain trace metals. The unfractionated samples (referred to as bulk samples) were separated into the following grain/size fractions: fine–coarse sand (2?0.100 mm), very fine sand (0.100?0.050 mm), silt (0.050?0.002 mm), and clay (0.002 mm). The sample into its fractions was carried out was in a glove box under high-purity N₂ atmosphere in order to minimize any alterations to the samples. The bulk samples were characterized in terms of physicochemical properties such as pH, redox potential, and grain size. The total organic carbon (TOC), total sulfur (S), iron (Fe) pyrite, Fe, and manganese (Mn), and trace metals lead (Pb), mercury (Hg), chromium (Cr), and nickel (Ni) were analyzed in the bulk samples and in each fraction. The sand fractions were also examined by scanning electron microscopy (SEM). Comparisons of the above parameters were made between fractions and between each fraction and the corresponding bulk sample. The fine–coarse sand fraction contained high levels of the primary elements of the geochemical processes that occur in marine sedimentary environments such as TOC, total Fe, Mn, and S. The net concentrations of these four elements were higher in the fine-coarse sand fraction than in the very fine sand fraction and were similar to the net concentrations in the silt and clay fractions. Detailed SEM analysis of the sand coarse fraction revealed the presence of Fe and aluminum oxyhydroxide coatings in the oxic layers, whereas the framboidal pyrites and coatings observed in the anoxic layers were Fe sulfides. The presence of the various coatings explains why the trace metal concentrations in the sand fine–coarse fraction were similar to those in the clay fraction and higher than those in the very fine sand fraction. The present results highlight the importance of the sand fraction, which is generally disregarded in geochemical and environmental studies of sedimentary layers.     

Depth-dependence and monthly variability of charophyte biomass production: consequences for the precipitation of calcium carbonate in a shallow <Emphasis Type="Italic">Chara</Emphasis>-lake

The month-to-month variability of biomass and CaCO₃ precipitation by dense charophyte beds was studied in a shallow Chara-lake at two depths, 1 and 3 m. Charophyte dry weights (d.w.), the percentage contribution of calcium carbonate to the dry weight and the precipitation of CaCO₃ per 1 m² were analysed from May to October 2011. Physical-chemical parameters of water were also measured for the same sample locations. The mean dry weight and calcium carbonate precipitation were significantly higher at 1 m than at 3 m. The highest measured charophyte dry weight (exceeding 2000 g m^?2) was noted at 1 m depth in September, and the highest CaCO₃ content in the d.w. (exceeding 80 % of d.w.) was observed at 3 m depth in August. The highest CaCO₃ precipitation per 1 m² exceeded 1695 g at 1 m depth in August. Significant differences in photosynthetically active radiation (PAR) were found between 1 and 3 m depths; there were no significant differences between depths for other water properties. At both sampling depths, there were distinct correlations between the d.w., CaCO₃ content and precipitation and water properties. In addition to PAR, the water temperature and magnesium and calcium ion concentrations were among the most significant determinants of CaCO₃ content and d.w. The results show that light availability seems to be the major factor in determining charophyte biomass in a typical, undisturbed Chara-lake. The study results are discussed in light of the role of charophyte vegetation in whole ecosystem functioning, with a particular focus on sedimentary processes and the biogeochemical cycle within the littoral zone.     

Injury and loss concentration by sinkings in fishing fleets

Sinkings of fishing vessels, when accompanied by human loss, are accidents which lead to a great social upheaval, especially in the local area where they occur. In order to avoid or reduce these accidents, national governments must include in their legislation for this sector the appropriate safety measures. These resources and their distribution must be assigned in accordance with the needs of the accidentality, this requiring a detailed knowledge of the concentration of accidentality of a country’s fishing sector. In this context, the aim of the present work is twofold: first, to formulate a methodology for the fishing sector of a country, allowing the inequalities in the concentration of sinking accidents to be analysed; and second, to apply this methodology to the Spanish fishing fleet. Thus, two indices are constructed per region and type of fishing, for two variables: fishermen and vessels. Results are obtained both for the concentration of accidents and the associated Lorenz curves. An increase in the inequality in the spatial and functional distribution of these accidents is verified.