Forensic Evaluation of Metals (Cr,Cu, Pb,Zn), Isotopes (δ13C and δ15N), and C:N Ratios in Freshwater Sediment

A forensic approach was used to evaluate sediments from Portão Stream, including analysis of metals, carbon (C) and nitrogen (N) stable isotopes, and C:N ratios. Samples collected at various points located along the stream were tested in order to investigate a possible illegal leachate input. The studied stream is heavily impacted by sewage and industrial discharges from two cities along its course. Among the metals analyzed, chromium (Cr) was noticeably the main pollutant, showing the highest levels, above regulatory limits, downstream from some potential sources of effluents enriched with this metal. Isotope analyses revealed a general trend of depletion in the heavier isotope along the stream for C and N. The exception was one point near a hazardous waste landfill, where relatively more enriched δ¹³C and δ¹⁵N values were found. The isotope and metal analysis results indicated that this site was affected by a particular source, demonstrating the combination of these parameters could be used for the discrimination of sources in a heavily polluted stream. Nevertheless, further investigations are necessary to provide a comprehensive evaluation of the biogeochemical processes involved in the incorporation of leachate in sediments to use this analysis as evidence for the illegal leachate discharge.     

Polyurethanes Based on Atactic Poly[(R,S)-3-hydroxybutyrate]: Preliminary Degradation Studies in Simulated Body Fluids

The aliphatic polyurethanes based on atactic poly[(R,S)-3-hydroxybutyrate] (a-PHB) and commercial oligomerols: poly(ε-caprolactone)diol and polyoxytetramethylenediol were investigated. a-PHB was obtained by anionic ring-opening polymerization of (R,S)-β-butyrolactone. The 4,4′-methylenedicyclohexyl diisocyanate and 1,4-butanediol were used as contributors of hard segments. The aim of the study was to determine the influence of synthetic, atactic a-PHB in soft segments of polyurethanes on their degradability in simulated body fluids (SBF) and Ringer solution. The incubation of polymer samples in both degradative solutions was carried out for 36 weeks. It was concluded that the presence of a-PHB in polyurethane structure accelerated their degradation in SBF and in Ringer solution and, protected the calcification process.     

Opportunities for Increasing Resilience and Sustainability of Urban Social–Ecological Systems: Insights from the URBES and the Cities and Biodiversity Outlook Projects

Urban futures that are more resilient and sustainable require an integrated social–ecological system approach to urban policymaking, planning, management, and governance. In this article, we introduce the Urban Biodiversity and Ecosystem Services (URBES) and the Cities and Biodiversity Outlook (CBO) Projects as new social–ecological contributions to research and practice on emerging urban resilience and ecosystem services. We provide an overview of the projects and present global urbanization trends and their effects on ecosystems and biodiversity, as a context for new knowledge generated in the URBES case-study cities, including Berlin, New York, Rotterdam, Barcelona, and Stockholm. The cities represent contrasting urbanization trends and examples of emerging science–policy linkages for improving urban landscapes for human health and well-being. In addition, we highlight 10 key messages of the global CBO assessment as a knowledge platform for urban leaders to incorporate state-of-the-art science on URBES into decision-making for sustainable and resilient urban development.     

Cytogenetic biomonitoring of oral mucosa cells of crack cocaine users

The aim of the present study was to comparatively evaluate genomic damage (micronucleus) and cellular death (pyknosis, karyolysis, and karyorrhexis) in exfoliated oral mucosa cells from crack cocaine users by micronucleus test. A total of 30 crack cocaine users and 30 health controls (non-exposed individuals) were included in this setting. Individuals had epithelial cells from cheek mechanically exfoliated, placed in fixative, and dropped in clean slides, which were checked for the above nuclear phenotypes. The results pointed out significant statistical differences (p?<?0.05) of micronucleated oral mucosa cells from crack cocaine users. Exposure to crack cocaine caused an increase of other nuclear alterations closely related to cytotoxicity such as karyolysis in oral cells as well. In summary, these data indicate that crack cocaine is able to induce chromosomal breakage and cellular death in oral mucosa cells of users.     

Frequency of micronuclei and of other nuclear abnormalities in erythrocytes of the grey mullet from the Mondego,Douro and Ave estuaries—Portugal

Fish are bioindicators of water pollution, and an increased rate of their erythrocyte nuclear morphological abnormalities (ENMAs)—and particularly of erythrocyte micronuclei (EMN)—is used as a genotoxicity biomarker. Despite the potential value of ENMAs and MN, there is scarce information about fish captured in Iberian estuaries. This is the case of the Portuguese estuaries of the Mondego, Douro and Ave, suffering from different levels of environmental stress and where chemical surveys have been disclosing significant amounts of certain pollutants. So, the aim of this study was to evaluate genotoxicants impacts and infer about the exposure at those ecosystems, using the grey mullet (Mugil cephalus) as bioindicator and considering the type and frequency of nuclear abnormalities of erythrocytes as proxies of genotoxicity. Sampling of mullets was done throughout the year in the important Mondego, Douro and Ave River estuaries (centre and north-western Portugal). The fish (total n?=?242) were caught in campaigns made in spring–summer and autumn–winter, using nets or fishing rods. The sampled mullets were comparable between locations in terms of the basic biometric parameters. Blood smears were stained with Diff-Quik to assess the frequencies of six types of ENMAs and MN (given per 1,000 erythrocytes). Some basic water physicochemical parameters were recorded to search for fluctuations matching the ENMAs. Overall, the most frequent nucleus abnormality was the polymorphic type, sequentially followed by the blebbed/lobed/notched, segmented, kidney shaped, vacuolated, MN and binucleated. The total average frequency of the ENMAs ranged from 73?‰ in the Mondego to 108?‰ in the Ave. The polymorphic type was typically ≥50 % of the total ENMAs, averaging about 51?‰, when considering all three estuaries. The most serious lesion—the MN—in fish from Mondego and Douro had a similar frequency (≈0.38?‰), which was significantly lower than that in the Ave (0.75?‰). No significant seasonal differences existed as to the MN rates and seasonal differences existed almost only in the Douro, with the higher values in AW. In general, the pattern of ENMAs frequencies was unrelated with the water physicochemical parameters. Considering the data for both the total ENMAs and for each specific abnormality, and bearing in mind that values of MN in fish erythrocytes >0.3?‰ usually reflect pollution by genotoxicants, it is suggested that mullets were likely being chronically exposed to such compounds, even in the allegedly less polluted ecosystem (Mondego). Moreover, data supported the following pollution exposure gradient: Mondego?<?Douro?<?Ave. The scenario and inferences nicely agree with the published data from chemical monitoring.     

Impacts on effluent contaminants from mine sites: risk assessment,fate, and distribution of pollution at basin scale

The environmental implications of mining activities are of worldwide concern. An environmental evaluation at the basin level was conducted because of widespread mining in Cajamarca in Northern Peru. A sediment monitoring program was developed at the Jequetepeque basin, located in Cajamarca. A total of 16 sites were monitored at three different times between June 2009 and July 2010, and a total of 42 samples were collected. All samples were analyzed by microwave digestion and by a sequential extraction scheme following the three-stage European Community Bureau of Reference (three-stage BCR) protocol. Trace element mobilization from the sediments to the water column was assessed by the risk assessment code (RAC). Spatial and temporal distribution of trace elements was evaluated by principal component analysis and hierarchical cluster analysis. Cd, Zn, As, and Pb showed the highest concentrations independent of season. Notably, Cu concentration and mobility increased during the wet season for all samples. Additionally, Hg concentration and mobility increased during the wet season near the mine sites. According to the enrichment factor, the highest enrichments of Cd, Zn, Pb, and As were related to mine runoff. The effect of trace elements near the mine sites at the Jequetepeque basin was considered a significant threat to the environment due to Cd, Zn, Pb, and As, and the concentrations of Cu and Hg were also considered a concern. This work establishes a baseline for the environmental quality status of the Jequetepeque basin that may support water quality management in Peru.     

Water quality assessment of the Tubarão River through chemical analysis and biomarkers in the Neotropical fish Geophagus brasiliensis

The Tubarão River rises in Santa Catarina, Brazil, and has been historically affected by coal mining activities around its springhead. To evaluate its water conditions, an investigation regarding a possible decontamination gradient associated with the increased river flow toward the estuary, as well as the influence of seasonality over this gradient was performed through a series of biomarkers (vitellogenin, comet assay, lipid peroxidation, protein carbonylation, gluthatione, gluthatione S-transferase, acetylcholinesterase, light microscopy in liver, and scanning electron microscopy in gills) and chemical analysis (polycyclic aromatic hydrocarbons (PAHs) in bile and metal analysis in sediment) in the cichlid Geophagus brasiliensis. Two collections (summer and winter) were made in four distinct sites along the river, while sediments were sampled between those seasons. As expected, the contamination linked exclusively to mining activities was not observed, possibly due to punctual inputs of contaminants. The decontamination gradient was not observed, although seasonality seemed to have a critical role in the responses of biomarkers and availability of contaminants. In the summer, the fish presented higher histopathological damages and lower concentrations of PAHs, while in the winter they showed both higher genetic damage and accumulation of PAHs. The Tubarão suffers impacts from diverse activities, representing health risks for wild and human populations.     

High efficiencies in the electrochemical oxidation of an anthraquinonic dye with conductive-diamond anodes

Oxidation of anthraquinonic dye Acid Blue 62 by electrolysis with conductive-diamond electrodes is studied in this work. COD, TOC, and color have been selected to monitor the degradation of the molecule as a function of several operating inputs (current density, pH, temperature, and NaCl concentration). Results show that the electrochemical oxidation of this model of large molecules follows a first order kinetics in all the conditions assessed, and it does not depend on the pH and temperature. The occurrence of chloride ions in wastewaters increases the rate of color and COD removal as a consequence of the mediated oxidation promoted by the chlorinated oxidizing species. However, chloride occurrence does not have an influence on the mineralization rate. First-order kinetic-constants for color depletion (attack to chromophores groups), oxidation (COD removal), and mineralization (TOC removal) were found to depend on the current density and to increase significantly with its value. A single model was proposed to explain these changes in terms of the mediated oxidation processes. Rate of mineralization remained very close to that expected for a purely mass transfer-controlled process. This was explained assuming that mediated oxidation does not have a significant influence on the mineralization in spite it has some effect on intermediate oxidation stages. The efficiency of the oxidation was found to depend mainly on the concentration of COD being negligible the effect of the other inputs assessed except for the occurrence of chloride ions. Opposite, the efficiency of mineralization depends on concentration of TOC and current density and it did not depend on the chloride occurrence. This observation was found to have an important influence on the power required to remove a given percentage of the initial TOC or COD. To decrease COD efficiently, the occurrence of chloride in the solution is very important, while to remove TOC efficiently, it is more important to work at low current densities and chloride effect is negligible. Energy consumption could be decreased by folds using the proper conditions.     

Salt marsh plants as key mediators on the level of cadmium impact on microbial denitrification

The fate of excess nitrogen in estuaries is determined by the microbial-driven nitrogen cycle, being denitrification a key process since it definitely removes fixed nitrogen as N₂. However, estuaries receive and retain metals, which may negatively affect this process efficiency. In this study, we evaluated the role of salt marsh plants in mediating cadmium (Cd) impact on microbial denitrification process. Juncus maritimus and Phragmites australis from an estuary were collected together with the sediment involving their roots, each placed in vessels and maintained in a greenhouse, exposed to natural light, with tides simulation. Similar non-vegetated sediment vessels were prepared. After 3 weeks of accommodation, nine vessels (three per plant species plus three non-vegetated) were doped with 20 mg/L Cd²⁺ saline solution, nine vessels were doped with 2 mg/L Cd²⁺ saline solution and nine vessels were left undoped. After 10 weeks, vessels were dissembled and denitrification potential was measured in sediment slurries. Results revealed that the addition of Cd did not cause an effect on the denitrification process in non-vegetated sediment but had a clear stimulation in colonized ones (39 % for P. australis and 36 % for J. maritimus). In addition, this increase on denitrification rates was followed by a decrease on N₂O emissions and on N₂O/N₂ ratios in both J. maritimus and P. australis sediments, increasing the efficiency of the N₂O step of denitrification pathway. Therefore, our results suggested that the presence of salt marsh plants functioned as key mediators on the degree of Cd impact on microbial denitrification.     

Chemical and spectroscopic characterization of organic matter during the anaerobic digestion and successive composting of pig slurry

In this work, anaerobic digestion of pig slurry and successive composting of the digestate after centrifugation were studied by means of chemical analysis, FTIR and fluorescence spectroscopy as excitation–emission matrix (EEM). Chemical analysis highlighted the organic matter transformation occurring during the processes. A decrease of volatile solids and total organic carbon were observed in the digestate with respect to the fresh pig slurry as a consequence of the consumption of sugars, proteins, amino acids and fatty acids used by microorganisms as a C source. Water Extractable Organic Matter (WEOM) was obtained for all samples and fractionated into a hydrophilic and a hydrophobic fraction. The highest WEOM value was found in the pig slurry indicating a high content of labile organic C. The digestate centrifuged and the digestate composted showed lower hydrophilic and higher hydrophobic contents because of the decrease of labile C. Total phenolic content was lower in the digestate with respect to fresh pig slurry sample (36.7%) as a consequence of phenolic compounds degradation. The strong decrease of total reducing sugars in the digestate (76.6%) as compared to pig slurry confirmed that anaerobic process proceed mainly through consumption of sugars which represent a readily available energy source for microbial activity. FTIR spectra of pig slurry showed bands indicative of proteins and carbohydrates. A drop of aliphatic structures and a decrease of polysaccharides was observed after the anaerobic process along with the increase of the peak in the aromatic region. The composted substrate showed an increase of aromatic and a relative decrease of polysaccharides. EEM spectra provided tryptophan:fulvic-like fluorescence ratios which increased from fresh substrate to digestate because of the OM decompostion. Composted substrate presented the lowest ratio due to the humification process.