Removal of heavy metal ions from wastewaters using dendrimer-functionalized multi-walled carbon nanotubes

Dendrimer-functionalized multi-walled carbon nanotubes (MWCNT) for heavy metal ion removal from wastewaters were developed. Triazole dendrimers (TD) were built directly onto the carbon nanotube surface by successive click chemistry reactions affording the zero- and first-generation dendrimer-functionalized MWCNT (MWCNT-TD1 and MWCNT-TD2). The Moedritzer-Irani reaction carried out on the amino groups present on the MWCNT-TD2 sample gave the corresponding α-aminophosphonate nanosystem MWCNT-TD2P. Both MWCNT-TD2 and MWCNT-TD2P nanosystems have been characterized by physical, chemical, and morphological analyses. Their chelating abilities towards the toxic metal ions Pb²⁺, Hg²⁺, and Ni²⁺ and the harmless Ca²⁺ ion have been experimentally evaluated in the two different sets of experiments and at the salt concentrations of 1 mg/mL or 1 μg/mL by inductively coupled plasma mass spectrometry (ICP-MS). The results of these studies pointed out the interesting chelating behavior for the phosphonated nanosystem towards the Hg²⁺ ion. The complexation mode of the best chelating system MWCNT-TD2P with mercury was investigated through density functional theory (DFT) calculations, suggesting a chelation mechanism involving the two oxygen atoms of the phosphate group. The synthesized dendrimers, supported on the multi-walled carbon nanotubes, have shown the potential to be used for the selective toxic metal ion removal and recovery.     

Prediction of membrane fouling using artificial neural networks for wastewater treated by membrane bioreactor technologies: bottlenecks and possibilities

Membrane fouling is a major concern for the optimization of membrane bioreactor (MBR) technologies. Numerous studies have been led in the field of membrane fouling control in order to assess with precision the fouling mechanisms which affect membrane resistance to filtration, such as the wastewater characteristics, the mixed liquor constituents, or the operational conditions, for example. Worldwide applications of MBRs in wastewater treatment plants treating all kinds of influents require new methods to predict membrane fouling and thus optimize operating MBRs. That is why new models capable of simulating membrane fouling phenomenon were progressively developed, using mainly a mathematical or numerical approach. Faced with the limits of such models, artificial neural networks (ANNs) were progressively considered to predict membrane fouling in MBRs and showed great potential. This review summarizes fouling control methods used in MBRs and models built in order to predict membrane fouling. A critical study of the application of ANNs in the prediction of membrane fouling in MBRs was carried out with the aim of presenting the bottlenecks associated with this method and the possibilities for further investigation on the subject.     

Dental enamel as biomarker for environmental contaminants in relevant industrialized estuary areas in São Paulo,Brazil

Heavy metal contamination is a long-standing and very well-known public health problem, and its exposure can cause damage to several organs of human body, especially on the central nervous system of young children and teenagers. The aim of this article is to evaluate lead, cadmium, and manganese contamination in 125 children from 6 to 13 years old living in contaminated areas during the period from 2006 to 2009 (São Vicente, Cubatão Downtown, Bertioga and Cubatão Pilões/Água Fria). This estuary area is the most important example of environmental degradation by chemicals from industrial sources. This is a cross-sectional study through clinical examinations and dental enamel tests. All mothers from these children lived in the area since before the pregnancy. Lead, cadmium, and manganese levels (μg/g) were measured on dental enamel samples through graphite furnace atomic absorption spectrometry, searching for the occurrence of heavy metals. The mean lead concentrations were 139.48 μg/g in Cubatão Pilões/Água Fria, 170.45 μg/g in Cubatão Downtown, 213.52 μg/g in São Vicente, and 151.89 μg/g in Bertioga. The mean cadmium concentrations were 10.83 μg/g in Cubatão Pilões/Água Fria, 12.58 μg/g in Cubatão Downtown, 10.92 μg/g in São Vicente, and 14.57 μg/g in Bertioga. The mean manganese concentrations were 23.49 μg/g in Cubatão Pilões/Água Fria, 30.90 μg/g in Cubatão Downtown, 41.46 μg/g in São Vicente, and 42.00 μg/g in Bertioga. Dental surface enamel may be used as an efficient biomarker of past environmental exposure to lead, manganese, and cadmium which are associated to well-known sources of heavy metal contamination. The results suggest that the evaluated children were exposed to sources of lead, cadmium, and manganese since before their conceptions. Although Bertioga initially was chosen as a control area of this study, it was also was verified to have heavy metal contamination on examined children.     

Biosurfactants during in situ bioremediation: factors that influence the production and challenges in evalution

Research on the influence of biosurfactants on the efficiency of in situ bioremediation of contaminated soil is continuously growing. Despite the constant progress in understanding the mechanisms involved in the effects of biosurfactants, there are still many factors that are not sufficiently elucidated. There is a lack of research on autochthonous or exogenous microbial metabolism when biostimulation or bioaugmentation is carried out to produce biosurfactants at contaminated sites. In addition, studies on the application of techniques that measure the biosurfactants produced in situ are needed. This is important because, although the positive influence of biosurfactants is often reported, there are also studies where no effect or negative effects have been observed. This review aimed to examine some studies on factors that can improve the production of biosurfactants in soils during in situ bioremediation. Moreover, this work reviews the methodologies that can be used for measuring the production of these biocomposts. We reviewed studies on the potential of biosurfactants to improve the bioremediation of hydrocarbons, as well as the limitations of methods for the production of these biomolecules by microorganisms in soil.     

UV-C as a means to combat biofilm proliferation on prehistoric paintings: evidence from laboratory experiments

A laboratory investigation of UV-C effects was conducted over a 62-h period: a much higher dose than in classic UV-C treatment was applied to five pigments and two painting binders used by prehistoric humans. Colorimetric parameters were compared to a control to see if UV-C can change pigment and binder color. Infrared spectroscopy, scanning electron microscopy, inductively coupled plasma and X-ray crystallography were also carried out to confirm colorimetric measurement. In order to understand how microorganism may physically deteriorate paintings, limestone blocks were painted and monitored until their complete colonization by algae, cyanobacteria, fungi and/or mosses. The results show that UV-C has no effect on mineral compounds. Conversely, it is noteworthy that binder color changed under both UV-C light conditions as well as in visible light. Concerning painted blocks, a fast proliferation has been observed with deterioration of the paintings. These results show the high importance of treating biofilm as soon as possible. Moreover, these findings may be a promising avenue inducing cave managers to use friendly UV-C light to treat contaminated cave paintings and also in the prevention of biodeterioration by lampenflora.     

Effect of ferrate on green algae removal

Green algae Cladophora aegagropila, present in cooling water of thermal power plants, causes many problems and complications, especially during summer. However, algae and its metabolites are rarely eliminated by common removal methods. In this work, the elimination efficiency of electrochemically prepared potassium ferrate(VI) on algae from cooling water was investigated. The influence of experimental parameters, such as Fe(VI) dosage, application time, pH of the system, temperature and hydrodynamics of the solution on removal efficiency, was optimized. This study demonstrates that algae C. aegagropila can be effectively removed from cooling water by ferrate. Application of ferrate(VI) at the optimized dosage and under the suitable conditions (temperature, pH) leads to 100% removal of green algae Cladophora from the system. Environmentally friendly reduction products (Fe(III)) and coagulation properties favour the application of ferrate for the treatment of water contaminated with studied microorganisms compared to other methods such as chlorination and use of permanganate, where harmful products are produced.

     

Seasonal ecophysiology of an endangered coastal species,the yellow-horned poppy (Glaucium flavum Crantz)

Glaucium flavum Crantz. is a short-lived perennial herb distributed in coastal zones from the Black Sea to southern, western and north-western Europe. Despite its diminishing area of distribution and potential pharmacological value, little is known about the ecophysiological features of this coastal species. We investigated the photosynthetic performance of G. flavum by measuring gas exchange, chlorophyll fluorescence, photosynthetic pigment concentration and leaf water content over the space of a year in a coastal habitat of SW Spain. We also measured the variation in total concentrations of nitrogen, phosphorus, sulphur, potassium, calcium and magnesium, in the leaves and soil, throughout the study period. G. flavum showed a high resistance to summer drought conditions which appeared to be due to the high degree of stomatal control. The potential photochemical efficiency of photosystem II showed minimum values during the winter, indicating that low temperatures can produce negative effects within the photosynthetic apparatus. However, the marked decline in net photosynthesis during the winter seems to be mainly related to a loss of metabolic activity. Although leaf nutrient concentrations were, in general, within the normal ranges, phosphorus availability seems to be limited by the high calcium concentrations detected in the soil of the study site. Our study points out the efficiency of the different physiological adaptations of this rare and endangered coastal species in coping with the strong seasonal variability of the Mediterranean climate.     

Effects of agricultural pesticides on the health of Rana pipiens frogs sampled from the field

There is evidence that over the last 30 years, there have been mass declines in diverse geographic locations among amphibian populations due to disease outbreaks. Multiple causes have been suggested to explain this increase in disease incidence. Among these, climate changes, environmental pollution and reduced water quality are gaining attention. Indeed, some chemicals of environmental concerns are known to alter the immune system. It is possible that exposure to these pollutants could alter the immune system of anurans and render them more susceptible to different pathogens. In this study, we sampled Rana pipiens in five different sites near St. Lawrence River (Quebec, Canada) during the months of July and September in 2001. Two of these sites were protected areas, in which low levels of pesticides were detected, while the remaining three sites were located in areas with intensive corn and soybeans cultivations. Our results demonstrated that frogs living in agricultural regions are smaller in size and weight than frogs living in areas with lower levels of pesticides at both sampling times. Moreover, we have observed a significant decrease in the number of splenocytes (cellularity) and the phagocytic activity in frogs sampled in impacted sites. Taken together, these results suggest that frogs living in agricultural regions might be more vulnerable to infections and diseases through their smaller size and alteration of their immune system. Our results also contribute to the overall discussion on factors involved in amphibian declines.     

Organochlorine compounds in bovine milk from the state of Mato Grosso do Sul – Brazil

Organochlorines are highly hydrophobic, synthetic organic pollutants that accumulate in the environment and in food webs. The primary route of human exposure to organochlorines is through food-mainly fat-rich food of animal origin such as meat, fish, and dairy products. Here we determined the presence and concentration of organochlorine residues in pasteurized milk from Mato Grosso do Sul, Brazil, to monitor consumer exposure to these contaminants. Organochlorine pesticides in milk samples were analyzed using solid phase extraction in octadecyl silica-prepacked columns and identified by gas chromatography using an electron capture detector. Of the 100 composite samples analyzed, more than 90% contained residues of organochlorine pesticides: aldrin was present in 44% of the samples, followed by ∑DDT (36%), mirex (34%), endosulfan (32%), chlordane (17%), dicofol (14%), heptachlor (11%) and dieldrin (11%). Compared to the values established by law, the concentration of the compounds in some samples was above the reference values. Given the importance that milk and its products have in the human diet, it is essential to know whether the levels of pesticide residues are kept well below the recommended levels to minimize the risk to human health.     

Building resilience to water scarcity in southern Spain: a case study of rice farming in Doñana protected wetlands

Agricultural water management needs to evolve in view of increased water scarcity, especially when farming and natural protected areas are closely linked. In the study site of Doñana (southern Spain), water is shared by rice producers and a world heritage biodiversity ecosystem. Our aim is to contribute to defining adaptation strategies that may build resilience to increasing water scarcity and minimize water conflicts among agricultural and natural systems. The analytical framework links a participatory process with quantitative methods to prioritize the adaptation options. Bottom-up proposed adaptation measures are evaluated by a multi-criteria analysis (MCA) that includes both socioeconomic criteria and criteria of the ecosystem services affected by the adaptation options. Criteria weights are estimated by three different methods—analytic hierarchy process, Likert scale and equal weights—that are then compared. Finally, scores from an MCA are input into an optimization model used to determine the optimal land-use distribution in order to maximize utility and land-use diversification according to different scenarios of funds and water availability. While our results show a spectrum of perceptions of priorities among stakeholders, there is one overriding theme that is to define a way to restore part of the rice fields to natural wetlands. These results hold true under the current climate scenario and even more so under an increased water scarcity scenario.