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.     

Insights into aqueous carbofuran removal by modified and non-modified rice husk biochars

Biochar has been considered as a potential sorbent for removal of frequently detected pesticides in water. In the present study, modified and non-modified rice husk biochars were used for aqueous carbofuran removal. Rice husk biochars were produced at 300, 500, and 700 °C in slow pyrolysis and further exposed to steam activation. Biochars were physicochemically characterized using proximate, ultimate, FTIR methods and used to examine equilibrium and dynamic adsorption of carbofuran. Increasing pyrolysis temperature led to a decrease of biochar yield and increase of porosity, surface area, and adsorption capacities which were further enhanced by steam activation. Carbofuran adsorption was pH-dependant, and the maximum (161 mg g^?1) occurred in the vicinity of pH 5, on steam-activated biochar produced at 700 °C. Freundlich model best fitted the sorption equilibrium data. Both chemisorption and physisorption interactions on heterogeneous adsorbent surface may involve in carbofuran adsorption. Langmuir kinetics could be applied to describe carbofuran adsorption in a fixed bed. A higher carbofuran volume was treated in a column bed by a steam-activated biochar versus non-activated biochars. Overall, steam-activated rice husk biochar can be highlighted as a promising low-cost sustainable material for aqueous carbofuran removal.     

Determination of optimum polymeric coagulant in palm oil mill effluent coagulation using multiple-objective optimisation on the basis of ratio analysis (MOORA)

The main limitation of a conventional palm oil mill effluent (POME) ponding system lies in its inability to completely decolourise effluent. Decolourisation of effluent is aesthetically and environmentally crucial. However, determination of the optimum process parameters is becoming more complex with the increase of the number of coagulants and responses. The primary objective of this study is to determine the optimum polymeric coagulant in the coagulation–flocculation process of palm oil mill effluent by considering all output responses, namely lignin–tannin, low molecular mass coloured compounds (LMMCC), chemical oxygen demand (COD), ammonia nitrogen (NH₃-N), pH and conductivity. Here, multiple-objective optimisation on the basis of ratio analysis (MOORA) is employed to discretely measure multiple response characteristics of five different types of coagulants as a function of assessment value. The optimum coagulant is determined based on the highest assessment value and was identified as QF25610 (cationic polyacrylamide). On the other hand, the lowest assessment value was represented by AN1800 (anionic polyacrylamide). This study highlights the simplicity of MOORA approach in handling various input and output parameters, and it may be useful in other wastewater treatment processes as well.     

Influence of dissolved organic matter and oil on the biosorption of BTEX by macroalgae in single and multi-solute systems

The effect of dissolved organic matter (DOM) and oil on the removal of the water-soluble compounds benzene, toluene, ethylbenzene, and xylene isomers (BTEX) by two low-cost biosorbents Macrocystis pyrifera and Ulva expansa) was evaluated. DOM decreased the adsorption capacity of toluene, ethylbenzene, and xylenes of the two biosorbents. In contrast, the removal of benzene increased under the same conditions in single and multi-solute systems: this effect was dominant in U. expansa biomass treatments. In the presence of DOM and oil in solutions, the removal of BTEX notoriously increased, being oil that contributed the most. Solubility and hydrophobicity of pollutants played a key role in the adsorption process. The attractions between BTEX molecules and biosorbents were governed by π–π and hydrophobic interactions. Affinities of biosorbents for BTEX were mainly in the order of X > E > T > B. The Langmuir and Sips equations adjusted the adsorption isotherms for BTEX biosorption in deionized and natural water samples, but in the case of oily systems, the Freundlich equation seemed to have a better fit. The biosorption processes followed a pseudo-second-order rate in all the cases.     

Evaluation in situ of genotoxicity and stress in South American common toad <Emphasis Type="Italic">Rhinella arenarum</Emphasis> in environments related to fluorite mine

Little attention has been paid to the impact of wastewater generated by mining activities on fluoride. In this study, we evaluated the hematology responses of common South American toad Rhinella arenarum inhabiting natural and artificial environments associated with a fluorite mine from central Argentina. We analyzed three sampling stations associated with the fluorite mine: (I) Los Cerros Negros stream (CN), which runs on granitic rock with a high fluorite content; (II) Los Vallecitos stream (LV), which runs on metamorphic rock with low fluorite content; and (III) artificial decantation ponds (DP) containing sediments produced by fluorite flotation process. We calculated frequencies of micronuclei, erythrocyte nuclear abnormalities, mitosis, and immature erythrocytes. In addition, we performed a differential leukocyte count and determined neutrophils/lymphocyte ratio as a stress response estimator. We found high micronucleus (MN) and erythrocyte nuclear abnormality (ENA) frequencies in DP and CN but low frequencies in LV. The neutrophil/lymphocyte ratio was different among sites, with a significant increase in individuals from DP. Values registered in DP could be caused by exposure to mixture of compounds registered in dams that hold wastewater, while high values registered in CN stream might be due to natural concentrations of fluoride. Our results suggest that blood is an effective and non-destructive sensitive indicator for monitoring genotoxic agents in freshwater ecosystems.     

A new approach for the modelling of chestnut wood photo-degradation monitored by different spectroscopic techniques

The aim of this work is to study the colour and chemical modifications of the surfaces in chestnut wood samples as a consequence of irradiating in a controlled environment. The changes were investigated by a new analytical approach by combining traditional techniques such as reflectance spectrophotometry in the visible range and Fourier transform infrared spectroscopy with new hyperspectral imaging, in order to obtain forecast models to describe the phenomenon. The statistical elaboration of the experimental data allowed to validate the measurements and to obtain models enabling to relate the investigated parameters; the elaboration of the hyperspectral images by chemometric methods allowed for studying the changes in the reflectance spectra. A result of great importance is the possibility to correlate the oxidation of wood chemical components with the colour change in a totally non-invasive modality. This result is particularly relevant in the field of cultural heritage and in general in the control processes of wooden materials.     

Assessment of indoor climate of Mogiła Abbey in Kraków (Poland) and the application of the analogues method to predict microclimate indoor conditions

The microclimatic monitoring of the historic church of Mogi?a Abbey (Kraków, Poland) was carried out to study the impact of the environmental parameters on the organic and hygroscopic artworks. Specific indexes were proposed to objectively assess the quality of time series of temperature (T), relative humidity (RH), and carbon dioxide (CO₂) before applying the exploratory data analysis. The series were used to define the historic environmental conditions as stated in the European Standard EN 15757:2010 and with the use of the climate evaluation chart (CEC). It was found that the percentage of time in which T and RH values are within the allowable limits of the ASHRAE (2011) Class B is more than 85 %. This means that, for about 15 % of the time, there is a high risk of mechanical damage to highly vulnerable objects mainly due to the RH variability. The environment at the chancel resulted moister than that at the cornice, and the fungal growth is possible. In addition, the time-weighted preservation index (TWPI) is computed to evaluate the life expectancy of the objects, taking into account the environmental conditions of the site under study. The method of analogues, developed to predict the evolution of a system given observations of the past and without the knowledge of any equation among variables, was proposed and applied to the time series of temperature, relative humidity, and carbon dioxide with a 1-h sampling time to avoid the influence of the autocorrelation.     

Physicochemical characteristics,mutagenicity and genotoxicity of airborne particles under industrial and rural influences in Northern Lebanon

In this work, the main objectives were to assess the mutagenic and genotoxic effects of fine particulate matter collected in an industrial influenced site in comparison with a non-industrial influenced one (rural site) and to relate the particulate matter (PM) composition to the observed genotoxic effects. At the industrial influenced site, higher concentrations of phosphates, trace metals, and polycyclic aromatic hydrocarbons (PAHs) in particles could be related to the contributions of quarries, fertilizer producer, cement plants, and tires burning. Gasoline and diesel combustion contributions were evidenced in particles collected at both sites. Particles collected under industrial influence showed a higher mutagenic potential on three tested strains of Salmonella typhimurium (TA98, YG1041, and TA102), and especially on the YG1041, compared to particles from the rural site. Furthermore, only particles collected in the vicinity of the industrial site showed a tendency to activate the SOS responses in Escherichia coli PQ37, which is indicative of DNA damage as a result of exposure of the bacteria cells to the action of mutagenic samples. The mutagenicity and genotoxicity of the industrial PM_2.5–0.3 particulates may be attributed to its composition especially in organic compounds. This study showed that proximity of industries can affect local PM composition as well as PM genotoxic and mutagenic potential.     

Development of the hybrid cells in series model to simulate ammonia nutrient pollutant transport along the Umgeni River

Discharge of organic waste results in high nutrient pollution of the water bodies which is a major menace to the environment. A high quantity of nutrients such as ammonia causes a reduction in the dissolved oxygen level and induces algal growth in the water bodies. Water quality models have been the tools to evaluate the rate at which streams can disperse the pollutants they receive. Many water quality models are flawed either because of their inadequacy to completely simulate the advection component of the pollutant transport, or because of the limited application of the models, due to inaccurate estimation of model parameters. The hybrid cell in series (HCIS) developed by Ghosh et al. (2004) has been able to overcome such difficulties associated with the mixing cell-based models. Thus, the current study focuses on developing an analytical solution for the pollutant transport of the ammonia concentration through the plug flow, the first and second well-mixed cells of the HCIS model. The HCIS model coupled with the first order kinetic equation for ammonia nutrient was developed to simulate the ammonia pollutant concentration in the water column. The ammonia concentration at various points along the river system was assessed by considering the effects of the transformation of ammonia to nitrite, the uptake of ammonia by the algae, the respiration rate of the algae and the input of benthic source to the ammonia concentration in the water column. The proposed model was tested using synthetic data, and the HCIS-NH₃ model simulations for spatial and temporal variation of ammonia pollutant transport were analysed. The simulated results of the HCIS-NH₃ model agreed with the Fickian-based advection-dispersion equation (ADE) for simulating ammonia concentration solved using an explicit finite difference scheme. The HCIS-NH₃ model also showed a good agreement with the observed data from the Umgeni River, except during rainy periods.     

Improvement in rice straw pulp bleaching effluent quality by incorporating oxygen delignification stage prior to elemental chlorine-free bleaching

Environmental degradation by industrial and other developmental activities is alarming for imperative environmental management by process advancements of production. Pulp and paper mills are now focusing on using nonwood-based raw materials to protect forest resources. In present study, rice straw was utilized for pulp production as it is easily and abundantly available as well as rich in carbohydrates (cellulose and hemicelluloses). Soda-anthraquinone method was used for pulp production as it is widely accepted for agro residues. Bleaching process during paper production is the chief source of wastewater generation. The chlorophenolic compounds generated during bleaching are highly toxic, mutagenic, and bioaccumulative in nature. The objectives of study were to use oxygen delignification (ODL) stage prior to elemental chlorine-free (ECF) bleaching to reduce wastewater load and to study its impact on bleached pulp characteristics. ODL stage prior to ECF bleaching improved the optical properties of pulp in comparison to only ECF bleaching. When ODL stage was incorporated prior to bleaching, the tensile index and folding endurance of the pulp were found to be 56.6 ± 1.5 Nm/g and 140, respectively, very high in comparison to ECF alone. A potential reduction of 51, 57, 43, and 53% in BOD₃, COD, color, and AOX, respectively was observed on adding the ODL stage compared to ECF only. Generation of chlorophenolic compounds was reduced significantly. Incorporation of ODL stage prior to bleaching was found to be highly promising for reducing the toxicity of bleaching effluents and may lead to better management of nearby water resources.

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