Sorption thermodynamic and kinetic study of Cu(II) onto modified plant stem bark.

In this study, four types of "Juá" stem barks (Ziziphus joazeiro) were investigated for the removal of Cu(II) from aqueous solutions. The tested samples included natural coarse barks, and barks washed with water, ethanol-water, and NaOH solutions. The solvent-modified materials simulated the waste of the industrial extraction of saponins from bark. The valorization of these processing residues as sorbents was evaluated. The NaOH-washed sorbent exhibited the highest sorption capacity for Cu(II) (maximum sorption capacity ≈ 32 mg g-1). Ion exchange process between copper and exchangeable surface cations and electrostatic attraction of copper with carboxylate and phenolate groups were identified as the primary sorption mechanisms. Desorption tests revealed that a large portion of the metal sorbed (80%) was easily released from the sorbent thus suggesting, in line with the proposed mechanisms, the existence of weak sorbate-sorbent interactions. The sorptive process was found to be exothermic (∆H° = - 48.1 ± 13.5 kJ.mol-1) and thermodynamically favorable at lower temperatures.

Adsorption of phosphate in aqueous solution by ash from the fruit peel of Caryocar coriaceum Wittm: adsorption characteristics and behavior.

High phosphate concentrations in natural waters are associated with eutrophication problems that negatively affect the fauna and flora of ecosystems. As an alternative solution to this problem, we evaluated the adsorptive capacity of the fruit peel ash (PPA) of Caryocar coriaceum Wittm and its efficiency in removing phosphate (PO43-) from aqueous solutions. PPA was produced under an oxidative atmosphere and calcinated at 500 °C. The XRF and EDS analyses of PPA after contact with an aqueous PO43- solution showed an increase in its PO43- content, thus confirming the adsorption of PO43-. The Elovich and Langmuir models are the ones fitting the kinetics and the equilibrium state of the process, respectively. The highest PO43- adsorption capacity was approximately 79.50 mg g-1 at 10 °C. PO43- adsorption by PPA is a spontaneous, favorable, and endothermic process involving structural changes. The highest removal efficiency was 97.08% using a 100 mg.L-1 PO43- solution. In sight of this, PPA has shown potential as an excellent natural bioadsorbent.

Impacts of the Residual Trace Metals of Aquaculture in Net Cages on the Quality of Sediment.

Anthropogenic pollution by trace metals in aquatic environments in semiarid zones is a critical area of investigation. The objective of this study was to investigate the concentration and spatial distribution of trace metals in surface sediments in the Rosário reservoir, which is affected by the intensive aquaculture of Tilápia-do-Nilo (Oreochromis niloticus). Sediment samples were collected in three different areas, postculture (PCTV), cultivation (CTV) and control (CTRL) in the dry season in 2019. The granulometric composition, organic matter and concentrations of Fe, Mn, Zn, Cu, Cr, Cd, Pb and Ni metals were determined. Multivariate statistics were used. Geochemical and ecotoxicological indices and a comparison with sediment quality guidelines (SQG) were used. The sediment was characterized by silty clay loam with an average organic matter of 18.76 ± 4.27. The analytical merit figures demonstrated accuracy (metal recoveries in certified standards) between 89 to 99% and high precision (RSD < 5%). The concentration ranges for the metals were Fe: 0.11-0.85 (%), Mn: 14.46-86.91, Zn: 2.6-220.56, Cu: 26.89-98.75, Cr: 60.18-76.06, Cd: 0.38-0.59, Pb: 18.13-43.13, and Ni: 34.4-46.75, all in (mg/kg-1). The highest concentration values were found in the CTV areas (Fe: 40 ± 0.22, Mn: 66.48 ± 19.11, Zn: 114.83 ± 59.75 and Cr: 70.85 ± 2.62) and PCTV (Cd: 0.53 ± 0.04, Cu: 71.83 ± 21.20, Pb: 33.71 ± 4.34 and Ni: 44.60 ± 1.79). Pearson's correlation, hierarchical cluster analysis and principal component analysis confirmed the influence of fish farming on metals. Only Ni presented concentration values higher than the reference value established in the SQG. Thus, considering the probable geochemical and ecotoxicological effects, they comprise the two lowest levels of impact.

Removal of Methylene Blue from a synthetic effluent by ionic flocculation.

Methylene Blue (MB) is a dye widely used in the industrial sector and in human and veterinary pharmacology. This dye, if improperly disposed of, can cause a significant environmental impact due to its low biodegradability, as it is a stable and complex substance. Additionally, it may affect human health and generate highly toxic byproducts. Hence, the purpose of this work is to assess the removal efficiency of MB from a synthetic effluent using a ionic flocculation process. Such a process consists of the dissolution of a biodegradable anionic surfactant (obtained from soybean oil used for frying food) in the synthetic effluent and the subsequent addition of calcium to the system. The addition of Ca leads to the formation of insoluble surfactant flocs with a high capacity to adsorb organic pollutants. The FTIR testing showed the presence of OH- and C=O groups in the surfactant flocs, which favor the removal of MB by an adsorption process. The maximum adsorption capacity of MB was 101.38 mg g-1. The process is in fact a chemisorption and has an exothermic nature. Desorption studies showed a desorption efficiency of up to 47.81% using an ethanol 1:2 solution. An MB removal efficiency of up to 93.71% was attained in just 0.5 min for an initial MB concentration of 100 mg L-1, showing that ionic flocculation is a very fast and effective process for the treatment of effluents.

Equilibrium, kinetics and thermodynamics of lead (II) adsorption in bioadsorvent composed by Caryocar coriaceum Wittm barks.

The improper disposal of waste containing toxic metals promotes serious environmental problems. Biosorption stands out as a powerful technique in removing toxic metals from aqueous solutions, making it an efficient and low-cost technique, since it makes use of abundant materials and of natural origins. This work aimed to study the application of the bark of Caryocar coriaceum Wittm, as a possible bioabsorbent for the removal of Lead (II) present in aqueous solutions, for this, residues of this material were collected in a public market, where they were washed and dried, then crushed, sieved (32mesh) and washed again, to then be used in the kinetic, isotherm and thermodynamic tests of lead (II) ions adsorption. After the experiments, it was found that the increase of the temperature disfavored the rate of lead (II) adsorption, ranging from 15.6 to 13.5 mg.L-1, for temperatures of 5 °C and 35 °C, respectively. The pseudo-second order kinetic model best characterizes the adsorption velocity obtaining a linear regression coefficient of 0.9997, while the pseudo-first order obtained a value of 0.7117. Adsorption occurred by chemisorption, with intra-film diffusion. The isothermal model that best represented the adsorption was Langmuir's (R2 0.99). It was concluded that the bark of Caryocar coriaceum Wittm is a good alternative to be used as a bioabsorbent for solutions containing dissolved lead (II).

Removal of copper(II) ions and lead(II) from aqueous solutions using seeds of Azadirachta indica A. Juss as bioadsorvent.

In recent decades, aquatic environment pollution has become a global challenge due to a rapid industrial growth. In this context, adsorption has become one of the most used methods, gaining importance especially in the last decades, given the growing concern over environmental damages caused by these pollutants. Additionally, its low cost and bioavailability are attractive. Therefore, the present study proposed to investigate the adsorption potential of A. indica seeds for Cu(II) and Pb(II) removal in synthetic solutions. Equilibrium studies were carried out via isothermal adsorption in batch systems. Kinetic studies were used to evaluate the lowest equilibrium time. The two evaluated ions were better suited to the Langmuir model and Freundlich model. When applying Langmuir's model on Neem seed powder adsorption, maximum adsorption capacities of 11.54 mg g-1 and 17.96 mg g-1, in the crude form and 11.41 mg g-1 and 19.80 mg g-1 in the alkaline form were obtained for Cu(II) and Pb(II) ions, respectively. The equilibrium time was approximately 80 and 100 min for both ions. The kinetic model best adjusted to the phenomena was the pseudo-second order (Ho Model), suggesting adsorption mainly has a chemical nature for both the studied metals. The results showed Neem seed powder may be a sustainable, efficient and low cost alternative for the removal of Cu(II) and Pb(II) metal cations present in effluents.

Physical-chemical determinant properties of biological communities in continental semi-arid waters.

Throughout human history, water has undergone changes in quality. This problem is more serious in dry areas, where there is a natural water deficit due to climatic factors. The aims of this study, therefore, were (i) to verify correlations between physical attributes, chemical attributes and biological metrics and (ii) from the biological attributes, to verify the similarity between different points of a body of water in a tropical semi-arid region. Samples were collected every 2 months, from July 2009 to July 2011, at seven points. Four physical attributes, five chemical attributes and four biological metrics were investigated. To identify the correlations between the physicochemical properties and the biological metrics, hierarchical cluster analysis (HCA) and canonical correlation analysis (CCA) were applied. Nine classes of phytoplankton were identified, with the predominance of species of cyanobacteria, and ten families of macroinvertebrates. The use of HCA resulted in the formation of three similar groups, showing that it was possible to reduce the number of sampling points when monitoring water quality with a consequent reduction in cost. Group I was formed from the waters at the high end of the reservoir (points P1, P2 and P3), group II by the waters from the middle third (points P4 and P5), and group III by the waters from the lower part of the reservoir (points P6 and P7). Richness of the phytoplanktons Cyanophyceae, Chorophyceae and Bacillariophyceae was the attribute which determined dissimilarity in water quality. Using CCA, it was possible to identify the spatial variability of the physicochemical attributes (TSS, TKN, nitrate and total phosphorus) that most influence the metrics of the macroinvertebrates and phytoplankton present in the water. Low macroinvertebrate diversity, with a predominance of indicator families for deterioration in water quality, and the composition of phytoplankton showing a predominance of cyanobacteria, suggests greater attention to the management of water resources.

Background values for evaluation of heavy metal contamination in sediments in the Parnaíba River Delta estuary, NE/Brazil.

This study establishes regional background levels and upper thresholds (geochemical baseline) for Zn, Cu, Pb, Cr, Mn, and Fe from surface samples and profiles taken in 16 sedimentary environments of the Parnaíba River Delta estuary, NE-Brazil. Three approaches were applied to evaluate metal contamination: normalization to Fe, statistical analysis and sediment quality guidelines or environmental assessment criteria (TEL-PEL). Metal concentrations in sediments ranged from 2.4 to 31 mg Zn kg(-1), 1.5 to 48 mg Cu kg(-1), 1.3 to 28 mg Pb kg(-1), 1.5 to 38 mg Cr kg(-1); 145 to 1,356 mg Mn kg(-1), and 0.3% to 2.5% for Fe. All metals showed positive correlations with the <0.63 µm sediment fraction, indicating a significant association with rich lithogenic sources of iron oxide-hydroxides. Results suggest a low probability of adverse effects to the local aquatic biota. The background values of the area were lower than those reported for other areas of the northeastern coast of Brazil.