In the present work, the role of chemical compounds of one abundant vegetable waste, exhausted coffee, on Cr(VI), Cu(II), and Ni(II) sorption has been investigated. For this purpose, exhausted coffee was subjected to sequential extractions by using dichloromethane (DCM), ethanol (EtOH), water, and NaOH 1 %. The raw and treated biomass resulting from the extractions were used for metal ions sorption. Sorption results were discussed taking into consideration polarity and functional groups of raw and treated biomass. In general, the successive removal of extractives led to an insignificant increase in the studied metal ions sorption after DCM, EtOH, and water. The sorption results using free-extractive materials showed that metal sorption can be effectively achieved without this non-structural fraction of the sorbent. Alkaline hydrolysis destroyed in part the structural compounds of the sorbent resulting in an insignificant decrease of chromium removal while a significant increase of copper and nickel sorption was observed. The determination of elemental ratios of exhausted coffee and all treated biomass evidenced the involvement of oxygen functional groups in copper and nickel sorption. FTIR analysis confirmed the involvement of lignin moieties in the chromium sorption by exhausted coffee. As a final remark, this study shows that the sequential extraction opens new expectations to the total valorisation of lignocellulosic-based biomasses. The extractives can be removed and used as a biosource of valuable compounds, and the resulting waste can be used as a sorbent for metal ions keeping the same capacity for metal sorption as the non-extracted biomass.

The soil remediation field is still in development in Brazil. Currently, it is not known how many contaminated sites exist across the country; however, due to the country’s large size and its extensive urbanization and industrialization, it can be postulated that the number of contaminated sites must be very high. To remediate these sites, new sustainable technologies should be identified and evaluated. A technology that was born in the 1990s in the USA, and has been fairly investigated, is the use of nanoparticles (NPs) to degrade contaminants in soils and groundwater. This study aims to present a bibliographic review of nanotechnology application to remediation of soils and groundwater, as well as assess the potential of conducting research in this field in Brazil. This paper first presents an overview of the number of contaminated areas identified in the USA and Europe. The basic concepts of nanomaterials followed by classification, synthesis, and characterization of nanomaterials are explained. The main types of contaminants for which the technique was already applied as well as the chemical reactions between them and NPs are presented. The issues related to delivery and migration of NPs in the porous media is discussed. Concerns regarding the toxicity of nanomaterials are discussed. The in situ applications of nanomaterials for contaminated site remediation are presented. It is concluded that the issues involving remediation of soils and groundwater are site specific and it is not possible to directly transfer knowledge gained from sedimentary soils of temperate climates for residual soils found in tropical and subtropical climate regions. The research on nanotechnology for site remediation in Brazil has just begun, and more efforts are required from the technical and academic professionals to develop nanotechnology as practical technology for the remediation of contaminated sites.

Relative displacement of bromide (Br⁻) and coliphage P22 was analyzed in surface water and vadose zone solution from a 3-ha surface flow constructed wetland. In the vadose zone, water samples at 0.3-, 0.76-, 1.5-, and 3-m depth were collected to quantify Br⁻ and P22 simultaneously added into the wetland influent for a transport study. When P22 was detected, Br⁻ arrived earlier to the monitoring depths than the phage suggesting that preferential flow facilitated P22 displacement in the vadose zone. Concentrations for both tracers indicated that bacteriophage removal through the vadose zone profile was exceeding 99.21 % of the peak concentration observed in surface water samples. For transport parameter estimation, the temporal moment method (MOM) was used to calculate convective velocity (v) and longitudinal dispersion coefficient (D) from the outlet Br⁻ breakthrough curve. The transport parameters were estimated to be 55.7 m day⁻¹ and 1652 m² day⁻¹ for v and D, respectively. For P22 simulation, a first-order removal coefficient of 0.3 day⁻¹ (R ² = 0.943) was assessed. The observed results suggest that this method can be applied for solute transport simulation in constructed wetlands.

Scallop shell-Fe₃O₄ nanoparticles were synthesized by co-precipitation and hydrothermal methods. The removal efficiency of RB5 was studied as a function of pH, adsorbent dosage, initial RB5 concentration, ionic strength, and temperature. Coating of Fe₃O₄ nanoparticles onto Scallop shell was identified by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and energy dispersive X-ray (EDX) analysis. Maximum adsorption was obtained at pH 3. The removal efficiency of RB5 was increased with increasing adsorbent dosage. However, it was decreased with increasing initial RB5 concentration, temperature and in the presence of any anions. Adsorption kinetic study revealed that the pseudo-second order model better described the removal rate than the pseudo-first order model and intra-particle diffusion model. Adsorption isotherm was analyzed by both Langmuir and Freundlich equation. Experimental result was well described by the Langmuir equation. Maximum adsorption capacity was estimated to be 1111.11 mg/g. Thermodynamic studies indicated that the adsorption of RB5 onto Scallop shell-Fe₃O₄ nanoparticles was an endothermic (∆H = 178.14 KJ mol⁻¹) process. The negative values of free energy (∆G) for the adsorption indicated that adsorption of RB5 was spontaneous reaction. Adsorption activity of RB5 by Scallop shell-Fe₃O₄ nanoparticles was maintained even after six successive cycles.

This paper presents the efficacy of zero-valent iron nanoparticles (ZVINs), magnetic iron oxide nanoparticles (MINs), zero-valent iron nanoparticles/sugarcane bagasse (ZVIN-SB) composite and magnetic iron oxide nanoparticles/sugarcane bagasse (MIN-SB) composite in immobilizing chromium present in tannery sludge. The optimized values for the immobilization of chromium by the adsorbents were found to be 48 h, 100 g/kg and 7, respectively, for time, adsorbent dosage and pH. The maximum uptake capacity was found to be 429.75, 539.25, 587.25 and 625.8 mg/kg, respectively, for ZVIN, MIN, ZVIN-SB and MIN-SB. The desorption study of the unamended sludge and sludge amended by ZVIN, MIN, ZVIN-SB and MIN-SB was carried out with three different desorbing media (0.1 N HCL, DIW and 0.1 N NaOH). It was found that the cumulative concentration of leachate chromium was more in basic condition than in neutral and acidic conditions. In column studies, the concentration of leachate chromium attained 0 mg/L at 24, 15, 18 and 14 pore volumes, respectively, for the sludge amended by ZVIN, MIN, ZVIN-SB and MIN-SB. The experimental adsorption data fitted well with pseudo-first-order kinetics. The zero-order kinetics accurately predicted the experimental desorption capacity (q ₑ) of the sludge amended by ZVIN, MIN, ZVIN-SB and MIN-SB. The Fourier transform infrared spectroscopy (FTIR) analysis showed that the amine, carboxyl, iron compounds, etc. present in the adsorbents were the chief causes for the immobilization of chromium. The X-ray diffraction (XRD) analysis of the sludge showed the presence of trivalent chromium compounds at a higher concentration.

The changes in the availability of selected elements (Ca, Mg, K, Al, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) 16 years after amphibolite treatment were studied in the root zone of spruce (40 and 80 cm from the stem base) using the diffusive gradient in thin film (DGT) technique. The effective concentrations of some of the tested elements significantly increased (Ca (34 %), Mg (31 %), K (65 %), Al (143 %), Fe (242 %), and Pb (27 %)) in 80 cm distance from the stem, whereas the total and the water-soluble concentrations of the elements did not differ from the control. The changes in effective concentrations of the elements in soil were related to higher vitality of the trees on amended soil in contrast to the control.

Long-term fire retardant (LTR) use for forest fire suppression and/or prevention purposes can result in chemical leaching, from soil to the drainage water, during the annual rainfall period. Also, wildland fires can have an impact on the leaching of various chemicals from treated forest soils. Large quantities of ions in leachates, mainly due to ammonium (one of the major LTR components) soil deposition, could affect the groundwater quality. The alteration of pH, total hardness (TH), and electrical conductivity (EC) values in leachates mainly due to nitrogen-based LTR application (Fire Trol 931) was investigated in this laboratory study. The values of pH, TH, and EC were measured in the resulting leachates from pots with forest soil and pine trees alone and in combination with fire after a simulated rainfall period. pH, TH, and EC values in leachates from all treated pots were significantly greater than those from control pots.

New porous carbonaceous adsorbents were prepared from an oily sludge generated in a fuel oil storage tank using pyrolysis with and without activation by KOH at 600 °C. The pore characteristics of the activated carbonaceous adsorbent (AC), due to the formation of micropores and mesopores structure, were considerably better than those of non-activated carbonaceous adsorbent (NA). The adsorption of Cd from aqueous solutions on the produced carbonaceous adsorbents was optimized using the Taguchi method. Under optimum conditions, the Cd adsorption efficiency for the NA and AC was obtained to be 77.7 and 98.2 %, respectively. The initial concentration and the adsorbent dose were the most significant factors affecting the removal of Cd by NA and AC, respectively. The adsorption data for the AC were well fitted by the Langmuir, Freundlich, and Redlich-Peterson isotherms models. The regeneration and reuse of the adsorbents in the three cycles of Cd adsorption-desorption were possible. The carbonaceous adsorbents had acceptable efficiency for the removal of Cd from a mine wastewater. Based on the obtained results, the oily sludges available in huge amounts in the petroleum industry proved to be a potential precursor resource for the production of the porous carbonaceous adsorbents, particularly for application in the wastewater treatment.

Under various abiotic stresses, plants overproduce reactive oxygen species (ROS) such as superoxide anion (O₂•⁻), hydroxyl radical (OH•), and hydrogen peroxide (H₂O₂). When in excess, these highly reactive molecules cause oxidative stress, thus damaging proteins, lipids, and DNA. Therefore, plants evolved an enzymatic defense machinery that involves such enzymes as superoxide dismutase (SOD), catalase (CAT), and ascorbate peroxidase (APOX). Various plant families, species and even specimens differ in their ability to withstand the abiotic stress. A study has been undertaken to assess the differences in response to trace metals between two species: a resistant hyperaccumulator Indiana mustard (Brassica juncea) and a metal-sensitive pea (Pisum sativum). We observed that trace elements (Cu, Zn, Cd, Pb) changed the activity of antioxidative enzymes (SOD, APOX, CAT) and the rate of ROS generation. However, in the control plants and at a point 0′ of the treatment, we have noticed a large disproportion in the hydrogen peroxide level, with B. juncea maintaining naturally higher H₂O₂level (up to 40 times higher). We believe that this may be a distinguishing trait common to plants being resistant to oxidative stress.

The remediation of metal-impacted soils requires either the enhanced mobility (and capture) of the target analytes or their effective complexation/immobilisation. In this study, a range of ameliorants (activated carbon, bonemeal, bentonite and CaSx (calcium polysulphide)) were compared to assess their effectiveness in immobilising metals in soils. In addition to chemical analysis (pH and trace element analysis), microbial biosensors were used to assess changes in the water-soluble biotoxicity of metals as a consequence of ameliorant dosing. Management of soil ameliorants requires an enhancement of K d (solid/solution partition coefficient) if soil leachate is to meet predefined environmental quality standards. Of the ameliorants tested, CaSx was the most effective per unit added for both laboratory-amended and historically contaminated soils, regardless of the metal tested. At the ameliorant concentrations used to effectively immobilise the metals, the biosensor performance was not impaired. Microbial biosensors offered a rapid and relevant screening tool to validate the reduced toxicity associated with the ameliorant dosing and could be calibrated to complement chemical analysis. While laboratory-amended soils were a logical way to evaluate the performance of the ameliorants, they were generally associated with K d values an order of magnitude lower than those of historically contaminated soils.