Search Results (113)

Cobalt (Co) is an essential micronutrient for many organisms, but, at higher concentrations, it becomes harmful, primarily due to competitive interactions with other metal ions. Enzyme inhibition and disruption of nutrient homeostasis may lead to oxidative stress in Co-exposed cells. Compared to other heavy metals, such as Cd, Cu, Cr, Pb, or Ni, this element has been less studied in algae with respect to its toxicity and tolerance. Taking into account Co-induced oxidative stress and antioxidant response, the studies on algae usually did not cover a wider range of antioxidants and ROS-detoxifying enzymes monitored in one model. The aim of this study was to assess the impact of CoCl₂ on the model green microalga Chlamydomonas reinhardtii from a broader perspective. We monitored algal growth, photosynthetic pigment content, the maximum quantum yield of photosystem II (F_v/F_m), the efficiency of nonphotochemical quenching of chlorophyll fluorescence (NPQ), and oxidative stress markers (superoxide production, lipid peroxidation). The measured antioxidants included soluble thiols, ascorbate (Asc), proline (Pro), α-tocopherol (α-Toc), and plastoquinol (PQH₂-9). The superoxide dismutase (SOD), catalase (CAT), and ascorbate peroxidase (APX) activities were also determined. Exposure to CoCl₂ resulted in increased levels of thiols, Asc, α-Toc, PQH₂-9, and CAT activity. At lower concentrations of CoCl₂, no increase in oxidative stress markers was observed, suggesting efficient antioxidant protection. On the contrary, exposure to higher concentrations of CoCl₂ caused the inhibition of growth and chlorophyll (Chl) synthesis, as well as the reduction in the Chl a/Chl b ratio, the F_v/F_m parameter, the efficiency of NPQ induction, and the levels of lipophilic antioxidants, along with an increase in lipid hydroperoxides. An interesting and novel result is the inhibitory effect of Co toxicity on state transitions in exposed algae. Full article

Stingless bee cerumen is a mixture of wax and plant resins. Foragers of stingless bees are exposed to various chemical contaminants during their plant visits and collection activities. These contaminants have the potential to be transferred into the nest. This study aimed to elucidate the existence of chemical contaminants in Ecuadorian cerumen. To this end, the following aims were established: (i) to determine and quantify glyphosate (GLY), aminomethylphosphonic acid (AMPA), some other pesticides, metals and metalloids in cerumen and (ii) to establish possible risks associated with the presence of these chemical contaminants to the health of stingless bees and humans. The quantification of chemical contaminants was conducted using gas chromatography (GC), liquid chromatography (LC), and ion chromatography (IC) coupled to mass spectrometry (MS). Glyphosate (0.02–0.2 mg/kg) and AMPA (0.028 mg/kg) were detected in four of the pooled samples (n = 14) from the northern and southern highland regions. Other pesticide traces were not detected in any cerumen samples. Metals (Cd, Cr, Pb, Ni, Sn) and metalloids (As, Sb, Se) were found in all samples, including highlands and the lower Amazon. The potential risks of exposure to glyphosate and AMPA for stingless bees and humans appear to be minimal (except for the specific conditions given for Tetragonisca angustula) and safe, respectively. It seems that cerumen may serve as an effective biomonitoring matrix for assessing the environmental health of stingless bee nests. Establishing guidelines and regulations for the safe use and handling of products derived from the stingless bee consumption is therefore imperative. Full article

Next-generation recycling technologies must be urgently innovated to tackle huge volumes of spent batteries, photovoltaic panels or printed circuit boards (WPCBs). Current e-waste recycling industrial technology is dominated by traditional recycling technologies. Herein, ionic liquids (ILs), deep eutectic solvents (DESs) and promising oxidizing additives that can overcome some traditional recycling methods of metal ions from e-waste, used in our works from last year, are presented. The unique chemical environments of ILs and DESs, with the application of low-temperature extraction procedures, are important environmental aspects known as “Green Methods”. A closed-loop system for recycling zinc and manganese from the “black mass” (BM) of waste, Zn-MnO₂ batteries, is presented. The leaching process achieves a high efficiency and distribution ratio using the composition of two solvents (Cyanex 272 + diethyl phosphite (DPh)) for Zn(II) extraction. High extraction efficiency with 100% zinc and manganese recovery is also achieved using DESs (cholinum chloride/lactic acid, 1:2, DES 1, and cholinum chloride/malonic acid, 1:1, DES 2). New, greener recycling approaches to metal extraction from the BM of spent Li-ion batteries are presented with ILs ([N_8,8,8,1][Cl], (Aliquat 336), [P_6,6,6,14][Cl], [P_6,6,6,14][SCN] and [Benzet][TCM]) eight DESs, Cyanex 272 and D2EHPA. A high extraction efficiency of Li(I) (41–92 wt%) and Ni(II) (37–52 wt%) using (Cyanex 272 + DPh) is obtained. The recovery of Ni(II) and Cd(II) from the BM of spent Ni-Cd batteries is also demonstrated. The extraction efficiency of DES 1 and DES 2, contrary to ILs ([P_6,6,6,14][Cl] and [P_6,6,6,14][SCN]), is at the level of 30 wt% for Ni(II) and 100 wt% for Cd(II). In this mini-review, the option to use ILs, DESs and Cyanex 272 for the recovery of valuable metals from end-of-life WPCBs is presented. Next-generation recycling technologies, in contrast to the extraction of metals from acidic leachate preceded by thermal pre-treatment or from solid material only after thermal pre-treatment, have been developed with ILs and DESs using the ABS method, as well as Cyanex 272 (only after the thermal pre-treatment of WPCBs), with a process efficiency of 60–100 wt%. In this process, four new ILs are used: didecyldimethylammonium propionate, [N_10,10,1,1][C₂H₅COO], didecylmethylammonium hydrogen sulphate, [N_10,10,1,H][HSO₄], didecyldimethylammonium dihydrogen phosphate, [N_10,10,1,1][H₂PO₄], and tetrabutylphosphonium dihydrogen phosphate, [P_4,4,4,4][H₂PO₄]. The extraction of Cu(II), Ag(I) and other metals such as Al(III), Fe(II) and Zn(II) from solid WPCBs is demonstrated. Various additives are used during the extraction processes. The Analyst 800 atomic absorption spectrometer (FAAS) is used for the determination of metal content in the solid BM. The ICP-OES method is used for metal analysis. The obtained results describe the possible application of ILs and DESs as environmental media for upcycling spent electronic wastes. Full article

This study investigates the potential of biochars derived from agricultural waste biomass for the removal of heavy metal ions from aqueous solutions. Biochars were produced via slow pyrolysis at 793 K using almond shells (AS), walnut shells (WS), pistachio shells (PS), and rice husks (RH) as feedstocks. The physicochemical properties and adsorption performance of the resulting materials were evaluated with respect to Cd(II), Mn(II), Co(II), Ni(II), Zn(II), total Iron (Fe_tot), total Arsenic (As_tot), and total Chromium (Cr_tot) in model solutions. Surface morphology, porosity, and surface chemistry of the biochars were characterized by scanning electron microscopy (SEM), nitrogen adsorption at 77 K (for specific surface area and pore structure), Fourier-transform infrared spectroscopy (FTIR), and determination of the point of zero charge (pH_pzc). Based on their textural properties, biochars derived from WS, PS, and AS were classified as predominantly microporous, while RH-derived biochar exhibited mesoporous characteristics. The highest Brunauer–Emmett–Teller (S_BET) surface area was recorded for PS biochar, while RH biochar showed the lowest. The pistachio shell biochar exhibited the highest specific surface area (440 m²/g), while the rice husk biochar was predominantly mesoporous. Batch adsorption experiments were conducted at 25 °C, with an adsorbent dose of 3 g/L and a contact time of 24 h. The experiments in multicomponent systems revealed removal efficiencies exceeding 87% for all tested metals, with maximum values reaching 99.9% for Cd(II) and 97.5% for Fe_tot. The study highlights strong correlations between physicochemical properties and sorption performance, demonstrating the suitability of these biochars as low-cost sorbents for complex water treatment applications. Full article

Waste tobacco stems from the tobacco industry were used to obtain activated carbon by thermal conversion and chemical activation with KOH. The aim was to investigate its adsorption ability towards Zn(II), Cd(II), and Pb(II) from aqueous solutions. Fundamental physical and chemical properties were investigated, and the point of zero charge pH was detected. The results showed that the obtained activated carbon was characterized by a high specific surface area, pore volume, and negative surface charge, which could make it an efficient metal adsorbent. In the next step, the optimal adsorption conditions were determined using Central Composite Design. Finally, the adsorption kinetics and thermodynamics were studied. The adsorption rate is very high for Pb(II) and Cd(II), whereas it is noticeably lower for Zn(II). The negative value of Gibbs free energy change (∆G) confirmed that the adsorption process of the tested metal ions is feasible and proceeds spontaneously. The thermodynamics indicate that the adsorption of zinc and lead on the tested carbon is an exothermic process, and for cadmium, this process is endothermic. Full article

This study investigates the simultaneous adsorption of Pb(II), Cu(II), Cd(II), and Zn(II) ions from aqueous solutions using Urtica dioica leaves (UDLs) modified with sulfuric acid, followed by heat treatment to enhance adsorptive properties. The heat treatment significantly increased the adsorbent’s specific surface area to 451.93 m²·g⁻¹. Batch adsorption experiments were performed to determine the influence of the contact time, pH of the aqueous solution, adsorbent dosage, temperature, and initial metal concentration on the adsorption efficiency. The material (modified UDLs) was characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS). Maximum removal efficiencies were determined as 99.2%, 96.4%, 88.7%, and 83.6% for Pb(II), Cu(II), Cd(II), and Zn(II) ions, respectively. Adsorption isotherms and kinetics revealed that the process follows the Langmuir equation and pseudo-second-order models, indicating monolayer adsorption and chemisorption mechanisms. Furthermore, thermodynamic analysis indicated that the adsorption processes are spontaneous and endothermic in nature. The influence of competing ions on the adsorption of multiple heavy metals was also discussed. The results suggest that sulfuric acid and heat-treated Urtica dioica leaves can offer a promising, low-cost, and eco-friendly adsorbent for removing heavy metal ions from contaminated water. Full article

The newly discovered Erdaodianzi gold deposit in southern Jilin Province, Northeast China, is located in the eastern segment of the northern margin of the North China Craton (NCC). It is a large-scale gold deposit with reserves of 38.4 tons of gold. Gold mineralization in the ore district primarily occurs in gold-bearing quartz–sulfide veins. The gold ore occurs mainly as vein, veinlet, crumby, and disseminated structures. The hydrothermal process can be divided into three stages: stage I, characterized by quartz, arsenopyrite, and pyrite; stage II, featuring quartz, arsenopyrite, pyrite, pyrrhotite, chalcopyrite, sphalerite, and native gold; and stage III, consisting of quartz, pyrite, sphalerite, galena, electrum (a naturally occurring Au–Ag alloy), and calcite. Electrum and native gold primarily occur within the fissures of the polymetallic sulfides. To determine the enrichment mechanism of the Au element and the genetic types of ore deposits in the Erdaodianzi deposit, sourcing in situ trace element data, element mapping and sulfur isotope analysis were carried out on sphalerites from different stages using LA-ICP-MS. Minor invisible gold, in the form of Au–Ag alloy inclusions, is present within sphalerites, as revealed by time-resolved depth profiles. The LA-ICP-MS trace element data and mapping results indicate that trivalent or quadrivalent cations, such as Sb³⁺ and Te⁴⁺, exhibit a strong correlation with Au. This correlation can be explained by a coupled substitution mechanism, where these cations (Sb³⁺ and Te⁴⁺) replace zinc ions within the mineral structure, resulting in a strong association with Au. Similarly, the element Pb exhibits a close relationship with Au, which can be attributed to the incorporation of tetravalent cations like Te⁴⁺ into the mineral structure. The positive correlation between Hg and Au can be attributed to the formation of vacancies and defects within sphalerite, caused by the aforementioned coupled substitution mechanism. A slight positive relationship between Au and other divalent cations, including Fe²⁺, Mn²⁺, and Cd²⁺, may result from these cations simply replacing Zn within the sphalerite lattice. The crystallization temperatures of the sphalerite, calculated via the Fe/Zn ratio, range from 238 °C to 320 °C. The δ³⁴S values are divided into two intervals: one ranging from −1.99 to −1.12‰ and the other varying from 10.96 to 11.48‰. The sulfur isotopic analysis revealed that the ore-forming materials originated from magmatic rock, with some incorporation of metamorphic rock. Comparative studies of the Erdaodianzi gold deposit and other gold deposits in the Jiapigou–Haigou gold belt have confirmed that they are all mesothermal magmatic–hydrothermal lode gold deposits formed at the subduction of the Paleo-Pacific Plate beneath the Eurasian Plate during the Middle Jurassic. The Jiapigou–Haigou gold belt extends northwest to the Huadian area of Jilin province. This suggests potential for research on gold mineralization in the northwest of the belt and indicates a new direction for further gold prospecting in the region. Full article

This article presents a study of cadmium removal from nitrate medium using adsorption in calcined mesoporous silica (MCM-C), mesoporous silica doped (MCM_DIOPA), and calcined and impregnated mesoporous silica (MCM@DIOPA), with diisooctylphosphinic acid (DIOPA). The sorbents were synthesized via a sol–gel method. Several characterization techniques, such as XRD, FTIR spectroscopy, N₂ sorption and elemental analysis, have been used to determine the main structural, textural, and chemical properties of prepared sorbents. Batch adsorption and kinetics tests were carried out, where the influence of pH and contact time of the sorbents and their role in cation removal were studied. Experimental results show poor sorption efficiencies with MCM-C and MCM_DIOPA at pH 5.85. At the same pH, better cadmium extraction was attained by MCM@DIOPA and was achieved within 30 min. The pseudo-second-order model is the most appropriate model to describe the elimination mechanism of Cd(II) ions. The Langmuir equation was used to model the sorption isotherm and the maximum sorption capacity of Cd(II) is 22.16 mg/g (200 mmol/kg). The complex type of the probable extracted species isCdL2-HL. Full article

The aim of this research was to synthesize alginate beads. The beads were modified with a mixture of three different species of algae. Both synthesized beads were evaluated for the efficiency of Cd(II) removal from aqueous solutions as one of the currently most sustainable metal removal methods. The focus was on the characterization of synthesized beads and their stability. The characterization was performed using Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The specific surface area was determined. Cd(II) ion standard solutions were brought into contact with unmodified and modified beads. The experimental results showed that the most influential factors on biosorption are pH value and temperature. The maximum biosorption of Cd(II) ions was achieved at 181.0 mg/g. Kinetic and thermodynamic studies were carried out. The data obtained followed pseudo-second-order kinetics. Full article

The study proposed the use of aspen wood sawdust and biochar derived from this sawdust for the removal of Pb(II), Cd(II), and Cr(VI) ions from soil in systems containing single metals as well as a mixture of all the studied metals. The effectiveness of the applied sorbents was compared with the sorptive properties of activated carbon. The results showed that all the tested materials reduced the metal content in the soil, and the obtained biochar was able to sorb lead, cadmium, and chromium ions in both studied systems. The influence of the type of sorbent, its dose, process duration, and the impact of metal on the removal efficiency and sorption capacity was analyzed. A statistical analysis of the obtained results was also conducted, determining the influence of process parameters on the removal capabilities of metal ions. The highest Pb, Cd and Cr ion removal efficiencies were obtained in a 36-day process at a sorbent dose of 10%. Aspen sawdust, biochar and activated carbon removed 46%, 50% and 71% of Pb(II), 35%, 43% and 53% of Cd(II) and 15%, 27% and 38% of Cr(VI), respectively. In turn, the highest sorption capacity values were achieved in a 36-day process at a sorbent dose of 2%, obtaining results of 20.2 mg/g, 22.3 mg/g and 23.2 mg/g of Pb(II), 5.1 mg/g, 7.9 mg/g and 11.7 mg/g of Cd(II) and 3.8 mg/g, 5.8 mg/g and 8.5 mg/g of Cr(VI), respectively. It was found that both raw aspen wood sawdust and biochar derived from this wood are effective in removing toxic metal ions from soil, which presents a potential solution to their presence in the natural environment. Full article

This study aimed to investigate the efficacy of biochar, produced from different agricultural residues varying in lignin and cellulose content and subjected to different pyrolysis temperatures, in removing cadmium ions (Cd (II)) from an aqueous solution. This removal process is crucial for protecting human health and the environment. Specifically, the study focused on the adsorption behaviors of Cd (II) by the biochars made from rice husk biochar (RHB), maize straw biochar (MSB), peanut shell biochar (PSB), cottonseed shell biochar (CHB), and mulberry leaf biochar (MLB), which were prepared at 300 °C and 600 °C. The results indicated that the type of agricultural residue used to produce biochar significantly influenced the adsorption of Cd (II). Notably, mulberry leaf biochar prepared at 300 °C (MLB-300) demonstrated the highest adsorption efficiency, achieving a maximum adsorption capacity of 42.2 mg g⁻¹. Batch adsorption experiments assessed the impact of various factors, including system pH, NO₃⁻ concentration, and adsorption duration. The adsorption kinetics were better described by the pseudo-second-order model than the pseudo-first-order model. Moreover, the study found that the lignin content of the biochar plays a major role in determining the adsorption capacity. The surface characteristics of biochar, influenced by the types of agricultural residues and preparation temperature, directly impact its adsorption mechanism and capacity. While biochar produced at 300 °C showed optimal Cd(II) adsorption, those processed at 600 °C were less effective, likely due to the loss of functional groups at higher temperatures. Full article

Cadmium (Cd) and zinc (Zn) in seawater enter the human body through the food chain. Combined toxicity tests indicated that high concentrations of Cd(II) and low concentrations of Zn(II) had a synergistic effect on humans. Thus, there is an urgent need to prepare a sensor for rapid and simultaneous detection of Cd(II) and Zn(II) in seawater. Herein, a reduced graphene oxide/carboxylated multi-walled carbon nanotube (rGO/MWCNT-COOH)-modified glassy carbon electrode was prepared in the experiments using the dropping method. The synthesis of various materials achieved the purpose of expanding the surface area, and scanning electron microscopy was used to observe the structure of the composite membrane. Moreover, the large number of functional groups on the surface of the composite membrane can also increase the adsorption of ions. For the determination of trace cadmium (II) and zinc (II) in seawater, the method used was differential pulse voltammetry (DPV). The results show that the peak current, which was obtained in the range of 5–400 μg/L for Cd(II) and Zn(II), has a linear relationship with concentration, corresponding to the detection limits of 0.8 μg/L for Cd(II) and 0.98 μg/L for Zn(II). The modified electrode was used to determine the Cd(II) and Zn(II) content in the coastal seawater of the Maowei Sea, and the recovery rate was between 95.8 and 98.2% for Cd(II) and 96.7~99.4% for Zn(II), which provided a novel approach of detection to define trace Cd(II) and Zn(II) in seawater. Full article

The aim of the research was to prepare silica adsorbents using an environmentally friendly pathway, a template synthesis with saponin biosurfactant as a structure-directing agent. The adsorbents prepared in this way exhibit improved adsorption properties while maintaining environmental innocuousness. For the preparation of porous silica, the biosurfactant template sol–gel method was used with tetraethoxysilane as a silica precursor. The silica adsorbents were analyzed by FTIR spectroscopy, nitrogen adsorption–desorption and SEM/EDX microscopy, TEM/HRTEM microscopy, and thermogravimetric analyses. Batch tests were carried out to remediate Pb(II)/Cd(II) ions in single/binary aqueous solutions, and the effect of the surfactant on the adsorption properties was assessed. The optimal adsorption parameters (pH, contact time, initial concentration of metal ions) have been determined. The adsorption was fitted using Langmuir and Freundlich adsorption isotherms and kinetic models. Mathematical modeling of the retention process of Pb(II) and Cd(II) ions from binary solutions indicated a competitive effect of each of the two adsorbed metal ions. The experimental results demonstrated that saponin has the effect of modifying the silica structure through the formation of pores, which are involved in the retention of metal ions from aqueous solutions and wastewater. Full article

The adsorption of Pb(II) and Cd(II) on three commercial microporous activated carbons was analysed. Adsorption kinetics and statistics were investigated, and the results were described with different models. The highest values of the correlation coefficient R² were obtained for the pseudo-second-order kinetics model for all ions tested and all sorbents used. The adsorption process was found to be determined by both diffusion in the liquid layer and intraparticle diffusion. The adsorption equilibrium is very well described by Langmuir, Temkin, Thoth or Jovanovic isotherm models. Based on the values of n from the Freundlich isotherm and K_L from the Langmuir isotherm, the adsorption of cadmium and lead ions was found to be favourable. The highest monolayer capacities were obtained during the adsorption of lead ions (162.19 mg/g) and for cadmium (126.34 mg/g) for activated carbon WG-12. This carbon is characterised by the highest amount of acid functional groups and the largest specific surface area. The adsorption efficiency of the tested ions from natural water is lower than that from a model solution made from deionised water. The lowest efficiencies are obtained when the process occurs from highly mineralised water. Full article

Antimicrobial peptides are short cationic peptides that are present on biological surfaces susceptible to infection, and they play an important role in innate immunity. These peptides, like other compounds with antimicrobial activity, often have significant superoxide dismutase (SOD) activity. One direction of our research is the characterization of peptides modeling the CuZnSOD enzyme and the determination of their biological activity, and these results may contribute to the development of novel antimicrobial peptides. In the framework of this research, we have synthesized 10, 15, and 16-membered model peptides containing the amino acid sequence corresponding to the Cu(II) and Zn(II) binding sites of the CuZnSOD enzyme, namely the Zn(II)-binding HVGD sequence (80–83. fragments), the Cu(II)-binding sequence HVH (fragments 46–48), and the histidine (His63), which links the two metal ions as an imidazolate bridge: Ac-FHVHEGPHFN-NH₂ (L¹(10)), Ac-FHVHAGPHFNGGHVG-NH₂ (L²(15)), and Ac-FHVHEGPHFNGGHVGD-NH₂ (L³(16)). pH-potentiometric, UV-Vis-, and CD-spectroscopy studies of the Cu(II), Zn(II), and Cu(II)-Zn(II) mixed complexes of these peptides were performed, and the SOD activity of the complexes was determined. The binding sites preferred by Cu(II) and Zn(II) were identified by means of CD-spectroscopy. From the results obtained for these systems, it can be concluded that in equimolar solution, the –(NGG)HVGD- sequence of the peptides is the preferred binding site for copper(II) ion. However, in the presence of both metal ions, according to the native enzyme, the -HVGD- sequence offers the main binding site for Zn(II), while the majority of Cu(II) binds to the -FHVH- sequence. Based on the SOD activity assays, complexes of the 15- and 16-membered peptide have a significant SOD activity. Although this activity is smaller than that of the native CuZnSOD enzyme, the complexes showed better performance in the degradation of superoxide anion than other SOD mimics. Thus, the incorporation of specific amino acid sequences mimicking the CuZnSOD enzyme increases the efficiency of model systems in the catalytic decomposition of superoxide anion. Full article