Biochar-Assisted Bioengineered Strategies for Metal Removal: Mechanisms, Key Considerations, and Perspectives for the Treatment of Solid and Liquid Matrixes

Biochar has drawn the scientific community’s attention during the last few years due to its low production value and unique physicochemical properties, which are helpful for numerous applications. The development of biotechnological processes for the remediation of heavy metal environmental pollution is one central research avenue in which biochar application has shown promising results, due to its positive effect on the bacteria that catalyze these activities. Biochar stimulates bacterial activity through adsorption, adhesion, electron transport, and ion exchange. However, before biochar implementation, a complete understanding of its potential effects is necessary, considering that those interactions between biochar and bacteria may help improve the performance of biological processes designed for the remediation of environmental pollution by metals, which has been historically characterized by limitations related to the recalcitrance and toxicity of these pollutants. In this review, the key biochar–microorganism interactions and properties of unmodified biochar with the potential to improve metal bioremediation in both solid (mine tailings, polluted soils) and liquid matrixes (metal-laden wastewaters) are summarized. Knowledge gaps regarding the mechanisms involved in remediation strategies, the effect of long-term biochar use and the development of improved biochar technologies and their combination with existent remediation technologies is summarized. Additionally, an up-to-date summary of the development of biochar-assisted bioengineered strategies for metal passivation or removal from solid and liquid matrixes is presented, along with key perspectives for the application of biochar-based biotechnologies at full scale during the treatment of mining effluents in the real scale

Impact of Soil Amendment with Biochar on Greenhouse Gases Emissions, Metals Availability and Microbial Activity: A Meta-Analysis

The effect of soil amendment with biochar has been widely evaluated for its effects in mitigating greenhouse gas emissions (GHG) and remediating polluted soils with metals; however, a synergic understanding of the system, including biochar, soil, and microbial activity, is lacking. In this study, a meta-analysis of 854 paired data from 73 studies demonstrate that biochar application in soil affects GHG emissions and soil metal availability. First, several properties of biochar, soil, and microbial activity were considered as parameters in the meta-analysis. Then, the size effect was evaluated using the percentage of change (Pc) as obtained by the meta-analyzed data. Several parameters were related as influencer factors in GHG emissions and soil metal availability. Notably, biochar addition in soil resulted in a significant CO2 increase in emissions, whereas N2O emissions decreased; these results were directly correlated with microbial activity. Although this trend, demonstrated by the data analysis, differs from results of other studies found in the literature, it also emphasized the need for a deep understanding of the effect of biochar addition to soil (properties, nutrients, gas exchange, etc.) and to microorganisms (activity, diversity, etc.). Furthermore, it was also proved, that soil metal concentration decreases significantly when biochar was added (Cd > Zn > Pb > Cu > Fe). According to the results, biochar addition in soils contaminated with Cd and Cu was related to an increase in the microbial activity; while, soils amended with biochar but polluted with Pb, Zn, and Fe presented a higher inhibition effect on microorganisms. To improve the interpretation of soil amendment with biochar, it would be necessary to standardize the form for reporting results, particularly of the microbial activity and GHG emissions, in order to be used for future comparative studies

Impact of Soil Amendment with Biochar on Greenhouse Gases Emissions, Metals Availability and Microbial Activity: A Meta-Analysis

The effect of soil amendment with biochar has been widely evaluated for its effects in mitigating greenhouse gas emissions (GHG) and remediating polluted soils with metals; however, a synergic understanding of the system, including biochar, soil, and microbial activity, is lacking. In this study, a meta-analysis of 854 paired data from 73 studies demonstrate that biochar application in soil affects GHG emissions and soil metal availability. First, several properties of biochar, soil, and microbial activity were considered as parameters in the meta-analysis. Then, the size effect was evaluated using the percentage of change (Pc) as obtained by the meta-analyzed data. Several parameters were related as influencer factors in GHG emissions and soil metal availability. Notably, biochar addition in soil resulted in a significant CO2 increase in emissions, whereas N2O emissions decreased; these results were directly correlated with microbial activity. Although this trend, demonstrated by the data analysis, differs from results of other studies found in the literature, it also emphasized the need for a deep understanding of the effect of biochar addition to soil (properties, nutrients, gas exchange, etc.) and to microorganisms (activity, diversity, etc.). Furthermore, it was also proved, that soil metal concentration decreases significantly when biochar was added (Cd > Zn > Pb > Cu > Fe). According to the results, biochar addition in soils contaminated with Cd and Cu was related to an increase in the microbial activity; while, soils amended with biochar but polluted with Pb, Zn, and Fe presented a higher inhibition effect on microorganisms. To improve the interpretation of soil amendment with biochar, it would be necessary to standardize the form for reporting results, particularly of the microbial activity and GHG emissions, in order to be used for future comparative studies

Direct and Quinone-Mediated Palladium Reduction by <i>Geobacter sulfurreducens:</i> Mechanisms and Modeling

Palladium­(II) reduction to Pd(0) nanoparticles by <i>Geobacter sulfurreducens</i> was explored under conditions of neutral pH, 30 °C and concentrations of 25, 50, and 100 mg of Pd­(II)/L aiming to investigate the effect of solid species of palladium on their microbial reduction. The influence of anthraquinone-2,6-disulfonate was reported to enhance the palladium reaction rate in an average of 1.7-fold and its addition is determining to achieve the reduction of solid species of palladium. Based on the obtained results two mechanisms are proposed: (1) direct, which is fully described considering interactions of amide, sulfur, and phosphoryl groups associated to proteins from bacteria on palladium reduction reaction, and (2) quinone-mediated, which implies multiheme c-type cytochromes participation. Speciation analysis and kinetic results were considered and integrated into a model to fit the experimental data that explain both mechanisms. This work provides elements for a better understanding of direct and quinone-mediated palladium reduction by <i>G. sulfurreducens</i>, which could facilitate metal recovery with concomitant formation of valuable palladium nanoparticles in industrial processes

Analysis of the Solar Pyrolysis of a Walnut Shell: Insights into the Thermal Behavior of Biomaterials

The state of Sonora, Mexico, stands as one of the leading producers of pecan nuts in the country, which are commercialized without shells, leaving behind this unused residue. Additionally, this region has abundant solar resources, as shown by its high levels of direct normal irradiance (DNI). This study contributes to research efforts aimed at achieving a synergy between concentrated solar energy technology and biomass pyrolysis processes, with the idea of using the advantages of organic waste to reduce greenhouse gas emissions and avoiding the combustion of conventional pyrolysis through the concentration of solar thermal energy. The objective of this study is to pioneer a new experimental analysis methodology in research on solar pyrolysis reactors. The two main features of this new methodology are, firstly, the comparison of temperature profiles during the heating of inert and reactive materials and, secondly, the analysis of heating rates. This facilitated a better interpretation of the observed phenomenon. The methodology encompasses two different thermal experiments: (A) the pyrolysis of pecan shells and (B) the heating–cooling process of the biochar produced in experiment (A). Additionally, an experiment involving the heating of volcanic stone is presented, which reveals the temperature profiles of an inert material and serves as a comparative reference with experiment (B). In this experimental study, 50 g of pecan shells were subjected to pyrolysis within a cylindrical stainless-steel reactor with a volume of 156 cm3, heated by concentrated radiation from a solar simulator. Three different heat fluxes were applied (234, 482, and 725 W), resulting in maximum reaction temperatures of 382, 498, and 674 °C, respectively. Pyrolysis gas analyses (H2, CO, CO2, and CH4) and characterization of the obtained biochar were conducted. The analysis of heating rates, both for biochar heating and biomass pyrolysis, facilitated the identification, differentiation, and interpretation of processes such as moisture evaporation, tar production endpoint, cellulosic material pyrolysis, and lignin degradation. This analysis proved to be a valuable tool as it revealed heating and cooling patterns that were not previously identified. The potential implications of this tool would be associated with improvements in the design and operation protocols of solar reactors

Efficient Malathion Removal in Constructed Wetlands Coupled to UV/H2O2 Pretreatment

Intensive agriculture has led to the increasing application of pesticides, such as malathion, thus generating large volumes of untreated cropland wastewater (CropWW). In this work, a hybrid system constructed wetlands (CW) coupled in continuous with an optimized UV/H2O2 pretreatment was evaluated for the efficient removal of malathion contained in CropWW. In the first stage, 90 min UV irradiation time (UV IR) and 65 mM hydrogen peroxide (H2O2) were identified as optimal operation parameters through a central composite design. The second stage consisted of CW planted with Phragmites australis collected from the agricultural discharge area and operated as a piston flow reactor. Furthermore, CW hydraulic residence times (HRT) of 1, 2 and 3 days, including hydraulic coupling, were evaluated. The removal efficiencies obtained in the first stage (UV/H2O2) were 94 &plusmn; 2.5% of malathion and 45 &plusmn; 2.5% of total organic carbon (TOC). In stage two (CW) 65 &plusmn; 9.6% TOC removal was achieved during the first 17 days, from which around 24% was associated to the biosorption of malathion byproducts. Subsequently, and until the operation ends, CW removed about 80% of TOC for 2 and 3 days HRT, with no significant differences (p &gt; 0.2), which is higher than those reported in several studies involving only advanced oxidation processes (AOP) with UV IR times above 240 min and even for systems using catalysts. The results obtained indicate that the system UV/H2O2-CW is a technically suitable option for the treatment of CropWW with a high content of malathion mainly found in developing countries. Moreover, the hybrid system proposed also represent significant reduction in the size of the treatment plant

Magnetic Biochar Obtained by Chemical Coprecipitation and Pyrolysis of Corn Cob Residues: Characterization and Methylene Blue Adsorption

Biochar is a carbonaceous and porous material with limited adsorption capacity, which increases by modifying its surface. Many of the biochars modified with magnetic nanoparticles reported previously were obtained in two steps: first, the biomass was pyrolyzed, and then the modification was performed. In this research, a biochar with Fe3O4 particles was obtained during the pyrolysis process. Corn cob residues were used to obtain the biochar (i.e., BCM) and the magnetic one (i.e., BCMFe). The BCMFe biochar was synthesized by a chemical coprecipitation technique prior to the pyrolysis process. The biochars obtained were characterized to determine their physicochemical, surface, and structural properties. The characterization revealed a porous surface with a 1013.52 m2/g area for BCM and 903.67 m2/g for BCMFe. The pores were uniformly distributed, as observed in SEM images. BCMFe showed Fe3O4 particles on the surface with a spherical shape and a uniform distribution. According to FTIR analysis, the functional groups formed on the surface were aliphatic and carbonyl functional groups. Ash content in the biochar was 4.0% in BCM and 8.0% in BCMFe; the difference corresponded to the presence of inorganic elements. The TGA showed that BCM lost 93.8 wt% while BCMFe was more thermally stable due to the inorganic species on the biochar surface, with a weight loss of 78.6%. Both biochars were tested as adsorbent materials for methylene blue. BCM and BCMFe obtained a maximum adsorption capacity (qm) of 23.17 mg/g and 39.66 mg/g, respectively. The obtained biochars are promising materials for the efficient removal of organic pollutants