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The separation and recovery of pollutant-loaded magnetic carbon materials from organic contaminated environment is recently concerned, but the change of sorption ability and mechanism of activated carbon and biochar caused by magnetic particles modification still need to be explored. Here, the magnetic modification of two coconut shell-, coal-derived activated carbon and one biochar, and its effect on the removal of phenol from water were investigated. Magnetic activated carbon (MAC) and magnetic biochar (MBC) were prepared by co-precipitation. The increase of mass magnetic susceptibilities and energy dispersive X-ray spectroscopy (EDX) analysis showed that magnetic particles were successfully coated on the surface of virgin carbonaceous materials (VCMs). Magnetic modification enhanced the surface area and pore volume of activated carbon, and preserved those structure properties of biochar. Magnetic activated carbon had lower adsorption rates (10.641 g mg−1·min−1) than virgin activated carbon (20.575 g mg−1·min−1) while magnetic biochar exhibited higher adsorption rate (0.618 g mg−1·min−1) compared with virgin biochar (0.040 g mg−1·min−1), which were related to mass transport process. Data from Langmuir model results suggested that maximum adsorption capacities of three carbon adsorbents were increased by magnetic modification. The enhanced removal of phenol after magnetizing process may attribute to the increase of specific surface area and pore volume. Among VCMs/MCCs, magnetic coconut shell-derived carbon material with 951.84 m2/g surface area exhibited the most organic contaminant sorption performance. This finding gives insight into the adsorption mechanism of magnetic AC/BC for phenol, and provides a guidance to choose the appropriate magnetic composites to remove the organic contaminant effectively.

Metal oxide-Carbon composites have aroused great interesting towards specific anionic contaminants removal from the polluted environment. In this study, aiming at removing toxic chromate ion [Cr(VI)] from aqueous solutions, a novel approach was developed to produce surface-enhanced MgO-coated biochar adsorbent from sugarcane harvest residue (SHR). It was found that sulfuric acid hydrolysis and MgO-coating both facilitated the removal of Cr(VI) by biochars, and the maximum sorption capacities for the pristine biochar (SHR550), MgO-coated biochar (MgSHR550), and acid-assisted MgO-coated biochar (MgASHR550) that derived from the Langmuir isotherm model were 20.79, 54.64, and 62.89 mg g−1, respectively. Additionally, the Cr(VI) removal was a pseudo-second-order kinetic model controlled process with equilibrium reached within 24 h. The mechanism investigation revealed that Cr(VI) ions was directly sorbed by the MgO-coated biochars via the chemical interaction between MgO and Cr(VI), whereas the sorption-coupled reduction of Cr(VI) to Cr(III) governed the sorption of Cr(VI) on the SHR550. Although the increases of solution pH (>2.0) and KNO3 concentration (>0.05 mol L−1) reduced the Cr(VI) removal by biochars, while there were lower secondary pollution risks in MgO-coated biochar treatments due to the suppressed release of Cr(III) in solutions. This work could provide guidance for the production of efficient biochar for the removal of Cr(VI) from wastewater.

In this study, we investigated the feasibility on the utilization of coffee husk as biosorbents for the removal of heavy metal ions such as Pb2+ and Cd2+ from wastewater. Biochar was produced from coffee wastes and modified with sodium hydroxide to create functional groups on the surface and increase the specificic surface area. The resultant products were characterized by using various analytical methods such as scanning electron microscopy, specific area, surface functional group and zeta potential analysis. The as-prepared materials were employed as adsorbent to remove Pb2+ and Cd2+ ions from wastewater. The maximum sorption capacities of biosorbents were measured to be 116.3 and 139.5 mg g−1 for Cd2+ and Pb2+, respectively, which is comparable to the conventional adsorbents. Kinetic studies showed that the sorption of Pb2+ and Cd2+ on biosorbents can be described by the Freundlich isotherm and second-order kinetic model. The coffee husk-derived biosorbent was capable of removing 89.6% of Pb2+ and 81.5% Cd2+ ions from wastewater, and therefore can be considered as low-cost and efficient adsorbent to remove heavy metal ions from wastewater.

Biochar has received great attention as a biosorbent, but explanations of the underlying sorption mechanisms are still unclear. Here, batch sorption of cadmium (Cd(II)) and arsenate (As(V)) to Miscanthus biochar at different pH values and pyrolysis temperatures and the sorption mechanisms were comprehensively investigated. The maximum sorption capacities for both Cd(II) and As(V) were observed under alkaline conditions. Physisorption was identified as a common sorption mechanism for both Cd(II) and As(V) irrespective of pH; however, inner-sphere complexation with acidic functional groups (AFGs) and crystallized precipitation as otavite predominate at higher pH values for Cd(II), while hydrophobic attraction of arsenite and metallic As and electrostatic bridging with multivalent ions at deprotonated AFGs are presumed to be dominant sorption mechanisms for As(V). Inner-sphere complexes of Cd(II) (98.6%) and electrostatic bridging complexes of As(V) (89.5%) were the dominant sorption forms for B400, while inner-sphere complexes (45.9%) and precipitates (50.5%) of Cd(II) and physisorption and hydrophobic interactions of As (63.7%) were abundant. The results challenge the widely held notion that the sorption of anions decreases as pH increases, while that of cations increases with increasing pH. This unexpected phenomenon can be explained by reduction of As(V) and by the difference in the charge densities between As(V) and basic functional groups of the biochar. Such biochar-induced reduction would cause an unexpected risk of exposing human health and ecosystems to reduceable pollutants. These findings contribute to a better explanation for the environmental fate and behavior of inorganic pollutants in biochar applications.

Invasive plants pose a significant threat to natural ecosystems because of their high adaptability, rapid propagation and spreading ability in the environment. In this study, a typical aquatic invasive plant, Pistia stratiotes, was chosen as a novel feedstock for the preparation of nitrogen-doped biochars (NBs) for the first time, and the NBs were used as efficient sorbents to remove phthalate esters (PAEs) from aqueous solution. Characterization results showed that NBs possess great pore structure (up to 126.72 m2 g−1), high nitrogen (2.02%–2.66%) and ash (24.7%–34.1%) content, abundant surface functional groups, hydrophobicity and a graphene structure. Batch sorption experiments were performed to investigate the sorption performance, processes and mechanisms. The capacities for PAEs sorption onto NBs were high, especially with NBs pyrolyzed at 700 °C, ranging up to 161.7 mg g−1 for diethyl phthalate and 85.4 mg g−1 for dibutyl phthalate; these levels were better than many reported for other sorbents. With kinetic and isotherm results, Pseudo-second order and Freundlich models fit the sorption data well, and chemical interactions involving hydrogen bonding, Lewis acid-base interaction, functional group interaction, cation-π interaction and π-π stacking interaction were identified as possible rate-limited steps. Moreover, Intra-particle diffusion and Dubinin-Radushkevich models indicated that multiple pore filling and partitioning dominated the process of PAEs sorption onto NBs. This study opens the door for new methods of pollution control with waste treatment, since invasive plant biomass resources were converted into advanced biochars for efficient environmental remediation.

In this study, Levenberg Marquardt back propagation algorithm was used to train the Artificial Neural Network (ANN) and to predict the adsorptive removal of cationic dye Basic Violet 03 (BV03) by biochar derived from biowaste of groundnut hull. The experimental conditions such as solution pH, biochar dose, initial dye concentration, contact time and temperature were used as input variables and BV03 percentage removal as target. The hidden and the output layer of the network was trained by tangent sigmoid and liner transfer functions. The feasibility of the adsorption process is evaluated by the kinetic studies and it exhibited that pseudo-second order kinetic models fit well with experimental data. The adsorbent stability and adsorption mechanism has been discoursed by the thermodynamic characteristics and sorption free energy. The predicted target values were compared with the experiment resulted in a better correlation coefficient of 0.9920. Thus, the results attained from this ANN model was found to be effective in predicting the percentage removal of BV03 dye at any given operating condition.

Heavy metals in water and wastewater are taken into account as one of the most hazardous environmental issues that significantly impact human health. The use of biochar systems with different materials helped significantly remove heavy metals in the water, especially wastewater treatment systems. Nevertheless, heavy metal's sorption efficiency on the biochar systems is highly dependent on the biochar characteristics, metal sources, and environmental conditions. Therefore, this study implicates the feasibility of biochar systems in the heavy metal sorption in water/wastewater and the use of artificial intelligence (AI) models in investigating efficiency sorption of heavy metal on biochar. Accordingly, this work investigated and proposed 20 artificial intelligent models for forecasting the sorption efficiency of heavy metal onto biochar based on five machine learning algorithms and bagging technique (BA). Accordingly, support vector machine (SVM), random forest (RF), artificial neural network (ANN), M5Tree, and Gaussian process (GP) algorithms were used as the key algorithms for the aim of this study. Subsequently, the individual models were bagged with each other to generate new ensemble models. Finally, 20 intelligent models were developed and evaluated, including SVM, RF, M5Tree, GP, ANN, BA-SVM, BA-RF, BA-M5Tree, BA-GP, BA-ANN, SVM-RF, SVM-M5Tree, SVM-GP, SVM-ANN, RF-M5Tree, RF-GP, RF-ANN, M5Tree-GP, M5Tree-ANN, GP-ANN. Of those, the hybrid models (i.e., BA-SVM, BA-RF, BA-M5Tree, BA-GP, BA-ANN, SVM-RF, SVM-M5Tree, SVM-GP, SVM-ANN, RF-M5Tree, RF-GP, RF-ANN, M5Tree-GP, M5Tree-ANN, GP-ANN) are introduced as the novelty of this study for estimating the heavy metal's sorption efficiency on the biochar systems. Also, the biochar characteristics, metal sources, and environmental conditions were comprehensively assessed and used, and they are considered as a novelty of the study as well. For this aim, a dataset of sorption efficiency of heavy metal was collected and processed with 353 experimental tests. Various performance indexes were applied to evaluate the models, such as RMSE, R2, MAE, color intensity, Taylor diagram, box and whiskers plots. This study's findings revealed that AI models could predict heavy metal's sorption efficiency onto biochar with high reliability, and the efficiency of the ensemble models is higher than those of individual models. The results also reported that the SVM-ANN ensemble model is the most superior model among 20 developed models. The predictive model proposed that heavy metal's efficiency sorption on biochar can be accurately forecasted and early warning for the water pollution by heavy metal.

In order to successfully apply biochar to soil remediation such as immobilizing contaminants and sequestering carbon, the prerequisite is to maintain its strong sorption capacity for contaminants and stability after long-term aging. Simulated diagenesis was performed here to mimic real geochemical aging process of biochars with different mineral content. The results showed that biochars exhibited increasing aromaticity, thermal and chemical oxidation resistance, microporosity, but declined surface and total polarity after direct diagenesis. The involvement of minerals during diagenesis further increased the surface Fe, Al, and Si content, as well as surface polarity and thermal stability compared to direct diagenesis. Other property changes induced by mineral involvement were dependent on original biochar structure and mineral type. Diagenetic treatment slightly improved the sorption capacity of 450 and 600 °C biochars, regardless of mineral amendment. Only marginal effects were observed relating to their sorption capacity, while the structure of 250 °C biochars was most profoundly affected during diagenesis. Consequently, the simulated geochemical aging had positive effects on biochars long-term stability and ability to immobilize pollutants.

Pb, Ni, and Co are among the most toxic heavy metals that pose direct risks to humans and biota. There are no published studies on biochars produced at low temperatures (i.e., 300 °C), which possess high sorption capacity for heavy metal remediation and reclamation of contaminated sandy soils. This research studied the effect of catalytic microwave pyrolysis of switchgrass (SG) using bentonite and K3PO4 to produce biochar at low temperature (300 °C) with high sorption capacity for reducing the phytotoxicity of heavy metals, and investigated the synergistic effects of catalyst mixture on biochar sorption capacity. The quality of the biochars was examined in terms of their impacts on plant growth, reducing phytotoxicity and uptake of heavy metals in sandy soil spiked with Pb, Ni, and Co. All catalysts increased the micropore surface area and cation-exchange capacity of biochars, and resulted in biochars rich in plant nutrients, which not only decreased heavy metal phytotoxicity, but also boosted plant growth in the spiked soil by up to 140% compared to the sample without biochar. By mixing bentonite and K3PO4 with SG during microwave pyrolysis, the efficacy of biochar in reducing phytotoxicity and heavy metals uptake was further enhanced because of the highest micropore surface area (402 m2/g), moderate contents of Ca, Mg, K, and Fe for ion-exchange and moderate concentration of phosphorus for the formation of insoluble heavy metal compounds. Generally, the biochar created at 300 °C (300-30KP) showed similar performance to the biochar created at 400 °C (400-30KP) in terms of reducing heavy metal bioavailability.

Sandy soils in Florida are vulnerable to toxic metal pollution, and it is necessary to identify desirable amendments for the remediation of metal contaminated soils. Sorption and incubation experiments were conducted to compare the effectiveness of dolomite phosphate rock (DPR), humic acid activated dolomite phosphate rock (ADPR) and biochar (BC) in immobilizing Cd2+ and Pb2+ in two representative agricultural soils in south Florida (Alfisol-Riviera and Spodosol -Ankona series). The results showed that the soils had a low sorption capacity for metals with maximum sorption of 0.767–3.30 mg/g. Application of amendments increased the maximum sorption by 4.2–4.8 times for Pb2+ and 1.5–2.2 times for Cd2+ in Alfisol soil, and 7.1–7.9 times for Pb2+ and 1.7–3.1 times for Cd2+ in Spodosol soil. ADPR was the most effective amendment for increasing the soil’s sorption capacity for Cd2+ and Pb2+. 0.01 M CaCl2 extractable metals in the contaminated soils were significantly decreased by all the amendments, especially ADPR, which reduced extractable Cd2+ and Pb2+by 87.2 and 76.0% in Alfisol and 91.3 and 76.3% in Spodosol soil as compared to control. The amounts of extractable Cd2+ and Pb2+ were negatively correlated with soil pH and available P, indicating that the change of soil characteristics by amendments was the dominant mechanism for enhanced immobilization of metals in the contaminated soils. These results indicate that ADPR has great potential for remediating toxic levels of Cd2+ and Pb2+ in contaminated soils.

Unique zerovalent iron (Fe0) supported on biochar nanocomposite (Fe0-BRtP) was synthesized from Nephelium lappaceum (Rambutan) fruit peel waste and were applied for the simultaneous removal of 6 selected organochlorine pesticides (OCPs) from aqueous medium. During facile synthesis of Fe0-BRtP, Rambutan peel extract was used as the green reducing mediator to reduce Fe2+ to zerovalent iron (Fe0), instead of toxic sodium borohydride which were used for chemical synthesis. For comparison, chemically synthesized Fe0-BChe nanocomposite was also prepared in this work. Characterization study confirmed the successful synthesis and dispersion of Fe0 nanoparticles on biochar surface. Batch experiments revealed that Fe0-BRtP and Fe0-BChe nanocomposites combine the advantage of adsorption and dechlorination of OCPs in aqueous medium and up to 96–99% and 83–91% removal was obtained within 120 and 150 min, respectively at initial pH 4. Nevertheless, the reactivity of Fe0-BChe nanocomposite decreased 2 folds after being aged in air for one month, whilst Fe0-BRtP almost remained the same. Adsorption isotherm of OCPs were fitted well to Langmuir isotherm and then to Freundlich isotherm. The experimental kinetic data were fitted first to pseudo-second-order adsorption kinetic model and then to pseudo-first-order reduction kinetic model. The adsorption mechanism involves π-π electron-donor-acceptor interaction and adsorption is facilitated by the hydrophobic sorption and pore filling. After being reused five times, the removal efficiency of regenerated Fe0-BChe and Fe0-BRtP was 5–13% and 89–92%, respectively. The application of this Fe0-BRtP nanocomposite could represent a green and low-cost potential material for adsorption and subsequent reduction of OCPs in aquatic system.

Sorption and biodegradation are two major applicable techniques for organic pollutants removal. However, the desorption risk following the sorption process and the low bioavailability of trace pollutants to microbes are still hindering the efficient removal of pollutants. To take full advantages of both sorption (for contaminant accumulation) and microbial degradation, here we introduce a self-assembly method combining carbonaceous sorbents (i.e., biochars: RS350, RS500, and RS700) with fungal hyphae (Phanerochaete chrysosporium) which can efficiently degrade phenanthrene (PHE), one of the typical polycyclic aromatic hydrocarbons. By cultivating Phanerochaete chrysosporium in biochar-containing medium, fungus-biochar composite pellets (FBPs) were successfully synthesized with a 3D macrostructure of abundant hyphae and uniform pellet size (~2.5 mm in diameter). Benefiting from the high sorption ability of biochars, such FBPs showed up to triple sorption ability and 70 folds faster biodegradation rate than pure fungal pellets. The PHE concentration remaining in solution receiving co-sorption-degradation treatment after 22 d was only one third of that receiving sorption treatment alone. Continuous removal experiment indicated that these composite pellets could hold their removal ability of above 90 % in the first 4 cycles. This study points out a simple and promising self-assembly approach that could be easily scaled up to manufacture FBPs with high removal efficiency, fast biodegradation rate, easy separation ability and long-term stability.

In this study, the composite materials using different ratios of biochar (BC) to nano-hydroxyapatite (nHAP) were prepared for the remediation of lead (Pb) and cadmium (Cd) contaminated water and soil. The sorption and the immobilization experiments indicated a higher sorption capacity and immobilization efficiency of Pb compared to those of Cd. The characteristics of XRD, FTIR, SEM, and XPS manifested that dissolution-precipitation, cation exchange, complexation, and cation-π interaction were the main four mechanisms for the sorption of Pb2+ and Cd2+ using composite material PC1 (nHAP/BC = 1/1). From semi-quantitative analysis, the mineral effect accounted for the majority of the immobilization of Pb and Cd. Due to obvious Pb-precipitates in the sorbed material, dissolution-precipitation primarily affected the sorption of Pb using PC1, while the immobilization of Cd was mainly attributable to cation exchange. Such results corresponded to the stable Pb-precipitates and unstable Cd-compounds in soil, among which the latter was prone to be released into the environment. The sorption capacity in aqueous solutions and the immobilization efficiencies in the soil for both Pb and Cd increased with the addition of nHAP, which were linearly correlated to the nHAP proportion in the composite materials. In future practical applications, the percentages of composite materials can be designed according to the specific pollutant concentration. This study sheds light on the explicit immobilization mechanisms for Pb and Cd in aqueous solutions to better understand their behaviors in the soil remediated by relevant materials.

Biosorption using modified biochar has been increasingly adopted for the sustainable removal of uranium-contaminated from an aqueous solution. In this research study, the facile preparation and surface characteristics of magnetized biochar derived from waste watermelon rind to treat U(VI) contaminated water were investigated. The porosity, specific surface area, adsorption capacity, reusability, and stability were effectively improved after the magnetization of biochar. The kinetics and isotherm studies found that the U(VI) adsorption was rate-limiting monolayer sorption on the homogeneous surface of magnetized watermelon rind biochar (MWBC). The maximum adsorption capacity was found to be 323.56 mg of U(VI) per g of MWBC at pH 4.0 and 293 K that was higher than that of watermelon rind biochar (WBC) (135.86 mg g−1) and other sourced biochars. The surface interaction mechanism, environmental feasibility, applicability for real-filed water treatment studied in the electromagnetic semi-batch column, and reusability of MWBC were also explored. Furthermore, salient raised the ion exchange and complexation action capacity of MWBC due to the presence of Fe oxide. The overall results indicated that MWBC was not only inexpensive and had a high removal capacity for U(VI), but it also easily enabled phase separation from an aqueous solution, with more than three times reusability at a minimum removal capacity of 99%.

This study was conducted to investigate the potential of Jujube (Ziziphus jujube L) wood waste-derived biochar (BC) and its derivative polymer-modified biochar (PBC) in removing hexavalent chromium (CrVI) from aqueous solutions and in achieving Cr stabilization in tannery waste-contaminated soil. BC was produced at three different pyrolysis temperature (300 °C, 500 °C, 700 °C) and was polymerized with acrylamide and N, N1 methylenebisacrylamide. The results showed that CrVI adsorption is a function of the pH and CrVI initial concentration of the solution. The PBC showed highest sorption efficiency for CrVI removal, which amounted to 76.4%–99.6% of the CrVI overall initial concentrations (5–40 mg L−1) at an initial pH of 2. In greenhouse, wheat (Triticum aestivum L) was cultivated as a test crop in pots with tannery waste-contaminated soil along with BCs and PBCs amendments. The BC and PBC amended soil showed 47.7% and 65% less Cr uptake by the plant roots in comparison with unamended soil, respectively. In addition, zero concentration of Cr in the plant shoots was noted with the PBC-amended soil, while the Cr concentration in the shoots was decreased by 89% with the BC-amended soil. Thus, it was concluded that BC and PBC have great potential in removing CrVI from aqueous phases and in decreasing the Cr mobility and bioavailability in soil.

Phosphorus (P) is a valuable resource, while it is vastly lost with wastewater causing eutrophication. In this study, to recover P, composite biochars were prepared by pyrolyzing biowaste impregnated with FeCl3 or MgCl2. It was found that inherent mineral profiles in the biowastes played important roles in interacting with metal chlorides and determined P sorption and precipitation. Specifically, two biowastes containing distinct mineral contents, sawdust and sediment, were selected as model components, being alone or mixed at 1:1 (w/w) to prepare biochars with low, moderate and high mineral contents. Results showed that biochar itself could not absorb P, while loading FeCl3 or MgCl2 achieved P recovery rates of approximate 60–100% and 50–100%, respectively, via electrostatic attraction or ligand exchange of PO43− with –OH/-COOH, which was attributed to the enhanced positive charges and –OH/-COOH on the materials by these metal chlorides. Inherent minerals inhibited FeCl3 transforming into Fe3O4 in pyrolysis and promoted generation of Fe4(PO4)3(OH)3 in P sorption, thus high-mineral content was more appropriate for FeCl3 loading; however, precursors with low-mineral content was suitable for MgCl2 loading, since the bulk-C in biochar acted as porous structure to support MgO crystals with high superficial area (∼255.85 m2 g−1). Besides, FeCl3 and MgCl2 both drove dissolution of inherent minerals significantly, while inherent minerals inhibited release of soluble Fe and Mg2+ into solution, which minimized secondary pollution. This study implied that in constructing composite biochar for catching P, the type of metal chloride should match the inherent minerals in biowastes to maximize P recovery and minimize secondary pollution.

Biochars are one of carbon-rich substances that have attracted enormous attention because of its values in energy storage, carbon sequestration, and environment remediation. Apart from the carbon structure, biochars also contain inherent mineral component and polar functional groups. However, the importance of the inherent minerals to the stability of biochars as well as the sorption of organic compounds remains unclear. In this work, the demineralized treatment by the hydrofluoric acid was employed to remove the inorganic minerals from biochars produced at 300 and 500 °C. The inorganic minerals in biochars were identified and quantified by XRD, XPS and SEM-EDS techniques. Approximately 75% of biochar minerals belonged to the Si- and Al-containing minerals, which connected with carbon skeletons. The impact of these minerals to bisphenol A (BPA) and sulfamethoxazole (SMX) sorption was investigated. The mineral removal decreased BPA sorption but increased SMX sorption. Moreover, the relative contributions of surface adsorption and partition processes were quantified for both compounds through isotherm modeling. The BPA sorption was regulated by the joint effect of adsorption and partition, while more than 82% of the SMX sorption was dominated by the partition process. Such understanding of biochar minerals and carbon structure to the migration of organic contaminants will benefit biochar production and application.

The knowledge about lead (Pb) sorption on soil-derived black carbons (SBCs) under different cultivation intensities of soils is limited. In this study, chemical and spectroscopic methods were applied to investigate the Pb sorption mechanisms on SBCs in soils from a forest land, a rubber plantation area, and a vegetable farm with none, less and highly intensive cultivation, respectively, that are located in the Hainan Island of China. Results showed that the specific surface area and cation exchange capacity of the SBCs from the less and highly intensive cultivation soils were 4.5- and 2.7-fold, and 1.3- and 1.8-fold higher compared to that of SBC from the no-cultivation soil, which subsequently enhanced the Pb sorption capacities of SBCs in iron exchange fraction. Ion exchange and hydrogen bonded Pb fractions together accounted for about 80% of total Pb sorbed on all SBCs at an externally added 1000 mg L−1 Pb solution concentration. The O[dbnd]C–O groups also played key roles in Pb sorption by forming complexes of O[dbnd]C–O–Pb–O and/or O[dbnd]C–O–Pb. Overall, SBCs in soils under all studied cultivation intensities showed high potential to sorb Pb (with the maximum absorbed Pb amount of 46.0–91.3 mg g−1), and increased Pb sorption capacities of the studied soils by 18.7–21.1 mg kg−1 in the stable fraction (complexation). Therefore, SBC might be a potential environment-friendly material to enhance the Pb immobilization capacity of soil Refereed/Peer-reviewed

In this study, goethiete (α-FeOOH) -biochar (BC) composites were successfully developed from a co-precipitation reaction under alkaline conditions (pH = 11.93) and used as the adsorbent for phosphate recovery from urine. The morphology and crystallinity of α-FeOOH-BC composites were characterized by scanning electron microscopy and X-ray diffraction. α-FeOOH loaded BC was found to be amorphous. This may be caused by the Si residue in BC. The Elovich model and the Langmuir model fit better to the kinetic and isotherm results of α-FeOOH-600BC, respectively, indicating that phosphate adsorption is mainly a chemisorption and monolayer adsorption process. The α-FeOOH-600BC with amorphous structure showed higher adsorption capacity than crystalline α-FeOOH, and the maximum phosphate sorption capacity reached 57.39 mg g−1. Additionally, the extractable phosphate of this material was approximately 967.5 mg P·kg−1 suggesting the α-FeOOH-600BC after adsorption could be a promising alternative as a slow-phosphate-release fertilizer. Fourier-transform infrared and X-ray induced photoelectron spectroscopy results showed that the active sites of the adsorption of phosphate were the Fe-OH bonds that formed inner-sphere complexes (Fe-O-P).

Sorption of sulfonamides (SAs) on magnetite-coated biochar (MBC) is a promising approach for the remediation of antibiotic contaminants, due to its extended adsorption capacity and irreversibility. However, the actual sorption mechanisms of SAs on MBC remain unclear and the gap in knowledge hinders understanding of the fate of SAs in soils or sediments. In this study, various MBCs were prepared under different pyrolysis temperatures, with batch sorption experiments conducted using SMT as the model pollutant. Results of a two-compartment kinetic model demonstrated that aromatic components of MBCs dominated slow-sorption mechanisms, whereas the embedded magnetite further accelerated fast-sorption due to H-bonding. Modification of BC with magnetite improved the distribution coefficient (Kd) and isotherm linearity of SMT. Multi-parameter model results indicated that the pH-dependence of SMT sorption on BCs and MBCs occurred via a dominant mechanism of π-bond assisted H-bonding. Compared to pristine BCs, the change in pH-dependent sorption characteristics of SMT on MBC results from the regulation of π-bonding and proton configuration. Simultaneous transformation of SMT to sulfate ions on BCs or MBCs was also observed. The degradation of SMT occurred because of persistent free radicals (PFRs) on BCs or the inherent redox of iron minerals on MBCs. However, the small fraction of SMT transformed on BCs or MBCs was not found to result in overestimation of SMT sorption. This study presents the critical mechanisms of SMT sorption on pyrochars and provides novel understanding of the fate of SMT on carbonaceous materials during practical remediation applications.

Adsorption rate is a critical parameter in the design of effective biosorbent treatment systems for heavy metals removal. Though numerous studies have identified the physico-chemical properties of biosorbents that exert influence on the adsorption rate, such influence has not been mathematically defined, limiting the effective design of adsorption systems. This study quantifies the influence of biosorbent physico-chemical properties including, specific surface area, surface functional groups, pore size, pore volume and zeta potential on the adsorption rate in relation to three divalent metal cations. Mathematical equations were developed to predict the influence of physico-chemical properties on pseudo second order kinetic constant and thereby predict the adsorption rate. Tea factory waste and coconut shell biochar were mixed in different weight percentages to vary the physico-chemical properties under consideration. Four different initial metal ion concentrations were used. Relationship between pseudo second order kinetic constant at each concentration with physico-chemical properties was quantified using regression analysis. The experimental analysis revealed that among the physico-chemical properties, acidic surface functional groups had the most profound influence on sorption mechanisms. Reliability and accuracy of the predictive models were significantly improved when separate models were developed for two ranges of initial metal ion concentrations. The outcomes of this study will contribute to the effective design and optimization of biosorbent mixtures with the capacity to remove Pb2+, Cu2+ and Cd2+ in wastewater.

© 2020 Elsevier Ltd The capacity of biochars derived from agricultural wastes to remove Cd(II) and Cu(II) from aqueous solution and contaminated mine water was evaluated using laboratory-based batch sorption experiments. To examine immobilization of heavy metals, biochars produced in a commercial-scale mobile pyrolizer from feedstocks: poultry litter; lucerne shoot; vetch shoot; canola shoot; wheat straws; and sugar-gum wood, were tested in a liquid-based system. Biochars were characterized by FTIR, XPS and XRD before and after the mine water treatment. Lucerne biochar had the highest Langmuir sorption capacity of Cd(II) (6.28 mg g−1) and vetch-derived biochar had the highest Cu(II) sorption capacity (18.0 mg g−1) at pH 5.5. All the biochars exhibited higher sorption capacity for Cu(II) than for Cd(II). The smaller ionic radius and higher electronegativity of Cu(II), and the PO43−, CO32− and N-containing functional groups of biochars enhanced their binding affinity. The results demonstrated that poultry litter-derived biochar was effective at removal of the Cd(II) and Cu(II) from mine water up to the levels recommended by the World Health Organisation. The results revealed that precipitation with CO32− and PO43−, complexation with –OH and –COOH groups and electrostatic interaction with O-containing surface functional groups were the main mechanisms involved in the removal of multi-metals by biochars, and that selection of feedstock materials for biochar production is important to maximise remediation of multi-metals in contaminated water.

An important pathway for biochar to alter the availability of soil phosphorus (P) is to change P sorption characteristics of the soil. The aim of this study was to understand the mechanisms of biochar effects on P sorption in acid upland red soils in the presence of different concentrations of exogenous P. Rice straw biochar (RSB) was prepared and applied at rates of 0, 1%, 3%, and 5% (w/w) to three red soils (MZ1, MZ2, and QY1) differing in initial pH (pH = 4.31, 4.82, and 5.68, respectively). The P sorption characteristics of these red soils were described using the Langmuir and Temkin equations and their relationships with soil basic physicochemical properties were analyzed. Furthermore, a representative red soil (MZ2) was selected to analyze the zeta potential of soil colloids and the chemical properties of sorption equilibrium solution, in order to understand their relationships with P sorption characteristics. Results showed that within a certain range of P concentration in the equilibrium solution, the amount of P sorbed by the three red soils decreased and the corresponding amount of P desorbed increased with increasing amendment rate of RSB. RSB showed the greatest effect on P desorption characteristics of MZ2 soil in the presence of higher exogenous P concentration. With increasing RSB amendment rate, the maximum P sorption of MZ1 soil decreased, while those of MZ2 and QY1 soils increased after an initial decrease. Phosphate sorption equilibrium constant and maximum P buffer capacity of each soil first increased and then decreased. However, a single physicochemical property could not interpret complex changes in multi-factors that jointly determine the P sorption characteristics of red soils. In the case of MZ2 soil, RSB amendment shifted the zeta potential of soil colloids to the negative direction; this decreased the positive charge and increased the negative charge on the soil surface, thus reducing P sorption in the MZ2 soil. In the presence of the same concentration of exogenous P, RSB amendment altered the pH, dissolved organic C (DOC), humification index (HIX), and maximum fluorescence intensity (Fmax) in the sorption equilibrium solution. In most cases, the amount of P sorbed by the MZ2 soil was negatively correlated with the pH value, DOC concentration, HIX value, and Fmax value of humic-like dissolved organic matter (DOM), and positively correlated with the Fmax value of protein-like DOM (P

Biochars that were produced from pig manure at two different temperatures were incubated with three different minerals to examine the effects of soil minerals on biochar properties and sorption capacities. Biochars freshly mixed with minerals showed dramatic decreases in the sorption of atrazine (maximum decrease by 70.9% at Ce = 0.5 Sw) and phenanthrene (maximum decrease by 69.5% at Ce = 0.5 Sw) compared to unmixed biochars. Following the incubation, minerals were tightly attached to the biochar surface and insert into inner pores, thus changing the elemental composition and surface area of biochars in a manner dependent on the types of biochars and minerals involved. The changes in biochar properties in turn affected biochar sorption capacities. The sorption of both atrazine and phenanthrene by the pig manure biochar produced at 300 °C (BC300) decreased after aging due to an increase in surface hydrophilicity. In contrast, the sorption of atrazine and phenanthrene by BC700 increased after aging with minerals, which could be attributed to the increase in surface area caused by the minerals. However, the sorption capacities of the aged BC700 were still lower than those of the fresh BC700.

Biochar is increasingly deemed a potential sorbent for contaminants in soil and water remediation. We tested three biochars from different feedstocks (cattle manure, grain husk, and wood chips) produced at relatively low pyrolysis temperature (450 °C), for their sorption behavior towards trichloroethylene (TCE) and tetrachloroethylene (PCE) in single- and bi-solute systems. In single-solute experiments, all biochars show stronger sorption for TCE (about 50% based on solubility-normalized Freundlich coefficients). The lower sorption of PCE is attributed to steric effects, e.g. size exclusion in small micropores and specific interactions. Plant-derived, carbon-rich biochars with high specific surface area and microporosity predominantly sorb via pore-filling, as also observed in activated carbon. Biochar produced from manure, with higher ash content and polarity, and smaller total pore volume (PV tot ), shows significant contribution of partitioning. These findings also apply to bi-solute systems. TCE and PCE show different competition behavior depending on biochar properties. Plant-based biochars are pore-filling-dominated and show strong competition. However, competition behavior in microporous biochars depends on the concentration range. Manure biochar with high polarity and low PV tot shows significant partitioning and therefore less competition. Compared to the plant-based chars competition in manure biochar is not concentration-dependent. These results indicate that biochars with a large fraction of non-carbonized phase facilitate non-competitive sorption and might be a valuable sorbent in mixed contaminant systems.

Biochar improves soil fertility and promotes long-term terrestrial carbon sequestration. However, biochar seems not to be stable enough due to physical, chemical and biological reactions. In this study, a novel, stable, and magnesium (Mg)-impregnated biochar was prepared from cow dung and applied to decrease P leaching from soil. XPS, FTIR, XRD, SEM and EDS were used to evaluate the effect of modification and phosphorus(P) sorption on the oxidation resistance of biochar. The results showed that the oxidation resistance of the Mg-impregnated biochar was improved by the formation of MgO on its surface. The soil column experiment indicated that the Mg-impregnated -biochar decreased P loss from leaching by 89.25%. In addition, the available P content of the soil surface layer under Mg-impregnated biochar treatment increased by 3.5-fold relative to that under the control treatment. P sorption also enhanced the oxidation resistance of biochar. The relative contents of CO, CO, and COOH on the surface of P-laden biochar was 20.97% and was lower than those on the surface of biochar without P sorption (33.15%). Oxidation resistance was enhanced by the formation of new MgP crystals, which prevented the oxidation of CC, CC, and CH into CO, CO, and COOH, respectively, by acting as a physical barrier between the biochar surface and oxygen. The results of XRD, SEM and EDS provided evidence for the formation of MgP crystals. Overall, results indicated that the Mg-impregnated biochar can reduce P leaching loss from soil and has enhanced stability.

Biochar(BC)-supported nanoscaled zinc oxide (nZO) was encapsulated either with (nZORc/BC) or with no (nZOR/BC) sodium carboxymethyl cellulose (CMC). The X-ray diffraction and ultraviolet (UV)-visible-near infrared spectrophotometry revealed that nZO of 16, 10, and 20 nm with energy band gaps of 2.79, 3.68 and 2.62 eV were synthesized for nZOR/BC, nZORc/BC and nZO/BC, respectively. The Langmuir isotherm predicted saturated sorption of methylene blue (MB) was 17.01 g kg−1 for nZORc/BC, over 19 times greater than nZOR/BC and nZO/BC. Under UV irradiation, 10.9, 61.6, 83.1, and 41.6% of MB were degraded for nZORc/BC, nZO/BC, nZOR/BC and BC. The scavenging experiment revealed hydroxyl radical dominated CMC degradation. Exogenous CMC (2 g L−1) increased MB sorption from 10.6% to 73.1%, but decreased MB degradation from 80.7% to 41.1%, relative to nZOR/BC. Thus, CMC could increase MB sorption by electrostatic attraction and other possible mechanisms. The compromised MB degradation may be ascribed to reduced availability of hydroxyl and superoxide radicals to degrade MB, and increased band gap energy of ZnO.

Biochar (BC) was produced by pyrolyzing the date palm leaf waste at 600 °C and then loaded with phosphorus (P) via sorption process. Greenhouse pot experiment was conducted to investigate the application effects of BC and P-loaded biochar (BCP) on growth and availability of P and heavy metals to maize (Zea mays L.) plants grown in contaminated mining soil. The treatments consisted of BC and BCP (at application rates of 5, 10, 20, and 30 g kg−1 of soil), recommended NK and NPK, and a control (no amendment). Sorption experiment showed that Langmuir predicted maximum P sorption capacity of BC was 13.71 mg g−1. Applying BCP increased the soil available P, while BC and BCP significantly decreased the soil labile heavy metals compared to control. Likewise, heavy metals in exchangeable and reducible fractions were transformed to more stable fraction with BC and BCP applications. The highest application rate of BCP (3%) was most effective treatment in enhancing plant growth parameters (shoot and root lengths and dry matter) and uptake of P and heavy metals by 2–3 folds. However, based on metal uptake and phytoextraction indices, total heavy metals extraction by maize plants was very small for practical application. It could be concluded that using P-loaded biochar as a soil additive may be considered a promising tool to immobilize heavy metals in contaminated mining areas, while positive effects on the biomass growth of plants may assist the stabilization of contaminated areas affected by wind and water erosion.

Hard wood derived biochar (BCH) and rice husk (RCH) were applied to soils having upland and saturated conditions to investigate their effects on adsorption and desorption of Cd by conducting incubation and batch experiments. The results obtained from the experiments indicated that BCH increased Cd sorption by 59-71% onto saturated soil (SS), while by 57-84% onto upland soil (US). The application of RCH also increased the sorption of Cd onto the soils under both water conditions but the increases were less as compared to BCH. With RCH application, 21-41% increases in sorption of Cd on SS and 38-54% on US soils were observed. The Langmuir equation fitted sorption of Cd better than Freundlich with R2 > 0.95 for all selected treatments. Both electrostatic and non-electrostatic mechanisms played their important roles in the adsorption of Cd in the amended soils. BCH enhanced non-electrostatic adsorption as compared to RCH and thus control and induced greater specific adsorption capacity. High desorption percentage of pre-adsorbed Cd on soils were observed both with and without amendments. Decreases in desorption percentage of pre-adsorbed Cd on both soils were observed with BCH with a highest decrease on SS (39%). The application of selected amendments into different soils increased Cd adsorption of soils through both electrostatic and non-electrostatic mechanisms and the contribution of both the mechanisms varied with types of amendments and soil conditions. BCH material showed promising results in Cd adsorption as compared to RCH for different selected soils and conditions but cost-benefit analysis is needed in field condition.

Novel sorbent (HBC) is prepared by introducing nano-particles (Maghemite and EDTA functionalized layered double hydroxides) on biochar surface. FTIR, XRD, SEM and EDS are used to characterize the biochar nanocomposites. Pb(II) sorption is highly dependent on solution pH. Sorption kinetics and isotherms indicate that Pb(II) sorption onto the sorbents follows pseudo-second order model and Langmuir isotherm. The maximum sorption capacity of Pb(II) onto HBC is up to146.84 mg g−1, higher than previously reported sorbents. The magnetic particles enable easy separation of HBC from aqueous solution by external magnetic fields. HBC can be used as effective sorbent for removal of heavy metals from wastewater.

Biochar is a promising novel material for managing phosphorus (P), a nutrient often limiting for primary production but can also be a pollutant, in the environment. Reducing P input to the environment and finding cost-effective approaches to remediate P contamination are major challenges in P management. There is currently no review that systematically summarizes biochar effects on soil P availability and its P removal potential from water systems. In this paper, we comprehensively reviewed biochar effects on soil P availability and P removal from water systems and discussed the mechanisms involved. Biochar affects soil P cycling by altering P chemical forms, changing soil P sorption and desorption capacities, and influencing microbial population size, enzyme activities, mycorrhizal associations and microbial production of metal-chelating organic acids. The porous structure, high specific surface area, and metal oxide and surface functional groups make biochars effective materials for removing P from eutrophic water via ligand exchange, cation bridge, and P precipitation. Because soil and biochar properties are widely variable, the effect of biochar on the fate of P in soil and water systems is inconsistent among different studies. Knowledge gaps in the economic practicability of large-scale biochar application, the longevity of biochar benefits, and the potential ecological risks of biochar application should be addressed in future research.

Metal organic framework (MOF) nanoparticles are recognized for their effective removal of metal ions from aqueous systems. However, the application of nanoparticles in a powder form as synthesized is not practical and recovery is not easy. We prepared a recyclable magnetic MOF nanoparticle phase and used a widely available waste biomass to generate biochar to support magnetic nanoparticles applied in the treatment of aqueous antimony pollution. A mushroom waste biochar was used to support a magnetic UIO-66-2COOH (denoted as BSMU). Adsorption of trivalent antimony (Sb (III)) onto the BSMU was evaluated. The results showed that optimum conditions for preparation of the BSMU were the mass ratio of MMOF to biochar 4:1, the temperature 70 °C, the time 4 h, and the initiator 4 mM. Under such conditions, sorption capacity reached 56.49 mg/g for treatment of Sb (III) solution at 100 mg/L and pH 9.1. Alkaline conditions (such as pH 9.1) are more favorable for adsorption than acidic conditions, and coexisting ions including NO3−, Cl−, SO42−, and PO43− had no significant negative effect in adsorption, and with the use of low dose, higher adsorption density achieved. The adsorption followed a pseudo second order kinetics model and Freundlich isotherm model. It resulted in a higher enthalpy changes ( Δ H θ ) and activation energy (Ea) of 97.56 and 8.772 kJ/mol, respectively, and enhanced the rate pf random contact between antimony and the BSMU, as indicated by a higher entropy change ( Δ S θ ) up to 360 J/mol·K. As a result, it readily absorbs antimony. These adsorption properties identified in this study would provide a valuable insights into the application of nanoparticles loaded biochar from abundant biomass in environmental remediation.

Three types of hierarchically porous magnetic biochars (HMBs) were prepared by pyrolyzing low-cost wheat straw and potassium ferrate (K2FeO4) under a nitrogen atmosphere at 600, 700 and 800 °C, respectively, which could be used as amendments for cadmium (Cd) in water and soil. HMB fabricated at 700 °C (HMB700) had the best remediation performance for Cd in water and soil, which was mainly due to its largest specific surface area and micropore volume. Batch sorption experiments showed that Cd(II) sorption onto HMBs were well-described by a pseudo-second-order model and Sips (Freundlich-Langmuir) model, indicating that HMBs removed Cd(II) mainly through chemical adsorption. MINTEQ modeling evidenced that HMBs adsorbed Cd(II) mainly through precipitation rather than surface complexation. The adsorption behavior of HMB700 to Cd(II) could be explained by surface complexation (–OCd, –COOCd), precipitation (Cd(OH)2 and CdCO3), physical adsorption (rich pore structure) and ion exchange (K+, Ca2+, Mg2+). Furthermore, adding HMBs (1 wt%) (incubation 60 days) could also significantly increase soil pH and electrical conductivity (EC), and significantly reduce the available Cd content in soil (47.97%–61.38%). Adding HMBs could promote the conversion of bioavailable to less bioavailable Cd forms. These results provided a new idea for fabricating agricultural waste-based HMBs to remediate Cd in water and soil.

Generally, biochar plays an important role in controlling migration and accumulation of pollutants in soil. In this dissertation, biochars derived from wheat straws at various pyrolysis temperatures are used to investigate how biochar amendment affects adsorption and microbial degradation of atrazine (typical diffuse herbicide) in soils. In order to explore the influence of soil components, soil samples with different organic matter content are collected from typical agricultural sites, which are characterized as black soils in the northeast region of China. The basic sorption characteristics of biochars from wheat straws prepared at diverse pyrolysis temperature are analyzed, along with the comparisons of the sorption difference in the raw soil and soil amended with biochars at four levels of ratio (0.1%, 0.5%, 1.0% and 2.0%). By incubation experiments, atrazine degradation in non-sterile and sterile soils and effects of atrazine degradation rate after biochar amendment are also studied. Atrazine degradation is significantly enhanced in biochar amended soils, which may be because that biochar supplement can promote the growth and metabolism of microorganisms in the soil. Our findings reveal that wheatstraw- derived biochars may be effective remediation reagents for activating degradation of the soil functional microorganism and enhancing sorption of organic matter content, which can be applied to environmental-friendly accelerate the remediation of atrazine contaminated black soils.

In this work, nZVI was immobilized by bamboo derived biochars (nZVI/BB), hydrogen peroxide (H2O2) (nZVI/PBB) and nitric acid (HNO3) (nZVI/HBB) modified BB. H2O2 and HNO3 deceased surface area and pore volume of pristine biochars. Total iron (Fe) contents were 16.50, 24.40, and 13.08% for nZVI/BB, nZVI/PBB and nZVI/HBB, respectively. The X-ray diffraction revealed that nZVI in biochar matrix was dominantly metallic Fe coated with Fe oxides. The transmission electron microscopy indicated nZVI particle sizes were 41.5, 30.5 and 6.1 nm for nZVI/BB, nZVI/HBB and nZVI/PBB, respectively. The removal capacities of arsenate (AsV) and silver ions (Ag+) by nZVI nanocomposites were compared in a batch experiment. Greater reductive removal of Ag+ (1217 g kg-1 nZVI) and sorptive removal of AsV (109.1 g kg-1 nZVI) were achieved in nZVI/PBB, indicating smaller-sized nZVI was more reactive. Thus, particle size of nZVI affected the sorptive and reductive capacities for AsV and Ag+.

Bench- and pilot-scale sorption tests were used to probe the performance of several biochars at removing perfluoroalkyl acids (PFAA) from field waters, compared to granular activated carbon (GAC). Screening tests using organic matter-free water resulted in hardwood (HWC) ( K d = 41 L g −1 ) and pinewood (PWC) ( K d = 49 L g −1 ) biochars having the highest perfluorooctanoic acid (PFOA) removal performance that was comparable to bituminous coal GAC ( K d = 41 L g −1 ). PWC and HWC had a stronger affinity for PFOA sorbed in Lake Mead surface water (K F = 11 mg (1−n) L n g −1 ) containing a lower (2 mg L −1 ) dissolved organic carbon (DOC) concentration than in a tertiary-filtered wastewater (K F = 8 mg (1−n) L n g −1 ) with DOC of 4.9 mg L −1 . A pilot-scale study was performed using three parallel adsorbers (GAC, anthracite, and HWC biochar) treating the same tertiary-filtered wastewater. Compared to HWC, and anthracite, GAC was the most effective in mitigating perfluoropentanoic acid (PFPnA), perfluorohexanoic acid (PHxA), PFOA, perfluorooctane sulfonic acid (PFOS), and DOC (45–67% removed at 4354 bed volumes) followed by HWC, and then anthracite. Based on bench- and pilot-scale results, shorter-chain PFAA [perfluorobutanoic acid (PFBA), PFPnA, or PFHxA] were more difficult to remove with both biochar and GAC than the longer-chain, PFOS and PFOA.

Biomass-derived biochar is a carbon-rich product for soil amendment and sulfapyridine (SPY) is a typical sulfonamide of antibiotics in the soil. Amendment with biochar for soil could control SPY sorption or mobility. However, the pristine biochar inevitably goes through the long-term ageing in the environment and the information on such ageing impact on SPY sorption is not fully recognized. The simulated ageing process methods were employed for high-temperature and freeze-thraw climate to treat the biochar for two months in the present study. The batch adsorption of SPY and leaching column experiments were conducted for comparison of the fresh/aged biochar-soil system. The results showed that biochar addition could increase soil pH and saturated moisture, aged biochars own more O-containing functional groups and exhibit higher hydrophilicity and polarity. The sorption mechanism of unamended soil with SPY primarily resulted from the weak hydrophobic distribution. All fresh and aged biochar amended soil increased SPY sorption due to improvement of H-bonding interaction between SPY and biochar surface functional groups, indicating such initiative adsorption was stronger than passive partitioning. It is of importance for us to reconsider that aged biochar-amended soil, especially two-month high-temperature aged biochar-amended soil showed the highest adsorption performance and the lowest desorption capacity towards SPY. Both SPY leaching column experiments and the acid rain leaching tests suggested that the application of biochar in tropical or high-temperature climate regions for organics polluted soil remediation is favorable, but we should be aware of the uncertainty of soil amendment with biochar in cold regions.