Adsorption Potential, Speciation Transformation, and Risk Assessment of Hg-, Cd-, and Pb-Contaminated Soils Using Biochar in Combination with Potassium Dihydrogen Phosphate.

The objective of this study is to develop a remediation technology for composited heavy metal-contaminated soil. Biochars (BC300, BC400, and BC500) derived from corn were combined with potassium dihydrogen phosphate (KH2PO4) to immobilize and remove heavy metal ions, including mercury (Hg2+), cadmium (Cd2+), and lead (Pb2+). The adsorption kinetics of metal ions in aqueous solutions with different concentrations was tested, and the fitting effects of the two models were compared. The findings demonstrate that the joint application of biochar and KH2PO4 could markedly enhance the immobilization efficacy of Pb2+, whereas the utilization of KH2PO4 on its own exhibited a more pronounced immobilization impact on Cd2+. Furthermore, the present study underscores the shortcomings of various remediation techniques that must be taken into account when addressing heavy metal-contaminated soils. It also emphasizes the value of comprehensive remediation techniques that integrate multiple remediation agents. This study offers a novel approach and methodology for addressing the intricate and evolving challenges posed by heavy metal contamination in soil. Its practical value and potential for application are significant.

Investigating the potential of mineral precipitation in co-pyrolysis biochar: Development of a novel Cd (II) adsorption material utilizing dual solid waste.

Ionic cadmium (Cd (II)) in water is a significant threat to ecosystems, the environment, and human health. Research is currently focused on developing efficient adsorption materials to combat Cd (II) pollution in water. One promising solution involves co-pyrolyzing solid residue from anaerobic digestion of food waste with oil-based drill cuttings pyrolysis residue to create a biochar with high organic matter content. This biochar has a lower heavy metal content and leaching toxicity compared to China's national standards, making it both safe and resourceful. It exhibits a high adsorption capacity for Cd (II) in water, reaching up to 47.80 ± 0.37 mg/g. Raising the pyrolysis temperature above 600 °C and increasing the amount of pyrolysis residue beyond 30 % enhances the biochar's adsorption capacity. The adsorption process is primarily driven by mineral precipitation, offering a promising approach for dual waste resource management and reducing heavy metal pollution.

Coupling machine learning and theoretical models to compare key properties of biochar in adsorption kinetics rate and maximum adsorption capacity for emerging contaminants.

Insights into key properties of biochar with a fast adsorption rate and high adsorption capacity are urgent to design biochar as an adsorbent in pollution emergency treatment. Machine learning (ML) incorporating classical theoretical adsorption models was applied to build prediction models for adsorption kinetics rate (i.e., K) and maximum adsorption capacity (i.e., Qm) of emerging contaminants (ECs) on biochar. Results demonstrated that the prediction performance of adaptive boosting algorithm significantly improved after data preprocessing (i.e., log-transformation) in the small unbalanced datasets with R2 of 0.865 and 0.874 for K and Qm, respectively. The surface chemistry, primarily led by ash content of biochar significantly influenced the K, while surface porous structure of biochar showed a dominant role in predicting Qm. An interactive platform was deployed for relevant scientists to predict K and Qm of new biochar for ECs. The research provided practical references for future engineered biochar design for ECs removal.

Sustainable biochar application in anammox process: Unveiling novel pathways for enhanced nitrogen removal and efficient start-up at low temperature.

This study explored the use of biochar to accelerate the establishment of anaerobic ammonium oxidation (anammox) reactors operating at 15 ± 1℃. Incorporating 10 g/L bamboo charcoal in S1 accelerated the start-up of anammox in 87 days, which was significantly shorter than 103 days in S0 (without biochar). After 140 days, S1 exhibited a 10.9 % increase in nitrogen removal efficiency due to a 28.9 % elevation in extracellular polymeric substances, bolstering anammox bacterial resilience. Predominant anammox bacteria (Cadidatus Brocadia and Cadidatus Jettenia) showed relative abundances of 3.19 % and 0.38 % in S1, respectively, which were significantly higher than 0.40 % and 0.05 % in S0. Biochar provides favorable habitats for the enrichment of anammox bacteria and accelerates the establishment of anammox at low temperatures. This finding holds promise for enhancing the efficiency of anammox in cold climates and advancing sustainable wastewater nitrogen removal.

Novel enhanced defluorination of perfluorooctanoic acids by biochar-assisted ultrasound coupling ferrate: Performance and mechanism.

An ultrasound (US)/biochar (BC)/ferrate (Fe (VI)) system was firstly proposed to enhance perfluorooctanoic acid (PFOA) defluorination. It achieved 93 % defluorination optimally, higher than the sum of 77 % (28 % and 49 % for US/BC and US/Fe (VI) respectively), implying synergistic effect. Besides, the mechanism study confirmed that, this system can not only increase the specific surface area of BC and the generation of reactive oxidant species (ROS), enriching the active sites and forming new oxygen-containing functional groups, but also promote the formation of intermediate iron species. The PFOA degradation in the US/BC/Fe (VI) was probably an adsorption-degradation process, both ROS and electron transfer promoted the defluorination. Additionally, its sustainability was also demonstrated with 14 % reduced defluorination percentage after five cycles of BC. Overall, the synergistic effect of the US/BC/Fe (VI) and its enhancing mechanism for PFOA defluorination were clarified firstly, which contributes to the development of biochar for assisting polyfluoroalkyl substances degradation.

Ionic liquid catalyzed low-temperature hydrothermal carbonization of sewage sludge to produce hydrochar with low heavy metal content and positive energy recovery.

An ionic liquid (IL, [DMAPA]HSO4) was prepared to facilitate the removal of heavy metals by hydrothermal carbonization (HTC) in sewage sludge (SS) and to obtain a positive energy recovery (ER, (Energyoutput/Energyinput - 1) > 0). The results found that the removal efficiencies of the Fe, Mn, Zn, Co, and Cd from SS exceeded 75 % with positive ER (6 %) at 20 wt% IL dosage (IL:SS). IL promoted the HTC reactions of proteins and polysaccharides to produce fixed carbon and small molecule polymers. The process mainly relies on IL to catalyze the dehydration and graphitization of SS and to destroy the heavy metal binding sites such as carboxyl and hydroxyl groups. Additionally, IL aids in constructing the macropore structures in hydrochar, thereby facilitating the release of heavy metals and water during the HTC process. This discovery holds promise for removing heavy metals from SS by one-pot HTC processes with positive energy recovery.

Novel chitosan-modified biochar prepared from a Chinese herb residue for multiple heavy metals removal: Characterization, performance and mechanism.

In this study, the sorption properties of Cr(VI), As(III), and Pb(II) on chitosan-modified magnetic biochar (CMBC) derived from residues of Ligusticum chuanxiong Hort. were investigated. CMBC was found to be a valuable material for removing three heavy metals from water simultaneously. Kinetic analysis suggested Cr(VI), As(III), and Pb(II) were chemisorbed onto CMBC, while isotherm data conformed well to Langmuir model, the maximum adsorption capacity of CMBC was found to be 65.74 mg/g for Cr(VI), 49.32 mg/g for As(III), and 69.45 mg/g for Pb(II). Experiments, characterization, and density functional theory (DFT) calculations were employed to explore the mechanisms. Furthermore, CMBC demonstrated excellent removal rates of over 95% for Cr(VI), 99% for As(III) and Pb(II) from contaminated water bodies. This work shows that CMBC holds significant potential for wastewater treatment of heavy metals and provides an effective solution for the utilization of Chinese herb residues in environmental remediation.

Characteristics of advanced anaerobic digestion sludge-based biochar and its application for sewage sludge conditioning.

The utilization of sludge-based biochar, characterized by abundant pore structures, proves advantageous in enhancing sludge dewatering performance. In this study, advanced anaerobic digestion sludge underwent pyrolysis to produce biochar, subsequently employed for sludge conditioning. Results revealed that biochar, obtained at 800 °C, exhibited the highest specific surface area (105.3 m2/g) and pore volume (0.17 cm3/g). As the pyrolysis temperature increased, the sludge's functional groups tended to aromatize. When used to condition sludge, particularly at a 20 % (dry solid) dosage, biochar significantly reduced sludge capillary suction time and floc size. The addition of biochar enhanced the conditioning effect of cationic polyacrylamide by absorbing extracellular polymeric substances, creating water molecule channels, and forming skeletons for sludge flocs. These findings introduce a novel approach to sludge reuse and provide valuable data supporting the use of biochar as a sludge conditioner.

Modified lignin can achieve mitigation of ammonia and greenhouse gas emissions simultaneously in composting.

The constant ammonia gas (NH3) and greenhouse gases (GHG) emissions were considered as a deep-rooted problem in composting which caused air pollution and global climate change. To achieve the mitigation of NH3 and GHG, a novel additive derived from wasted straw, with modified structure and functional groups, has been developed. Results showed that the adsorption capacity of modified lignin (ML) for both ammonium and nitrate was significantly increased by 132.5-360.8 % and 313.7-454.3 % comparing with biochar (BC) and phosphogypsum (PG) after reconstructing porous structure and grafting R-COOH, R-SO3H functional groups. The application of ML could reduce 36.3 % NH3 emission during composting compared with control. Furthermore, the synergetic mitigation NH3 and GHG in ML treatment resulted in a reduction of global warming potential (GWP) by 31.0-64.6 % compared with BC and PG. These findings provide evidence that ML can be a feasible strategy to effectively alleviate NH3 and GHG emissions in composting.

Comparing the adsorption of micropollutants on activated carbon from anaerobically stored, organics-depleted, and nitrified urine.

Separate collection and treatment of urine optimizes nutrient recovery and enhances micropollutant removal from municipal wastewater. One typical urine treatment train includes nutrient recovery in three biological processes: anaerobic storage, followed by aerobic organics degradation concurrently with nitrification. These are usually followed by activated carbon adsorption to remove micropollutants. However, removing micropollutants prior to nitrification would protect nitrifiers from potential inhibition by pharmaceuticals. In addition, combining simplified biological treatment with activated carbon adsorption could offer a cheap and robust process for removing micropollutants where nutrient recovery is not the first priority, as a partial loss of ammonia occurs without nitrification. In this study, we investigated whether activated carbon adsorption could also take place between the three biological treatment steps. We tested the effectiveness of micropollutant removal with activated carbon after each biological treatment step by conducting experiments with anaerobically stored urine, organics-depleted urine, and nitrified urine. The urine solutions were spiked with 19 pharmaceuticals: amisulpride, atenolol, atenolol acid, candesartan, carbamazepine, citalopram, clarithromycin, darunavir, diclofenac, emtricitabine, fexofenadine, hydrochlorothiazide, irbesartan, lidocaine, metoprolol, N4-acetylsulfamethoxazole, sulfamethoxazole, trimethoprim, venlafaxine, and two artificial sweeteners, acesulfame and sucralose. Batch experiments were conducted with powdered activated carbon (PAC) to determine how much activated carbon achieve which degree of micropollutant removal and how organics, pH, and speciation change from ammonium to nitrate influence adsorption. Micropollutant removal was also tested in granular activated carbon (GAC) columns, which is the preferred technology for micropollutant removal from urine. The carbon usage rates (CUR) per person were lower for all urine solutions than for municipal wastewater. The results showed that organics depletion would be needed when micropollutant removal was the sole aim of urine treatment, as the degradation of easily biodegradable organics prevented clogging of GAC columns. However, CUR did hardly improve with organics-depleted urine compared to stored urine. The lowest CUR was achieved with nitrified urine. This resulted from the additional organics removal during nitrification and not the lower pH or the partial conversion of ammonium to nitrate. In addition, we showed that the relative pharmaceutical removal in all solutions was independent of the initial pharmaceutical concentration unless the background organics matrix changed considerably. We conclude that removal of micropollutants in GAC columns from organics-depleted urine can be performed without clogging, but with the drawback of a higher carbon usage compared to removal from nitrified urine.

Chicken manure-derived biochar enhanced the potential of Comamonas testosteroni ZG2 to remediate Cd contaminated soil.

The combined remediation of Cd-contaminated soil using biochar and microorganisms has a good application value. In this study, the effect of chicken manure-derived biochar on CdCO3 precipitation induced by Comamonas testosteroni ZG2 was investigated. The results showed that biochar could be used as the carrier of strain ZG2, enhance the resistance of strain ZG2 to Cd, and reduce the toxicity of Cd to bacterial cells. Cd adsorbed by biochar could be induced by strain ZG2 to form CdCO3 precipitation. Strain ZG2 could also induce CdCO3 precipitation when biochar was added during precipitation formation and fermentation broth formation. The CdCO3 precipitation could enter the pores of the biochar and attach to the surface of the biochar. The single and combined effects of strain ZG2 and biochar could realize the remediation of Cd-contaminated soil to a certain extent. The overall effect was in the order of strain ZG2 with biochar > biochar > strain ZG2. The combination of strain ZG2 and biochar reduced soil available Cd by 48.2%, the aboveground biomass of pakchoi increased by 72.1%, and the aboveground Cd content decreased by 73.3%. At the same time, it promoted the growth and development of the root system and improved the microbial community structure of the rhizosphere soil. The results indicated that chicken manure-derived biochar could enhance the stability of CdCO3 precipitation induced by strain ZG2, and strain ZG2 combined with biochar could achieve a more stable remediation effect on Cd-contaminated soil.

Adsorption of Cu (II) and Zn (II) in aqueous solution by modified bamboo charcoal.

Due to the development of industries such as mining, smelting, industrial electroplating, tanning, and mechanical manufacturing, heavy metals were discharged into water bodies seriously affecting water quality. Bamboo charcoal, as an environmentally friendly new adsorbent material, in this paper, the virgin bamboo charcoal (denoted as WBC) was modified with different concentrations of KMnO4 and NaOH to obtain KMnO4-modified bamboo charcoal (KBC) and NaOH-modified bamboo charcoal (NBC) which was used to disposed of water bodies containing Cu2+ and Zn2+. The main conclusions were as following: The adsorption of Cu2+ by WBC, KBC and NBC was significantly affected by pH value, and the optimum pH was 5.0. Differently, the acidity and alkalinity of the solution doesn't effect the adsorption of Zn2+ seriousely. Meanwhile, surface diffusion and pore diffusion jointly determine the adsorption rate of Cu2+ and Zn2+. The test result of EDS showed that Mn-O groups formed on the surface of K6 (WBC treated by 0.06 mol/L KMnO4) can promote the adsorption of Cu2+ and Zn2+ at a great degree. The O content on N6(WBC treated by 6 mol/L NaOH) surface increased by 30.95% compared with WBC. It is speculated that the increase of carbonyl group on the surface of NBC is one of the reasons for the improvement of Cu2+ and Zn2+ adsorption capacity. Finally, the residual concentrations of Cu2+ and Zn2+ in wastewater are much lower than 0.5 mg/L and 1.0 mg/L, respectively. Thus it can be seen, KBC and NBC could be a promising adsorbent for heavy metals.

Pepsin immobilization on activated carbon and functionalized with glutaraldehyde and genipin for the synthesis of antioxidant peptides of goat casein.

In this article, the synthesis of antioxidant peptides in the enzymatic hydrolysis of caprine casein was analyzed at three different time points (60 min, 90 min, and 120 min) using immobilized pepsin on activated and modified carbon (AC, ACF, ACG 50, ACG 100). The immobilization assays revealed a reduction in the biocatalysts' activity compared to the free enzyme. Among the modified ones, ACG 50 exhibited greater activity and better efficiency for reuse cycles, with superior values after 60 min and 90 min. Peptide synthesis was observed under all studied conditions. Analyses (DPPH, ß-carotene/linoleic acid, FRAP) confirmed the antioxidant potential of the peptides generated by the immobilized enzyme. However, the immobilized enzyme in ACG 50 and ACG 100, combined with longer hydrolysis times, allowed the formation of peptides with an antioxidant capacity greater than or equivalent to those generated by the free enzyme, despite reduced enzymatic activity.

Heavy metals immobilization and bioavailability in multi-metal contaminated soil under ryegrass cultivation as affected by ZnO and MnO2 nanoparticle-modified biochar.

Pollution by heavy metals (HMs) has become a global problem for agriculture and the environment. In this study, the effects of pristine biochar and biochar modified with manganese dioxide (BC@MnO2) and zinc oxide (BC@ZnO) nanoparticles on the immobilization and bioavailability of Pb, Cd, Zn, and Ni in soil under ryegrass (Lolium perenne L.) cultivation were investigated. The results of SEM-EDX, FTIR, and XRD showed that ZnO and MnO2 nanoparticles were successfully loaded onto biochar. The results showed that BC, BC@MnO2 and BC@ZnO treatments significantly increased shoots and roots dry weight of ryegrass compared to the control. The maximum dry weight of root and shoot (1.365 g pot-1 and 4.163 g pot-1, respectively) was reached at 1% BC@MnO2. The HMs uptake by ryegrass roots and shoots decreased significantly after addition of amendments. The lowest Pb, Cd, Zn and Ni uptake in the plant shoot (13.176, 24.92, 32.407, and 53.88 µg pot-1, respectively) was obtained in the 1% BC@MnO2 treatment. Modified biochar was more successful in reducing HMs uptake by ryegrass and improving plant growth than pristine biochar and can therefore be used as an efficient and cost effective amendment for the remediation of HMs contaminated soils. The lowest HMs translocation (TF) and bioconcentration factors were related to the 1% BC@MnO2 treatment. Therefore, BC@MnO2 was the most successful treatment for HMs immobilization in soil. Also, a comparison of the TF values of plant showed that ryegrass had a good ability to accumulate all studied HMs in its roots, and it is a suitable plant for HMs phytostabilization.

A Wooden Carbon-Based Photocatalyst for Water Treatment.

Due to a large number of harmful chemicals flowing into the water source in production and life, the water quality deteriorates, and the use value of water is reduced or lost. Biochar has a strong physical adsorption effect, but it can only separate pollutants from water and cannot eliminate pollutants fundamentally. Photocatalytic degradation technology using photocatalysts uses chemical methods to degrade or mineralize organic pollutants, but it is difficult to recover and reuse. Woody biomass has the advantages of huge reserves, convenient access and a low price. Processing woody biomass into biochar and then combining it with photocatalysts has played a complementary role. In this paper, the shortcomings of a photocatalyst and biochar in water treatment are introduced, respectively, and the advantages of a woody biochar-based photocatalyst made by combining them are summarized. The preparation and assembly methods of the woody biochar-based photocatalyst starting from the preparation of biochar are listed, and the water treatment efficiency of the woody biochar-based photocatalyst using different photocatalysts is listed. Finally, the future development of the woody biochar-based photocatalyst is summarized and prospected.

Sorption Behavior of Azo Dye Congo Red onto Activated Biochar from Haematoxylum campechianum Waste: Gradient Boosting Machine Learning-Assisted Bayesian Optimization for Improved Adsorption Process.

This work aimed to describe the adsorption behavior of Congo red (CR) onto activated biochar material prepared from Haematoxylum campechianum waste (ABHC). The carbon precursor was soaked with phosphoric acid, followed by pyrolysis to convert the precursor into activated biochar. The surface morphology of the adsorbent (before and after dye adsorption) was characterized by scanning electron microscopy (SEM/EDS), BET method, X-ray powder diffraction (XRD), and Fourier-transform infrared spectroscopy (FTIR) and, lastly, pHpzc was also determined. Batch studies were carried out in the following intervals of pH = 4-10, temperature = 300.15-330.15 K, the dose of adsorbent = 1-10 g/L, and isotherms evaluated the adsorption process to determine the maximum adsorption capacity (Qmax, mg/g). Kinetic studies were performed starting from two different initial concentrations (25 and 50 mg/L) and at a maximum contact time of 48 h. The reusability potential of activated biochar was evaluated by adsorption-desorption cycles. The maximum adsorption capacity obtained with the Langmuir adsorption isotherm model was 114.8 mg/g at 300.15 K, pH = 5.4, and a dose of activated biochar of 1.0 g/L. This study also highlights the application of advanced machine learning techniques to optimize a chemical removal process. Leveraging a comprehensive dataset, a Gradient Boosting regression model was developed and fine-tuned using Bayesian optimization within a Python programming environment. The optimization algorithm efficiently navigated the input space to maximize the removal percentage, resulting in a predicted efficiency of approximately 90.47% under optimal conditions. These findings offer promising insights for enhancing efficiency in similar removal processes, showcasing the potential of machine learning in process optimization and environmental remediation.

Tetracycline (TC) removal from wastewater with activated carbon (AC) obtained from waste grape marc: activated carbon characterization and adsorption mechanism.

In this study, activated carbons were obtained from grape marc for tetracycline removal from wastewater. Activated carbons were obtained by subjecting them to pyrolysis at 300, 500, and 700 °C, respectively, and the effect of pyrolysis temperature on activated carbons was investigated. The physicochemical and surface properties of the activated carbons were evaluated by SEM, FTIR, XRD, elemental analysis, N2 adsorption/desorption isothermal, thermal gravimetric (TG) and derivative thermogravimetric (DTG), and BET surface area analysis. When the BET surface areas were examined, it was found that 4.25 m2/g for activated carbon was produced at 300 °C, 44.23 m2/g for activated carbon obtained at 500 °C and 44.23 m2/g at 700 °C, which showed that the BET surface areas increased with increasing pyrolysis temperatures. The pore volumes of the synthesized activated carbons were 0.0037 cm3/g, 0.023 cm3/g, and 0.305 cm3/g for pyrolysis temperatures of 300, 500, and 700 °C, respectively, while the average pore size was found to be 8.02 nm, 9.45 nm, and 10.29 nm, respectively. A better adsorption capacity was observed due to the decrease in oxygen-rich functional groups with increasing pyrolysis temperature. It was observed that the activated carbon obtained from grape skins can easily treat hazardous wastewater containing tetracycline due to its high carbon content and surface functional groups. It was also shown that the activated carbon synthesized in this study has a higher pore volume despite its low surface area compared to the studies in the literature. Thanks to the high pore volume and surface active groups, a successful tetracycline removal was achieved.

The boom era of emerging contaminants: A review of remediating agricultural soils by biochar.

Emerging contaminants (ECs) are widely sourced persistent pollutants that pose a significant threat to the environment and human health. Their footprint spans global ecosystems, making their remediation highly challenging. In recent years, a significant amount of literature has focused on the use of biochar for remediation of heavy metals and organic pollutants in soil and water environments. However, the use of biochar for the remediation of ECs in agricultural soils has not received as much attention, and as a result, there are limited reviews available on this topic. Thus, this review aims to provide an overview of the primary types, sources, and hazards of ECs in farmland, as well as the structure, functions, and preparation types of biochar. Furthermore, this paper emphasizes the importance and prospects of three remediation strategies for ECs in cropland: (i) employing activated, modified, and composite biochar for remediation, which exhibit superior pollutant removal compared to pure biochar; (ii) exploring the potential synergistic efficiency between biochar and compost, enhancing their effectiveness in soil improvement and pollution remediation; (iii) utilizing biochar as a shelter and nutrient source for microorganisms in biochar-mediated microbial remediation, positively impacting soil properties and microbial community structure. Given the increasing global prevalence of ECs, the remediation strategies provided in this paper aim to serve as a valuable reference for future remediation of ECs-contaminated agricultural lands.

Green synthesis of nZVI-modified biochar significantly enhanced the removal of Cr(VI) from aqueous solution.

Water contamination by hexavalent chromium (Cr(VI)) seriously jeopardizes human health, which is a pressing environmental concern. Biochar-loaded green-synthesized nZVI, as a green and environmentally friendly material, can efficiently reduce Cr(VI) to Cr(III) while removing Cr(VI) from water. Therefore, in this study, an efficient green-modified biochar material (TP-nZVI/BC) was successfully prepared using tea polyphenol (TP) and sludge biochar (BC) using a low-cost and environmentally friendly green synthesis method. The preparation conditions of TP-nZVI/BC were optimized using response surface methodology (RSM), revealing that the dosage of tea polyphenols plays a crucial role in the removal performance (R2 = 1271.09), followed by reaction time and temperature. The quadratic regression model proved accurate. The optimal preparation conditions are as follows: tea polyphenols (TP) dosage at 48 g/L, reaction temperature at 75 ℃, and a reaction time of 3 h. TP-nZVI/BC removed Cr(VI) from water at a rate 7.6 times greater than BC. The pseudo-second-order kinetic model (R2 = 0.987) accurately describes the adsorption process, suggesting that chemical adsorption predominantly controls the removal process. The adsorption of Cr(VI) by TP-nZVI/BC can be well described by the Langmuir model, and the maximum adsorption capacity reached 105.65 mg/g. FTIR and XPS analyses before and after adsorption demonstrate that nZVI plays a crucial role in the reduction process of Cr(VI), and the synergistic effects of surface adsorption, reduction, and co-precipitation enhance Cr(VI) removal. In summary, using green-modified biochar for Cr(VI) removal is a feasible and promising method with significant potential.

Systematic evaluation of methods for iron-impregnation of biochar and effects on arsenic in flooded soils.

There is a need for innovative strategies to decrease the mobility of metal(loids) including arsenic (As) and cadmium (Cd) in agricultural soils, including rice paddies, so as to minimize dietary exposure to these toxic elements. Iron (Fe)-modified biochars (FBCs) are used to immobilize As and Cd in soil-water systems, but there is a lack of clarity on optimal methods for preparing FBCs because there are only limited studies that directly compare BCs impregnated with Fe under different conditions. There is also a lack of information on the long-term performance of FBCs in flooded soil environments, where reductive dissolution of Fe (oxy)hydroxide phases loaded onto biochar surfaces may decrease the effectiveness of FBCs. This study uses material characterization methods including FTIR, SEM-EDX, BET, and adsorption isotherm experiments to investigate the effects of Fe-impregnation methods (pH, pyrolysis sequence, and sonication) on the morphology and mineralogy of Fe loaded onto the biochar surface, and to FBC adsorbent properties for arsenate (As(V)), arsenite (As(III)), and Cd. Acidic impregnation conditions favored the adsorption of As(III) onto amorphous Fe phases that were evenly distributed on the biochar surface, including within the biochar pore structure. The combination of sonication with acidic Fe-impregnation conditions led to the best adsorption capacities for As(V) and As(III) (4830 and 11,166 µg As g-1 biochar, respectively). Alkaline Fe-impregnation conditions led to the highest Cd adsorption capacity of 3054 µg Cd g-1 biochar, but had poor effectiveness as an As adsorbent. Amending soil with 5% (w/w) of an acid-impregnated and sonicated FBC was more effective than an alkaline-impregnated FBC or ferrihydrite in decreasing porewater As concentrations. The acid-impregnated FBC also had greater longevity, decreasing As by 54% and 56% in two flooded phases, probably due to the greater stability of Fe(III) within the biochar pore structure that may have a direct chemical bond to the biochar surface. This study demonstrates that FBCs can be designed with selectivity towards different As species or Cd and that they can maintain their effectiveness under anaerobic soil conditions. This is the first study to systematically test how impregnation conditions affect the stability of FBCs in soils under multiple drying-rewetting cycles.