Metals In Biochar Research Articles

Biochar in the Bioremediation of Metal-Contaminated Soils

Biochar is produced from a wide variety of feedstocks (algal biomass, forest, agricultural and food residues, organic fraction of municipal waste, sewage sludge, manure) by thermochemical conversion. In general, it is a dark, porous material with a large surface area, low density, high cation exchange capacity, and alkaline pH. By reducing the content of harmful substances in the soil, the application of biochar increases the activity, number, and diversity of microorganisms and improves plant growth in contaminated areas. The aim of the review was to explore the advantages and drawbacks of biochar use in soil bioremediation. General issues such as methods of biochar production, its physical and chemical properties, and various applications are presented. As biochar is an efficient adsorbent of heavy metals, the review focused on its benefits in (I) soil bioremediation, (II) improvement of soil parameters, (III) reduction of metal toxicity and bioaccumulation, (IV) positive interaction with soil microorganisms and soil enzymatic activity, and (V) promotion of plant growth. On the other hand, the potential risks of biochar formulation and utilization were also discussed, mainly related to the presence of heavy metals in biochar, dust hazard, and greenhouse gases emission.

Immobilization of Heavy Metals in Biochar Derived from Biosolids: Effect of Temperature and Carrier Gas

Slow pyrolysis was carried out in biosolids under three different temperatures (400, 500 and 600 °C) and two different carrier gases (CO2 and N2) on a fluidized bed reactor. The total concentration, chemical fractionation, and plant availability of the heavy metals in biochar were assessed by standard methods. The total concentration of Fe, Zn, Cu, Mn, Cr, Ni and Pb increased with the conversion of biosolids to biochar and with increasing pyrolysis temperature. The community’s Bureau of Reference (BCR) sequential extraction identified the migration of metals from toxic and bioavailable to potentially stable available or non-available forms at higher pyrolysis temperatures. Diethylenetriamine penta-acetic acid (DTPA)-extractable metals (Cu, Zn, Cd, Cu, Fe and Pb) were significantly lower in biochar compared to biosolids. By replacing N2 with CO2, the total metal concentration of heavy metals was significantly different for Mn, Ni, Cd, Pb and As. There were larger amounts of metals in the residual and oxidizable fractions compared to when N2 was used as a carrier gas. Consequently, the biochar produced at higher temperatures (500 and 600 °C) in the N2 environment exhibited lower potential ecological risks than in CO2 environments (69.94 and 52.16, respectively, compared to values from 75.95 to 151.38 for biochars prepared in N2). Overall, the results suggest that the higher temperature biochar can support obtaining environmentally safe biochar and can be effective in attenuating the ecological risks of biosolids.

Exploring the traits and possible ecological risks of heavy metals in biochars derived from rice husk and sugar beet pulp.

This research investigated the properties and potential environmental hazards associated with biochars derived from rice husk (RH) and sugar beet pulp (SBP), both of which are rich in heavy metals (HMs). The results indicated that the concentration of various HM fractions is significantly affected by the type of feedstock and the pyrolysis temperature. Specifically, the total concentrations of HMs in biochars produced at 600°C were found to be 10-140% higher than those in the original biomasses, a phenomenon attributed to the precipitation of HMs. Cd was a notable exception, exhibiting a reduction of 3-7% in the resultant biochars when compared to biomass, likely attributable to its volatilization. The results also revealed that the F1 + F2 fraction of HMs were largely transformed into F3 + F4 fraction during combustion, indicating that pyrolysis may reduce the ecotoxicity of HMs present in contaminated biomass. However, the process did not effectively diminish the F1 and F2 fractions of Cr and Cd. Elevated pyrolysis temperature significantly enhanced the reduction of HMs phytoavailability. Specifically, the phytoavailability of HMs in biochars produced at 600°C exhibited a decrease ranging from 10 to 92% when compared to the original biomass. Conversely, an unexpected rise in the phytoavailable fractions of Cr and Cd was noted in both RH and SBP biochars as the pyrolytic temperature increased, which correspondingly raised the potential ecological risk index (PERI). All materials analyzed exhibited a very high risk level, with PERI values exceeding 800, primarily due to the significant toxicity of Cd. Excluding Cd from consideration, the biomasses and their resultant biochars displayed PERI values ranging from 7 to 13. It is important to acknowledge that pyrolysis may not effectively diminish the environmental toxicity associated with HMs present in contaminated biomass, thereby limiting its safe application.

Environmental risks and agronomic benefits of industrial sewage sludge-derived biochar.

The main objective of the present work was to assess the ecotoxicological safety of the use of thermochemically treated sewage sludge from the wastewater treatment plant (WWTP) of a distillery plant as a soil additive in agricultural soils based on its physicochemical characteristics and the bioaccumulation of selected elements in the plant tissues of maize (Zea mays). We have carried out physicochemical characterization (pH, EC, Corg, Cinorg, CEC, N, H, ash content, PAHs) of sewage sludge feedstock (SS) and sludge-derived biochar (BC) produced by slow pyrolysis at a temperature of 400 °C. The effect of 1% (w/w) amendment of SS and BC on soil physicochemical properties (pH, EC, Cinorg), germination of ryegrass, soil rhizobacteria and microorganisms, as well as on the accumulation and translocation of selected elements in maize (Zea mays) was studied. The results show that pyrolysis treatment of distillery WWTP sludge at 400 °C increases pH (from 7.3 to 7.7), Corg(from 28.86% to 36.83%), N (from 6.19% to 7.53%), ash content (from 23.59% to 50.99%) and decreases EC (from 2.35 mS/cm to 1.06 mS/cm), CEC (from 118.66 cmol/kg to 55.66 cmol/kg), H (from 6.76% to 1.98%) and Σ18 PAHs content (from 4.03 mg/kg to 3.38 mg/kg). RFA analysis of SS and BC showed that pyrolysis treatment multiplies chromium (Cr) (2.2 times), nickel (Ni) (2.96 times), lead (Pb) (2.13 times), zinc (Zn) (2.79 times), iron (Fe) (1.26 times) in the obtained BC, but based on an ecotoxicological test with earthworms Eisenia fetida, we conclude that pyrolysis treatment reduced the amount of available forms of heavy metals in BC compared to SS. We demonstrated by a pot experiment with a maize that a 1% addition of BC increased soil pH, decreased EC and Cinorg and had no significant effect on heavy metal accumulation in plant tissues. According to the results of the three-level germination test, it also does not affect the germination of cress seeds (Lepidium sativum). There was a significant effect of 1% BC addition on soil microbial community, and we observed a decrease in total microbial biomass and an increase in fungal species variability in the soil. Based on these results, we conclude that BC represents a promising material that can serve as a soil additive and source of nutritionally important elements after optimization of the pyrolysis process.

Endogenous iron-enriched biochar derived from steel mill wastewater sludge for tetracycline removal: Heavy metals stabilization, adsorption performance and mechanism

Steel mill wastewater sludge, as an iron-enriched solid waste, was expected to be converted into iron-enriched biochar with acceptable environmental risk by pyrolysis. The purpose of our study was to evaluate the chemical speciation transformation of heavy metals in biochar under various pyrolysis temperatures and its reutilization for tetracycline (TC) removal. The experimental data indicated that pyrolysis temperature was a key factor affecting the heavy metals speciation and bioavailability in biochar, and biochar with pyrolysis temperature at 450 °C was the most feasible for reutilization without potential risk. The endogenous iron-enriched biochar (FSB450) showed highly efficient adsorption towards TC, and its maximum adsorption capacity could reach 240.38 mg g−1, which should be attributed to its excellent mesoporous structure, abundant functional groups and endogenous iron cycling. The endogenous iron was converted to a stable iron oxide crystalline phase (Fe3O4 and MgFe2O4) by pyrolysis, which underwent a valence transition to form a coordination complex with TC by electron shuttling in the FSB450 matrix. The study provides a win-win approach for resource utilization of steel wastewater sludge and treatment of antibiotic contamination in wastewater.

Optimization of liquefaction process based on global meta-analysis and machine learning approach: Effect of process conditions and raw material selection on remaining ratio and bioavailability of heavy metals in biochar

<abstract> <p>Although liquefaction technology has been extensively applied, plenty of biomass remains tainted with heavy metals (HMs). A meta-analysis of literature published from 2010 to 2023 was conducted to investigate the effects of liquefaction conditions and biomass characteristics on the remaining ratio and chemical speciation of HMs in biochar, aiming to achieve harmless treatment of biomass contaminated with HMs. The results showed that a liquefaction time of 1–3 h led to the largest HMs remaining ratio in biochar, with the mean ranging from 84.09% to 92.76%, compared with liquefaction times of less than 1 h and more than 3 h. Organic and acidic solvents liquefied biochar exhibited the greatest and lowest HMs remaining ratio. The effect of liquefaction temperature on HMs remaining ratio was not significant. The C, H, O, volatile matter, and fixed carbon contents of biomass were negatively correlated with the HMs remaining ratio, and N, S, and ash were positively correlated. In addition, liquefaction significantly transformed the HMs in biochar from bioavailable fractions (F1 and F2) to stable fractions (F3) (<italic>P</italic> < 0.05) when the temperature was increased to 280–330 ℃, with a liquefaction time of 1–3 h, and organic solvent as the liquefaction solvent. N and ash in biomass were positively correlated with the residue state (F4) of HMs in biochar and negatively correlated with F1 or F2, while H, O, fixed carbon, and volatile matter were negatively correlated with F4 but positively correlated with F3. Machine learning results showed that the contribution of biomass characteristics to HMs remaining ratio was higher than that of liquefaction factor. The most prominent contribution to the chemical speciation changes of HMs was the characteristics of HMs themselves, followed by ash content in biomass, liquefaction time, and C content. The findings of this meta-analysis contribute to factor selection, modification, and application of liquefied biomass to reducing risks.</p> </abstract>

Effect of different calcium salts on phosphorus availability and immobilization of heavy metals in municipal sludge derived biochar

Transforming municipal sludge (MS) into biochar via co-pyrolysis with calcium salts enhances phosphorus (P) recovery and reduces the risk of heavy metal contamination. In this study, the performance and mechanism of bioavailable P conversion and heavy metal stabilization were systematically compared under co-pyrolysis of MS with CaCO3, CaO, and CaCl2 at mass ratios of 2.5–10 % at 700 °C. The results showed that CaCl2 had the best ability to convert P from non-apatite inorganic P to apatite P, followed by CaO and then CaCO3. CaO and CaCO3 addition induced more Ca5(PO4)3OH formation, while CaCl2 induced more Ca2PO4Cl and Ca5(PO4)3Cl formation. The degree of stabilization of heavy metals (e.g., Cd, Cr, Cu, Ni, Pd, and Zn) was significantly improved after co-pyrolysis of MS with these salts, thus reducing the potential environmental risk. In particular, because of the dual action mechanism of chloride ions and calcium ions, co-pyrolysis with CaCl2 exhibited the lowest risk of heavy metal contamination compared with CaCO3 and CaO. These findings suggest that addition of 2.5 % CaCl2 can optimize the production of bioavailable P and the stabilization of heavy metals in biochar. This treatment is recommended for the safe utilization of P resources derived via MS pyrolysis.

Influence of the pyrolysis temperature on fresh and pelletised chicken litter with focus on sustainable production and utilisation of biochar

AbstractThis study focused on determining the influence of temperature (500–700 °C) during pyrolysis of pelletised chicken litter (PCL) and fresh chicken litter (FCL). The composition of all pyrolysis products was analysed, and their potential applications were discussed. An analysis of phosphorus speciation in FCL and PCL along with their derived biochars revealed that the share of water-soluble phosphorus was greatly reduced in the biochar, implying lower risk of eutrophication in agricultural applications of biochar when used as a soil improver. Indeed, water-soluble phosphorus decreased from 60% for PCL to as low as 3% for the biochars. In addition, the concentration of other nutrients and heavy metals in biochar, and its potential for agriculture application was discussed. Heavy metals content was below the upper limits set out in the European Fertilising Products Regulation only for biochars produced at 500 °C, but biochars produced at higher temperatures did not meet the limits for Zn and Ni content. The energy balance analysis showed that pelletisation of chicken litter is not necessary, as the properties of both PCL and FCL allow for energetically sustainable pyrolysis when hot pyrolysis gas is combusted, and biochar recovered for nutrient recycling.

Co-thermal conversion, atmosphere, and blend type controls over heavy metals in biochars and bottom slags of textile dyeing sludge and durian shell

The co-thermal conversions of textile dyeing sludge ((TDS) with biomass may be turned into a feasible and green technology to valorize energy and products, but the transformation behavior of heavy metals remains unclear. This study aimed to quantify the migrations and distributions of HMs in biochars and bottom slags and their environmental risks in response to the co-pyrolysis and co-combustion of durian shell (DS) and TDS, atmosphere type, blend ratio, and temperature. The co-combustion interaction of DS and TDS raised the residual HM contents of the bottom slag. Co-pyrolysis reduces the environmental risks of HMs of the TDS, and the effect of CO2 atmosphere is better. In 80N220O2, Cr, Zn, and Cu in the TDS bottom slag had the highest leaching toxicity concentrations at 900 °C. At 800 °C, the leaching toxicity concentrations of HMs were Cr > Cu > Zn > Mn in TDS. The O2 concentration and atmosphere type did not significantly affect the HM morphology and transformation. K increased the temperature of converting solid-phase Ni to slag-phase NiO in DS sample and affected the transformation temperature and strength of Ni, Zn, and Pb in other sample at the high temperature. The combined results of all the three optimizations of HM contents, forms, and risks pointed to add 50 % DS in the N2 atmosphere and add 50 % DS in 50N250O2 and 80CO220O2 atmospheres as the optimal co-pyrolysis/combustion settings, respectively.

Fate and distribution of phosphorus in coking wastewater treatment: From sludge to its derived biochar

Due to the phosphorus (P) deficiency in coking wastewater, sufficient P needs to be provided in the treatment process to maintain biotic activity. However, most of the dosed P sources are transferred to the sludge phase out of the chemical equilibrium. After an in-depth investigation of P morphology changes in coking wastewater treatment, it is found that above 71.6 % P applied to the full-scale O/H/H/O (oxic-hydrolytic & denitrification-hydrolytic & denitrification-oxic) process for coking wastewater treatment is ended up in the sludge phase of the aerobic reactors in the forms of non-apatite inorganic phosphorus (NAIP). Theoretical simulations suggest that the P forms precipitates such as FePO4·2H2O, AlPO4·2H2O, MnHPO4 at pH < 7, and Ca5(PO4)3OH at pH > 7. Microbial utilization of P in coking wastewater treatment is swayed by precipitation, pH and sludge retention time (SRT). By pyrolysis treatment of the waste sludge at 700 °C, phosphoric substances in coking sludge are enriched and converted into Ca5(PO4)3OH, Ca5(PO4)3Cl, Ca3(PO4)2, etc. with apatite phosphorus (AP) accounting for 65.7 % of total phosphorus. Moreover, the heavy metals in biochar were below the national standard limits for discharge. This study shows that hazardous waste (coking sludge) can be transformed into bioavailable products (P-rich biochar) through comprehensive management of the fate of P. Combined with the O/H/H/O process, the mechanisms of phosphorus consumption in coking wastewater treatment are revealed for the first time, which will facilitate a reduced consumption of phosphorus and provide a demonstration for other phosphorus-deficient industrial wastewater treatment.

Component Properties and Heavy Metal Accumulation Characteristics of Contaminated Rice Straw Biochar During Oxygen-controlled Pyrolysis

Pyrolysis is an important technology to achieve the harmlessness and recycling of contaminated biomass. In this study, the effects of oxygen-controlled atmosphere on the component properties and heavy metal accumulation characteristics of contaminated rice straw biochar were studied. The results showed that low-oxygen pyrolysis could effectively produce biochar using contaminated rice straw and improve the stability of heavy metals in biochar. Under the nitrogen atmosphere, the yield of rice straw biochar was 29.4%-34.9%. The aromatization index (SUVA254) of dissolved organic matter (DOM) increased first and then decreased with the increase in pyrolysis temperature, whereas the fluorescent components were mainly humic-like acid substances. Meanwhile, Ca mainly existed in the form of CaCO3 in biochar. Compared with the pure nitrogen condition, the biochar yield was reduced by 5.6%-13.5% and 14.9%-15.7% under the pyrolysis atmosphere containing 10% and 20% oxygen content, respectively. Ca existed in the form of CaO in biochar, which increased the pH value of the biochar by more than 0.5 units. The oxygen of the pyrolysis atmosphere accelerated the degradation of the lignin component, resulting in the gradual decrease in SUVA254 of DOM. With the increase in oxygen content in the pyrolysis atmosphere, humic-like acid substances in DOM were transformed into fulvic-like acid substances. Under the conditions of 400℃ and a 10% oxygen-containing atmosphere, the exchangeable fractions of Cu, Cd, Pb, Ni, and As in biochar were decreased by 5.2%, 3.7%, 1.7%, 0.8%, and 0.7%, respectively, indicating that heavy metals are transformed into more stable states. The results suggested that the higher biochar yield and heavy metal stability could be obtained by introducing a proper amount of nitrogen into the air (controlling the oxygen content of approximately 10%) for pyrolysis treatment of contaminated rice straw, providing an economic and feasible technology for the achievement of harmlessness and recovery of contaminated rice straw.

Particle size of biochar significantly regulates the chemical speciation, transformation, and ecotoxicity of cadmium in biochar

The pyrolysis of biomass containing excessive heavy metals is likely to produce heavy metal contaminated biochar (BC). Although multiple lines of evidence indicate that higher charring temperature leads to enhanced immobilization of heavy metals in BC, we find that particle size could also play a critical role in the content of heavy metals in BC and BC ecotoxicity. Here, BC derived from cadmium (Cd) enriched rice straw was prepared at different temperatures (300–600 °C) and divided into macro-, colloidal-, and nano-sized fractions, respectively. The content and chemical forms of Cd in BC fractions as well as related algal toxicity were examined. The results show that for the same temperature BC the content of Cd followed an order of colloidal-BC > macro-BC > nano-BC; and the residual fractions of Cd significantly decreased (3.47–16.08%) while that of acid soluble and reducible fractions significantly increased (4.13–16.51% and 0.24–1.71%, respectively) with decreasing particle size of BC. Consistently, colloidal-BC exhibited the highest ecotoxicity for Scenedesmus obliquus. The acid soluble fractions of Cd in macro- and colloidal-BC played a dominating role in their algal toxicity (p < 0.05). However, the ecotoxicity of nano-BC was more dependent on the total content of Cd than specific fractions probably due to the phagocytosis by algal cells. These results indicate that the chemical forms and ecotoxicity of Cd in BC could be remarkably modified by its particle size, which has profound implications for understanding the behavior and potential risk of heavy metal contaminated BC in the environment.

Co-pyrolysis of sewage sludge and poplar sawdust under controlled low-oxygen conditions: Biochar properties and heavy metals behavior

Biochar production by pyrolysis of sewage sludge (SS) is one of effective ways to realize resource recovery and harmless treatment of SS. However, biochar prepared by direct pyrolysis of SS has a lower specific surface area and higher heavy metal content. This study was aimed to evaluate the effect of low-oxygen and addition of poplar sawdust (PS) on sludge-derived biochar. The properties of biochar and heavy metals behavior were systematically characterized. The presence of 10% O2 during SS pyrolysis had a significant effect on the specific surface area of the pyrolytic biochar and the chemical species of heavy metals. In comparison with the pyrolytic biochar under N2 atmosphere, the yield of co-pyrolytic biochar from 10% O2 decreased by 6.7% at 350 °C and 8.3% at 650 °C, while it had the highest fixed carbon content of 19.6%. Moreover, the addition of PS also increased the specific surface area of pyrolysis biochar to 26.8 m2 g−1 at 650 °C. With the increase of pyrolysis temperature, heavy metals including Zn, Cr, and Cu in SS were transformed from the exchangeable and reducible states to oxidizable states and residue states. Especially, the presence of 10% O2 can also promote the formation of oxidizable states of heavy metals in biochar. Based on risk assessment code analysis, the ecotoxicity of heavy metals in biochar with the presence of O2 was evidently lowered. Therefore, a low oxygen atmosphere and co-pyrolysis of sludge and biomass could be effective ways to improve the quality of sludge-based biochar.

Influence of Technical Parameters of the Pyrolysis Process on the Surface Area, Porosity, and Hydrophobicity of Biochar from Sunflower Husk Pellet

Biochar is a product that has been of interest to many researchers in recent years. The use and positive effect of biochar depend on its properties, which in turn result primarily from the type of substrate used for production and the technical parameters of the pyrolysis process used. From the point of view of sustainable development, agricultural raw materials, such as sunflower husks, are good materials for biochar synthesis. The research aimed to determine the effect of changing the technical parameters of the pyrolysis process (i.e., temperature, heating rate, and residence time) on the properties of biochar obtained from sunflower husk pellets. The pellets were heated to 480 °C, 530 °C, and 580 °C. The applied heating rate for 480 °C was 4.00 and 7.38 °C·min−1, for 530 °C it was 4.42 and 8.15 °C·min−1 and for 580 °C it was 4.83 and 8.92 °C·min−1. Determining these properties is important due to the use of biochar, e.g., in the processes of sorption of pollutants from the water and soil environment. The technical parameters of the pyrolysis process used allowed us to obtain hydrophilic materials with porosity in the range of 10.11% to 15.43% and a specific surface area of 0.93 m2·g−1 to 2.91 m2·g−1. The hydrophilic nature of biochar makes it possible to use them in the processes of removing inorganic pollutants and polar organic pollutants. The presence of macropores in biochar may contribute to the improvement of water management in the soil and affect the assimilation of microelements by plants. The low content of heavy metals in biochar does not pose a threat to the environment.

Immobilization effect of heavy metals in biochar via the copyrolysis of sewage sludge and apple branches

The excess sludge produced by sewage treatment plants can be recycled into energy through pyrolysis, and the byproduct biochar can be used for soil remediation. However, the heavy metals in sludge are retained in biochar after pyrolysis and may cause secondary pollution during its soil application. Herein, a fast copyrolysis method of activated sludge (AS) and apple branches (AT) was proposed to immobilize heavy metals while improving bio-oil yield. The results showed that the heavy metal release from the copyrolyzed biochar was markedly reduced compared with that from the biochar produced through the pyrolysis of AS alone (78% for Cr and 28% for Pb). The kinetic behavior of ion release from different biochars could be described by a first-order kinetic model. The excellent fixation of heavy metals was attributed to complexation by abundant oxygen-containing surface functional groups (–O–, =O, and –CHO) that were mainly donated by AT. Furthermore, high-temperature pyrolysis was conducive to the fixation of metals, and the release of Pb2+ and Cr3+ from the biochar pyrolyzed at 600 °C was approximately 2/3 and 1/10 of that from the biochar pyrolyzed at 400 °C, respectively. A growth experiment on Staphylococcus aureus and Escherichia coli revealed that the toxicity of the copyrolyzed biochar was greatly reduced. This work can provide a method for heavy metal fixation and simultaneous resource recovery from organic wastes.

Immobilization of heavy metals in biochar by co-pyrolysis of sludge and CaSiO3

Sludge pyrolysis has become an important method of sludge recycling. Stabilizing heavy metals in sludge is key to sludge recycling. Currently, research on the co-pyrolysis of sludge and industrial waste is limited. This study aims to explore the impact and mechanism of the co-pyrolysis of sludge and CaSiO3 (the main component of slag) and to achieve the concept of “treating waste with waste”. To this end, we added different proportions of CaSiO3 (0%, 3%, 6%, 9%, 12%, and 15%) for the co-pyrolysis with sludge, and varied the pyrolysis temperatures (300, 400, 500, 600, and 700 °C) and retention times (15, 30, 60, and 120 min) to study heavy-metal stabilization in sludge. Consequently, the optimum dosage of CaSiO3 required for the immobilization of different heavy metals was 9% (Cu, Zn, Pb, and Cr) and 15% (Ni). The contents of Cu, Zn, Pb, Cr, and Ni in the stable state (oxidized and residual states) were 92.73%, 79.23%, 99.55%, 92.43% and 90.33% respectively. At a pyrolysis temperature of 700 °C, the steady-state proportions of Cr, Pb, and Zn were 88.12%, 90.21%, and 77.21%, respectively. At a pyrolysis temperature of 400 °C, the stable-Cu and -Ni contents were 97.21% and 99.43%, respectively. The optimal dwelling time was 15 min. The results showed that the CaSiO3 addition weakened the O–H stretching vibration peak intensity, promoted the formation of aromatic and epoxy ring structures, and enhanced the heavy-metal immobilization. Furthermore, the CaSiO3 decomposition during co-pyrolysis produced SiO2, CaO, and Ca(OH)2, which helped stabilize heavy metals.

Advancement pathway of biochar resources from macroalgae biomass: A review

Macroalgae, with short growth cycles, and high CO2 fixation capacity, are third-generation biomass mainstays that play an essential role as a global carbon sink. Macroalgal biochar plays a crucial role in soil improvement, pollutant adsorption, electrodes, and capacitors, and it has already contributed to both ecological and economic fields. However, the physicochemical properties of macroalgal biochar are challenging to control, and the way macroalgal biochar is pyrolyzed and activated largely determines its physicochemical properties and areas of application. In this study, five standard methods (conventional pyrolysis, hydrothermal carbonization, microwave pyrolysis, co-pyrolysis, and drying) for the pyrolysis of macroalgal biochar and two activation methods (physical and chemical) are reviewed to screen for optimal preparation and activation methods under different conditions and in different application contexts. The conventional pyrolysis process is mature and simple, but the yield is low, which is suitable for industrial production. Hydrothermal carbonization can reduce the content of alkali metals in biochar without prior drying. Microwave pyrolysis has low energy consumption and uniform product properties, which is suitable for biochar with high stability requirements. Co-pyrolysis is a low-cost pyrolysis method if suitable co-pyrolysis materials can be found. The drying ash content is high, but the surface performance is weak, which is generally used as pretreatment. From laboratory to practical applications, macroalgal biochar still needs to be investigated in terms of cost reduction, yield improvement, and optimization of preparation and activation methods.

Co-pyrolysis of sewage sludge with polyvinyl chloride (PVC)/CaO: Effects on heavy metals behavior and ecological risk

As an attractive method to recover energy and reduce heavy metals in the resultant biochar, co-pyrolysis of sewage sludge with polyvinyl chloride (PVC) plastics may increase the ecological risk of heavy metals. Considering the sound performance of CaO in dechlorination and immobilization of heavy metals, pyrolysis experiments were performed on four feedstocks and combined with the analysis of heavy metals to investigate the effects of temperature and added PVC/CaO on the behavior of As, Cr, Cu, Ni, Pb, and Zn. The results indicated that, increased temperature and added PVC could reduce the content of As, Pb, and Zn in biochar while CaO had the opposite effect, and the temperature set here had limited effect on the volatilization of Cr, Cu, and Ni with more than 90% of them remaining in biochar. Besides, compared with untreated sewage sludge, higher temperature and extra CaO could reduce the ecological risk of heavy metals in biochar by transforming them into more stable forms while the added PVC inhibited the transformation. When both PVC and CaO were present in pyrolysis system, although the ecological risk of heavy metals in biochar caused by PVC could be partially offset by increasing temperature and introducing CaO, it was still higher than that of other biochar. This study provides valuable insights for the treatment of heavy metals during sludge pyrolysis.

Co-pyrolysis of sewage sludge and metal-free/metal-loaded polyvinyl chloride (PVC) microplastics improved biochar properties and reduced environmental risk of heavy metals

Co-pyrolysis of sewage sludge and plastics have been utilized for producing biochars as a strategy to fix plastic pollution. However, comparative studies on the characteristics and environmental risk of heavy metals in biochars obtained by the co-pyrolysis of sludge and microplastic with/without metal additives are seldom. Here we demonstrated the effects of simulated co-pyrolysis (at 400 °C) of sewage sludge and metal-free or metal-loaded polyvinyl chloride (PVC) microplastics at different mass ratios (1:0, 19:1, 3:1, 1:3, sewage sludge: PVC (w/w)) respectively. Results revealed that co-pyrolysis of metal-loaded PVC and sewage sludge resulted in higher electrical conductivity, ash content, and an acidic pH of biochars as compared to the co-pyrolysis of metal-free PVC and sewage sludge. Addition of metal-loaded PVC increased total concentrations of calcium (Ca), magnesium (Mg), cadmium (Cd), and lead (Pb) in biochars, but reduced the bioavailability of Cd, chromium (Cr), nickel (Ni), and zinc (Zn) in biochars. Analysis of chemical speciation showed that heavy metals (except Pb) in biochars derived from co-pyrolysis of sewage sludge and metal-loaded PVC had higher percentage of more stable fraction (residual fraction) and lower potential ecological risk index (RI) value. S1AP3 (sludge: metal-loaded PVC = 1:3) biochar had the lowest environmental risk based on RI value (14.41). To sum up the present study suggests that the addition of metal-loaded PVC microplastic in sewage sludge had a positive impact on the immobilization of heavy metals during co-pyrolysis process.

Co-Pyrolysis of Sewage Sludge and Wetland Biomass Waste for Biochar Production: Behaviors of Phosphorus and Heavy Metals.

Large amounts of sewage sludge (SS) and wetland plant wastes are generated in the wastewater treatment system worldwide. The conversion of these solid wastes into biochar through co-pyrolysis could be a promising resource utilization scheme. In this study, biochar was prepared by co-pyrolysis of SS and reed (Phragmites australis, RD) using a modified muffle furnace device under different temperatures (300, 500, and 700 °C) and with different mixing ratios (25, 50, and 75 wt.% RD). The physicochemical properties of biochar and the transformation behaviors of phosphorus (P) and heavy metals during the co-pyrolysis process were studied. Compared with single SS pyrolysis, the biochar derived from SS-RD co-pyrolysis had lower yield and ash content, higher pH, C content, and aromatic structure. The addition of RD could reduce the total P content of biochar and promote the transformation from non-apatite inorganic phosphorus (NAIP) to apatite phosphorus (AP). In addition, co-pyrolysis also reduced the content and toxicity of heavy metals in biochar. Therefore, co-pyrolysis could be a promising strategy to achieve the simultaneous treatment of SS and RD, as well as the production of value-added biochar.