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Observed nowadays wide pollution of the environment with microplastic and phthalic acid esters (PAEs) (such as dimethyl phthalate, DMP; diethyl phthalate, DEP; dibutyl phthalate, DBP; benzyl butyl phthalate, BBP; di-(2-ethylhexyl) phthalate, DEHP and di-n-octyl phthalate, DNOP) is a result of their increased production and usage. Weak bonding with polymer matrix enables their easier mobilization in the environment and increased bioavailability. The aim of the presented studies was the estimation of the fate of six priority PAEs in the soil-vegetable system and the application of biochar to immobilize PAEs in the soil preventing their bioavailability to lettuce. Both the acute (one full lettuce development period) and prolongated effect (lettuce cultivated after 10 weeks from the first PAEs contamination) were estimated to examine the long-time exposure under crop rotation. The addition of 1 % of corn-derived biochar immobilized PAEs in the soil efficiently (up to 4 times increased concentration) with the following order: DBP < DEP < DMP < DEHP < DNOP < BBP. Bioavailable PAEs were determined in lettuce roots (DMP, BBP, DEHP), and lettuce leaves (DEP, DBP, DNOP) but the presence of biochar lowered their content. PAEs, although not available for lettuce, were available for other organisms, confirming that the bioavailability or lack of nutrients is of great importance in PAEs-polluted soil. In long-time experiments, without biochar amendment, all PAEs were 3-12 times more bioavailable and were mainly accumulated in lettuce roots. The biochar addition significantly reduces (1.5-11 times) PAEs bioavailability over time. However, the PAEs content in roots remained significantly higher in samples with crop rotation compared to samples where only lettuce was grown. The results confirmed that biochar addition to the soil reduces their bioavailability and mobility inside the plant, limiting their transport from roots to leaves and reducing the exposure risk but confirming that lettuce leaves may be a safe food when cultivated in PAEs-polluted soil., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Agricultural or environmental application of biochar (BC) is connected with the introduction of biochar-derived components among which polycyclic aromatic hydrocarbons (PAHs) and heavy metals are the most toxic. Their presence and bioavailability are crucial considering biochar toxicity. The effect of feedstock and pyrolysis temperature on the physicochemical properties of produced biochar and contaminant content was established and combined with toxicity to a broad range of living organisms. The obtained data revealed that predicting the bioavailability of PAHs using the total content is misleading. The toxicity was influenced by factors in the following way: the bioavailable PAHs > ash > total PAHs content in BC stressing the role of BC physicochemical characteristics. Among tested BC properties, surface functionalization, e.g. presence of oxygen-containing functional groups was crucial in revealing the toxicity. The data clearly indicate that additional research is required to determine BC's impact on various organisms and performing one ecotoxicity test is not sufficient., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Bozena Czech reports financial support was provided by National Science Centre Poland. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Persistent free radicals (PFRs) in biochar can influence biochar reactivity, promoting organic contaminant degradation or even causing certain toxic impacts. However, the PFR generation mechanism is not still well understood. An investigation of the relationship between PFR formation and the chemical structure of biochar is essential for understanding the PFR formation mechanism. Our in situ measurement results showed that PFR intensities increased from 0-509.5 to 146-5678 a.u. after being pyrolyzed at 300 °C for 60 min. The significant positive correlation between PFR intensities and the peak areas of C═O and aromatic C═C groups indicated that the generation of PFRs was highly dependent on the C═O and aromatic C═C structures. The reduction of biochars by KBH 4 resulted in a 32.2 ± 2.49% decrease in the C═O content and a relative increase in the C-O content, while other physicochemical properties did not change. Thus, the observed 49.3% decrease in PFR signals after this reduction suggested that the reducible C═O groups, possibly in aldehydes, aromatic ketones, and quinones, were closely associated with PFRs in biochars. This study provides an in situ insight into the PFR generation mechanism and guides the corresponding biochar design and property manipulation.

The aim of this study was to determine the effect of abiotic aging of sewage sludge (SSL)-derived biochars on their physicochemical properties and in consequence on their stability. Biochars produced at 500 or 700 °C from SSLs with a different composition and properties were incubated at different temperatures (-20, 4, 20, 60, and 90 °C) for 6 and 12 months. Pristine and aged biochars were characterized in terms of their composition and properties using a range of complementary methods. The results showed that SSL-derived biochars will not be as stable as previously thought in the long term. The stability of the SSL-derived biochars was closely related to the content and character of C. The biochars that had more C in their composition and, apart from aromatic C, also aliphatic matter/carbon substances deposited in surface pores (i.e. those produced from SSL with a lower initial ash content and a lower degree of aromaticity) were less stable than the biochars with a lower C content and a typically aromatic character of C (i.e. those derived from SSL with a higher initial ash content and a higher degree of aromaticity). Their oxidation led to partial mineralization of aliphatic chains or organic surface film and manifested itself in a greater changes in their properties. The low-temperature biochars (BC-500) with lower aromaticity were found to be more susceptible to oxidation than the high-temperature ones (BC-700) with higher aromaticity. The more aromatic structure of C limited access of O 2 molecules to biochar interior, due to which the processes occurring during aging were concentrated in their surface layer and their properties were less change. It can therefore be concluded that pyrolysis of SSL with higher aromaticity and a lower organic content and higher pyrolysis temperatures will lead to obtaining more stable SSL-derived biochars., (Copyright © 2021. Published by Elsevier Ltd.)

The contamination of sediments by polycyclic aromatic hydrocarbons (PAHs) has been widely spread for years due to human activities, imposing the research and development of effective remediation technologies for achieving efficient treatment and reuse of sediments. In this context, the amendment of biochar in PAH-contaminated sediments has been lately proposed as an innovative and sustainable technology. This review provides detailed information about the mechanisms and impacts associated with the supplementation of biochar to sediments polluted by PAHs. The properties of biochar employed in these applications have been thoroughly examined. Sorption onto biochar is the main mechanism involved in PAH removal from sediments. Sorption efficiency can be significantly improved even in the presence of a low remediation time (i.e. 30 d) when a multi-PAH system is used and biochar is provided with a high dosage (i.e. by 5% in a mass ratio with the sediment) and a specific surface area of approximately 360 m 2  g -1 . The use of biochar results in a decrease (i.e. up to 20%) of the PAH degradation during bioaugmentation and phytoremediation of sediments, as a consequence of the reduction of PAH bioavailability and an increase of water and nutrient retention. In contrast, PAH degradation has been reported to increase up to 54% when nitrate is used as electron acceptor in low-temperature biochar-amended sediments. Finally, biochar is effective in co-application with Fe 2+ for the persulfate degradation of PAHs (i.e. up to 80%), mainly when a high catalyst dose and an acidic pH are used., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The total and available (water extracted) content of selected metal were determined in co-pyrolyzed SSL with willow (8:2, 6:2 w/w) at 500, 600, and 700 °C using two different carrier gases (N 2 or CO 2 ). The study investigated the relationship of metal content and bioavailability to toxicity of biochars towards bacteria (Vibrio fischeri), plants (Lepidium sativum), and arthropods (Folsomia candida). For the biochar produced at a ratio of 6:4 (SSL:willow), the content of most metals significant decrease (P ≤ 0.05) from 5.9% to 28.9%. Co-pyrolysis of SSL with willow decreased water extractable metal concentrations (Ba, Cd, Cu, Fe, Mn, Ni, and Zn) from 8.0% to 100%. The CO 2 resulted from 6 to 200 % increase (P ≤ 0.05) of metal content relative to the biochar pyrolyzed in N 2 . An increase in pyrolysis temperature caused a higher concentration of the metals in the biochars. The available content of most metals decreased from 9 to 100 %. The adverse effect of these biochars on living organisms was reduced due to a stronger binding of the metals (especially Cu and Cd) with the biochar matrix. The negative impact of Cd, Cr, and Cu on living organisms was also confirmed by principal component analysis (PCA)., (Copyright © 2020 The Author(s). Published by Elsevier B.V. All rights reserved.)

There is a discussion in the literature whether PAHs introduced with biochar are safe and whether they are persistent in the environment. The persistence of PAHs (C tot - total and C free - freely dissolved) in sewage sludge (SSL) or SSL-derived biochar-amended soils was investigated. Biochar were produced at 500, 600 and 700 °C. We also compared the persistence of PAHs in these experimental treatments depending on the plants cultivated (grass, clover and thale cress). We showed that the C tot PAHs in the biochar-amended soils exhibited higher persistence than in the SSL-amended soil. The opposite trend was observed for C free PAHs. A higher reduction of C free PAHs was noted in the biochar-amended soils than in SSL-amended soil. The persistence of both C free and C tot PAHs clearly varied between the biochars produced at different temperatures. It should be stated that despite that for biochar the persistence of C tot PAHs is higher compared to SSL-amended soils, an opposite trend is observed for the fraction of C free (which is directly responsible for the toxic effect), and this entails a lower risk to the environment (lower mobility and bioavailability). The plants had a significant impact on C tot PAHs content depending on the number of PAH rings., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The goal of the present work was to evaluate the speciation of cadmium (Cd), copper (Cu) and lead (Pb) in sewage sludge (SL) amended soil and SL-biochar (BC) amended soil in a long-term field experiment. SL or SL with biochar (at the dose of 2.5%, 5.0% or 10%) were applied to the soil. The dose of SL in the soil was 11 t dw /ha. At the beginning of the study, after 12 and 18 months the distribution of Cd, Cu and Pb was determined between the following fractions: (1) water soluble, exchangeable and bound to carbonates (F1), (2) bound to Fe-Mn oxides (F2), (3) bound to organic matter (F3) and (4) bound to quartz, feldspars, etc. (F4). The soil, SL and biochar were characterized by different distribution of Pb, Cu and Cd. The highest mobility of Cd and Cu was observed in the control soil, while Pb in SL. Addition of SL to the soil caused the increased of the mobility index of Cu and Pb, increasing the risk associated with the presence of these metals in the mobile soil fraction (F1). However, the addition of biochar to SL before application to the soil modified the distribution of studied elements. The most mobile and bioavailable fractions (F1) were transferred to less bioavailable (F2, F3) and potentially immobile fractions (F4)., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Organic-solvent extractable (C tot ) and freely dissolved (C free ) polycyclic aromatic hydrocarbons (PAHs) (US EPA 16 PAHs) were determined in biochars produced from the mixture of sewage sludge and sewage sludge and willow (8:2 or 6:4, w/w). The pyrolysis was carried out at 500, 600, and 700 °C using two different carrier gases (N 2 or CO 2 ). Addition of willow and the change of carrier gas from N 2 to CO 2 reduced C tot PAHs (from 7.0 to 52%) and C free PAHs (15-29%) content. Co-application of willow and SSL and the use of CO 2 as a carrier gas also beneficially affected the PAHs profile. The biochars produced with willow addition and/or in a CO 2 atmosphere were characterized by a lower (from 9.0 to 62.8%) percentage of 3-6-ring PAHs (C tot ) than the biochars derived from sewage sludge alone in N 2 atmosphere. The contribution of individual C free PAHs did not differ significantly between biochars. The presence of willow during pyrolysis influenced the direction of the changes in the C tot PAH content depending on the pyrolysis temperature. For SSL alone, regardless of the carrier gas used, the content of C tot PAHs was observed to decrease with increasing temperature, whereas in the presence of willow temperature did not affect significantly (P ≥ 0.05) the C tot PAHs content. The change of carrier gas from N 2 to CO 2 increased the affinity of the biochars to PAHs as confirmed by the distribution coefficients log K TOC ., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The goal of the study was to evaluate the application of biochar (BC) to the sewage sludge (SL) on the adsorption and desorption capacity of Cd(II), Cu(II), Ni(II) and Zn(II). The effect of biochar contribution in the sewage sludge (2.5, 5 and 10%) was investigated. The isotherms data were fitted to the Langmiur (LM), Freundlich (FM) and Temkin (TM) models. The best fitting for kinetic study was obtained for the pseudo-second-order equation. The best fitting of the experimental data was observed for the LM in the case of SL and BC, and for the FM in the case of SL- and SL/BC-amended soil. SL was characterized by even four-order higher sorption capacity than BC. The addition of the BC to the SL and next to the soil increased the adsorption capacity of the soil and the SL-amended soil. In the case of all investigated potentially toxic elements (PTEs), the highest adsorption capacity was achieved for SL-amended soil in comparison with the control soil. In the case of other experimental variants, the adsorption capacity of metal ions was as follows: 2.5% BC > 5.0% BC > 10% BC. The negative correlation between hydrated radius of metal ions and the kinetics of sorption was observed. However, the desorption of PTEs from BC/SL-amended soil was significantly lower than for SL-amended soil (except of Cd) and non-amended soil. It can be concluded that the addition of the biochar enhanced the immobilization of PTEs and reduced their bioavailability and mobility in the soil amended by the sewage sludge.

The promising characteristics of nanoscale zero-valent iron (nZVI) have not been fully exploited owing to intrinsic limitations. Carbon-enriched biochar (BC) has been widely used to overcome the limitations of nZVI and improve its reaction with environmental pollutants. This work reviews the preparation of nZVI/BC nanocomposites; the effects of BC as a supporting matrix on the nZVI crystallite size, dispersion, and oxidation and electron transfer capacity; and its interaction mechanisms with contaminants. The literature review suggests that the properties and preparation conditions of BC (e.g., pore structure, functional groups, feedstock composition, and pyrogenic temperature) play important roles in the manipulation of nZVI properties. This review discusses the interactions of nZVI/BC composites with heavy metals, nitrates, and organic compounds in soil and water. Overall, BC contributes to the removal of contaminants because it can attenuate contaminants on the surface of nZVI/BC; it also enhances electron transfer from nZVI to target contaminants owing to its good electrical conductivity and improves the crystallite size and dispersion of nZVI. This review is intended to provide insights into methods of optimizing nZVI/BC synthesis and maximizing the efficiency of nZVI in environmental cleanup., (Copyright © 2019. Published by Elsevier B.V.)

The aim of the present study was to determine changes in the physicochemical properties and toxicity of soil amended with sewage sludge (10t dw /ha) or sewage sludge (10t dw /ha) with biochar addition (2.5, 5 or 10% of sewage sludge). The study was carried out as a field experiment over a period of 18months. Samples for analysis were taken at the beginning of the experiment as well as after 6, 12 and 18months. The study investigated toxicity of the unamended soil, sewage sludge-amended soil and sewage sludge-amended soil with biochar addition towards Folsomia candida (collembolan test) and Lepidium sativum (Phytotoxkit F). Moreover, toxicity of aqueous extracts obtained from the tested soils towards Vibrio fischeri (Microtox®) and Lepidium sativum (elongation test) was determined. The study showed that addition of biochar to the sewage sludge and soil reduced leaching of nutrients (mainly phosphorus and potassium) from the amended soil. Biochar significantly reduced sewage sludge toxicity, exhibiting a stimulating effect on the tested organisms. The stimulating effect of biochar addition to the sewage sludge persisted throughout the entire experiment. Apart from the remediatory character of biochar, this is also evidence of its fertilizing character. In the tests with L. sativum (leachates and solid phase) and V. fischeri (leachates), increasing the rate of biochar in the sewage sludge increased root growth stimulation (L. sativum) and bacteria luminescence (V. fischeri). However, increasing biochar rate decreased F. candida reproduction stimulation, which could have been an effect of reduced nutrient bioavailability due to the biochar., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The aim of this study was to determine the effect of biochar aging on the content of polycyclic aromatic hydrocarbons (PAHs) (the total content - C tot , and the freely dissolved - C free ) in biochar and its ecotoxicity. Two biochars (BCS and BCM) with varying properties were aged for 420 days at different temperatures (-20 °C, 4 °C, 20 °C, 70 °C), at a variable temperature (-20/20 °C), in the presence of nutrients, and in the presence of inoculum and nutrients. After the aging process, C tot and C free PAHs were determined in samples obtained and an ecotoxicological analysis was performed, which involved tests with bacteria (Vibrio fischeri), invertebrates (Folsomia candida) and plants (Lepidium sativum). Aging significantly affected all the parameters tested. The range of changes in the studied parameters depended on the type of biochar and ageing conditions. In the case of most of the aging methods, PAH content (C tot , C free ) and toxicity were found to decrease. Aging in the presence of microorganisms and nutrients and in the presence of nutrients alone caused the greatest reduction in C tot PAH content (a reduction from 30 to 100% relative to non-aged biochar), C free PAH content (a reduction from 12 to 100%), root growth inhibition (a reduction from 73 to 90%), and luminescence inhibition (a reduction from 24 to 100%). In the case of C free PAHs and toxicity to F. candida, some aging methods caused their increase. The study also found a significant relationship between the changes in C tot PAH content during aging and inhibition of root growth (BCS, BCM) and inhibition of V. fischerii luminescence (BCM). In no case was a significant correlation (P ≥ 0.05) between C free PAHs and the investigated toxicity parameters found., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The bioavailable PAHs (freely dissolved concentration, Cfree) were determined in sewage sludge (SL) or sewage sludge and biochar (BC) amended soil. SL or SL with a 2.5, 5 or 10% of BC was applied to the soil. The study was conducted as a long-term field experiment. Addition of BC to SL at a dose of 2.5 and 5% did not affect the content of Cfree PAHs in soils. However a significant difference (by 13%) in Cfree PAHs content was noted in experiment with 10% addition of BC. During the experiment, the concentration of Cfree PAHs in SL- and SL/BC-amended soil decreased. In particular sampling terms the content of Cfree PAHs in SL/BC-amended soil was significantly lower comparing to the Cfree PAHs content in SL-amended soil. After 18 months, Cfree PAH content was significantly lower in SL/BC-amended soil than in the experiment with SL alone, and did not differ significantly from the Σ16 Cfree content in the control soil. The largest decrease relative to the soil with sewage sludge alone was observed for 3-, 5- and 6-ring PAHs. This is the first field-based evidence that biochar soil amendment was effective to reduce of the Cfree of PAHs in sewage sludge-amended soils., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Biochar is characterised by a large specific surface area, porosity, and a large amount of functional groups. All of those features cause that biochar can be a potentially good material in the optimisation of the process of composting and final compost quality. The objective of this study was to compile the current knowledge on the possibility of biochar application in the process of composting and on the effect of biochar on compost properties and on the content of contaminants in compost. The paper presents the effect of biochar on compost maturity indices, composting temperature and moisture, and also on the content and bioavailability of nutrients and of organic and inorganic contaminants. In the paper note is also taken of the effect of biochar added to composted material on plants, microorganisms and soil invertebrates., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The objective of the study was to investigate the ability of biochars prepared under different temperatures (400 °C and 600 °C) from the residue of biogas production (RBP) for the adsorption of cadmium (Cd(II)) and nickel (Ni(II)) ions from aqueous solution. Furthermore, the RBP biochars adsorption capacity was compared with adsorption capacity of biochar produced from wheat straw at 600 °C (BCS600). The kinetics of the adsorption, the sorption isotherms, the influence of solution pH and the interfering ions (chlorides and nitrates) were investigated. The desorption of Cd(II) and Ni(II) by hydrochloric and nitric acid from biochars was also investigated. The different types of feedstock used for biochar (BC) preparation (RBP and biomass) determined the physico-chemical properties of biochars and hence their adsorption abilities. Generally, biochars produced from RBPs (regardless of temperature) had the greater capacity to adsorb Cd(II) and Ni(II) than the biochar produced from wheat straw. Of the tested models (Freundlich and Langmuir), the Langmuir model was demonstrated to be the best to describe the sorption of Cd(II) and Ni(II). For the kinetic study, the adsorption process proceeded the fastest for BCU400 than BCU600. Furthermore, BCU600 was the most resistant to the influence of interfering ions on adsorption. For the desorption study, BCU400 was characterized by the highest reproducibility of the surface. The comparison of the results obtained in each adsorption step between RBP biochars and BCS600 suggested that the residue from biogas production could be successfully applied for the removal of Cd(II) and Ni(II) ions from aqueous solutions., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The aim of the present study was to determine the effect of activated carbon (AC) or biochars on the bioaccessibility (C bioacc ) of polycyclic aromatic hydrocarbons (PAHs) in soils vegetated with willow (Salix viminalis). The study determined the effect of willow on the C bioacc PAHs and the effect of the investigated amendments on changes in dissolved organic carbon (DOC), crop yield and the content of PAHs in plants. PAH-contaminated soil was amended with 2.5 wt% AC or biochar. Samples from individual plots with and without plants were collected at the beginning of the experiment and after 3, 6, 12 and 18 months. The C bioacc PAHs were determined using sorptive bioaccessibility extraction (SBE) (silicon rods and hydroxypropyl-β-cyclodextrin). Both AC and biochar caused a decrease in the C bioacc PAHs. Immediately after adding AC, straw-derived biochar or willow-derived biochar to the soil, the reduction in the sum of 16 (Σ16) C bioacc PAHs was 70.3, 38.0, and 29.3%, respectively. The highest reduction of C bioacc was observed for 5- and 6-ring PAHs (from 54.4 to 100%), whereas 2-ring PAHs were reduced only 8.0-25.4%. The reduction of C bioacc PAHs increased over time. Plants reduced C bioacc in all soils although effects varied by soil treatment and PAH. Willow grown in AC- and biochar-amended soil accumulated less phenanthrene than in the control soil. The presence of AC in the soil also affected willow yield and shoot length and DOC was reduced from 53.5 to 66.9% relative to unamended soils. In the biochars-amended soil, no changes in soil DOC content were noted nor effects on willow shoot length., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The objective of the study was to determine the effect of various methods of biochar activation on the ecotoxicity of soils with various properties and with various content and origin of contaminants. The biochar produced from willow (at 700°C) was activated by 1) microwaves (in a microwave reactor under an atmosphere of water vapour), 2) carbon dioxide (in the quartz fluidized bed reactor) and 3) superheated steam (in the quartz fluidized bed reactor). Three different soils were collected from industrial areas. The soils were mixed with biochar and activated biochars at the dose of 5% and ecotoxicological parameters of mixture was evaluated using two solid phase test - Phytotoxkit F (Lepidium sativum) and Collembolan test (Folsomia candida) and one liquid phase test - Microtox® (Vibrio fischeri). Biochar activation had both positive and negative impacts, depending on the activation method, kind of bioassay and kind of soil. Generally, biochar activated by microwaves increased the effectiveness of ecotoxicity reduction relative to non-activated biochars. Whereas, biochar activated with CO 2 most often cause a negative effect manifested by deterioration or as a lack of improvement in relation to non-activated biochar or to non-amended soil. It was also demonstrated that the increase of biochar specific surface area caused a significant reduction of toxicity of water leachates from the studied soils. Effectiveness of the reduction of leachate toxicity was weakened in the presence of dissolved organic carbon in the soil., (Copyright © 2016 Elsevier Inc. All rights reserved.)

The aim of this study was to investigate co-application of biochar and nano zero-valent iron (nZVI) in order to increase the degradation of PAHs and reduce the toxicity of soils historically contaminated with these compounds. To performed the experiment biochar, biochar with nZVI (2 g kg -1 or 10 g kg -1 soil), or nZVI alone (2 g kg -1 or 10 g kg -1 soil) were added to the PAHs contaminated soils. The soils alone and soils with amendments were aged by mixing for 7 and 30 days. After that the chemical analysis were carried out and total (C tot ) and C free PAH content in the samples were determined. Moreover, the toxicity of aqueous extracts were investigated using the Microtox ® (Vibrio fischeri) method. Results showed that any of used nZVI dose did not reduce the content of C tot or C free PAHs in contaminated soils, but biochar applied both alone and together with the nZVI significantly reduced C tot and C free PAHs. However, no significant differences in PAH reduction were found between biochar alone and biochar with nZVI addition. This indicates that the observed reduction was mostly associated with the sorption properties of biochar. Moreover, only in the case of co-application of biochar and nZVI reduction of the toxicity of nZVI to V. fischeri was observed. The toxic effect was different and depend on the type of soil and their properties including total organic carbon and black carbon content, which may affect the PAHs reduction efficiency., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Analyses were carried out for biochars produced at three temperatures of pyrolysis (400, 600 and 800°C) from solid residue from biogas production (RBP). Separated and non-separated RBP from biogas plants employing different biogas production conditions were pyrolyzed. The contents of heavy metals and polycyclic aromatic hydrocarbons (PAHs) (16 PAH US EPA) were analyzed in biochars. The analyses showed that with an increased pyrolysis temperature, there was an increase in the contents of PAHs and of certain heavy metals (Cr, Cu, Cd, Pb and Mn). In the ecotoxicological tests, it was noted that the effect depended on the temperature of pyrolysis and on the feedstock from which the biochar was produced. The least harmful effect on the test organisms was from biochar produced by separated RBP in a biogas plant operating in mesophilic conditions. The most negative effect on the test organisms was characteristic of biochar produced from non-separated mesophilic RBP. This study shows that the main factors determining the level of toxicity of biochars produced from RBP towards various living organisms are both the method of feedstock production and the temperature at which the process of pyrolysis is conducted., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Due to an increased content of polycyclic aromatic hydrocarbons (PAHs) frequently found in sewage sludges, it is necessary to find solutions that will reduce the environmental hazard associated with their presence. The aim of this study was to determine changes of total and freely dissolved concentration of PAHs in sewage sludge-biochar-amended soil. Two different sewage sludges and biochars with varying properties were tested. Biochars (BC) were produced from biogas residues at 400 °C or 600 °C and from willow at 600 °C. The freely dissolved PAH concentration was determined by means of passive sampling using polyoxymethylene (POM). Total and freely dissolved PAH concentration was monitored at the beginning of the experiment and after 90 days of aging of the sewage sludge with the biochar and soil. Apart from chemical evaluation, the effect of biochar addition on the toxicity of the tested materials on bacteria - Vibrio fischeri (Microtox ® ), plants - Lepidium sativum (Phytotestkit F, Phytotoxkit F), and Collembola - Folsomia candida (Collembolan test) was evaluated. The addition of biochar to the sewage sludges decreased the content of C free PAHs. A reduction from 11 to 43% of sewage sludge toxicity or positive effects on plants expressed by root growth stimulation from 6 to 25% to the control was also found. The range of reduction of C free PAHs and toxicity was dependent on the type of biochar. After 90 days of incubation of the biochars with the sewage sludge in the soil, C free PAHs and toxicity were found to further decrease compared to the soil with sewage sludge alone. The obtained results show that the addition of biochar to sewage sludges may significantly reduce the risk associated with their environmental use both in terms of PAH content and toxicity of the materials tested., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The objective of this study was to estimate the effectiveness of application of sewage sludge-derived biochars for the immobilisation of freely dissolved (Cfree) and bioaccessible (Cbioacc) polycyclic aromatic hydrocarbons (PAHs) in contaminated soils. Soil SL-COK collected from the area of a coking plant and soil SL-BIT collected from the area of a plant producing bituminous materials were chosen for the study. The biochars were produced from sewage sludge at temperatures of 500 °C (BC500) or 700 °C (BC700). The biochars were mixed with the soil at the dose of 5% and incubated for a period of 60 d. The content of PAHs was determined with the use of polyoxymethylene (POM) (Cfree) or a solution of cyclodextrins and silicon rod elastomer (Cbioacc). Biochars reduced the content of Cfree and Cbioacc PAHs in soils. A higher level of reduction was noted for Cfree PAHs than for Cbioacc PAHs. Biochar produced at 700 °C was more effective in the reduction of Cfree and Cbioacc PAHs than biochar produced at 500 °C. It was found that in the soil in which the source of contamination were processes related with the production of bituminous materials (SL-BIT), the effect of reduction of Cfree and Cbioacc was greater than in soil SL-COK where the source of PAHs were coking processes. It also needs to be emphasised that soil SL-BIT, for which better reduction of PAHs was noted, was also characterised by a lower affinity towards those compounds than soil SL-COK., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The aim of this study was to evaluate the effect of soils on the sorption of phenanthrene (PHE) and pyrene (PYR) by sewage sludge-derived biochars (SS-derived biochars). The SS-derived biochars were added to soils with varying properties as well as with a different degree and source of polycyclic aromatic hydrocarbons (PAHs) contamination. The biochars (BCs) were produced from sewage sludge during pyrolysis at temperatures of 500 °C (BC500) and 700 °C (BC700). The addition of biochars to the soils (5 %, w/w) increased the sorption of PHE from 8.3 to 20.3 % and PYR from 14.5 to 31.7 % by amended soil. BC700 biochar was characterized by better sorption capacity than BC500 biochar. Nevertheless, the presence of soil reduces the effectiveness of biochars in binding the compounds studied. The sorption capacity of the biochars decreased several times after they had been mixed with the soil compared to pure biochars. The study found dissolved organic carbon (DOC) and clay minerals present in the soils to have a significant effect on reducing the efficiency of PHE and PYR sorption by biochar. A greater impact of fouling was observed in the case of BC500 biochar characterized by lower porosity than BC700 biochar.

The aim of this study was to determine the effect of steam activation of biochars on the immobilization of freely dissolved (Cfree) and bioaccessible fraction (Cbioacc) of PAHs in soils. Additionally, the toxicity to various organisms like Vibrio fischeri, Lepidium sativum and Folsomia candida was measured before and after the amendment of biochars to soils. Three biochars produced from willow, coconut and wheat straw were steam activated and added to three different soils with varying content and origin of PAHs (coke vs. bitumen). The soils with the addition of the biochars (activated and non-activated) were incubated for a period of 60days. Steam activation of the biochars resulted in more pronounced reduction of both Cfree and Cbioacc. The range of the increase in effectiveness was from 10 to 84% for Cfree and from 50 to 99% for Cbioacc. In contrast, the effect of activation on the toxicity of the soils studied varied greatly and was specific to a particular test and soil type. Essentially, biochar activation did not result in a change of phytotoxicity, but it increased or decreased (depending on the parameter, type of biochar, contaminant source, and soil and soil type) the toxic effect to F. candida, and decreased the toxicity of leachates to V. fischeri., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The presence of polycyclic aromatic hydrocarbons (PAHs) in biochars hinders their environmental use. The aim of this study was to determine the freely dissolved (Cfree) PAH content in soil amended with biochar in a long-term (851 days) field experiment. Biochar was added to the soil at a rate of 30 and 45 t/ha. The addition of biochar to the soil resulted in a decrease in Σ13 Cfree PAHs by 25 and 22%, in the soil with the addition of biochar at the rate of 30 and 45 t/ha, respectively. As far as individual PAHs are concerned, in most cases a reduction in Cfree was also observed (from 3.6 to 66%, depending on the biochar rate). During the first 105 days of the experiment, the content of Σ13 Cfree in the biochar-amended soil significantly decreased by 26% (30 t/ha) and 36% (45 t/ha). After this period of time until the end of the experiment, no significant changes in Cfree were observed, regardless of the biochar rate. However, the behavior of individual PAH groups differed depending on the number of rings and experimental treatment. Ultimately, after 851 days of the experiment the content of Σ13 Cfree PAHs was lower by 29% (30 t/ha) and 35% (45 t/ha) compared to the beginning of the study as well as lower by 40% (30 t/ha) and 42% (45 t/ha) than in the control soil. The log KTOC coefficients calculated for the biochar-amended soils were higher immediately after adding biochar and subsequently they gradually decreased, indicating the reduced strength of the interaction between biochar and the studied PAHs. The obtained results show that the addition of biochar to soil does not create a risk in terms of the content of Cfree PAHs., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Coal production negatively affects the environment by the emission of polycyclic aromatic hydrocarbons (PAHs). Two soils (KOK and KB) from a coking plant area was investigated and their total PAH concentration was 40 and 17 mg/kg for the sum (∑) 16 US EPA PAHs, respectively. A third soil was sampled from a bitumen plant area and was characterized by 9 mg/kg ∑16 US EPA PAHs. To reduce the freely dissolved concentration (Cfree) of the PAHs in the soil pore water, active carbon (AC) and two biochars pyrolysed from wheat straw (biochar-S) and willow (biochar-W) were added to the soils at 0.5-5 % (w/w), each. The AC performed best and reduced the Cfree by 51-98 % already at the lowest dose. The biochars needed doses up to 2.5 % to significantly reduce the Cfree by 44-86 % in the biochar-S and by 37-68 % in the biochar-W amended soils. The high black carbon (BC) content of up to 2.3 % in the Silesian soils competed with the sorption sites of the carbon amendments and the performance of the remediation was a consequence of the contaminant's source and the distribution between the BC and the AC/biochars. In contrast, the carbon amendment could best reduce the Cfree in the Lublin soil where the BC content was normal (0.05 %). It is therefore crucial to know the contaminant's source and history of a sample/site to choose the appropriate carbon amendment not only for remediation success but also for economic reasons.

The aim of this study was to evaluate the effect of sewage sludge pyrolysis on freely dissolved (Cfree) polycyclic aromatic hydrocarbon (PAH) contents in biochars. Four sewage sludges with varying properties and PAH contents were pyrolysed at temperatures of 500 °C, 600 °C or 700 °C. Cfree PAH contents were determined using polyoxymethylene (POM). The contents of Cfree PAHs in the sludges ranged from 262 to 294 ng L(-1). Sewage sludge-derived biochars have from 2.3- to 3.4-times lower Cfree PAH contents comparing to corresponding sewage sludges. The Cfree PAH contents in the biochars ranged between 81 ng L(-1) and 126 ng L(-1). As regards agricultural use of biochar, the lower contents of Cfree PAHs in the biochars compared to the sewage sludges makes biochar a safer material than sewage sludge in terms of PAH contents., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Activated carbon (AC), biochar from wheat straw (BCS), and biochar from willow (BCW) were added to the soils sampled from areas of strong anthropogenic influence at doses of 0.5%, 1%, 2.5%, or 5% (w/w) and incubated for 2 mo. At the end of this period, the toxicity of the soils was measured. The effect of AC and biochars on the toxicity of the soils varied based on soil, type of amendment, dose, and test organism. For most of the parameters tested, the highest effectiveness of AC in terms of reduction of toxicity was observed in soil POPI (from bitumen processing plant area). In the case of the remaining soils, after the addition of AC varied results were observed, in which a reduction or an increase of toxicity, relative to the control soil, occurred. As in the case of AC, biochars also caused a significant reduction of phytotoxicity of soil POPI. In soils KB (from coking plant area, industrial waste deposit) and KOK (from coking plant area, coking battery), the reduction or increase of toxicity depended on biochar dose. Compared with the biochars, the effectiveness of AC in the reduction of toxicity depended also on soil, type of amendment, dose, and test organism. Generally, the AC was more effective than biochars in relation to mortality and reproduction of Folsomia candida (in all soils) and for reduction of luminescence inhibition of Vibrio fischeri (in POPI soil)., (© 2015 SETAC.)

In the present study the persistence of polycyclic aromatic hydrocarbons (PAHs) applied with biochar to acidic soil (loamy sand) was studied in two and half year field experiment. An experiment was carried out in three experimental plots (15 m(2) each). The biochar was introduced in the following doses: soil without fertilization - control (C-BC00), soil with 30 t ha(-1) (B-BC30) and soil with 45 t ha(-1) (A-BC45) of biochar. Biochar addition to soils resulted in an increase in the PAHs content from 0.239 μg g(-1) in control soil to 0.526 μg g(-1) and 1.310 μg g(-1) in 30 and 45 t ha(-1) biochar-amended soil respectively. However during the experimental period the PAHs content decreased to a level characteristic for the control soil. The highest losses of PAHs were observed during the first 105 days of the experiment. Three and four rings PAHs were the most susceptible for degradation and leaching. Migration of PAHs from 0-10 cm to 10-20 cm soil horizon was also observed., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The goal of the presented work was the evaluation and comparison of two biochars (produced from Sida hermaphrodita - BCSH/laboratory produced and from wheatstraw - BCS/commercial available) to adsorb heavy metal ions (Cd(II), Cu(II) and Zn(II)) from water. Kinetics of the sorption as well as sorption isotherms, the influence of solution pH and interfering ions were investigated. Different physico-chemical properties of biochars had the great influence on adsorption capacity. The greater adsorption efficiency was observed for BCSH than for BCS in the case of all investigated metals. The adsorption efficiency of BCSH was correlated with higher content of carbon and oxygen, what is equal with higher content of polar-groups on the BCSH surface e.g., -COOH. Furthermore, the molar ratio of O/C as well as polarity index (which was higher for BCSH) was also important parameters., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The present study investigated the sorption of phenanthrene (PHE) and pyrene (PYR) by sewage sludges and sewage sludge-derived biochars. The organic carbon normalized distribution coefficient (log K(OC) for C(w) = 0.01 S(w)) for the sewage sludges ranged from 5.62 L kg(-1) to 5.64 L kg(-1) for PHE and from 5.72 L kg(-1) to 5.75 L kg(-1) for PYR. The conversion of sewage sludges into biochar significantly increased their sorption capacity. The value of log K(OC) for the biochars ranged from 5.54 L kg(-1) to 6.23 L kg(-1) for PHE and from 5.95 L kg(-1) to 6.52 L kg(-1) for PYR depending on temperature of pyrolysis. The dominant process was monolayer adsorption in the micropores and/or multilayer surface adsorption (in the mesopores), which was indicated by the significant correlations between log K(OC) and surface properties of biochars. PYR was sorbed better on the tested materials than PHE., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

In the present research, the potential of two biochars produced by the thermal decomposition of wheat straw (BCS) and wicker (BCW) for Cr(VI) ions removing from wastewater was investigated. The pH and the presence of chlorides and nitrates were also investigated. The Freundlich and Langmuir models were applied for the characterization of adsorption isotherms. The Langmuir model has better fitting of adsorption isotherms than the Freundlich model. The sorption process can be described by the pseudo second-order equation. The optimal adsorption capacities were obtained at pH 2 and were 24.6 and 23.6 mg/g for BCS and BCW, respectively. X-ray photoelectron spectroscopy (XPS) studies confirmed that Cr(III) ions were the most abundant chromium species on the biochars' surface. The results indicated that the sorption mechanism of Cr(VI) on biochar involves anionic and cationic adsorption combined with Cr(VI) species reduction.

The objective of the study was to identify the effect of various biochars on the content of freely dissolved (Cfree) PAHs in sewage sludge. Apart from the evaluation of biochars obtained from various materials, the study also included the determination of the effects of biochar particle sizes and biochar production temperature on their ability to bind PAHs in sewage sludge. Increase in biochar dose caused a gradual reduction of Cfree PAHs content, but only up to the biochar dose of 5%. Depending on the kind of initial material from which the biochar was produced, the reduction of Cfree PAHs content in sewage sludge varied from 17.4% to 58.0%. Both the temperature and the particle size of biochar had an effect on PAH free concentration reduction. Biochars characterised by a low polarity index (O/C or (O+N)/C) reduced the level of Cfree PAHs better than biochars with a higher polarity index value., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The objectives of the study were the identification of the source of contamination of soils and estimation of the potential cancer risk that may be caused by contact with soils situated in the vicinity of biochar production sites. Samples of soils collected in the immediate vicinity of traditional biochar-producing plants, located within the area of the Bieszczady National Park (Poland), were analysed for the content of polycyclic aromatic hydrocarbons (PAHs). The sum of the content of 16 PAHs varied within the range of 1.80-101.3 μg/g, exceeding the norms permitted in many European countries. The calculated coefficients on the basis of which one can determine the origin of PAHs (molecular diagnostic ratios) demonstrated that the potential source of PAHs in the soils may be processes related with the production of biochar. Estimation on the basis of the results of incremental lifetime cancer risks (ILCRs) within the range of 2.33 · 10(-4)-1.05 · 10(-1) indicated that the soils studied may constitute a significant cancer risk for persons who have contact with them. The values of ILCRS should be considered as at least high, which permits the conclusion that sites of that type may create a hazard to human health.

The objective of the study was the determination of the content of contaminants and toxicity of four different biochars. The properties of the biochars, content of trace metals and polycyclic aromatic hydrocarbons (16 PAHs) were determined. Toxicological estimation of the biochars was performed on the basis of a battery of biotests with plants (Lepidium sativum), bacteria (Vibrio fischeri and 11 different strains from MARA), alga (Selenastrum capricornutum), protozoa (Tetrahymena thermophila) and crustaceans (Daphnia magna). The content of trace metals depended on the biochar and was comparable to uncontaminated soils. PAHs sum varied from 1124 to 28,339 μg/kg. The toxicity of the biochars depended both on their kind and on the test applied. The most sensitive organism was D. magna. Relatively the least sensitive to extracts from the biochars proved to be S. capricornutum and T. thermophila. A significant correlation between the content of PAHs and toxicity was noted only in the case of D. magna., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The aim of the present study was to evaluate the secondary ecotoxicological effects of soil amendment materials that can be added to contaminated soils in order to sequester harmful pollutants. To this end, a nonpolluted agricultural soil was amended with 0.5, 2, and 5% of the following four amendments: powder activated carbon (PAC), granular activated carbon, corn stover biochar, and ferric oxyhydroxide powder, which have previously been proven to sequester pollutants in soil. The resulting immediate effects (i.e., without aging the mixtures before carrying out tests) on the springtail Folsomia candida, the earthworm species Aporectodea caliginosa and Eisenia fetida, the marine bacteria Vibrio fischeri, a suite of ten prokaryotic species, and a eukaryote (the yeast species Pichia anomalia) were investigated. Reproduction of F. candida was significantly increased compared to the unamended soil when 2% biochar was added to it. None of the treatments caused a negative effect on reproduction. All amendments had a deleterious effect on the growth of A. caliginosa when compared to the unamended soil, except the 0.5% amendment of biochar. In avoidance tests, E. fetida preferred biochar compared to all other amendments including the unamended soil. All amendments reduced the inhibition of luminescence to V. fischeri, i.e., were beneficial for the bacteria, with PAC showing the greatest improvement. The effects of the amendments on the suite of prokaryotic species and the eukaryote were variable, but overall the 2% biochar dose provided the most frequent positive effect on growth. It is concluded that the four soil amendments had variable but never strongly deleterious effects on the bacteria and invertebrates studied here during the respective recommended experimental test periods.

The goal of the research was to determine the phytotoxicity (using Lepidium sativum) of two activated carbon/biochar-amended sewage sludges. Apart from the impact of the AC/biochar dose, the influence of biochar particle diameter (<300, 300-500 and >500 μm) and the influence of the contact time (7, 60, 90 days) between AC/biochar and sewage sludges on their phytotoxicity was also assessed. No negative impact of sewage sludges on seed germination was observed (P>0.05). The application of AC or biochar to the sludges positively affected root growth by reducing the harmful effect by 7.8 to 42% depending on the material used. Furthermore, the reduction range clearly depended on the type of sewage sludge. No differences were observed in the inhibition of the toxic effect between both biochar types used and the biochar particle size. The extension of the contact time between AC/biochar and sewage sludges had a negative impact on root growth., (Copyright © 2012 Elsevier Inc. All rights reserved.)

The aim of the research was to determine the influence of biochar and activated carbon (AC) on the freely dissolved concentration of polycyclic aromatic hydrocarbons (PAHs) in sewage sludge. Two different biochars (MSB and PMW) and two ACs (CP1 and BP2) were used in the present experiment. Addition of AC/biochar to sewage sludge caused significant decrease of freely dissolved PAHs concentration. Depending on the dose, the reduction of freely dissolved PAHs ranged from 56% to 95% (ACs) and from 0% to 57% (biochars). Only for the biochars was there a significant difference between short 7-d and long 30/60-d mixing time. It is concluded that both AC and biochar are effective at reducing PAH pore-water concentrations, the more expensive and non-carbon negative AC having the greatest effect., (Copyright © 2012 Elsevier Ltd. All rights reserved.)