Functional use of carbon dioxide for the sustainable valorization of orange peel in the pyrolysis process.

Although biomass is carbon-neutral, its use as a primary feedstock faces challenges arising from inconsistent supply chains. Therefore, it becomes crucial to explore alternatives with reliable availability. This study proposes a strategic approach for the thermochemical valorization of food processing waste, which is abundantly generated at single sites within large-scale processing plants. As a model biomass waste from the food industry, orange peel waste was particularly chosen considering its substantial consumption. To impart sustainability to the pyrolysis system, CO2, a key greenhouse gas, was introduced. As such, this study highlights elucidating the functionality of CO2 as a reactive feedstock. Specifically, CO2 has the potential to react with volatile pyrolysates evolved from orange peel waste, leading to CO formation at ≥490 °C. The formation of chemical constituents, encompassing acids, ketones, furans, phenols, and aromatics, simultaneously decreased by 15.1 area% in the presence of CO2. To activate the efficacy of CO2 at the broader temperature spectrum, supplementary measures, such as an additional heating element (700 °C) and a nickel-based catalyst (Ni/Al2O3), were implemented. These configurations promote thermal cracking of the volatiles and their reaction kinetics with CO2, representing an opportunity for enhanced carbon utilization in the form of CO. Finally, the integrated process of CO2-assisted catalytic pyrolysis and water-gas shift reaction was proposed. A potential revenue when maximizing the productivity of H2 was estimated as 2.62 billion USD, equivalent to 1.11 times higher than the results from the inert (N2) environment. Therefore, utilizing CO2 in the pyrolysis system creates a promising approach for enhancing the sustainability of the thermochemical valorization platform while maximizing carbon utilization in the form of CO.

Naturally manufactured biochar materials based sensor electrode for the electrochemical detection of polystyrene microplastics.

In recent times, microplastics have become a disturbance to both aquatic and terrestrial ecosystems and the ingestion of these particles can have severe consequences for wildlife, aquatic organisms, and even humans. In this study, two types of biochars were manufactured through the carbonization of naturally found starfish (SF-1) and aloevera (AL-1). The produced biochars were utilized as sensing electrode materials for the electrochemical detection of ∼100 nm polystyrene microplastics (PS). SF-1 and AL-1 based biochars were thoroughly analyzed in terms of morphology, structure, and composition. The detection of microplastics over biochar based electrodes was carried out by electrochemical studies. From electrochemical results, SF-1 based electrode exhibited the detection efficiency of ∼0.2562 µA/µM∙cm2 with detection limit of ∼0.44 nM whereas, a high detection efficiency of ∼3.263 µA/µM∙cm2 was shown by AL-1 based electrode and detection limit of ∼0.52 nM for PS (100 nm) microplastics. Process contributed to enhancing the sensitivity of AL-1 based electrode might associate to the presence of metal-carbon framework over biochar's surfaces. The AL-1 biochar electrode demonstrated excellent repeatability and detection stability for PS microplastics, suggesting the promising potential of AL-1 biochar for electrochemical microplastics detection.

Changes in oral bioaccessibility of heavy metals in non-digestive sucking habits due to the formation of complexes between digestive fluid components and metals/metalloids.

Humans, especially infants, are exposed to harmful substances through various means, including non-nutritive sucking behaviors. Here, we compared the "one-compartment model" and the "three-compartment model" within the "suck model" to assess the oral bioaccessibility of heavy metals in various products and evaluated whether these models can be employed to assess 12 heavy metals present in consumer products. Several certified reference materials, including plastic, paint, glass, and metals, were employed to ensure sample homogeneity. By comparing the two models, we validated that a considerable amount of complexes were formed between saliva components and the extracted heavy metals and that some of these complexes dissociated during reactions with the gastric/intestinal fluids. Furthermore, we observed that in the cases of Cu and Pb, additional complexes were formed as a result of reactions with gastric/intestinal fluids. We measured the total concentrations of the extracted heavy metals using artificial saliva through acid digestion and found that up to 99.7% of the heavy metals participated in the formation of complexes, depending on the characteristics of the sample (e.g., composition) and the target element. This result indicates that the current suck model may notably underestimate the oral bioaccessibility of heavy metals in products associated with sucking behaviors. Therefore, we propose a more conservative and simpler test method for assessing oral bioaccessibility of heavy metals that involves measuring the total concentrations of heavy metals extracted from consumer products using artificial saliva. By doing so, we can account for potential variations in the digestive milieu (e.g., due to ingested food) and the inconsistency in complex formation-dissociation characteristics.

Sustainable valorization of styrofoam and CO2 into syngas.

Plastic is a versatile material broadly used in a variety of industries. However, the current disposal practices for plastic wastes (incineration/landfilling) add the hazardous materials into the environment. To offer a sustainable valorization platform for plastic waste, this study adopted the catalytic pyrolysis process using CO2 as a co-feedstock. A model plastic waste collected from a seaport was waste buoy (WB), which has been widely used in fishing industry. Prior to the pyrolysis tests, the exact type of plastic in WB and the thermolytic characteristics of WB were examined. Since the WB was made of polystyrene, it was mainly converted into styrene monomer (styrene), dimer (diphenyl-1-butene), and trimer (2,4,6-triphenyl-1-hexene) from pyrolysis of WB. To further valorize/detoxify styrene derivatives into value-added syngas, catalytic pyrolysis of WB was practiced using the Ni-based catalysts (2/5/10 wt% Ni/SiO2). The yield of H2 from the catalytic pyrolysis process of WB was more than one magnitude higher comparing to that from the non-catalytic one. H2 formation also increased as catalyst loading increased. When flow gas was switched from inert gas to CO2, CO gas formation was enhanced due to the chemical reactions between CO2 and styrene derivatives over Ni catalysts. Syngas (H2/CO) formation under the CO2 condition was 5 times higher in comparison to the N2 condition in catalytic pyrolyses of WB with 10 wt% Ni/SiO2. CO2 also effectively suppressed coke deposition on a Ni catalyst. This study proposes a sustainable valorization and disposal platform for used plastic waste and greenhouse gas (CO2), converting them into value-added fuel.

Assessment of soil washing for heavy metal contaminated paddy soil using FeCl3 washing solutions.

In this study, soil washing is applied for the remediation of heavy-metal (Pb, Cu and Zn) contaminated paddy soil located near an abandoned mine area. FeCl3 washing solutions were used in bench-scale soil washing experiments at concentrations in the range of 0.1 to 1 M. The strong acid, HCl was also used in this study for comparison. The washing process was performed at room temperature, mixing at 200 RPM for 1 h and a liquid to solid ratio of 2. A sequential extraction technique was performed to evaluate the chemical fractions of Pb in the soils. The soil washing effectiveness was evaluated and compared against regulations applicable to residential districts (Korean warning standards). The soil washing results showed that the heavy metal concentrations were reduced with increasing concentrations of FeCl3. Moreover, the lowest heavy metal concentrations were obtained with a 1 M FeCl3 washing solution. In the case of Pb removal, a 0.3 M FeCl3 washing solution was required to comply with the Korean warning standard of 200 mg/kg. The lowest Pb concentration of 117 mg/kg was obtained with 1 M FeCl3. Similar washing results were also obtained with HCl. The initial total concentrations for Cu and Zn were below the Korean warning standards of 150 and 300 mg/kg, respectively. Consequently, the reduction in Cu and Zn from the contaminated paddy soil using FeCl3 washing solutions was rather limited. The sequential extraction results showed that the exchangeable and weak acid-soluble fractions of Pb were significantly reduced upon FeCl3 washing.

Heavy metals biosorption mechanism of partially delignified products derived from mango (Mangifera indica) and guava (Psidium guiag) barks.

This paper evaluates the biosorption of toxic metal ions onto the bioadsorbents derived from mango (Mangifera indica) and guava (Psidium guiag) barks and their metal fixation mechanisms. Maximum metal biosorption capacities of the mango bioadsorbent were found in the following increasing order (mg/g): Hg (16.24) < Cu (22.24) < Cd (25.86) < Pb (60.85). Maximum metal biosorption capacities of guava bioadsorbent follow similar order (mg/g): Hg (21.48) < Cu (30.36) < Cd (32.54) < Pb (70.25), but with slightly higher adsorption capacities. The removal mechanisms of heavy metals using bioadsorbents have been ascertained by studying their surface properties and functional groups using various spectrometric, spectroscopic, and microscopic methods. Whewellite (C2CaO4·H2O) has been identified in bioadsorbents based on the characterization of their surface properties using X-ray techniques (XPS and XRD), facilitating the ion exchange of metal ions with Ca2+ bonded with carboxylate moieties. For both the bioadsorbents, the Pb2+, Cu2+, and Cd2+ are biosorbed completely by ion exchange with Ca2+ (89-94%) and Mg2+ (7-12%), whereas Hg2+ is biosorbed partially (57-66%) by ion exchange with Ca2+ (38-42%) and Mg2+ (19-24%) due to involvement of other cations in the ion exchange processes. Bioadsorbents contain lignin which act as electron donor and reduced Cr(VI) into Cr(III) (29.87 and 37.25 mg/g) in acidic medium. Anionic Cr(VI) was not adsorbed onto bioadsorbents at higher pH due to their electrostatic repulsion with negatively charged carboxylic functional groups.

Catalytic Pyrolysis of Polystyrene over Steel Slag under CO2 Environment.

As the consumption of plastic materials has been dramatically increased, the abundant presence of their debris has become a significant problem worldwide. Thus, this study proposes a sustainable plastic conversion platform for energy recovery. In detail, polystyrene pyrolysis was examined as a case study under CO2 atmosphere in reference to N2 condition. The major gaseous and liquid products from polystyrene pyrolysis include permanent gases (syngas and C1-2 hydrocarbons) and condensable aromatic compounds. Under CO2 environment, the reduction of polycyclic aromatic hydrocarbons (PAHs) was achieved during polystyrene pyrolysis, in comparison with N2 condition. Since its slow reaction kinetics, conversion of condensable hydrocarbons into permanent gases was not fully activated. Therefore, a cheap industrial waste, steel slag (SS), was employed as a catalyst to increase reaction kinetics. The synergistic effects of SS and CO2 contributed to doubling H2 production, while CO formation increased more than 300 times, in reference to non-catalytic pyrolysis. Because CO2 acted as an oxidant for CO production, control of H2/CO ratio was achieved in different conditions. Thus, the utilization of CO2 would suggest a promising way to reduce the formation of PAHs, adopting the reliable platform to produce syngas from plastic waste.

Carbonation/granulation of mine tailings using a MgO/ground-granule blast-furnace-slag binder.

A carbonation/granulation process for treating mine tailings using a MgO/ground-granule blast-furnace-slag (GGBS) binder was developed. The materials were mixed and granules produced using a granulator, then the granules were cured in a CO2 atmosphere. The optimum granulator rotation speed and retention time were 60 rpm and 7 min, respectively. The binder composition MgO0.5GGBS0.5 and binder: mine tailings ratio 3:10 gave the strongest granules. Carbonation generally increased the granule strength, but different CO2 concentrations, between 0.04% and 100%, changed the granule strength to different degrees. Granules cured in 20% CO2 for 28 d had a strength of 4.71 MPa, which was higher than the strengths of granules cured in other CO2 concentrations and of granules produced using Portland cement. The granules had relatively high CO2 storage capacities of 0.157-0.167 kg CO2/kg binder and good acid-neutralizing capacities (higher than the acid-neutralizing capacity of granules produced using Portland cement). The strength of the granules cured in 20% CO2 for 28 d was probably mainly attributed to the formation of hydromagnesite during carbonation. The hydromagnesite contributed dense and connected structures within the granules. The granules produced show great potential for use as aggregates for reclamation work and backfilling in mining areas.

Predicting mercury bioavailability in soil for earthworm Eisenia fetida using the diffusive gradients in thin films technique.

In general, the diffusive gradients in thin films (DGT) technique is an effective tool for evaluating metal bioavailability; however, its applicability is subject to the type of metal and organism involved. In this study, the accumulated masses of Hg in DGT probes and in the earthworm species Eisenia fetida were monitored for 10 days, to test if the DGT technique can be used as a predicting method for the bioavailability of soil Hg to earthworms. In the Hg exposure tests using soils prepared with different peat moss concentrations of 5, 10, 15, and 20% and varying pH values of 4.6, 5.6, and 6.2, the experimentally determined DGT-soil accumulation factor (DSAF) and biota-soil accumulation factor (BSAF) both increased as the peat moss content decreased and the pH increased. According to a one compartment model, this was a result of the increased Hg uptake rate constant (k1) and the relatively stable Hg elimination constant (k2) under lower peat moss and higher pH conditions. It is interesting to note that the Hg uptake rates by DGT and earthworms were considerably higher for fresh soils than for aged soils, while porewater (and acid-extractable) Hg concentrations were rather similar between the two types of soils. Across diverse soil properties, steady-state Hg in earthworm tissue showed a strong positive correlation with DGT-measured Hg flux ([earthworm Hg] = 354(DGT-Hg flux)-34, r2 = 0.88), while meager correlations were found between Hg concentration in earthworms and that in porewater (and acid-extractable). The overall results indicate that DGT-measured Hg flux is a better tool than conventional methods for predicting Hg bioavailability for earthworms inhabiting diverse types of soil.

Orange peel valorization by pyrolysis under the carbon dioxide environment.

To valorize biomass waste, pyrolysis of orange peel was mainly investigated as a case study. In an effort to establish a more sustainable thermolytic platform for orange peel, this study particularly employed CO2 as reactive gas medium. Accordingly, this study laid great emphasis on elucidating the mechanistic role of CO2 in pyrolysis of orange peel. The thermo-gravimetric analysis (TGA) confirmed that no occurrence of the heterogeneous reactions between the solid sample and CO2. However, the gaseous effluents from pyrolysis of orange peel experimentally proved that CO2 effectively suppressed dehydrogenation of volatile matters (VMs) evolved from the thermolysis of orange peel by random bond scissions. Moreover, CO2 reacted VMs, thereby resulting in the formation of CO. Note that the formation of CO was being initiated at temperatures ≥550 °C. The two identified roles of CO2 led to the compositional modification of pyrolytic oil by means of lowering aromaticity.

Soil lead immobilization by biochars in short-term laboratory incubation studies.

Exchangeable lead (Pb) extracted by ammonium acetate from three independent incubation studies was assessed to understand the influence of feedstock, pyrolysis temperatures, and production conditions on Pb immobilization capacities of different biochars. Vegetable waste biochar, pine cone, wood bark, cocopeat, red pepper stalk, and palm kernel shell were used as feedstocks (food supply and agricultural wastes) to produce biochars at 200-650 °C with and without N2/CO2. Biochars were applied at 5 and 2.5% (w w-1) to a Pb contaminated (i.e., 1445 mg kg-1) agricultural soil collected near an old mine. Lead immobilization in biochar treated soils at the end of incubation period was normalized per gram of biochar applied. Biochar produced from vegetable waste at 500 °C showed the highest Pb immobilization (87%) and highest total exchangeable cations (13.5 cmol(+) kg-1) at the end of the 45 d incubation period. However, on the basis of Pb immobilization per gram of biochar, red pepper stalk biochar produced in CO2 at 650 °C was the best in Pb immobilization (0.09 mg kg-1 g-1 biochar) compared to the other biochars. The enhanced ability to immobilize Pb by biochar produced in CO2 could be due to the presence of siloxanes (SiOSi) on biochar surface. Pearson correlation analysis revealed that alkaline pH, ash%, and N% of biochars influence in Pb immobilization and exchangeable cation availability in soil. Biochar production atmosphere considerably change its properties that influence Pb immobilization. Further studies are needed on the modification of properties and Pb immobilization by biochars produced from various feedstocks in CO2.

Impacts of biochar application on upland agriculture: A review.

Soil degradation has become an emerging global problem limiting sustainable upland crop production. Soil erosion, soil acidity, low fertility, inorganic/organic contamination, and salinization challenge food security and lead to severe economic constraints. Therefore, a new research agenda to develop cost-beneficial amendments for improving upland soil quality and productivity is urgently required. Biochar has been used in recent years to mitigate the problems mentioned above. Application of biochar improves the upland soil quality through significant changes in soil physicochemical and biological properties, thereby substantially increasing crop yield. This review article aims to discuss the effects of biochar on upland soil quality and productivity based on biochar-soil interactions. The yield of various upland crops can be enhanced by biochar-induced increases of nutrient availability and topsoil retention/recovery. Furthermore, biochar can assist in controlling unsuitable soil acidity/alkalinity/salinity and remediating a contaminated soil while increasing the retention of soil organic carbon, water content, and thereby high crop yield. Biochar is strongly recommended as one of the best management practices to meet the challenges of upland agriculture. However, the properties of biochar and soil type should be considered carefully prior to application.

Stabilization of lead (Pb) and zinc (Zn) in contaminated rice paddy soil using starfish: A preliminary study.

Lead (Pb) and zinc (Zn) contaminated rice paddy soil was stabilized using natural (NSF) and calcined starfish (CSF). Contaminated soil was treated with NSF in the range of 0-10 wt% and CSF in the range of 0-5 wt% and cured for 28 days. Toxicity characteristic leaching procedure (TCLP) test was used to evaluate effectiveness of starfish treatment. Scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX) analyses were conducted to investigate the mechanism responsible for effective immobilization of Pb and Zn. Experimental results suggest that NSF and CSF treatments effectively immobilize Pb and Zn in treated rice paddy soil. TCLP levels for Pb and Zn were reduced with increasing NSF and CSF dosage. Comparison of the two treatment methods reveals that CSF treatment is more effective than NSF treatment. Leachability of the two metals is reduced approximately 58% for Pb and 51% for Zn, upon 10 wt% NSF treatment. More pronounced leachability reductions, 93% for Pb and 76% for Zn, are achieved upon treatment with 5 wt% CSF. Sequential extraction results reveal that NSF and CSF treatments of contaminated soil generated decrease in exchangeable/weak acid Pb and Zn soluble fractions, and increase of residual Pb and Zn fractions. Results for the SEM-EDX sample treated with 5 wt% CSF indicate that effective Pb and Zn immobilization is most probably associated with calcium silicate hydrates (CSHs) and calcium aluminum hydrates (CAHs).

Factors influencing As(V) stabilization in the mine soils amended with iron-rich materials.

Chemical stability of As(V) in amended mine-impacted soils was assessed according to functions of incubation period (0, 1, 2, 4, and 6 months), amendment dose (2.5 and 5%), and application timing (0 and 3rd month). Six soils contaminated with 26-209 mg kg-1 of As(V) were collected from two abandoned mine sites and were treated with two alkaline iron-rich materials (mine discharge sludge (MS) and steel-making slag (SS)). Seventeen to 23% of As(V) in soils was labile. After each designated time, As(V) stability was assessed by the labile fractions determined with sequential extraction procedures (F1-F5). Over 6 months, a reduction (26.9-70.4%) of the two labile fractions (F1 and F2) and a quantitative increase (7.4-29.9%) of As(V) in F3 were observed (r 2 = 0.956). Two recalcitrant fractions (F4 and F5) remained unchanged. Temporal change of As(V) stability in a sample was well described by the two-domain model (k fast, k slow, and Ffast). The stabilization (%) correlated well with the fast-stabilizing domain (Ffast), clay content (%), and Fe oxide content (mg kg-1), but correlated poorly with kinetic rate constants (k fast and k slow). Until the 3rd month, the 2.5%-MS amended sample resulted in lower As(V) stabilization (25-40%) compared to the 5% sample (50-60%). However, the second 2.5% MS addition on the 2.5% sample upon the lapse of the 3rd month led to a substantial reduction (up to 38%) of labile As(V) fraction in the following 4th and 6th months. As a result, an additional 15-25% of As(V) stability was obtained when splitting the amendment dose into 3-month intervals. In conclusion, the As(V) stabilization by Fe-rich amendment is time-dependent and its efficacy can be improved by optimizing the amendment dose and its timing.

Sorption of sulfathiazole in the soil treated with giant Miscanthus-derived biochar: effect of biochar pyrolysis temperature, soil pH, and aging period.

Agricultural soil was treated with biochar (5% w/w) produced from two pyrolysis temperatures (400 and 700 °C) of giant Miscanthus (GMC-400 and GMC-700, respectively), and the subsequent sorption of sulfathiazole (STZ) was evaluated as a function of pH (2, 5, and 7) and aging period (0, 3, and 6 months). Because sorption was nonlinear, with 0.51 < N < 0.75, the linearized sorption coefficient (K d*) was used for the comparison across samples. The K d* of GMC-400 treatment (3.96-9.96 L kg-1) was higher than that of GMC-700 treatment (1.27-3.38 L kg-1). In laps of aging period over 6 months, the sorption of GMC-400-treated soil had gradually increased to be 3.3 times higher than that of untreated soil, whereas there was no statistical difference for GMC-700 treatment. Results of FTIR and SEM analyses revealed that the number of O-containing functional groups in the GMC-400 treatment increases and the micropores of GMC-700 are deformed over time. Sorption was also pH-dependent in the order of pH 2 > pH 5 > pH 7. The sorption hysteresis (H) index for the GMC-400 treatment was higher at pH 7 (3.99) than at pH 5(2.53), and both values had increased after 6 months (4.18 and 3.17, respectively). The results of this study clearly demonstrate that the sorption of STZ on GMC-treated soils is greatly enhanced, mainly through the greater micropore surfaces, the abundance of hydrophilic functional groups over time, and π+-π electron donor-acceptor interaction at low pH.

Quality improvement of acidic soils by biochar derived from renewable materials.

Biochar derived from waste plant materials and agricultural residues was used to improve the quality of an acidic soil. The acidic soil was treated for 1 month with both soy bean stover-derived biochar and oak-derived biochar in the range of 1 to 5 wt% for pH improvement and exchangeable cation enhancement. Following 1 month of treatment, the soil pH was monitored and exchangeable cations were measured. Moreover, a maize growth experiment was performed for 14 days with selected treated soil samples to confirm the effectiveness of the treatment. The results showed that the pH of the treated acidic soil increased by more than 2 units, and the exchangeable cation values were greatly enhanced upon treatment with 5 wt% of both biochars, after 1 month of curing. Maize growth was superior in the 3 wt% biochar-treated samples compared to the control sample. The presented results demonstrate the effective use of biochar derived from renewable materials such as waste plant materials and agricultural residues for quality improvement of acidic soils.

Influence of an iron-rich amendment on chemical lability and plant (Raphanus sativus L.) availability of two metallic elements (As and Pb) on mine-impacted agricultural soils.

Variation of the chemical extractability and phytoavailability of two metallic elements (e.g., As and Pb) on amendment-treated soils was investigated. Four mine-impacted agricultural soils contaminated with both As (174-491 mg kg-1) and Pb (116-357 mg kg-1) were amended with an iron-rich sludge at the rate of 5 % (w/w). After a 4-, 8-, and 16-week incubation, the extractability of metallic elements was assessed by sequential extraction procedure (SEP; F1-F5). The control without amendment was also run. In amended soils, the labile element mass (i.e., F1 + F2) promptly decreased (15-48 % of As and 5-10 % of Pb) in 4 weeks, but the decrement was continued over 16 weeks up to 70 and 28 % for As and Pb, respectively. The labile mass decrement was quantitatively corresponded with the increment of F3 (bound to amorphous metal oxides). In plant test assessed by radish (Raphanus sativus) grown on the 16-week soils, up to 57 % of As and 28 % of Pb accumulation was suppressed and 10-43 % of growth (i.e., shoot/root elongation and fresh weight) was improved. For both the control and amended soils, element uptake by plant was well correlated with their labile soil concentrations (r 2 = 0.799 and 0.499 for As and Pb, respectively). The results confirmed that the iron-rich material can effectively suppress element uptake during R. sativus seedling growth, most likely due to the chemical stabilization of metallic elements in growth medium.

Impact of soybean stover- and pine needle-derived biochars on Pb and As mobility, microbial community, and carbon stability in a contaminated agricultural soil.

Biochar is gaining attention as a potential soil amendment to remediate and revitalize the contaminated soils. Simultaneous effects of biochar on metals mobility, microbial abundance, bacterial diversity and carbon storage in soil are scarcely addressed. This study assessed the effect of biochars on metal mobility, microbial abundance, bacterial community, and carbon storage in an agricultural soil contaminated with heavy metals. Biochars derived from soybean stover at 300 and 700 °C (S-BC300 and S-BC700, respectively) and pine needles at the same temperatures (P-BC300 and P-BC700, respectively) were used. A maximum reduction of Pb mobility by 95% was observed from a soil treated with S-BC700, associated with precipitation of chloropyromorphite and hydroxylpyromorphite. In contrast, As was desorbed from soil particles because of P competition. The abundance of Gram-positive and negative bacteria, fungi, actinomycetes, and arbuscular mycorrhizal fungi increased in the soils treated with biochar produced at 300 °C, possibly due to the high dissolved organic and active organic carbons. Microbial abundance in the soils treated with S-BC700 and P-BC700 was constant due to the existence of fixed or non-labile carbon. Changes to bacterial communities in the biochar-treated soils depended on feedstock type and pyrolysis temperature. Actinobacteria substantially increased whereas Acidobacteria and Chloroflexi decreased in the biochar-treated soils. The non-labile carbon fraction was ∼25 fold higher in the biochar-treated soil than the control soil, indicating long-term carbon storage.

Assessment of waste oyster shells and coal mine drainage sludge for the stabilization of As-, Pb-, and Cu-contaminated soil.

A novel treatment mix was designed for the simultaneous immobilization of As, Cu, and Pb in contaminated soils using natural (waste oyster shells (WOS)) and industrial (coal mine drainage sludge (CMDS)) waste materials. The treatments were conducted using the standard U.S. sieve size no. 20 (0.85 mm) calcined oyster shells (COS) and CMDS materials with a curing time of 1 and 28 days. The As immobilization treatments were evaluated using the 1-N HCl extraction fluid, whereas the Pb and Cu immobilization treatments were evaluated using the 0.1-N HCl extraction fluid based on the Korean leaching standards. The treatment results showed that the immobilization of As, Cu, and Pb was best achieved using a combination mix of 10 wt% COS and 10 wt% CMDS. This treatment mix was highly effective leading to superior leachability reductions for all three target contaminants (>93 % for As and >99 % for Cu and Pb) for a curing period of 28 days. The X-ray absorption near-edge structure (XANES) results showed that As was present in the form of As(V) in the control sample and that no changes in As speciation were observed following the COS-CMDS treatments. The scanning electron microscopy (SEM)-energy dispersive X-ray spectroscopy (EDX) sample treated with 10 wt% COS and 10 wt% CMDS indicated that As immobilization may be associated with the formation of Ca-As and Fe-As precipitates while Pb and Cu immobilization was most probably linked to calcium silicate hydrates (CSHs) and calcium aluminum hydrates (CAHs).

Metals Bioaccumulation Mechanism in Neem Bark.

The aim of this work was to define the bioaccumulation mechanism of metals onto the non-living biomaterial prepared from an extensively available plant bark biomass of neem (Azadirachta indica). Based on maximum ultimate fixation capacities (mmol/g) of the product, metals ions could be arranged as Hg(2+) < Cd(2+) < Pb(2+) ≅ Cu(2+). Surface properties of the biomaterial were characterized by X-ray photoelectron spectroscopy and X-ray diffraction techniques for their sorption mechanism. Whewellite (C2CaO4 · H2O) was identified in the biomaterial, which indicated that calcium ions are electrovalently bonded with carboxylate ions facilitating the ion exchange mechanism with metal ions. Bioaccumulation of metal ions was also studied by Fourier transform infrared spectroscopy, which indicated the presence of functional groups implicated in adsorbing metal ions. Biomaterial did not adsorb anionic As(III), As(V) and Cr(VI), because of their electrostatic repulsion with carboxylic functional groups. Neem bark can be used as bioindicators, bioaccumulators and biomonitors while determining environmental pressures. Metal bioaccumulative properties and structural investigation of plant bark has potential in providing quantitative information on the metal contamination in the surrounding environment.