Magnetic biochars have lower adsorption but higher separation effectiveness for Cd2+ from aqueous solution compared to nonmagnetic biochars.

Magnetic biochars were prepared by chemical co-precipitation of Fe3+/Fe2+ onto rice straw (M-RSB) and sewage sludge (M-SSB), followed by pyrolysis treatment, which was also used to prepare the corresponding nonmagnetic biochars (RSB and SSB). The comparison of adsorption characteristics between magnetic and nonmagnetic biochars was investigated as a function of pH, contact time, and initial Cd2+ concentration. The adsorption of nonmagnetic biochars was better described by pseudo-second-order kinetic model, and the adsorption of RSB and SSB was better described by Langmuir and Freundlich models, respectively. Magnetization of the biochars did not change the applicability of their respective adsorption models, but reduced their adsorption capabilities. The maximum capacities were 42.48 and 4.64 mg/g for M-RSB and M-SSB, respectively, underperforming their nonmagnetic counterparts of 58.65 and 7.22 mg/g for RSB and SSB. Such a reduction was fundamentally caused by the decreases in the importance of cation-exchange and Cπ-coordination after magnetization, but the Fe-oxides contributed to the precipitation-dependent adsorption capacity for Cd2+ on magnetic biochars. The qualitative and quantitative characterization of adsorption mechanisms were further analyzed, in which the contribution proportions of cation-exchange after magnetization were reduced by 31.9% and 12.1% for M-RSB and M-SSB, respectively, whereas that of Cπ-coordination were reduced by 3.4% and 31.1% for M-RSB and M-SSB, respectively. These reductions suggest that for adsorbing Cd2+ the choice of conventional biochar was more relevant than whether the biochar was magnetized. However, magnetic biochars are easily separated from treated solutions, depending largely on initial pH. Their easy of separation suggests that magnetic biochars hold promise as more sustainable alternatives for the remediation of moderately Cd-contaminated environments, such as surface water and agriculture soil, and that magnetic biochars should be studied further.

High-efficiency removal capacities and quantitative adsorption mechanisms of Cd2+ by thermally modified biochars derived from different feedstocks.

Adsorption characteristics of Cd2+ on the three biochars modified by pyrolysis and calcination were investigated that were derived from rice straw (TRSB), chicken manure (TCMB) and sewage sludge (TSSB). The pH effect, adsorption kinetics, isotherms and thermodynamics, and desorption were determined, and qualitative analysis of adsorption mechanisms was performed by SEM, XRD, FTIR and XPS. Maximum adsorption capacities reached 177.28, 96.03 and 74.04 mg/g for TCMB, TRSB and TSSB, respectively, which were higher than that of many previously reported biochars. Even after five adsorption-desorption cycles, TCMB showed the strongest reusability without losing significantly adsorption capacity. This suggested that thermally modified biochars, particularly TCMB, could be a preferred adsorbent for Cd2+. Relative distribution of adsorption mechanisms was examined by direct and indirect calculation, in which the precipitation and cation-exchange dominated the whole chemisorption process, jointly accounting for 84% (TRSB) to 95% (TCMB) of total adsorption. While the complexation was of minor importance in total adsorption accounting for 5%-16%. The relationship of each mechanism with the properties of biochar was also discussed. These provided new insights on the adsorption effectiveness and mechanisms for Cd2+ in the aqueous solution that was critical for evaluating the application of modified biochars.

Qualitative and quantitative characterization of adsorption mechanisms for Cd2+ by silicon-rich biochar.

The adsorption characteristics of rice-husk biochar (RHB) rich in silicon (Si) for Cd2+ in solution and soil were investigated. Three biochars were produced at different pyrolytic temperatures of 300 °C(RHB300), 500 °C(RHB500) and 700 °C (RHB700). The pH effect, adsorption kinetics and isotherms were examined, and chemical analyses of Cd2+-loaded biochars were conducted by SEM-EDS, FTIR, XRD and Boehm titration. Biochars produced at higher temperature have much larger pH and surface area, resulting in greater adsorption capacities and faster adsorption kinetics. Maximum adsorption capacities calculated from Langmuir isotherm were 62.75, 77.37 and 93.50 mg/g for RHB300, RHB500 and RHB700, respectively. Cd2+ adsorption was primarily attributed to cation exchange and precipitation, which jointly contributed 59.55% (RHB300) to 76.05% (RHB700) of the total adsorption, but the mechanisms of complexation and coordination were of minor importance in total adsorption. The relationship of each mechanism with biochar's properties was further discussed. Si-containing minerals within biochar made a much larger contribution to precipitation than total adsorption, as the respective contribution proportion were 33.92% and 8.33% on average. When added to highly Cd-polluted soil, the biochars could effectively reduce the availability of Cd2+ after incubation for 35 days, and ameliorate soil acidification through the speediness of Si released into soil solutions. These demonstrate that rice husk-derived biochar, produced at high temperatures, can be suitable applied to mitigate Cd-contamination of soil and water, and the presented analyses shed light on the mechanisms underlying the adsorption by this Si-rich biochar.

Adsorption Behavior and Relative Distribution of Cd2+ Adsorption Mechanisms by the Magnetic and Nonmagnetic Biochars Derived from Chicken Manure.

The present study investigated the adsorption of Cd2+ by nonmagnetic and magnetic biochars (CMB and M-CMB) derived from chicken manure, respectively. The adsorption characteristics were investigated as a function of initial pH, contact time, initial Cd2+ concentration and magnetic separation. Adsorption process of both biochars were better described by Pseudo-second-order kinetic equation and Freundlich isotherm model, which were spontaneous and endothermic in nature. It was found that maximum capacities were 60.69 and 41.07 mg/g obtained at the initial Cd2+ concentration of 180 mg/L for CMB and M-CMB, and the turbidity of adsorption-treated solution was reduced from 244.3 to 11.3 NTU after magnetic separation of 0.5 min. These indicated that M-CMB had lower adsorption capacity of Cd2+ than CMB, though it was successfully separated from the treated solutions. Furthermore, both biochars before and after adsorption were analyzed by SEM-EDS, XRD and FTIR. Adsorption mechanisms mainly included precipitation, ion-exchange, complexation and Cπ-coordination, in which precipitation and ion-exchange dominated the adsorption process by CMB, while in M-CMB, precipitation was always predominant mechanism, followed by ion-exchange. The two other mechanisms of complexation and Cπ-coordination were trivial in both biochars, jointly contributing 7.21% for CMB and 5.05% for M-CMB to total adsorption. The findings deepen our understanding of the mechanisms governing the adsorption process, which are also important for future practical applications in the removal of heavy metals from wastewater by the biochars.

[Effect of covalent functionalization on DNA cleavage activity and ROS formation of single-walled carbon nanotubes].

Biotoxicity of selected covalent functionalizaed single-walled carbon nanotubes (SWNTs) was investigated by plasmid DNA cleavage assay. The effect of covalent functionalization on the physical structural and chemical activity of SWNTs was also studied by Vis-NIR spectroscopy, Raman spectroscopy and ROS assay. The DNA cleavage intensity was promoted by covalent functionalization, and the intensity of DNA damage caused by the three types of carbon nanotubes in a descending order was found to be carboxylated SWNTs (SWNT-COOH) > polyethyleneglycol-lated SWNTs (SWNT-PEG) > uncovalent functionalized SWNTs (uSWNTs). SWNTs were efficient intermediate to trigger electron transfer from electron donor to O2 in dark condition which lead to superoxide radical (O2*-) formation. The electron transfer intensity caused by selected SWNTs was also SWNT-COOH > SWNT-PEG > SWNTs. The reason is that defect sites which changed from sp2-hybridized carbon atom on the side wall of carbon nanotubes were more reactive than the perfect ones.

The effects of nutrient amendment on biodegradation and cytochrome P450 activity of an n-alkane degrading strain of Burkholderia sp. GS3C.

The promotion of hexadecane biodegradation activity by an n-alkane degrading strain of Burkholderia cepacia (GS3C) with yeast extract amendment was studied using various carbon, nitrogen, vitamin, and amino acid amendments. Cytochrome P450 monooxygenase enzymes play a very important role and are especially required to introduce oxygen in n-alkane degradation. These enzymes from GS3C were located and detected using amino acid amendments. It was shown that biodegradation activity was promoted with amino acids amendments. However, only specific amino acids (L-phenylalanine, L-glutamic acid, L-proline, L-lysine, L-valine and L-leucine) have biodegradation promoting ability for GS3C. Cell protein concentration and cytochrome P450 activity were promoted significantly with the addition of L-phenylalanine and yeast extract. Furthermore, a significant positive linear relationship between cytochrome P450 activity and biodegradation efficiency of GS3C was observed. The results indicate that amino acid is the primary factor of nutrient amendment in promoting hexadecane biodegradation by influencing cytochrome P450 activity in GS3C.