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The study of the sorption of contaminants to lignin is significant for understanding the migration of contaminants in the environment as well as developing low cost sorbent. In this study, sorption of three polycyclic aromatic hydrocarbons (PAHs), naphthalene, acenaphthene and phenanthrene, to lignin was investigated. Sorption isotherms were well described by both linear and Freundlich sorption models. Sorption coefficients of PAHs to lignin from water obtained from regression of both linear model (K d) and Freundlich model (K f) were highly positively correlated with hydrophobicity of PAHs. The amorphous structure of lignin provided sufficient sorption domain for partitioning of PAHs, and the attraction between PAHs molecules and aromatic fractions in lignin via π-π electron-donor-acceptor (π-π EDA) interaction is hypothesized to provide a strong sorption force. Thermodynamic modeling revealed that sorption of PAHs to lignin was a spontaneous and exothermic process.

Veterinary antibiotics in groundwater may affect natural microbial denitrification process. A microcosm study was conducted to evaluate the influence of sulfamethazine and chlortetracycline at different concentrations (0, 0.01, 0.1, and 1.0 mg/L) on nitrate reduction in groundwater under denitrifying condition. Decrease in nitrate removal and nitrite production was observed with the antibiotics. Maximum inhibition of nitrate removal was observed after seven days of incubation with 0.01 mg/L sulfamethazine (17.0%) and 1.0 mg/L chlortetracycline (15.4%). The nitrite production was inhibited with 1.0 mg/L sulfamethazine to 82.0% and chlortetracycline to 31.1%. The initial/final nitrate concentrations indicated that 0.01 mg/L sulfamethazine and 1.0 mg/L chlortetracycline were most effective in inhibiting activity of denitrifying bacteria in groundwater. After 12 days of incubation, the sulfamethazine biodegradation was observed whereas chlortetracycline was persistent. Sulfamethazine and chlortetracycline in groundwater could inhibit the growth and capability of naturally occurring denitrifying bacteria, thereby threatening nitrate pollution in groundwater.

Soybean stover-derived biochar was used to immobilize lead (Pb) in military firing range soil at a mass application rate of 0 to 20 wt.% and a curing period of 7 days. The toxicity characteristic leaching procedure (TCLP) was performed to evaluate the effectiveness of the treatment. The mechanism responsible for Pb immobilization in military firing range soil was evaluated by scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDX) and x-ray absorption fine structure (XAFS) spectroscopy analyses. The treatment results showed that TCLP Pb leachability decreased with increasing biochar content. A reduction of over 90 % in Pb leachability was achieved upon treatment with 20 wt.% soybean stover-derived biochar. SEM-EDX, elemental dot mapping and XAFS results in conjunction with TCLP leachability revealed that effective Pb immobilization was probably associated with the pozzolanic reaction products, chloropyromorphite and Pb-phosphate. The results of this study demonstrated that soybean stover-derived biochar was effective in immobilizing Pb in contaminated firing range soil.

Trichloroethylene (TCE) is one of the most hazardous organic pollutants in groundwater. Biochar produced from agricultural waste materials could serve as a novel carbonaceous adsorbent for removing organic contaminants from aqueous media. Biochars derived from pyrolysis of soybean stover at 300 °C and 700 °C (S-300 and S-700, respectively), and peanut shells at 300 °C and 700 °C (P-300 and P-700, respectively) were utilized as carbonaceous adsorbents to study batch aqueous TCE remediation kinetics. Different rate-based and diffusion-based kinetic models were adopted to understand the TCE adsorption mechanism on biochars. With an equilibrium time of 8-10 h, up to 69 % TCE was removed from water. Biochars produced at 700 °C were more effective than those produced at 300 °C. The P-700 and S-700 had lower molar H/C and O/C versus P-300 and S-300 resulting in high aromaticity and low polarity accompanying with high surface area and high adsorption capacity. The pseudo-second order and intraparticle diffusion models were well fitted to the kinetic data, thereby, indicating that chemisorption and pore diffusion were the dominating mechanisms of TCE adsorption onto biochars.

The resin capsule system (RCS) was tested as a means of providing data on the presence and forms of volatile hydrocarbons. Results indicated that resin capsules provided data showing sensitivity to soil variables (texture and moisture content) and time. The objectives of this paper are to evaluate the RCS methodology and to determine whether carbonaceous resin capsules provide results that can be described by fundamental chemical partitioning and kinetic principles. Findings revealed a significant relationship between quantities of benzene, toluene, ethylbenzene, and xylene adsorbed on the capsule and quantities partitioned into the vapor phase. Kinetic evaluation indicated that the vapor adsorption by the resin capsule is regulated by diffusion processes. No verification of rate-limiting processes was possible due to limitations imposed by the experimental design, but it appears that during early stages, adsorption rate was limited by vapor diffusion through the soil. The resin capsule data also reflected differences that would be expected due to properties of the organic liquids present. These results provide further evidence that the RCS could be developed to suggest direct in situ monitoring to reveal quantities and nature of organic substances in soils.

Chelating agents added to contaminated soils may increase solubility and phytoextraction efficiency of soil metals. However, they can create negative effects on soil biological quality. A 90-day incubation experiment was conducted to evaluate mixed effects of chelating agents and poultry manure on changes in available Cd, Pb and As, CO2-C efflux, microbial biomass C, dissolved organic C (DOC), and N mineralization in metal-polluted agricultural soil. Application of poultry manure resulted in a considerable increase in soil pH, DOC, CO2-C efflux, net N mineralization, net N nitrification, and microbial biomass C compared to those in unmanured soil. Availability of arsenic increased twice in manure amended soil due to changes in pH and DOC. However, adding poultry manure did not affect the concentrations of available Pb and Cd compared to those in control soil. Chelating agents increased CO2-C efflux, DOC, and metal availability but decreased microbial biomass C and net N mineralization. Maximum decrease in microbial biomass C, net N mineralization, and net N nitrification, was observed in EDTA applied soil possibly due to high metal availability to soil microorganisms. Overall results revealed that the application of synthetic chelators in combination with poultry manure enhances available As and demonstrates better environment for soil biota., (Copyright © 2013 Elsevier B.V. All rights reserved.)

In this study, pine needles were converted to biochar (BC) at different pyrolysis temperatures of 300, 500, and 700 °C to sorb trichloroethylene (TCE), and the changes in BC properties with each temperature were evaluated. Pyrolysis temperature showed a pronounced effect on BC properties. Decreases in molar H/C and O/C ratios resulted from removing O- and H-containing functional groups with increasing temperature, and produced high aromaticity and low polarity BCs. BCs produced at higher temperature showed greater TCE removal efficiency from water due to their high surface area, micro-porosity, and carbonized extent. The performance of various BCs for TCE removal was assessed by the Freundlich, Langmuir, Temkin, and Dubinin-Radushkevich adsorption models, among which the Temkin and Dubinin-Radushkevich models best described TCE adsorption onto various BCs, indicating prevailing sorption mechanism as pore-filling., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Conversion of crop residues into biochars (BCs) via pyrolysis is beneficial to environment compared to their direct combustion in agricultural field. Biochars developed from soybean stover at 300 and 700 °C (S-BC300 and S-BC700, respectively) and peanut shells at 300 and 700 °C (P-BC300 and P-BC700, respectively) were used for the removal of trichloroethylene (TCE) from water. Batch adsorption experiments showed that the TCE adsorption was strongly dependent on the BCs properties. Linear relationships were obtained between sorption parameters (K(M) and S(M)) and molar elemental ratios as well as surface area of the BCs. The high adsorption capacity of BCs produced at 700 °C was attributed to their high aromaticity and low polarity. The efficacy of S-BC700 and P-BC700 for removing TCE from water was comparable to that of activated carbon (AC). Pyrolysis temperature influencing the BC properties was a critical factor to assess the removal efficiency of TCE from water., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

This study evaluated the effectiveness of eggshell and calcined eggshell on lead (Pb) immobilization in a shooting range soil. Destructive and non-destructive analytical techniques were employed to determine the mechanism of Pb immobilization. The 5% additions of eggshell and calcined eggshell significantly decreased the TCLP-Pb concentration by 68.8% due mainly to increasing soil pH. Eggshell and calcined-eggshell amendments decreased the exchangeable Pb fraction to ≈ 1% of the total Pb in the soil, while the carbonate-associated Pb fraction was increased to 40.0-47.1% at >15% application rates. The thermodynamic modeling on Pb speciation in the soil solution predicted the precipitation of Pb-hydroxide [Pb(OH)(2)] in soils amended with eggshell and calcined eggshell. The SEM-EDS, XAFS and elemental dot mapping revealed that Pb in soil amended with calcined eggshell was associated with Si and Ca, and may be immobilized by entrapping into calcium-silicate-hydrate. Comparatively, in the soil amended with eggshell, Pb was immobilized via formation of Pb-hydroxide or lanarkite [Pb(2)O(SO(4))]. Applications of amendments increased activities of alkaline phosphatase up to 3.7 times greater than in the control soil. The use of eggshell amendments may have potential as an integrated remediation strategy that enables Pb immobilization and soil biological restoration in shooting range soils., (Copyright © 2012 Elsevier B.V. All rights reserved.)