Xiaoyan Cao

Removal of copper and cadmium from aqueous solution using switchgrass biochar produced via hydrothermal carbonization process

Biochar produced from switchgrass via hydrothermal carbonization (HTC) was used as a sorbent for the removal of copper and cadmium from aqueous solution. The cold activation process using KOH at room temperature was developed to enhance the porous structure and sorption properties of the HTC biochar. The sorption efficiency of HTC biochar and alkali activated HTC biochar (HTCB) for removing copper and cadmium from aqueous solution were compared with commercially available powdered activated carbon (PAC). The present batch adsorption study describes the effects of solution pH, biochar dose, and contact time on copper and cadmium removal efficiency from single metal ion aqueous solutions. The activated HTCB exhibited a higher adsorption potential for copper and cadmium than HTC biochar and PAC. Experiments conducted with an initial metal concentration of 40 mg/L at pH 5.0 and contact time of 24 h resulted in close to 100% copper and cadmium removal by activated HTCB at 2 g/L, far greater than what was observed for HTC biochar (16% and 5.6%) and PAC (4% and 7.7%). The adsorption capacities of activated HTCB for cadmium removal were 34 mg/g (0.313 mmol/g) and copper removal was 31 mg/g (0.503 mmol/g).

Influence of Molecular Structure and Adsorbent Properties on Sorption of Organic Compounds to a Temperature Series of Wood Chars

Chars from wildfires and soil amendments (biochars) are strong adsorbents that can impact the fate of organic compounds in soil, yet the effects of solute and adsorbent properties on sorption are poorly understood. We studied sorption of benzene, naphthalene, and 1,4-dinitrobenzene from water to a series of wood chars made anaerobically at different heat treatment temperatures (HTT) from 300 to 700 °C, and to graphite as a nonporous, unfunctionalized reference adsorbent. Peak suppression in the NMR spectrum by sorption of the paramagnetic relaxation probe TEMPO indicated that only a small fraction of char C atoms lie near sorption sites. Sorption intensity for all solutes maximized with the 500 °C char, but failed to trend regularly with N2 or CO2 surface area, micropore volume, mesopore volume, H/C ratio, O/C ratio, aromatic fused ring size, or HTT. A model relating sorption intensity to a weighted sum of microporosity and mesoporosity was more successful. Sorption isotherm linearity declined progressively with carbonization of the char. Application of a thermodynamic model incorporating solvent-water and char-graphite partition coefficients permitted for the first time quantification of steric (size exclusion in pores) and π-π electron donor-acceptor (EDA) free energy contributions, relative to benzene. Steric hindrance for naphthalene increases exponentially from 9 to 16 kJ/mol (∼ 1.6-2.9 log units of sorption coefficient) with the fraction of porosity in small micropores. π-π EDA interactions of dinitrobenzene contribute -17 to -19 kJ/mol (3-3.4 log units of sorption coefficient) to sorption on graphite, but less on chars. π-π EDA interaction of naphthalene on graphite is small (-2 to 2 kJ/mol). The results show that sorption is a complex function of char properties and solute molecular structure, and not very predictable on the basis of readily determined char properties.

Effects of Biomass Types and Carbonization Conditions on the Chemical Characteristics of Hydrochars

Effects of biomass types (bark mulch versus sugar beet pulp) and carbonization processing conditions (temperature, residence time, and phase of reaction medium) on the chemical characteristics of hydrochars were examined by elemental analysis, solid-state ¹³C NMR, and chemical and biochemical oxygen demand measurements. Bark hydrochars were more aromatic than sugar beet hydrochars produced under the same processing conditions. The presence of lignin in bark led to a much lower biochemical oxygen demand (BOD) of bark than sugar beet and increasing trends of BOD after carbonization. Compared with those prepared at 200 °C, 250 °C hydrochars were more aromatic and depleted of carbohydrates. Longer residence time (20 versus 3 h) at 250 °C resulted in the enrichment of nonprotonated aromatic carbons. Both bark and sugar beet pulp underwent deeper carbonization during water hydrothermal carbonization than during steam hydrothermal carbonization (200 °C, 3 h) in terms of more abundant aromatic C but less carbohydrate C in water hydrochars.

Structural convergence of maize and wheat straw during two-year decomposition under different climate conditions.

Straw decomposition plays an important role in soil carbon sequestration. Litter quality and climate condition are considered to be key factors that regulate straw decomposition. This study investigated the decomposition characteristics of wheat and maize straw under cold temperate, warm temperate, and midsubtropic climate conditions, and examined whether the chemical structures of straw residues became similar during decomposition under different climate conditions. Straws were put in 0.074-mm-mesh size litter bags to exclude soil fauna and buried in black soil plots at three experimental stations located in the aforementioned climate regions to rule out the impact of soil type. The decomposition rate constants of wheat straw and maize straw increased linearly with temperature, and the former was more sensitive to temperature. Climate conditions and straw quality had marked effects on the residual material structure in the first half year of decomposition, but then decreased. Wheat and maize straw showed common decomposition characteristics with a decrease of O/N-alkyl carbons and di-O-alkyls, and a simultaneous increase of alkyl carbons, aromatic carbons, aromatic C-O groups, and COO/N-C ═ O groups. Overall, the results indicated that the chemical compositions of the two types of straw became similar after 2-year decomposition under different climate conditions.

Advanced solid-state NMR spectroscopy of natural organic matter

Solid-state NMR is essential for the characterization of natural organic matter (NOM) and is gaining importance in geosciences and environmental sciences. This review is intended to highlight advanced solid-state NMR techniques, especially a systematic approach to NOM characterization, and their applications to the study of NOM. We discuss some basics of how to acquire high-quality and quantitative solid-state 13C NMR spectra, and address some common technical mistakes that lead to unreliable spectra of NOM. The identification of specific functional groups in NOM, primarily based on 13C spectral-editing techniques, is described and the theoretical background of some recently-developed spectral-editing techniques is provided. Applications of solid-state NMR to investigating nitrogen (N) in NOM are described, focusing on limitations of the widely used 15N CP/MAS experiment and the potential of improved advanced NMR techniques for characterizing N forms in NOM. Then techniques used for identifying proximities, heterogeneities and domains are reviewed, and some examples provided. In addition, NMR techniques for studying segmental dynamics in NOM are reviewed. We also briefly discuss applications of solid-state NMR to NOM from various sources, including soil organic matter, aquatic organic matter, organic matter in atmospheric particulate matter, carbonaceous meteoritic organic matter, and fossil fuels. Finally, examples of NMR-based structural models and an outlook are provided.

Sorption Selectivity in Natural Organic Matter Studied with Nitroxyl Paramagnetic Relaxation Probes

Sorption site selectivity and mechanism in natural organic matter (NOM) were addressed spectroscopically by the sorption of paramagnetic nitroxyl compounds (spin probes) of different polarity, TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) and HTEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl). The sorbents were Pahokee peat, Beulah-Zap lignite, and a polystyrene-poly(vinyl methyl ether) (PS-PVME) polymer blend representing the mixed aliphatic-aromatic, polar-nonpolar character of NOM. Nuclear-electron spin interaction serves as an efficient relaxation pathway, resulting in attenuation of the (13)C-CP/TOSS NMR signal for (13)C nuclei in proximity to the N-O· group (r(-6) dependence). In the natural solids the spin probes sorbed more specifically (greater isotherm nonlinearity) and had lower rotational mobility (broader electron paramagnetic resonance signals) than in PS-PVME. Titration with spin probe indicated almost no selectivity for the different carbon functional groups of PS-PVME, and little to no selectivity for the different carbon moieties of Pahokee and Beulah, including aromatic, alkyl, O-alkyl, di-O-alkyl, and O-methyl. In any case, sorption site selectivity of spin probes to NOM was always weaker than partition selectivity found in model solvent-water (toluene, hexadecane, anisole, octanol) and cellulose-water systems. The results indicate little or no preferential sorption in NOM based on functional group chemistry or putative microdomain character, but rather are consistent with the filling of pores whose walls have an average chemical environment reflecting the bulk chemical composition of the solid. This work demonstrates for the first time the use of paramagnetic probes to study sorption specificity.

Characterization of oil shale, isolated kerogen, and postpyrolysis residues using advanced 13C solid-state nuclear magnetic resonance spectroscopy

Characterization of oil shale kerogen and organic residues remaining in postpyrolysis spent shale is critical to the understanding of the oil generation process and approaches to dealing with issues related to spent shale. The chemical structure of organic matter in raw oil shale and spent shale samples was examined in this study using advanced solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Oil shale was collected from Mahogany zone outcrops in the Piceance Basin. Five samples were analyzed: (1) raw oil shale, (2) isolated kerogen, (3) oil shale extracted with chloroform, (4) oil shale retorted in an open system at 500C to mimic surface retorting, and (5) oil shale retorted in a closed system at 360C to simulate in-situ retorting. The NMR methods applied included quantitative direct polarization with magic-angle spinning at 13 kHz, cross polarization with total sideband suppression, dipolar dephasing, CHn selection, 13C chemical shift anisotropy filtering, and 1H-13C long-range recoupled dipolar dephasing. The NMR results showed that, relative to the raw oil shale, (1) bitumen extraction and kerogen isolation by demineralization removed some oxygen-containing and alkyl moieties; (2) unpyrolyzed samples had low aromatic condensation; (3) oil shale pyrolysis removed aliphatic moieties, leaving behind residues enriched in aromatic carbon; and (4) oil shale retorted in an open system at 500C contained larger aromatic clusters and more protonated aromatic moieties than oil shale retorted in a closed system at 360C, which contained more total aromatic carbon with a wide range of cluster sizes.

Biosorption of nonylphenol by pure algae, field-collected planktons and their fractions

Algal samples were fractionated into lipid (LP), lipid free (LF), alkaline nonhydrolyzable carbon (ANHC), and acid nonhydrolyzable carbon (NHC) fractions, and were characterized by the quantitative (13)C multiCP NMR technique. The biosorption isotherms for nonylphenol (NP) were established and compared with previously published data for phenanthrene (Phen). The log KOC values are significantly higher for the field-collected plankton samples than for the commercial algae and cultured algae samples, correlating with their lipid contents and aliphatic carbon structure. As the NHC fraction contains more poly(methylene) carbon, it exhibits a higher biosorption capacity. The sorption capacities are negatively related to the polarity index, COO/N-C=O, polar C and O-alkyl C concentrations, but are positively related to the H/O atomic ratios and poly(methylene) carbon. The higher sorption capacities observed for NP than for Phen on the investigated samples are explained by specific interactions such as hydrogen bonding and π-π interaction.

Hydrothermal preparation and characterization of novel corncob-derived solid acid catalysts.

Novel corncob-derived solid acid catalysts were successfully synthesized for the first time by the hydrothermal method. The influences of different preparation conditions were investigated, and the structure-function relationships of the resulting catalysts were also discussed on the basis of the analysis of structure and composition. In comparison to conventional solid acid catalysts, the corncob-derived catalyst synthesized under optimized conditions exhibited higher catalytic activity in esterification reactions, yielding nearly 90% methyl oleate in only 2 h. The catalyst retained satisfactory catalytic activity for esterification, even after 8 reaction cycles. Solid-state magic angle spinning (MAS) (13)C nuclear magnetic resonance (NMR) investigations further indicated that the catalyst was composed of polycyclic aromatic carbon sheets bearing -SO3H, -COOH, and -OH groups in adequate amounts and with proper proportions, contributing to its excellent catalytic activity. This work provides a green method to synthesize solid acid catalysts from biomass wastes and may contribute to a holistic approach for biomass conversion.

Sorption Selectivity in Natural Organic Matter Probed with Fully Deuterium-Exchanged and Carbonyl-13C-Labeled Benzophenone and 1H–13C NMR Spectroscopy

Specific functional-group or domain interactions of fully deuterium-exchanged, carbonyl-(13)C-labeled benzophenone and different types of natural organic matter (NOM) were investigated through two-dimensional (1)H-(13)C heteronuclear correlation NMR spectroscopy. The sorbents included Beulah-Zap lignite, type II kerogen (IL-6), Pahokee peat, Amherst humic acid, and a polystyrene-poly(vinylmethyl ether) (PS-PVME) blend. PS-PVME consists of PS and PVME chains that are mixed on a scale of <5 nm. The NOM sorbents all consist predominantly of a mixed aromatic-alkyl or aromatic-O-alkyl matrix that is homogeneous on the 3 nm scale, as evidenced by fast equilibration of aromatic and alkyl (1)H magnetization. In addition, Beulah lignite and IL-6 kerogen exhibit small fractions of distinct polymethylene (CH2)n domains, and Pahokee peat contains significant fractions of polar and nonpolar alkyl domains. Benzophenone-((13)C═O)-d10 shows proximity to both aromatic rings and alkyl segments in all samples but preferentially interacts with aromatic rings in PS-PVME and Beulah lignite, possibly due to π-π electron donor-acceptor interactions. The data for IL-6 kerogen are also compatible with preferential location of benzophenone near the alkyl-substituted edges of aromatic rings, while in Pahokee peat, clear signatures of benzophenone affinity to both aromatic-rich and nonpolar alkyl domains have been detected. Amherst humic acid shows evidence of some affinity to polar alkyl segments but which is weaker than that to aromatic rings. Our results indicate that specific interactions of the sorbate and the presence of domains in the sorbent influence the magnitude and selectivity of sorption.