Jingdong Mao

Hydrothermal Carbonization of Municipal Waste Streams

Hydrothermal carbonization (HTC) is a novel thermal conversion process that can be used to convert municipal waste streams into sterilized, value-added hydrochar. HTC has been mostly applied and studied on a limited number of feedstocks, ranging from pure substances to slightly more complex biomass such as wood, with an emphasis on nanostructure generation. There has been little work exploring the carbonization of complex waste streams or of utilizing HTC as a sustainable waste management technique. The objectives of this study were to evaluate the environmental implications associated with the carbonization of representative municipal waste streams (including gas and liquid products), to evaluate the physical, chemical, and thermal properties of the produced hydrochar, and to determine carbonization energetics associated with each waste stream. Results from batch carbonization experiments indicate 49-75% of the initially present carbon is retained within the char, while 20-37% and 2-11% of the carbon is transferred to the liquid- and gas-phases, respectively. The composition of the produced hydrochar suggests both dehydration and decarboxylation occur during carbonization, resulting in structures with high aromaticities. Process energetics suggest feedstock carbonization is exothermic.

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).

Nonaromatic Core−Shell Structure of Nanodiamond from Solid-State NMR Spectroscopy

The structure of synthetic nanodiamond has been characterized by (13)C nuclear magnetic resonance (NMR) spectral editing combined with measurements of long-range (1)H-(13)C dipolar couplings and (13)C relaxation times. The surface layer of these approximately 4.8-nm diameter carbon particles consists mostly of sp(3)-hybridized C that is protonated or bonded to OH groups, while sp(2)-hybridized carbon makes up less than 1% of the material. The surface protons surprisingly resonate at 3.8 ppm, but their direct bonding to carbon is proved by fast dipolar dephasing under homonuclear decoupling. Long-range (1)H-(13)C distance measurements, based on (13)C{(1)H} dipolar dephasing by surface protons, show that seven carbon layers, in a shell of 0.63 nm thickness that contains approximately 60% of all carbons, predominantly resonate more than +8 ppm from the 37-ppm peak of bulk diamond (i.e., within the 45-80 ppm range). Nitrogen detected in (15)N NMR spectra is mostly not protonated and can account for some of the high-frequency shift of carbon. The location of unpaired electrons (approximately 40 unpaired electrons per particle) was studied in detail, based on their strongly distance-dependent effects on T(1,C) relaxation. The slower relaxation of the surface carbons, selected by spectral editing, showed that the unpaired electrons are not dangling bonds at the surface. This was confirmed by detailed simulations, which indicated that the unpaired electrons are mostly located in the disordered shell, at distances between 0.4 and 1 nm from the surface. On the basis of these results, a nonaromatic core-shell structural model of nanodiamond particles has been proposed.

The influence of natural organic matter on the toxicity of multiwalled carbon nanotubes

Engineered carbon nanostructures, such as multiwalled carbon nanotubes (MWNTs), are inherently hydrophobic and are not readily stable in aqueous media. However, the aqueous stability and bioavailability of these nanotubes may be influenced by the water quality parameters such as ionic strength, pH, and natural organic matter (NOM). Natural organic matter adsorbs onto the surface of MWNTs, effectively covering the hydrophobic surface and resulting in increased aqueous stability. This enhanced stability is likely to lead to an increased residence time in the water column and increased exposure times for pelagic organisms. In the current study, NOM from three different river systems in the southeast United States increased the stability of MWNT suspensions. The effects of these suspensions were evaluated using acute and chronic bioassays with Daphnia magna and Ceriodaphnia dubia. The 96-h LC50 for D. magna exposed to MWNTs suspended in Suwannee River (USA) NOM was approximately 2.0 mg/L and was not significantly influenced by NOM concentrations ranging from 1.79 to 18.5 mg/L DOC. However, there were differences in 96-h LC50 values among different sources of NOM (Suwannee, Black, and Edisto Rivers, USA). Daphnid growth was reduced in both D. magna and C. dubia, whereas reproduction was reduced in C. dubia. Characterization of the different NOM sources and MWNT suspensions was conducted. Visual inspection using transmission electron microscopy (TEM) and gut elimination observations suggested that the toxicity was attributable to ingested MWNTs clogging the gut tract of D. magna. The TEM micrographs indicated that MWNTs can disaggregate within the gut tract, but single MWNTs are unable to absorb across the gut lumen.

Fe(III) photocatalytic reduction of Cr(VI) by low-molecular-weight organic acids with α-OH

The photochemical reduction of Cr(VI) by four low-molecular-weight organic acids (tartaric acid, citric acid, malic acid, and n-butyric acid) in the presence of either dissolved Fe(III) in dilute aqueous solution or adsorbed Fe(III) on clay mineral surfaces (kaolinite, montmorillonite and illite) was investigated using batch reactors at a pH range from 3.5 to 4.5 at 25 degrees C. The results indicate that Fe(III) photocatalytic reduction of Cr(VI) by organic acids with alpha-OH is extremely fast. During a reaction period when less than 80% initial Cr(VI) was consumed, the reaction can be described as pseudo-first-order with respect to Cr(VI) when organic acid in excess. By plotting ln[Cr(VI)] as a function of reaction time, rate constants of Cr(VI) reduction by organic acids are obtained. The rate constants involving the four acids are in the order: tartaric acid (with 2 carboxylic groups and 2 alpha-OH groups)>citric acid (with 3 carboxylic groups and 1 alpha-OH group) approximately malic acid (with 2 carboxylic groups and 1 alpha-OH group)>>n-butyric acid (with 1 carboxylic group and no alpha-OH group). This order suggests that the number of alpha-OH but not the number of carboxylic groups is an important determinant of kinetics. With light, the reduction of Cr(VI) by citric acid is accelerated by clay minerals. The enhancement of Cr(VI) reduction is attributed to the catalysis of Fe(III) adsorbed on clay mineral surfaces. However, such an acceleration is markedly suppressed by introducing NaF into the reaction system since NaF forms a complex with Fe(III). It is concluded that the complex formation between Fe(III) and organic acid is a key step for the photocatalytic reduction of Cr(VI) in the presence of Fe(III) and organic acids with alpha-OH.

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.

Influence of complex reagents on removal of chromium(VI) by zero-valent iron

The removal of Cr(VI) by zero-valent iron (Fe(0)) and the effect of three complex reagents, ethylenediaminetetraacetic acid (EDTA), NaF and 1,10-phenanthroline, on this reaction were investigated using batch reactors at pH values of 4, 5 and 6. The results indicate that the removal of Cr(VI) by Fe(0) is slow at pH 5.0 and that three complex reagents play different roles in the reaction. EDTA and NaF significantly enhance the reaction rate. The zero-order rate constants at pH 5.0 were 5.44 microM min(-1) in the presence of 4mM EDTA and 0.99 micrM min(-1) in the presence of 8 mM NaF, respectively, whereas that of control was only 0.33 micrM min(-1), even at pH=4.0. This enhancement is attributed to the formation of complex compounds between EDTA/NaF and reaction products, such as Cr(III) and Fe(III), which eliminate the precipitates of Cr(III), Fe(III) hydroxides and Cr(x)Fe(1-)(x)(OH)(3) and thus reduce surface passivation of Fe(0). In contrast, 1,10-phenanthroline, a complex reagent for Fe(II), dramatically decreases Cr(VI) reduction by Fe(0). At pH=4.0, the zero-order rate constant in the presence of 1mM of 1,10-phenanthroline was 0.02 micrM min(-1), decreasing by 99.7% and 93.9%, respectively, compared with the results in the presence and absence of EDTA. The results suggest that a pathway of the reduction of Cr(VI) to Cr(III) by Fe(0) may involve dissolution of Fe(0) to produce Fe(II), followed by reduction of Cr(VI) by Fe(II), rather than the direct reaction between Cr(VI) and Fe(0), in which Fe(0) transfers electrons to Cr(VI).

Characterization of plant-derived water extractable organic matter by multiple spectroscopic techniques.

Water extractable organic matter (WEOM) derived from fresh- or early-stage decomposing soil amendment materials may play an important role in the process of organic matter accumulation. In this study, eight WEOM samples extracted with a 40:1 (v/w) water to sample ratio from alfalfa (Medicago sativa L.), corn (Zea mays L.), crimson clover (Trifolium incarnatum L.), hairy vetch (Vicia villosa L.), lupin (Lupinus albus L.), soybean (Glycine max L. Merr.), wheat (Triticum aestivum L.), and dairy manure were investigated using ultraviolet (UV)–visible, Fourier transform infrared (FT-IR), solution 31P nuclear magnetic resonance (NMR), and solid state 13C NMR spectroscopies. UV–visible and FT-IR spectra of the plant-derived WEOM samples were typical for natural organic matter, but possessed less humic-like characteristics than dairy manure-derived WEOM. Solution 31P NMR spectra indicated that WEOM samples extracted from alfalfa, corn, and soybean shoots contained both orthophosphate and monoester P. Of the monoester P in WEOM from soybean shoot, 70% was phytate P. WEOM from crimson clover, hairy vetch, lupin, and wheat shoots contained orthophosphate only. The solid-state 13C NMR spectra of the seven plant-derived WEOM samples indicated that they all were primarily composed of sugars, amino acids or peptides, and low molecular mass carboxylic acids. Carbohydrates were dominant components with very few aromatics present in these samples. In addition, WEOM from crimson clover and lupin, but not other three leguminous plant WEOM samples, contained significant asparagine. On the other hand, WEOM from corn and wheat contained less amino acids or peptides. The spectra of WEOM of dairy manure revealed the presence of significant amounts of nonprotonated carbons and lignin residues, suggesting humification of the manure-derived WEOM. Significant carbohydrates as well as aromatics were present in this WEOM. The P and C bonding information for these WEOM samples may be useful for understanding the effects of WEOM on soil nutrient availability to plants.

Recoupled long-range C–H dipolar dephasing in solid-state NMR, and its use for spectral selection of fused aromatic rings

This work introduces a simple new solid-state 13C NMR method for distinguishing various types of aromatic residues, e.g. those of lignin from fused rings of charcoal. It is based on long-range dipolar dephasing, which is achieved by recoupling of long-range C-H dipolar interactions, using two 1H 180 degrees pulses per rotation period. This speeds up dephasing of unprotonated carbon signals approximately threefold compared to standard dipolar dephasing without recoupling and thus provides much more efficient differential dephasing. It also reduces the effects of spinning-speed dependent effective proton-proton dipolar couplings on the heteronuclear dephasing. Signals of unprotonated carbons with two or more protons at a two-bond distance dephase to <3% within less than 0.9 ms, significantly faster than those of aromatic sites separated from the nearest proton by three or more bonds. Differential dephasing among different unprotonated carbons is demonstrated in a substituted anthraquinone and 3-methoxy benzamide. The data yield a calibration curve for converting the dephasing rates into estimated distances from the carbon to the nearest protons. This can be used for peak assignment in heavily substituted or fused aromatic molecules. Compared to lignin, slow dephasing is observed for the aromatic carbons in wood charcoal, and even slower for inorganic carbonate. Direct 13C polarization is used on these structurally complex samples to prevent loss of the signals of interest, which by design originate from carbons that are distant from protons and therefore crosspolarize poorly. In natural organic matter such as humic acids, this combination of recoupled dipolar dephasing and direct polarization at 7-kHz MAS enables selective observation of signals from fused rings that are characteristic of charcoal.

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.