Molecular characterization of biochars and their influence on microbiological properties of soil.

The tentative connection between the biochar surface chemical properties and their influence on microbially mediated mineralization of C, N, and S with the help of enzymes is not well established. This study was designed to investigate the effect of different biomass conversion processes (microwave pyrolysis, carbon optimized gasification, and fast pyrolysis using electricity) on the composition and surface chemistry of biochar materials produced from corn stover (Zea mays L.), switchgrass (Panicum virgatum L.), and Ponderosa pine wood residue (Pinus ponderosa Lawson and C. Lawson) and determine the effect of biochars on mineralization of C, N, and S and associated soil enzymatic activities including esterase (fluorescein diacetate hydrolase, FDA), dehydrogenase (DHA), ß-glucosidase (GLU), protease (PROT), and aryl sulfatase (ARSUL) in two different soils collected from footslope (Brookings) and crest (Maddock) positions of a landscape. Chemical properties of biochar materials produced from different batches of gasification process were fairly consistent. Biochar materials were found to be highly hydrophobic (low H/C values) with high aromaticity, irrespective of biomass feedstock and pyrolytic process. The short term incubation study showed that biochar had negative effects on microbial activity (FDA and DHA) and some enzymes including ß-glucosidase and protease.

Electron and force microscopy characterization of particle size effects and surface phenomena associated with individual natural organic matter fractions.

Natural organic matter (NOM) generically refers to organic substances found in soils, waters, and sediments. It is the brown-to-black, heterogeneous organic material produced through the diagenetic alteration of plant tissue and microbial biomass via a myriad of biotic and abiotic reactions. Since NOM is the primary source of organic carbon in the earth's surficial environment, understanding the processes by which NOM is produced is integral to understanding carbon sequestration, contaminant fate and transport, and other earth surface processes. NOM samples (HA0) consist of nonamphiphilic (HA1), lipid-like (L0 and L1), and strongly amphiphilic (HA2) components. Here we present the structure and morphology of self-assembled NOM components based on scanning electron microscopy (SEM), atomic force microscopy (AFM), and electrostatic force microscopy (EFM) characterizations. Effects of surface charge and hydrophobicity/hydrophilicity of the amphiphile on the interaction and resulting structures were investigated using SEM, AFM, and EFM. Data shows that the component's amphiphilic nature plays a key role in the formation of NOM. SEM data show that aggregates form while AFM/EFM analysis verifies the existence of hydrophobic/hydrophilic moieties in different fractions of HA0. Subsequently, the amphiphilic nature of HA2 will have a substantial effect on interfacial interactions and subsequent self-assembly of HA0's components.

Rapid fractionation of natural organic matter in water using a novel solid-phase extraction technique.

This paper introduces a novel natural organic matter (NOM) fractionation technique using solid-phase extraction cartridges. The new technique requires only 6 hours of fractionation time, which is much faster than traditional fractionation techniques (24 hours). It uses three Bond Elute ENV cartridges (Varian, Inc., Lake Forest, California), one Strata X-C cartridge (Phenomenex, Torrance, California), and one Strata X-AW cartridge (Phenomenex) in series and was tested by using to fractionate NOM from Suwannee River, Georgia (SRNOM) and Red River, Minnesota (RRNOM). Hydrophobic acid was a major fraction and accounted for 66 to 70% and 36% of SRNOM and RRNOM, respectively. The NOM fractions obtained from the developed method were characterized using Fourier transformed infrared spectroscopy and 13C nuclear magnetic resonance. The acid fractions of SRNOM mainly consisted of carboxylic acids. An application of this new technique was demonstrated by using it to investigate the effectiveness of water treatment processes in removing different NOM fractions.

Structural organization of humic acid in the solid state.

Studies of the structural organization of humic acid in solution have suggested that it is composed of three fractions, two humic acid-like and one lipid-like, that have distinct roles in the process of its self-organization. The present work extends the study of humic acid's structural organization to the solid state by directly comparing its organization with a physical mixture composed of its three fractions using differential scanning calorimetry. Comparative measurements of the specific heat capacity as a function of temperature reveal differences between the original humic acid and the mixture with the same chemical composition. These differences provide direct evidence that humic acid's solid state structure is more than just a mixture of components and is determined by specific interactions between its components. This study indicates that humic acid in the solid state has a hierarchical or "structure within a structure" architecture. The lower-level structure is determined by the self-assembly of amphiphilic components of humic acid with lipids into a nanostructured composite material. A higher-level structure is formed by the association of this composite material with the nonamphiphilic components of humic acid.

Exploring the high-mass components of humic acid by laser desorption ionization mass spectrometry.

Leonardite and Elliot soil humic acids have been analyzed by laser desorption ionization mass spectrometry (LDI MS) in the m/z 4000-200,000 range. Positive ion mass spectra for each humic acid obtained under optimum conditions showed a broad high-mass distribution between m/z 20,000 and 80,000. The dependence of the mass distribution on instrumental parameters and solution conditions was used to investigate the nature of the high-mass peaks from humic acid spectra. Our data suggests that macromolecular ions and humic acid aggregates have the same probability of occurrence while cluster ion formation has a low probability of occurrence.

The influence of lipids on the energetics of uptake of polycyclic aromatic hydrocarbons by natural organic matter.

Although most of the organic carbon in soils and sediments may be composed of humic substances, their interaction with other compounds, especially their sorption interactions, may be significantly affected by the presence of small amounts of the other components of natural organic matter (NOM). In this investigation, the influence of the lipid fraction of NOM on the sorption thermodynamics of fluorene, phenanthrene, and pyrene to several geosorbent samples was examined before and after extraction of lipids. Batch experiments were performed at the same concentration for all polycyclic aromatic hydrocarbons (PAHs) (0.025 x their solubility in water) at different temperatures (10, 20, 30, and 40 degrees C), and the thermodynamic parameters were calculated. Removal of the lipids increases the sorption capacity of the samples as well as the exothermicity of the process. The free energy change was negative for all the samples and no significant differences were noticed on lipid removal. The entropy changes were small and positive for the whole geosorbent samples, but even smaller or more negative when the lipids were removed. This indicates that the interaction of PAHs with soils and sediments in the absence of extractable lipids is stronger and the mechanisms involved may be different, changing from a partitioning-like mechanism to specific adsorption. Because of the competition between lipids and PAHs for the same sorption sites, the lipids can be viewed as an "implicit sorbate."

Formation of bound residues by naphthalene and cis-naphthalene-1,2-dihydrodiol.

The formation of bound residues by naphthalene and its metabolite, cis-naphthalene-1,2-dihydrodiol, in a sediment (1% OC), a silty loam soil (2.9% OC) and a peat (26% OC) was examined. The experiments were carried out under both sterile and nonsterile conditions for up to 35 days. The samples containing bound contaminant were hydrolyzed at an alkaline pH and fractionated using 3,000 and 500 Da molecular weight cutoff ultrafiltration membranes in series. The results for all the geosorbents examined showed that bound residue formation is low for naphthalene and between 5 and 20 times higher for the metabolite. The amount of bound residues released by hydrolysis was higher for the metabolite than for the parent compound for all the samples. The molecular weight distribution of bound radioactivity after hydrolysis showed binding to the high molecular weight components of the sediment organic matter and to the low molecular weight components for soil and peat organic matter when incubated with cis-naphthalene-1,2-dihydrodiol. Experiments performed with naphthalene-UL-(14)C showed larger amounts of bound residue found than in experiments with naphthalene-1-(14)C.