Investigation of sorbate-induced plasticization of Pahokee peat by solid-state NMR spectroscopy

Purpose

Sorbate-induced swelling and plasticization of sorbent have been linked to sorption hysteresis of organic compounds in the natural organic matter of isolated humic acids, soils, and coals. The above processes, which have important implications for the fate and bioavailability of organic and inorganic contaminants, are mostly based on macroscopic changes and require molecular-level confirmation. This study aimed to investigate the presence or absence of sorbate-induced plasticization of Pahokee peat soil as a function of different sorbates.

Materials and methods

The plasticization of Pahokee peat soil was studied upon sorption of different proton-free solutes including C₆D₆, CDCl₃, CCl₄, C₂Cl₄, CBr₄, C₆D₅Cl, and C₅D₅N, covering apolar and polar aromatic and aliphatic compounds. The swelling and plasticization of Pahokee peat soil were verified at the molecular level by ¹H wideline and two-dimensional wideline separation (2D WISE) NMR. The use of ¹H wideline shapes is the traditional technique for studying molecular dynamics but hampered by the lack of spectral resolution, with one dimension displaying ¹³C chemical shifts and the second showing ¹H wideline shapes, is capable of providing information on molecular dynamics of specific functional groups.

Results and discussion

Our results showed that the segments of Pahokee peat soil sorbed with C₆D₆, C₂Cl₄, and C₅D₅N became more mobile, but the changes due to the plasticization were small. Both C₆D₆ and C₅D₅N selectively increased the mobility of specific components, C₆D₆ of the nonpolar alkyl domains, and C₅D₅N of both the nonpolar alkyl domains and aromatic components.

Conclusions

Some liquid solutes at high concentrations (2–5 wt%) are capable of slightly “softening” natural organic matter of a soil, and this provides support for the hypothesis that natural organic matter in Pahokee peat soil is in a glassy state that is subject to plasticization.

     

Differences in the chemical composition of dissolved organic matter from waste material of different sources

The chemical composition of waste-material-derived dissolved organic matter (DOM) was characterized by chemolytic analyses and ¹H, ¹³C and ³¹P nuclear magnetic resonance (NMR) spectroscopy. Dissolved organic matter was extracted by water from an aerobic fermented urban waste compost, a sewage sludge and a pig slurry and then fractionated using the XAD-8 method. The amount of water-extractable dissolved organic carbon (DOC) ranged from 3% in the sewage sludge to 22% in the pig slurry. Dissolved organic matter isolated from pig slurry was equally distributed between hydrophilic and hydrophobic DOC, whereas in the sewage-sludge-derived material the hydrophobic fraction was predominant. Dissolved organic C from the urban waste compost was mainly within the hydrophilic fraction. Wet-chemical analysis and ¹H- and ¹³C-NMR spectra showed that both DOM fractions from the urban waste compost were low in neutral, acidic and amino sugars as well as in lignin-derived compounds. In turn, the materials were rich in low-molecular-weight aliphatic compounds. The chemical structure of both fractions is probably the result of the intensive transformation of urban waste compost during its fermentation. The hydrophilic fractions of DOM from sewage sludge and pig slurry contained considerable amounts of carbohydrates but were also rich in low-molecular-weight aliphatics. The respective hydrophobic fractions had the largest contents of CuO-extractable phenols which may in part derive from sources other than lignin. By contrast with the other materials, the hydrophobic fraction from the pig slurry seemed to contain polymeric rather than low-molecular-weight material. The ³¹P-NMR spectrum of the hydrophilic DOM fraction from urban waste compost did not show signals of inorganic or organic P compounds while the spectrum of the hydrophobic fraction revealed traces of monoester P, diester P, and orthophosphate. ³¹P-NMR spectroscopy suggested that both the hydrophobic and hydrophilic fractions from pig slurry did not contain organic P. The hydrophilic DOM fraction from sewage sludge contained orthophosphate, organic monoester P and a little pyrophosphate. The hydrophobic fraction contained mainly organic diester P and smaller amounts of teichoic acids and organic monoester P. Considering that water-soluble fractions of urban waste compost contained no easily plant-available P and a low content of labile organics, we conclude that this material contains less labile nutrients and is more refractory than the soluble constituents of pig slurry and sewage sludge.     

Book reviews,Hunting the Wild Potato in the South American Andes: Memories of the British Empire Potato Collecting Expedition to South America 1938– 1939. J. [John ‘Jack’] G. [Gregory] Hawkes.Botanical and Experimental Garden,University of Nijmegen,The Netherlands 2004. 224 pp.ISBN 90-9018021-4.

Book Review

Book reviews, Hunting the Wild Potato in the South American Andes: Memories of the British Empire Potato Collecting Expedition to South America 1938– 1939. J. [John ‘Jack’] G. [Gregory] Hawkes.Botanical and Experimental Garden, University of Nijmegen, The Netherlands 2004. 224 pp.ISBN 90-9018021-4.     

Über die Sorptionseigenschaften von Waldböden bezüglich gelöster organischer Substanzen

About the sorption of dissolved organic matter to forest soils This investigation characterizes the major forest soils of the temperate climatic zones (leptosols, vertisols, cambisols, luvisols, podzols, stagnosols, gleysols) as sorbents for dissolved organic matter (DOM). Sorption isotherms were obtained for 135 soil horizons from 36 profiles. When solutions containing no DOC were added, the release of dissolved organic carbon (DOC) was highest for horizons rich in organic C (A and Bh horizons). In subsoil horizons DOC release was much lower. Most of the investigated top soils (A and E horizons) and Bh, Bg, and C horizons showed a weak DOC sorption. This was caused by low contents of sorbents (clay and sesquioxides) and/or high contents of organic C. Organic C seems to reduce the DOC sorption by occupying binding sites. Subsoils rich in clay and sesquioxides like Bs, Bt, and Bw horizons showed a strong retention of DOC. Under the aerobic conditions of the experiments, some of the subsoils of stagnosols and gleysols also showed a strong sorption of DOC. However, in sorption experiments conducted after an anaerobic incubation, the DOC sorption decreased significantly.     

A structural mechanism for MscS gating in lipid bilayers

The mechanosensitive channel of small conductance (MscS) is a key determinant in the prokaryotic response to osmotic challenges. We determined the structural rearrangements associated with MscS activation in membranes, using functorial measurements, electron paramagnetic resonance spectroscopy, and computational analyses. MscS was trapped in its open conformation after the transbilayer pressure profile was modified through the asymmetric incorporation of lysophospholipids. The transition from the closed to the open state is accompanied by the downward tilting of the transmembrane TM1-TM2 hairpin and by the expansion, tilt, and rotation of the TM3 helices. These movements expand the permeation pathway, leading to an increase in accessibility to water around TM3. Our open MscS model is compatible with single-channel conductance measurements and supports the notion that helix tilting is associated with efficient pore widening in mechanosensitive channels.     

Growth of SiO2 at room temperature with the use of catalyzed sequential half-reactions

Films of silicon dioxide (SiO2) were deposited at room temperature by means of catalyzed binary reaction sequence chemistry. The binary reaction SiCl4 + 2H2O --> SiO2 + 4HCl was separated into SiCl4 and H2O half-reactions, and the half-reactions were then performed in an ABAB ellipsis sequence and catalyzed with pyridine. The pyridine catalyst lowered the deposition temperature from >600 to 300 kelvin and reduced the reactant flux required for complete reactions from approximately 10(9) to approximately 10(4) Langmuirs. Growth rates of approximately 2.1 angstroms per AB reaction cycle were obtained at room temperature for reactant pressures of 15 millitorr and 60-second exposure times with 200 millitorr of pyridine. This catalytic technique may be general and should facilitate the chemical vapor deposition of other oxide and nitride materials.     

The global circulation of seasonal influenza A (H3N2) viruses

Antigenic and genetic analysis of the hemagglutinin of approximately 13,000 human influenza A (H3N2) viruses from six continents during 2002-2007 revealed that there was continuous circulation in east and Southeast Asia (E-SE Asia) via a region-wide network of temporally overlapping epidemics and that epidemics in the temperate regions were seeded from this network each year. Seed strains generally first reached Oceania, North America, and Europe, and later South America. This evidence suggests that once A (H3N2) viruses leave E-SE Asia, they are unlikely to contribute to long-term viral evolution. If the trends observed during this period are an accurate representation of overall patterns of spread, then the antigenic characteristics of A (H3N2) viruses outside E-SE Asia may be forecast each year based on surveillance within E-SE Asia, with consequent improvements to vaccine strain selection.     

Hf-W chronometry of lunar metals and the age and early differentiation of the Moon

The use of hafnium-tungsten chronometry to date the Moon is hampered by cosmogenic tungsten-182 production mainly by neutron capture of tantalum-181 at the lunar surface. We report tungsten isotope data for lunar metals, which contain no 181Ta-derived cosmogenic 182W. The data reveal differences in indigenous 182W/184W of lunar mantle reservoirs, indicating crystallization of the lunar magma ocean 4.527 +/- 0.010 billion years ago. This age is consistent with the giant impact hypothesis and defines the completion of the major stage of Earth's accretion.     

Fluorescence-force spectroscopy maps two-dimensional reaction landscape of the holliday junction

Despite the recent advances in single-molecule manipulation techniques, purely mechanical approaches cannot detect subtle conformational changes in the biologically important regime of weak forces. We developed a hybrid scheme combining force and fluorescence that allowed us to examine the effect of subpiconewton forces on the nanometer scale motion of the Holliday junction (HJ) at 100-hertz bandwidth. The HJ is an exquisitely sensitive force sensor whose force response is amplified with an increase in its arm lengths, demonstrating a lever-arm effect at the nanometer-length scale. Mechanical interrogation of the HJ in three different directions helped elucidate the structures of the transient species populated during its conformational changes. This method of mapping two-dimensional reaction landscapes at low forces is readily applicable to other nucleic acid systems and their interactions with proteins and enzymes.