Exfoliation and intercalation of montmorillonite by small peptides.

Understanding structural changes in clay minerals induced by complexation with organic matter is relevant to soil science and agricultural applications. In this study, the effect of peptide storage in montmorillonite and the thermal stability of peptide-clay complexes was examined through characterization by X-ray diffraction (XRD), electron microscopy, UV absorption, and thermogravimetric analysis (TGA). XRD analysis of small peptide-montmorillonite clay complexes produced profiles consisting of reflections associated with the smectite 001 reflection and related peaks similar to that produced by a mixed layer clay mineral structure. Shifts in higher order diffraction maxima were attributed to disorder caused by the intercalation with the peptides. Increasing peptide concentrations resulted in greater shifts towards smaller 2θ from 6.37° (1.39 nm) to 5.45° (1.62 nm) as the interlayer space expanded. The expansion was accompanied by broadening of the 001 reflection (FWHM increases from 0.51 to 1.22° 2θ). The XRD line broadening was interpreted as caused by poorer crystallinity resulting from intercalation and tactoid exfoliation. SEM images revealed montmorillonite platelets with upwardly rolled edges that tend toward cylindrical structures with the production of tubules. High-resolution TEM images revealed bending of montmorillonite platelets, confirming exfoliation. The distribution of basal spacings in the micrographs was determined from the spatial frequencies obtained by Fourier analysis of density profiles. The distribution indicated the presence of discrete coherent crystallite domains. XRD and TGA results indicated that higher peptide concentrations resulted in a greater fraction of intercalated peptides and that surface adsorption of peptides mediated intercalation. Therefore, higher peptide concentration led to more stable organoclay complexes. However, UV absorption and TGA found that peptide adsorption onto montmorillonite had a finite limit at approximately 16% by weight.

The effects of trace narasin on the biogeochemical N-cycle in a cultivated sandy loam.

Narasin is an antibiotic administered to broiler chickens to prevent coccidiosis. After storage, excreta containing parent narasin compounds is commonly spread as nitrogen fertilizer, yielding initial soil concentrations in the low µg·kg-1 range. In soil, antibiotics have been found to modify one or more pathways in the biogeochemical nitrogen cycle. The concentrations tested are often too high to be considered environmentally relevant, despite evidence that sub-therapeutic doses may also be disruptive. We conducted soil mesocosm experiments to determine the overall impact of trace narasin on major nitrogen pools and fluxes in soils treated with 0, 1, 10, 100, or 1000 ng·kg-1 narasin. Water content in the mesocosms varied from 40% to 80% water-filled pore space (WFPS), simulating a range of different redox conditions. Under aerobic conditions (40% WFPS), exposure to narasin inhibited nitrification, yielding increases in soil ammonium by up to 76%, perhaps by targeting nitrifying fungi. Under the same conditions, narasin caused soil nitrate concentrations to decline 17-39%. When the soil was near saturation (80% WFPS), nitrate increased by an average of 30%. Mass balances and isotopic enrichment of N2O indicate that NAR may also affect anammox and the rate of nitrifier nitrification/denitrification. In aerobic soils, N2O flux increased with antibiotic dose and the rise in flux strongly correlates to the N2O:N2 product ratio from dentification. This relationship suggests that N2O flux may increase in soils exposed to narasin even when total denitrification is modestly inhibited. We conclude that trace concentrations of narasin can significantly modify biogeochemical activities in soil on short timescales. Our results indicate the potential for extremely low concentrations of antibiotics to impact agricultural productivity, terrestrial N2O flux, and non-point source nitrogen pollution.

Composition and spatial distribution of elements and isotopes of a giant human bladder stone and environmental implications.

The composition and spatial distribution of minerals, trace elements, as well as carbon and nitrogen isotopes from the outer crust to inner nucleus of a 20-year old giant human bladder stone comprising thirteen layers were intensively investigated. Calcium oxalate monohydrate (COM) was found to concentrate in the inner and middle layers, struvite was concentrated in middle and outer layers, and fluorapatite occurred in almost all layers. The spatial distribution of minerals has the potential to provide preliminary knowledge regarding the long-term urine composition, or even the physiological condition of the patient. The stable carbon isotope ratio (δ13C) and stable nitrogen isotope ratio (δ15N) were measured in each layer and significant correlation was found between δ13C with calcium oxalate monohydrate content and between δ15N and struvite content. Nearly constant values of -23.2‰ and 7.1‰ for δ13C and δ15N, respectively, were found in the organic components of the stone. Both isotope ratios indicate a long-term fixed diet consisting mainly of C3 plants, such as rice and wheat, for the 20-year time period of the stone formation. In addition, eighteen elements (Ca, P, Mg, K, Na, Al, Fe, Zn, Pb, Cu, Sr, Ba, Ti, V, Cr, Ni, Mn and Co) were measured in all the layers. The trace elements Al, Fe, Cu, Zn, Pb, Sr, Ba and Ti showed a similar spatial distribution pattern from the outer crust to the inner core. Although there were complex correlations between elements and minerals, Factor Analysis suggests that the occurrence of these elements in stones may be mainly the result of environmental exposure to metals during the formation of the stone, indicating that urinary stones may serve as potential long-term biomonitors. In particular, Ni and Cr showed a distinct distribution pattern in the stone, which may relate to human metabolic activities.

Heteroaggregation of an enveloped bacteriophage with colloidal sediments and effect on virus viability.

Four sediments in the colloidal size range: goethite, montmorillonite, illite, and kaolinite, were suspended with the bacteriophage φ6, a model enveloped virus, to determine relative rates of heteroaggregation and the effect of aggregation on virus viability. Turbidity was measured on combinations of virus and each sediment type at low concentration to determine aggregation rates. Aggregation of sediment with virus occurred regardless of mineral type, and larger fraction of virus is expected to aggregate with increasing sediment concentration leading to higher deposition rates. The negatively charged sediments, aggregated with φ6 (also negatively charged at neutral pH) at a faster rate than the positively charged sediments, yielding turbidity slopes of 4.94 × 10-3 s-1 and 7.50 × 10-4 s-1 for φ6-montmorillonite and φ6-illite aggregates, respectively, and 2.98 × 10-5 s-1 and 2.84 × 10-5 s-1, for φ6-goethite and φ6-kaolinite, respectively. This indicates that the interaction between sediments and virus is hydrophobic, rather than electrostatic. Large numbers of virions remained viable post-aggregation, despite the fragility of the viral envelope, indicating that small-sized aggregates, which may travel more readily through porous media, may pose an infection risk. The fraction of φ6 that remained viable varied with sediment type, with montmorillonite-φ6 aggregates experiencing the greatest reduction in infectivity at 35%. TEM analyses reveal that in all sediment-φ6 combinations, infectivity loss was likely due to disassembly of the viral envelope as a result of aggregation.

Spatial and vertical distribution of metals in sediment cores from Río Espíritu Santo estuary, Puerto Rico, United States.

The concentration and distribution of Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn were investigated in three sediment cores representing 100-150years of accumulation in upriver, midriver, and estuarine environments in Río Espíritu Santo (RES), Puerto Rico. Grain-size distribution, organic matter and carbonate content were determined to assess their influence on metal concentrations. Minimum biotoxicity levels of Ni and Cu were exceeded in the upriver and midriver sites, while the minimum biotoxicity level of Cu was exceeded in the estuarine location. Pb concentration decreased by ~35% in the upper portion of the midriver and estuarine cores compared to downcore concentrations as a consequence of leaded gasoline regulation. Enrichment Factors and Geoaccumulation Indices were calculated for each metal revealing high levels of Cu in all three cores, likely from an igneous source. Our results provide a baseline for metal contamination in an area facing further land use change.

Disassembly of the cystovirus ϕ6 envelope by montmorillonite clay.

Prior studies of clay-virus interactions have focused on the stability and infectivity of nonenveloped viruses, yielding contradictory results. We hypothesize that the surface charge distribution of the clay and virus envelope dictates how the components react and affect aggregation, viral stability, and infectivity. The bacteriophage Cystoviridae species φ6 used in this study is a good model for enveloped pathogens. The interaction between φ6 and montmorillonite (MMT) clay (the primary component of bentonite) is explored by transmission electron microscopy. The analyses show that MMT-φ6 mixtures undergo heteroaggregation, forming structures in which virtually all the virions are either sequestered between MMT platelet layers or attached to platelet edges. The virions swell and undergo disassembly resulting in partial or total envelope loss. Edge-attached viral envelopes distort to increase contact area with the positively charged platelet edges indicating that the virion surface is negatively charged. The nucleocapsid (NCs) remaining after envelope removal also exhibit distortion, in contrast to detergent-produced NCs which exhibit no distortion. This visually discernible disassembly is a mechanism for loss of infectivity previously unreported by studies of nonenveloped viruses. The MMT-mediated sequestration and disassembly result in reduced infectivity, suggesting that clays may reduce infectivity of enveloped pathogenic viruses in soils and sediments.