Gas-phase and transpiration-driven mechanisms for volatilization through wetland macrophytes

Natural and constructed wetlands have gained attention as potential tools for remediation of shallow sediments and groundwater contaminated with volatile organic compounds (VOCs). Wetland macrophytes are known to enhance rates of contaminant removal via volatilization, but the magnitude of different volatilization mechanisms, and the relationship between volatilization rates and contaminant physiochemical properties, remain poorly understood. Greenhouse mesocosm experiments using the volatile tracer sulfur hexafluoride were conducted to determine the relative magnitudes of gas-phase and transpiration-driven volatilization mechanisms. A numerical model for vegetation-mediated volatilization was developed, calibrated with tracer measurements, and used to predict plant-mediated volatilization of common VOCs as well as quantify the contribution of different volatilization pathways. Model simulations agree with conclusions from previous work that transpiration is the main driver for volatilization of VOCs, but also demonstrate that vapor-phase transport in wetland plants is significant, and can represent up to 50% of the total flux for compounds with greater volatility like vinyl chloride.     

Composition of a protein-like fluorophore of dissolved organic matter in coastal wetland and estuarine ecosystems

This study demonstrates the compositional heterogeneity of a protein-like fluorescence emission signal (T-peak; excitation/emission maximum at 280/325 nm) of dissolved organic matter (DOM) samples collected from subtropical river and estuarine environments. Natural water samples were collected from the Florida Coastal Everglades ecosystem. The samples were ultrafiltered and excitation-emission fluorescence matrices were obtained. The T-peak intensity correlated positively with N concentration of the ultrafiltered DOM solution (UDON), although, the low correlation coefficient (r(2)=0.140, p<0.05) suggested the coexistence of proteins with other classes of compounds in the T-peak. As such, the T-peak was unbundled on size exclusion chromatography. The elution curves showed that the T-peak was composed of two compounds with distinct molecular weights (MW) with nominal MWs of about >5 x 10(4) (T(1)) and approximately 7.6 x 10(3) (T(2)) and with varying relative abundance among samples. The T(1)-peak intensity correlated strongly with [UDON] (r(2)=0.516, p<0.001), while T(2)-peak did not, which suggested that the T-peak is composed of a mixture of compounds with different chemical structures and ecological roles, namely proteinaceous materials and presumably phenolic moieties in humic-like substances. Natural source of the latter may include polyphenols leached from senescent plant materials, which are important precursors of humic substances. This idea is supported by the fact that polyphenols, such as gallic acid, an important constituent of hydrolysable tannins, and condensed tannins extracted from red mangrove (Rhizophora mangle) leaves exhibited the fluorescence peak in the close vicinity of the T-peak (260/346 and 275/313 nm, respectively). Based on this study the application of the T-peak as a proxy for [DON] in natural waters may have limitations in coastal zones with significant terrestrial DOM input.     

Biostimulation of iron reduction and subsequent oxidation of sediment containing Fe-silicates and Fe-oxides: effect of redox cycling on Fe(III) bioreduction

Sediment containing a mixture of iron (Fe)-phases, including Fe-oxides (mostly Al-goethite) and Fe-silicates (illites and vermiculite) was bioreduced in a long-term flow through column experiment followed by re-oxidation with dissolved oxygen. The objective of this study was (a) to determine the nature of the re-oxidized Fe(III), and (b) to determine how redox cycling of Fe would affect subsequent Fe(III)-bioavailability. In addition, the effect of Mn on Fe(III) reduction was explored.(57)Fe-M?ssbauer spectroscopy measurements showed that biostimulation resulted in partial reduction (20%) of silicate Fe(III) to silicate Fe(II) while the reduction of goethite was negligible. Furthermore, the reduction of Fe in the sediment was uniform throughout the column. When, after biostimulation, 3900 pore volumes of a solution containing dissolved oxygen was pumped through the column over a period of 81 days, approximately 46% of the reduced silicate Fe(II) was re-oxidized to silicate Fe(III). The M?ssbauer spectra of the re-oxidized sample were similar to that of pristine sediment implying that Fe-mineralogy of the re-oxidized sediment was mineralogically similar to that of the pristine sediment. In accordance to this, batch experiments showed that Fe(III) reduction occurred at a similar rate although time until Fe(II) buildup started was longer in the pristine sediment than re-oxidized sediment under identical seeding conditions. This was attributed to oxidized Mn that acted as a temporary redox buffer in the pristine sediment. The oxidized Mn was transformed to Mn(II) during bioreduction but, unlike silicate Fe(II), was not re-oxidized when exposed to oxygen.     

Effects of nonionic surfactants on the cell surface hydrophobicity and apparent hamaker constant of a Sphingomonas sp

Nonionic surfactants of the form CxEy were studied for their ability to alter the cell surface hydrophobicity and apparent Hamaker constants of a Sphingomonas sp. Through contact angle measurements on hydrated and dried bacterial lawns, it was found that the cell surface hydrophobicity changed systematically with both the alkyl (x) and polyoxyethylene (y) chain lengths. While differences in contact angles were observed between hydrated and dried lawns, they could not be attributed to the mere presence or absence of water, suggesting that reorientation of cell surface components may occur during drying. All surfactants examined reduced the hydrophilicity of the bacterial cell surface, with one surfactant (C18E10) making the cells hydrophobic. Effective bacterial Hamaker constants for bacteria interacting across a vacuum (Abb) and water (Abwb) and bacteria interacting in water with quartz sand (Abws) were calculated from the contact angles. It was found that the surfactants have the potential to reduce the Hamaker constants, but that the overall effects differed between dried and hydrated lawns, indicating that lawn preparation method can have a significant impact in interpretation of cell surface properties. The results also indicate that the Abws value of 10-20 J, which is often assumed in bacterial attachment and transport studies, may be an order of magnitude higher than the actual value. Finally, the results suggest that alteration of bacterial adhesion due to the presence of surfactants cannot be attributed to a single cell surface property but is rather due to multiple interactions.     

Distal 10q trisomy syndrome with unusual cardiac and pulmonary abnormalities

AIM: To evaluate the use of local transdermic anesthetics in fine needle aspiration biopsy (FNAB) in breast lesions. METHODS: Prospective randomized study of 119 patients having breast lesions, all being indicated for FNAB. The patients were divided into three groups: 40 patients entered in the active group (lidocaine + prilocaine); 40 patients underwent the placebo group (aqueous extract of Triticum vulgaris); and a control group of 39 women in whom FNAB was performed without the administration of any substance. Both the anesthetic and placebo were administered an hour before FNAB. Pain was quantified through a visual analogic scale of pain. The type of pain was also classified in terms of occurrence: only during the puncture, only during the movements and both. RESULTS: The visual linear analogic scale of pain showed an average of 3.3 in the active group, 3.5 in the placebo and 4.0 in the control group (NS). Analysis of the type of pain which was referred by the patient showed that 15% of the patients in the active group, 12.5% of those in the placebo group and 5.1% in the control group did not refer to any sensation of pain. Pain, when felt, was similar in all three groups (p < 0.4). CONCLUSIONS: Both the quantification and the type of pain referred to were similar in all three groups. However, there was a tendency of the patient to refer to less pain when the active substance or the placebo were used, when results were compared to the control group.     

Chemical ecology of the palm weevilRhynchophorus palmarum (L.) (Coleoptera: Curculionidae): Attraction to host plants and to a male-produced aggregation pheromone

Attraction to host plants by adultRhynchophorus palmarum (L.) palm weevils was studied in the field and in the laboratory. Chemical analysis revealed the presence of ethanol and ethyl-acetate in stems of coco palms and in pineapple fruits and of pentane, hexanal, and isopentanol in coco stems. In the olfactometer, the first two compounds and isoamyl-acetate were attractive to the insects and the last three compounds, although not attractive by themselves, increased attractiveness when mixed with the first two compounds. Mixtures of these compounds, in proportions similar to the one occurring in attractive plant tissue, were as attractive as natural coconut tissue. In the field, the chemical compounds, either presented alone or as a mixture, did not attract the weevil. Males produce an aggregation pheromone when smelling ethyl-acetate. Rhynchophorol, 2(E)-6-methyl-2-hepten-4-ol, the known active component of the aggregation pheromone, attracts weevils in the olfactometer and in the field only if plant tissue, ethyl-acetate, or the above-mentioned odor mix are present. We propose that a complex mix of ethanol, ethyl-acetate, pentane, hexanal, isolamyl-acetate, and/or isopentanol serve as a short-range orientation cue to fresh wounds on the plant and that additional host odors, attracting weevils from a distance, have still to be discovered. Rhynchophorol can be considered to be a Synergist, having an anemotactic action at a distance. We recommend the use of retention traps baited with rhynchophorol, ethyl-acetate, and sugar cane as an alternative control method for the pest.     

Intertidal trace metal concentrations in some sediments from the Humber estuary

The trace concentrations of a number of metals including chromium, zinc, lead, vanadium and copper have been determined in intertidal sediments from the south bank of the Humber estuary. The values have been associated with the particle size and organic carbon content of the sediments and the levels of metal concentration are compared generally with levels found elsewhere in estuarine and river sediments. The high values and trends in metal content of the sediments compared with “natural” levels may be ascribed to industrial and domestic effluents discharged into the estuary from a number of outfalls within the area. Methods of analysis to distinguish between natural and effluent metal contents of sediments are discussed.     

Mesoporous high surface area Ce0.9Gd0.1O1.95 synthesized by spray drying

Mesoporous gadolinium doped cerium dioxide with high surface area was produced by spray drying using Pluronic 123 as surfactant. The powder, when calcined at 400 °C, had a BET surface area of 136 m² g⁻¹ and was polycrystalline as confirmed by XRD and TEM. XEDS confirmed Ce, Gd and O, as the only elements present in the powders. Nitrogen adsorption measurements showed that the material was mesoporous with pore diameters of approximately 10 nm, which was later confirmed by TEM studies. TEM-EELS were used to confirm that Ce was in the +4 oxidation state. SEM studies showed particles of 10 nm diameter, corresponding to the crystallite size calculated from XRD data. The similar size range of the mesopores and the observed crystallite size indicates that the porosity is partly formed from intergranular mesoporosity. Using the spray drying method of a surfactant assisted liquid precursor solution it can be possible to manufacture mesoporous gadolinium doped ceria in large quantities in a continuous production.