Environmental Dynamics of Dissolved Black Carbon in Wetlands

Wetlands are ecosystems commonly characterized by elevated levels of dissolved organic carbon (DOC), and although they cover a surface area less than 2 % worldwide, they are an important carbon source representing an estimated 15 % of global annual DOC flux to the oceans. Because of their unique hydrological characteristics, fire can be an important ecological driver in pulsed wetland systems. Consequently, wetlands may be important sources not only of DOC but also of products derived from biomass burning, such as dissolved black carbon (DBC). However, the biogeochemistry of DBC in wetlands has not been studied in detail. The objective of this study is to determine the environmental dynamics of DBC in different fire-impacted wetlands. An intensive, 2-year spatial and temporal dynamics study of DBC in a coastal wetland, the Everglades (Florida) system, as well as one-time sampling surveys for the other two inland wetlands, Okavango Delta (Botswana) and the Pantanal (Brazil), were reported. Our data reveal that DBC dynamics are strongly coupled with the DOC dynamics regardless of location, season or recent fire history. The statistically significant linear regression between DOC and DBC was applied to estimate DBC fluxes to the coastal zone through two main riverine DOC export routes in the Everglades ecosystem. The presence of significant amounts of DBC in these three fire-impacted ecosystems suggests that sub-tropical wetlands could represent an important continental-ocean carrier of combustion products from biomass burning. The discrimination of DBC molecular structure (i.e. aromaticity) between coastal and terrestrial samples, and between samples collected in wet and dry season, suggests that spatially-significant variation in DBC source strength and/or degree of degradation may also influence DBC dynamics.

Effects of Simulated Drought on the Carbon Balance of Everglades Short-Hydroperiod Marsh

Hydrology drives the carbon balance of wetlands by controlling the uptake and release of CO2 and CH4. Longer dry periods in between heavier precipitation events predicted for the Everglades region, may alter the stability of large carbon pools in this wetland's ecosystems. To determine the effects of drought on CO2 fluxes and CH4 emissions, we simulated changes in hydroperiod with three scenarios that differed in the onset rate of drought (gradual, intermediate, and rapid transition into drought) on 18 freshwater wetland monoliths collected from an Everglades short-hydroperiod marsh. Simulated drought, regardless of the onset rate, resulted in higher net CO2 losses net ecosystem exchange (NEE) over the 22-week manipulation. Drought caused extensive vegetation dieback, increased ecosystem respiration (Reco), and reduced carbon uptake gross ecosystem exchange (GEE). Photosynthetic potential measured by reflective indices (photochemical reflectance index, water index, normalized phaeophytinization index, and the normalized difference vegetation index) indicated that water stress limited GEE and inhibited Reco. As a result of drought-induced dieback, NEE did not offset methane production during periods of inundation. The average ratio of net CH4 to NEE over the study period was 0.06, surpassing the 100-year greenhouse warming compensation point for CH4 (0.04). Drought-induced diebacks of sawgrass (C3) led to the establishment of the invasive species torpedograss (C4) when water was resupplied. These changes in the structure and function indicate that freshwater marsh ecosystems can become a net source of CO2 and CH4 to the atmosphere, even following an extended drought. Future changes in precipitation patterns and drought occurrence/duration can change the carbon storage capacity of freshwater marshes from sinks to sources of carbon to the atmosphere. Therefore, climate change will impact the carbon storage capacity of freshwater marshes by influencing water availability and the potential for positive feedbacks on radiative forcing.

Synthesis and electron emission properties of aligned carbon nanotube arrays

Carbon nanotubes (CNTs) have become one of the most interesting allotropes of carbon due to their intriguing mechanical, electrical, thermal and optical properties. The synthesis and electron emission properties of CNT arrays have been investigated in this work. Vertically aligned CNTs of different densities were synthesized on copper substrate with catalyst dots patterned by nanosphere lithography. The CNTs synthesized with catalyst dots patterned by spheres of 500 nm diameter exhibited the best electron emission properties with the lowest turn-on/threshold electric fields and the highest field enhancement factor. Furthermore, CNTs were treated with NH3 plasma for various durations and the optimum enhancement was obtained for a plasma treatment of 1.0 min. CNT point emitters were also synthesized on a flat-tip or a sharp-tip to understand the effect of emitter geometry on the electron emission. The experimental results show that electron emission can be enhanced by decreasing the screening effect of the electric field by neighboring CNTs. In another part of the dissertation, vertically aligned CNTs were synthesized on stainless steel (SS) substrates with and without chemical etching or catalyst deposition. The density and length of CNTs were determined by synthesis time. For a prolonged growth time, the catalyst activity terminated and the plasma started etching CNTs destructively. CNTs with uniform diameter and length were synthesized on SS substrates subjected to chemical etching for a period of 40 minutes before the growth. The direct contact of CNTs with stainless steel allowed for the better field emission performance of CNTs synthesized on pristine SS as compared to the CNTs synthesized on Ni/Cr coated SS. Finally, fabrication of large arrays of free-standing vertically aligned CNT/SnO2 core-shell structures was explored by using a simple wet-chemical route. The structure of the SnO2 nanoparticles was studied by X-ray diffraction and electron microscopy. Transmission electron microscopy reveals that a uniform layer of SnO2 is conformally coated on every tapered CNT. The strong adhesion of CNTs with SS guaranteed the formation of the core-shell structures of CNTs with SnO2 or other metal oxides, which are expected to have applications in chemical sensors and lithium ion batteries.

Numerical heat transfer analysis of carbon-based foams for use in thermal protection system

The applicability of carbon-based foams as an insulating or active cooling material in thermal protection systems (TPSs) of space vehicles is considered using a computer modeling. This study focuses on numerical investigation of the performance of carbon foams for use in TPSs of space vehicles. Two kinds of carbon foams are considered in this study. For active cooling, the carbon foam that has a thermal conductivity of 100 W/m-k is used and for the insulation, the carbon foam having a thermal conductivity of 0.225 W/m-k is used. A 3D geometry is employed to simulate coolant flow and heat transfer through carbon foam model. Gambit has been used to model the 3D geometry and the numerical simulation is carried out in FLUENT. Numerical results from this thesis suggests that the use of CFOAM and HTC carbon foams in TPS's may effectively protect the aluminum structure of the space shuttle during reentry of the space vehicle.

Role of carbon nanotube dispersion in fracture toughening of plasma sprayed aluminum oxide - carbon nanotube nanocomposite coating

Aluminum oxide (A1203, or alumina) is a conventional ceramic known for applications such as wear resistant coatings, thermal liners, heaters, crucibles, dielectric systems, etc. However applications of A1203 are limited owing to its inherent brittleness. Due to its excellent mechanical properties and bending strength, carbon nanotubes (CNT) is an ideal reinforcement for A1203 matrix to improve its fracture toughness. The role of CNT dispersion in the fracture toughening of the plasma sprayed A1203-CNT nanocomposite coating is discussed in the current work. Pretreatment of powder feedstock is required for dispersing CNTs in the matrix. Four coatings namely spray dried A1203 (A-SD), A1203 blended with 4wt.% CNT (A4C-B), composite spray dried A1203-4wt.% CNT (A4C-SD) and composite spray dried A1203-8wt.% CNT (A8CSD), are synthesized by plasma spraying. Owing to extreme temperatures and velocities involved in the plasma spraying of ceramics, retention of CNTs in the resulting coatings necessitates optimizing plasma processing parameters using an inflight particle diagnostic sensor. A bimodal microstructure was obtained in the matrix that consists of fully melted and resolidified structure and solid state sintered structure. CNTs are retained both in the fully melted region and solid-state sintered regions of processed coatings. Fracture toughness of A-SD, A4C-B, A4C-SD and A8C-SD coatings was 3.22, 3.86, 4.60 and 5.04 MPa m1/2 respectively. This affirms the improvement of fracture toughness from 20 % (in A4C-B coating) to 43% (in A4C-SD coating) when compared to the A-SD coating because of the CNT dispersion. Fracture toughness improvement from 43 % (in A4C-SD) to 57% (in A8C-SD) coating is evinced because of the CNT content. Reinforcement by CNTs is described by its bridging, anchoring, hook formation, impact alignment, fusion with splat, and mesh formation. The A1203/CNT interface is critical in assisting the stress transfer and utilizing excellent mechanical properties of CNTs. Mathematical and computational modeling using ab-initio principle is applied to understand the wetting behavior at the A1203/CNTinterface. Contrasting storage modulus was obtained by nanoindentation (~ 210, 250, 250-350 and 325-420 GPa in A-SD, A4C-B, A4C-SD, and A8C-SD coatings respectively) depicting the toughening associated with CNT content and dispersion.

Multi-objective optimization of the molecular structure of refrigerants

The aim of this work was to develop a new methodology, which can be used to design new refrigerants that are better than the currently used refrigerants. The methodology draws some parallels with the general approach of computer aided molecular design. However, the mathematical way of representing the molecular structure of an organic compound and the use of meta models during the optimization process make it different. In essence, this approach aimed to generate molecules that conform to various property requirements that are known and specified a priori. A modified way of mathematically representing the molecular structure of an organic compound having up to four carbon atoms, along with atoms of other elements such as hydrogen, oxygen, fluorine, chlorine and bromine, was developed. The normal boiling temperature, enthalpy of vaporization, vapor pressure, tropospheric lifetime and biodegradability of 295 different organic compounds, were collected from open literature and data bases or estimated. Surrogate models linking the previously mentioned quantities with the molecular structure were developed. Constraints ensuring the generation of structurally feasible molecules were formulated and used in commercially available optimization algorithms to generate molecular structures of promising new refrigerants. This study was intended to serve as a proof-of-concept of designing refrigerants using the newly developed methodology.

Degradação fotocatalítica oxidativa do fenol utilizando carvão obtido da pirólise de diferentes biomassas

The modern industrial progress has been contaminating water with phenolic compounds. These are toxic and carcinogenic substances and it is essential to reduce its concentration in water to a tolerable one, determined by CONAMA, in order to protect the living organisms. In this context, this work focuses on the treatment and characterization of catalysts derived from the bio-coal, by-product of biomass pyrolysis (avelós and wood dust) as well as its evaluation in the phenol photocatalytic degradation reaction. Assays were carried out in a slurry bed reactor, which enables instantaneous measurements of temperature, pH and dissolved oxygen. The experiments were performed in the following operating conditions: temperature of 50 °C, oxygen flow equals to 410 mL min-1 , volume of reagent solution equals to 3.2 L, 400 W UV lamp, at 1 atm pressure, with a 2 hours run. The parameters evaluated were the pH (3.0, 6.9 and 10.7), initial concentration of commercial phenol (250, 500 and 1000 ppm), catalyst concentration (0, 1, 2, and 3 g L-1 ), nature of the catalyst (activated avelós carbon washed with dichloromethane, CAADCM, and CMADCM, activated dust wood carbon washed with dichloromethane). The results of XRF, XRD and BET confirmed the presence of iron and potassium in satisfactory amounts to the CAADCM catalyst and on a reduced amount to CMADCM catalyst, and also the surface area increase of the materials after a chemical and physical activation. The phenol degradation curves indicate that pH has a significant effect on the phenol conversion, showing better results for lowers pH. The optimum concentration of catalyst is observed equals to 1 g L-1 , and the increase of the initial phenol concentration exerts a negative influence in the reaction execution. It was also observed positive effect of the presence of iron and potassium in the catalyst structure: betters conversions were observed for tests conducted with the catalyst CAADCM compared to CMADCM catalyst under the same conditions. The higher conversion was achieved for the test carried out at acid pH (3.0) with an initial concentration of phenol at 250 ppm catalyst in the presence of CAADCM at 1 g L-1 . The liquid samples taken every 15 minutes were analyzed by liquid chromatography identifying and quantifying hydroquinone, p-benzoquinone, catechol and maleic acid. Finally, a reaction mechanism is proposed, cogitating the phenol is transformed into the homogeneous phase and the others react on the catalyst surface. Applying the model of Langmuir-Hinshelwood along with a mass balance it was obtained a system of differential equations that were solved using the Runge-Kutta 4th order method associated with a optimization routine called SWARM (particle swarm) aiming to minimize the least square objective function for obtaining the kinetic and adsorption parameters. Related to the kinetic rate constant, it was obtained a magnitude of 10-3 for the phenol degradation, 10-4 to 10-2 for forming the acids, 10-6 to 10-9 for the mineralization of quinones (hydroquinone, p-benzoquinone and catechol), 10-3 to 10-2 for the mineralization of acids.

Evaluation of degree of conversion and hardness of dental composites photo-activated with different light guide tips

Objective: The aim of this study was to evaluate the degree of conversion and hardness of different composite resins, photo-activated for 40 s with two different light guide tips, fiber optic and polymer. Methods: Five specimens were made for each group evaluated. The percentage of unreacted carbon double bonds (% C═C) was determined from the ratio of absorbance intensities of aliphatic C═C (peak at 1637 cm−1) against internal standard before and after curing of the specimen: aromatic C-C (peak at 1610 cm−1). The Vickers hardness measurements were performed in a universal testing machine. A 50 gf load was used and the indenter with a dwell time of 30 seconds. The degree of conversion and hardness mean values were analyzed separately by ANOVA and Tukey’s test, with a significance level set at 5%. Results: The mean values of degree of conversion for the polymer and fiber optic light guide tip were statistically different (P<.001). The hardness mean values were statistically different among the light guide tips (P<.001), but also there was difference between top and bottom surfaces (P<.001). Conclusions: The results showed that the resins photo-activated with the fiber optic light guide tip promoted higher values for degree of conversion and hardness.

(Table 1) Salinity and dissolved organic carbon concentration of marine water (ANT-XIX/2) and mangrove porewater (Brazil)

The chemical structure of refractory marine dissolved organic matter (DOM) is still largely unknown. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) was used to resolve the complex mixtures of DOM and provide valuable information on elemental compositions on a molecular scale. We characterized and compared DOM from two sharply contrasting aquatic environments, algal-derived DOM from the Weddell Sea (Antarctica) and terrigenous DOM from pore water of a tropical mangrove area in northern Brazil. Several thousand molecular formulas in the mass range of 300-600 Da were identified and reproduced in element ratio plots. On the basis of molecular elemental composition and double-bond equivalents (DBE) we calculated an average composition for marine DOM. O/C ratios in the marine samples were lower (0.36 ± 0.01) than in the mangrove pore-water sample (0.42). A small proportion of chemical formulas with higher molecular mass in the marine samples were characterized by very low O/C and H/C ratios probably reflecting amphiphilic properties. The average number of unsaturations in the marine samples was surprisingly high (DBE = 9.9; mangrove pore water: DBE = 9.4) most likely due to a significant contribution of carbonyl carbon. There was no significant difference in elemental composition between surface and deep-water DOM in the Weddell Sea. Although there were some molecules with unique marine elemental composition, there was a conspicuous degree of similarity between the terrigenous and algal-derived end members. Approximately one third of the molecular formulas were present in all marine as well as in the mangrove samples. We infer that different forms of microbial degradation ultimately lead to similar structural features that are intrinsically refractory, independent of the source of the organic matter and the environmental conditions where degradation took place.

Stable carbon and oxygen isotope composition of Recent, Tertiary and Cretaceous foraminifera (Table III)

Oxygen isotope analyses of Tertiary and Cretaceous planktic foraminifera indicate that species have been stratified with respect to depth in the water column at least since Albian time. There is a relationship between morphology and depth habitat. Species with globigerine morphology have consistently occupied shallower depths than have species with globorotalid morphology. Biserially arranged species occupied both shallow and deep levels in the water column. On the average, it appears that ancient species with shallow habitats have been more susceptible to dissolution and have been preserved less well than species dwelling in deeper habitats. This relationship is similar to that observed for Recent planktic foraminifera. Comparison of carbon isotope ratios of adult and juvenile forms indicates that either the source of the carbon found in the shell or the carbon isotopic fractionations which occur during calcite secretion change during the development of individual foraminifera. The carbon isotopic ratios do not provide a reliable means for reconstructing the depth habitats of ancient species. Temperature-depth profiles for tropical Tertiary oceans have been reconstructed from the isotopic temperatures of planktic and benthic foraminifera. The vertical thermal structure of Oligocene oceans resembled that of modern oceans most closely. Those of Paleocene and Maastrichtian times differed most from that of modern oceans.

Circumpolar dataset of Soil Organic Carbon north of treeline derived from ENVISAT ASAR GM, link to GeoTIFF

A new approach for the estimation of soil organic carbon (SOC) pools north of the tree line has been developed based on synthetic aperture radar (SAR; ENVISAT Advanced SAR Global Monitoring mode) data. SOC values are directly determined from backscatter values instead of upscaling using land cover or soil classes. The multi-mode capability of SAR allows application across scales. It can be shown that measurements in C band under frozen conditions represent vegetation and surface structure properties which relate to soil properties, specifically SOC. It is estimated that at least 29 Pg C is stored in the upper 30 cm of soils north of the tree line. This is approximately 25 % less than stocks derived from the soil-map-based Northern Circumpolar Soil Carbon Database (NCSCD). The total stored carbon is underestimated since the established empirical relationship is not valid for peatlands or strongly cryoturbated soils. The approach does, however, provide the first spatially consistent account of soil organic carbon across the Arctic. Furthermore, it could be shown that values obtained from 1 km resolution SAR correspond to accounts based on a high spatial resolution (2 m) land cover map over a study area of about 7 × 7 km in NE Siberia. The approach can be also potentially transferred to medium-resolution C-band SAR data such as ENVISAT ASAR Wide Swath with ~120 m resolution but it is in general limited to regions without woody vegetation. Global Monitoring-mode-derived SOC increases with unfrozen period length. This indicates the importance of this parameter for modelling of the spatial distribution of soil organic carbon storage.

Long-finned pilot whale population diversity and structure in Atlantic waters assessed through biogeochemical and genetic markers

Acknowledgements. Cetacean samples were collected under the auspices of stranding monitoring programs run by the Sociedade Portuguesa de Vida Selvagem, the Coordinadora para o Estudio dos Mamíferos Mariños (supported by the regional government Xunta de Galicia), the UK Cetacean Strandings Investigation Programme and the Scottish Agriculture College Veterinary Science Division (jointly funded by Defra and the Devolved Governments of Scotland and Wales), the Marine Mammals Research Group of the Institute of Marine Research (Norway), the Museum of Natural History of the Faroe Islands and the International Fund for Animal Welfare Marine Mammal Rescue and Research Program (USA). The authors thank all the members of these institutions and organizations for their assistance with data and sample collection. S.S.M., P.M.F. and M.F. were supported by PhD grants from the Fundação para a Ciência e Tecnologia (POPH/FSE ref SFRH/BD/ 38735/ 2007, SFRH/BD/36766/2007 and SFRH/BD/30240/ 2006, respectively). A.L. was supported by a postdoctoral grant from the Fundação para a Ciência e Tecnologia (ref SFRH/BPD/82407/2011). The work related to strandings and tissue collection in Portugal was partially supported by the SafeSea project EEAGrants PT 0039 (supported by Iceland, Liechtenstein and Norway through the EEA Financial Mechanism), the MarPro project Life09 NAT/PT/000038 (funded by the European Union program LIFE+) and the project CetSenti FCT RECI/AAG-GLO/0470/2012 (FCOMP- 01-0124-FEDER-027472) (funded by the program COMPETE and the Fundação para a Ciência e Tecnologia). G.J.P. thanks the University of Aveiro and Caixa Geral de Depósitos (Portugal) for financial support. The authors acknowledge the assistance of the chemical analysts at Marine Scotland Science with the fatty acid analysis.