Site-Specific Isotopes in Small Organic Molecules

Stable isotope geochemistry is a valuable toolkit for addressing a broad range of problems in the geosciences. Recent technical advances provide information that was previously unattainable or provide unprecedented precision and accuracy. Two such techniques are site-specific stable isotope mass spectrometry and clumped isotope thermometry. In this thesis, I use site-specific isotope and clumped isotope data to explore natural gas development and carbonate reaction kinetics. In the first chapter, I develop an equilibrium thermodynamics model to calculate equilibrium constants for isotope exchange reactions in small organic molecules. This equilibrium data provides a framework for interpreting the more complex data in the later chapters. In the second chapter, I demonstrate a method for measuring site-specific carbon isotopes in propane using high-resolution gas source mass spectrometry. This method relies on the characteristic fragments created during electron ionization, in which I measure the relative isotopic enrichment of separate parts of the molecule. My technique will be applied to a range of organic compounds in the future. For the third chapter, I use this technique to explore diffusion, mixing, and other natural processes in natural gas basins. As time progresses and the mixture matures, different components like kerogen and oil contribute to the propane in a natural gas sample. Each component imparts a distinct fingerprint on the site-specific isotope distribution within propane that I can observe to understand the source composition and maturation of the basin. Finally, in Chapter Four, I study the reaction kinetics of clumped isotopes in aragonite. Despite its frequent use as a clumped isotope thermometer, the aragonite blocking temperature is not known. Using laboratory heating experiments, I determine that the aragonite clumped isotope thermometer has a blocking temperature of 50-100°C. I compare this result to natural samples from the San Juan Islands that exhibit a maximum clumped isotope temperature that matches this blocking temperature. This thesis presents a framework for measuring site-specific carbon isotopes in organic molecules and new constraints on aragonite reaction kinetics. This study represents the foundation of a future generation of geochemical tools for the study of complex geologic systems.

Exploratory fishing for tunas and tuna tagging in the Marquesas, Tuamotu, Society, Pitcairn, and Gambier Islands

The Marquesas Islands are located in the Pacific Ocean at about 9 degrees south latitude and 140 degrees west longitude (Figure 1). It has been demonstrated by tagging (Anonymous, 1980b) that skipjack tuna, Katsuwonus pelamis, which occur in the northeastern Pacific Ocean have migrated to the Hawaiian Islands and Christmas Island in the central Pacific and also to the area between the Marshall and Mariana islands in the western Pacific. The Tuamotu, Society, Pitcairn, and Gambier islands, though the first two are not as close to the principal fishing areas of the eastern Pacific Ocean as are the Marquesas Islands, and the last two are small and isolated, are of interest for the same reasons that the Marquesas Islands are of interest, and thus skipjack should be tagged in those islands for the same reason that they should be tagged in the Marquesas Islands. The organizations which participated in the Marquesas Islands tagging and other scientific activities were the Inter-American Tropical Tuna Commission (IATTC), the South Pacific Commission (SPC), the Centre National pour l'Exploitation des Oceans (CNEXO), the Office de la Recherche Scientifique et Technique Outre-Mer (ORSTOM), the Service de la Peche de la Polynesie Francaise (SPPF), and the Service de l'Economie Rural (SER).

Re-estimation of small-scale fishery catches for U.S. flag-associated island areas in the western Pacific: the last 50 years

Nearshore fisheries in the tropical Pacific play an important role, both culturally and as a reliable source of food security, but often remain under-reported in statistics, leading to undervaluation of their importance to communities. We re-estimated nonpelagic catches for Guam and the Commonwealth of the Northern Mariana Islands (CNMI), and summarize previous work for American Samoa for 1950−2002. For all islands combined, catches declined by 77%, contrasting with increasing trends indicated by reported data. For individual island entities, re-estima-tion suggested declines of 86%, 54%, and 79% for Guam, CNMI, and American Samoa, respectively. Except for Guam, reported data primarily represented commercial catches, and hence under-represented contributions by subsistence and recreational fisheries. Guam’s consistent use of creel surveys for data collection resulted in the most reliable reported catches for any of the islands considered. Our re-estimation makes the scale of under-reporting of total catches evident, and provides valuable baselines of likely historic patterns in fisheries catches.

Catching and rearing postlarval cleaner shrimp for the aquarium trade: results from a WorldFish Center project in Solomon Islands

Between 1999 and 2003, the WorldFish Center in Solomon Islands conducted research into the feasibility of a new fishery based on the capture and culture of postlarval coral reef fish for the live fish trade. The work was carried out in two phases: a research phase from late 1999 to the end of 2002; and a “finetuning” phase in 2003. Most of the species were of value to the marine aquarium trade, with very few live reef food fish recorded. The most valuable ornamentals were the banded cleaner shrimp, Stenopus species. Cleaner shrimp were harvested using crest nets, the method being modified with the addition of a solid, water-retaining cod-end designed to increase survival at capture. Grow-out techniques were improved by rearing the shrimp separately in jars to prevent aggression. The jars were painted black to protect the shrimp from sunlight. An economic model using experimental catch data and farm gate prices indicates that the fishery based on shrimp, supplemented with small numbers of lobster and fish is economically viable. The next step will be setting up a demonstration farm in a village in the Western Province of Solomon Islands.

On the Distribution and Fishery Potential of the Japanese Red Crab Chaceon granulatus in the Palauan Archipelago, Western Caroline Islands

A deep-water trapping survey in the Palauan archipelago, Western Caroline Islands, has revealed an abundance of the Japanese red crab, Chaceon granulatus. The recorded depth range (250-900 m) is similar to that of other geryonids, but the large numbers of females caught below 700 m is atypical. Mean yields in excess of 5 kg crabs plus 1 kg shrimp, Heterocarpus laevigatus, by-catch per trap-night were attainable at optimum depths. Chaceon granulatus is apparently a very large geryonid, with maximum weights of 2.02 kg and 1.51 kg recorded for male and female specimens, respectively. A range of body colors was observed: Orange-red shades appear to dominate the deeper waters (below 500 m) while yellow-tan colors are more abundant in the upper reaches. Preliminary evidence suggests that Chaceon granulatus is highly marketable, and the infrastructure in Palau is such that crabs could either be marketed fresh locally or airfreighted to Japan as a quick-frozen product. The high post-trapping survival rates observed indicate that maintaining crabs in live-holding tanks may be a feasible option. The large catches and quality of deep-water crabs taken suggests that the Palauan population of Chaceon granulatus may be able to support a small-scale fishery. It is not yet known whether this population is unusually large or whether these findings typify the deep forereef fauna of the region.

Microbial community analysis of Acropora palamata mucus swabs, water and sediment samples from Hawksnest Bay, St. John, U.S. Virgin Islands

Colonies of the scleractinian coral Acropora palmata, listed as threatened under the US Endangered Species Act in 2006, have been monitored in Hawksnest Bay, within Virgin Islands National Park, St. John, from 2004 through 2010 by scientists with the US Geological Survey, National Park Service, and the University of the Virgin Islands. The focus has been on documenting the prevalence of disease, including white band, white pox (also called patchy necrosis and white patches), and unidentified diseases (Rogers et al., 2008; Muller et al., 2008). In an effort to learn more about the pathologies that might be involved with the diseases that were observed, samples were collected from apparently healthy and diseased colonies in July 2009 for analysis. Two different microbial assays were performed on Epicentre Biotechnologies DNA swabs containing A. palmata coral mucus, and on water and sediment samples collected in Hawksnest Bay. Both assays are based on polymerase chain reaction (PCR) amplification of portions of the small rRNA gene (16S). The objectives were to determine 1) if known coral bacterial pathogens Serratia marcescens (Acroporid Serratiosis), Vibrio coralliilyticus (temperature-dependent bleaching, White Syndrome), Vibrio shiloi (bleaching, necrosis), and Aurantimonas coralicida (White Plague Type II) were present in any samples, and 2) if there were any differences in microbial community profiles of each healthy, unaffected or diseased coral mucus swab. In addition to coral mucus, water and sediment samples were included to show ambient microbial populations. In the first test, PCR was used to separately amplify the unique and diagnostic region of the 16S rRNA gene for each of the coral pathogens being screened. Each pathogen test was designed so that an amplified DNA fragment could be seen only if the specific pathogen was present in a sample. A positive result was indicated by bands of DNA of the appropriate size on an agarose gel, which separates DNA fragments based on the size of the molecule. DNA from pure cultures of each of the pathogens was used as a positive control for each assay.

Temporal trends in reef fish assemblages inside Virgin Islands National Park and around St. John, U.S. Virgin Islands, 1988-2006

This report is a result of long-term fish monitoring studies supported by the National Park Service (NPS) at the Virgin Islands National Park since 1988 and is now a joint NPS and NOAA collaboration. Reef fish monitoring data collected from 1988 to 2006 within Virgin Islands National Park (VINP) and adjacent reefs around St. John, U.S. Virgin Islands (USVI) were analyzed to provide information on the status of reef fishes during the monitoring period. Monitoring projects were initiated by the National Park Service (NPS) in the 1980s to provide useful data for evaluation of resources and for development of a long-term monitoring program. Monthly monitoring was conducted at two reef sites (Yawzi Point and Cocoloba Cay) starting in November 1988 for 2.5 years to document the monthly/seasonal variability in reef fish assemblages. Hurricane Hugo (a powerful Category 4 storm) struck the USVI in September 1989 resulting in considerable damage to the reefs around St. John. Abundance of fishes was lower at both sites following the storm, however, a greater effect was observed at Yawzi Point, which experienced a more direct impact from the hurricane. The storm affected species differently, with some showing only small, short-term declines in abundance, and others, such as the numerically abundant blue chromis (Chromis cyanea), a planktivorous damselfish, exhibiting a larger and longer recovery period. This report provides: 1) an evaluation of sampling methods, sample size, and methods used during the sampling period, 2) an evaluation of the spatial and temporal variability in reef fish assemblages at selected reef sites inside and outside of VINP, and 3) an evaluation of trends over 17 years of monitoring at the four reference sites. Comparisons of methods were conducted to standardize assessments among years. Several methods were used to evaluate sample size requirements for reef fish monitoring and the results provided a statistically robust justification for sample allocation.

Larvae of Dactylopsaron dimorphicum (Perciformes: Percophidae) from oceanic islands in the southeast Pacific

Percophids are a family of small marine benthic fishes common over soft bottoms from inshore to the outer slopes in tropical to temperate regions of the Atlantic and in the Indo-West and southeast Pacific (Reader and Neira, 1998; Okiyama, 2000). Five species belonging to four genera have been recorded around the Salas y Gómez Ridge in the southeast Pacific, all of which are endemic to the area except for Chrionema chryseres, a species which also occurs off the Hawaiian Islands and Japan (Parin, 1985, 1990; Parin et al., 1997). Of these five species, larval stages have been described only for Osopsaron karlik and Chrionema pallidum (Belyanina 1989, 1990).

Ontogenetic shifts in natural diet during benthic stages of American lobster (Homarus americanus), off the Magdalen Islands

The natural diet of 506 American lobsters (Homarus americanus) ranging from instar V (4 mm cephalothorax length, CL) to the adult stage (112 mm CL) was determined by stomach content analysis for a site in the Magdalen Islands, Gulf of St. Lawrence, eastern Canada. Cluster and factor analyses determined four size groupings of lobsters based on their diet: <7.5 mm, 7.5 to <22.5 mm, 22.5 to <62.5 mm, and ≥62.5 mm CL. The ontogenetic shift in diet with increasing size of lobsters was especially apparent for the three dominant food items: the contribution of bivalves and animal tissue (flesh) to volume of stomach contents decreased from the smallest lobsters (28% and 39%, respectively) to the largest lobsters (2% and 11%, respectively), whereas the reverse trend was seen for rock crab Cancer irroratus (7% in smallest lobsters to 53% in largest lobsters). Large lobsters also ate larger rock crabs than did small lobsters.

Foods and diets of communities involved in inland aquaculture in Malaita Province, Solomon Islands

Solomon Islands has a population of just over half a million people, most of whom are rural-based subsistence farmers and fishers who rely heavily on fish as their main animal-source food and for income. The nation is one of the Pacific Island Counties and Territories; future shortfalls in fish production are projected to be serious, and government policy identifies inland aquaculture development as one of the options to meet future demand for fish. In Solomon Islands, inland aquaculture has also been identified as a way to improve ood and nutrition security for people with poor access to marine fish. This report undertaken by a Worldfish study under the CGIAR Research Program on Aquatic Agricultural Systems explores the e potential role of land-based aquaculture of Mozambique tilapia in Solomon Islands as it relates to household food and nutrition security. This nutrition survey aimed to benchmark the foods and diets of households newly involved in small homestead tilapia ponds and their neighboring households in the central region of Malaita, the most populous island of all the provinces in Solomon Islands. Focus group discussions and semistructured interviews were employed in 10 communities (five inland and five coastal), four clinics, and five schools.

Feeding habits of the sesarmid crab Perisesarma bidens (De Haan) in the mangroves of the Ryukyu Islands, Japan

Feeding habits of the sesarmid crab Perisesarma bidens (De Haan) was investigated in the mangroves of the Ryukyu Islands, Japan. Stomach content analysis showed that their diet consists mainly of mangrove leaves fragments, with small amounts of animal, algae and sediment matters, indicating that P. bidens is primarily detritivorous. The consumption rate of P. bidens was investigated under laboratory conditions by offering three different types of Kandelia candel mangrove leaves. Crab survived by eating green, yellow or brown leaves, preferring brown to either green or yellow leaves. Consumption rate of brown leaves was significantly higher when crabs were provided with green, yellow and brown leaves together, than when provided separately. It is considered that the brown leaves have a soft tissue, which is easily torn by the crab chelae and have apparently low C/N ratio. The C/N ratio of faeces, which indicated lower value than that of burrow leaves or sediments, derived from the symbiosis of bacteria in the stomach. The C/N ratio showed that sediments had C/N ratios 2/3 times lower than leaves sequestered in the burrow, indicating that mangrove sediments could have higher nutritional value than mangrove leaves. Perisesarma bidens showed significant consumption rates of mangrove detritus, therefore, it may have the important role as the grazer of mangrove detritus in view of the nutrient cycle in the mangroves.

Size distributions of quantum islands on stepped substrates

The size distributions of self-assembled quantum islands on stepped substrates are studied using kinetic Monte Carlo simulations. It is found that the energy barrier E-SW between the step and the terrace region is the key factor in affecting the size distribution of islands. With small E-SW (<= 0.1 eV), lines of uniform islands can be obtained at relative low surface coverage. As the surface coverage is increased, wirelike islands can be obtained. Scaling behavior is obeyed for the size distributions of the wirelike islands. When the size distributions are separated into their width and length components, however, scaling is only observed in the length distribution of the wirelike islands. With larger E-SW, the size distribution of islands shows a clear bimodal size distribution and anomalous growth temperature dependent island size evolutions are observed. The simulation results reproduce qualitatively the phenomena observed in the cases of InAs islands grown on stepped GaAs substrates. (c) 2009 American Institute of Physics. [doi:10.1063/1.3248367]

Effect of noncoherent islands on the optical properties of the 1.3 mu m InAs/GaAs quantum dots during rapid thermal annealing

The effect of thermal annealing of InAs/GaAs quantum dots (QDs) with emission wavelength at 1.3 mu m have been investigated by photoluminescence (PL) and transmission electron microscopy (TEM measurements. There is a dramatic change in the A spectra when the annealing temperature is raised up to 800 degrees C: an accelerated blushifit of the main emission peak of QDs together with an inhomogeneous broadening of the linewidth. The TEM images shows that the lateral size of normal QDs decreases as the annealing temperature is increased, while the noncoherent islands increase their size and densit. A small fraction of the relative large QDs contain dislocations when the annealing temperature increases up to 800 degrees C. The latter leads to the strong decrease of the PL intensity.

Photoluminescence characterization of 1.3 mu m In(Ga)As/GaAs islands grown by molecular beam epitaxy

1.3 mum wavelength In(Ga)As/GaAs nanometer scale islands grown by molecular beam epitaxy (MBE) were characterized by photoluminescence (PL) and atomic force microscopy (AFM) measurements. It is shown that inhomogeneous broadening of optical emission due to fluctuation of the In0.5Ga0.5As islands both in size and in compositions can be effectively suppressed by introducing a AlAs layer and a strain reduction In0.2Ga0.8As layer overgrown on top of the islands, 1.3mum emission wavelength with narrower line-width less than 20meV at room temperature was obtained.

Mineral provinces and material provenance of the surficial sediments near the Zhongsha Islands in the South China Sea

Characteristics and distribution patterns of elastic minerals (0.063 similar to 0.125 mm) in bottom sediments represent a significant indicator for the identification of the origin of sediment. One hundred and fourteen surface sediment samples, which were collected from the area near the Zhongsha Islands in the South China Sea, were analysed to identify the mineral suites and their distributions in the study area. The area can be divided into three mineral provinces: ( I) a province of biogenic minerals, which mainly originate from the Zhongsha Atoll; ( H) a province of volcanogenic minerals, which are mainly derived from local basaltic seamounts and small-scale volcanoes that are probably erupting, with some influences from the island-are volcanic region around the South China Sea; and (II) a mixed mineral province whose material source includes biogenic minerals, volcanogenic minerals and terrigenous minerals; the last province can be subdivided into a mixed mineral sub-province of the northeastern part of the study area, in which terrigenous minerals are mainly derived from China's Mainland and do not exceed 17 degrees N, and a mixed mineral sub-province of the southeastern part of the study area, in which terrigenous minerals are derived from Kalimantan and Indochina Peninsula and might be further transported into the deep sea basin through submarine canyons.