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Volatile Organic Compounds (Vocs) That Are Emitted from Marine Biota

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Volatile Organic Compounds (Vocs) That Are Emitted from Marine Biota ABSTRACT SABOLIS, ALYSSA WHITNEY. Quantifying Marine Emissions of Biogenic Volatile Organic Compounds Using Laboratory Measurements, Field Measurements and Remote Sensing Data. (Under the direction of Nicholas Meskhidze) The main focus of this work is to obtain a better understanding of carbon cycling between the ocean-biota-atmosphere interactions through trace gas production and environmental exchange. This work is divided into three sections: laboratory measurements, field measurements and comparison, and a case study to evaluate the possible role and eventual fate of emitted biogenic volatile organic compounds (BVOCs) into the atmosphere. An in- depth and rigorous sampling scheme was used in the first section to provide a large list of specie specific BVOC emissions dependent on different physiological conditions. We identified and quantified the production of isoprene, four different monoterpene compounds (α-pinene, β-pinene, camphene and D-limonene) and several different halocarbon compounds including chloroform, dichloromethane, iodomethane, tetrachloroethene and trichloroethene in six different species of phytoplankton. Other halocarbon species such as bromoform, diiodomethane, iodoethane, bromodichloromethane and dibromochloromethane were detected in only a few of the samples from specific phytoplankton species. We then focused on three key points: evaluating BVOC production 1) as a function of phytoplankton speciation, 2) as a function of light and 3) as a function of temperature. Diatoms were the largest emitters of most of the observed BVOC (including isoprene, monoterpenes, chloroform and iodomethane). The other four species showed variable production rates for different BVOC, showing a strong dependence on phytoplankton speciation for BVOC production. All phytoplankton species showed a rapid increase in isoprene, monoterpene, chloroform, and iodomethane production at low light levels (<150 μE m-2 s-1) and a gradual increase (between 150 to 420 μE m-2 s-1) until a constant production rate was reached at higher light levels (>150 μE m-2 s-1). As a function of temperature, isoprene production rates increased as temperature increases until 22°C for Thalassiosira pseudonana and 26°C for Thalassiosira weissflogii and then declined as temperature increased further. This same relationship was also observed for α-pinene, chloroform, iodomethane and tetrachloroethene. The second section comprises of field samples collected from the Neuse River, NC subjected to the same range of environmental parameters as the laboratory monocultures. Similarly to the monoculture experiments, isoprene production rates showed a dependence on light intensity, even at different temperatures for both sampling sites. For light levels >150 μE m-2 s-1, isoprene production rates for Site #1 show highest production at 26°C and Site #2 had maximum production rates at both 26 and 30°C. Production rate values were similar to those obtained from diatom species in the temperature dependent experiments. It should be noted, that both diatom species had the highest isoprene production rates out of the other six species sampled. Monoterpene production rates as a function of temperature showed highest emissions at 8 to 12°C below the water temperature the samples were collected at in the field. For the field samples, we observe an independent relationship of montoterpene production as a function of light and temperature as compared to isoprene measurements. We speculate that the unique temperature and light dependent production of monoterpenes may be caused by grazers still present in the samples. The last section of this work is used as a case study to deduce whether remote sensing data can be used to infer marine BVOC emissions over dynamic ecosystems (i.e. the Mediterranean Sea). Formaldehyde (HCHO) is an oxidation product of a wide range of volatile organic compounds (VOCs) and important atmospheric constituent found in both the polluted urban atmosphere and remote background sites. In this study remotely-sensed data of HCHO vertical column densities are analyzed over the Mediterranean Sea region using the Ozone Monitoring Instrument (OMI). Data analysis indicates a marked seasonal cycle with a summer maximum and winter minimum confined to the marine environment during a three year period (2005-2007). To investigate this observed formaldehyde "hot spot" over the Mediterranean we have identified possible sources, including transport of VOCs from continental air masses, shipping traffic, biomass burning, and two sources of locally produced biogenic VOCs from marine biota. We have also examined a possible retrieval artifact by comparing OMI and the SCanning Imaging Absorption SpectroMeter for Atmospheric CHartography (SCIAMACHY) HCHO columns over the Mediterranean and other water bodies. The comparison indicate that the two sensors agree reasonably well over Equatorial upwelling region, Gulf of Mexico, and the North Sea, but do not show similar magnitudes and seasonal variations over oligotrophic water bodies, such as the open ocean gyres and the Mediterranean Sea. The discrepancy between two sensors was reduced by using corrected air mass factors (AMF) for the OMI HCHO data products over the Mediterranean, but did not fully resolve the differences between OMI and SCIAMACHY Corrected OMI HCHO columns are then compared to several possible HCHO sources. Continental air mass transport of VOCs and shipping traffic may play a role in the HCHO hot spot but deserves further investigation. Biomass burning and CDOM photobleaching do not appear as major sources due to their lack of temporal and spatial correlation with respect to the HCHO observations. Lastly, phytoplankton produced VOCs may play a role in the formation of the HCHO hot spot, but the complexity of the primary productivity dynamics and uncertainty in emission estimates prove to be difficult in evaluating marine biota's impacts on the HCHO observations. We conclude that the OMI HCHO hot spot observed over the Mediterranean Sea is a real feature and grants further examination of its possible sources. Quantifying Marine Emissions of Biogenic Volatile Organic Compounds Using Laboratory Measurements, Field Measurements, and Remote Sensing Data. by Alyssa Whitney Sabolis A thesis submitted to the Graduate Faculty of North Carolina State University in partial fulfillment of the requirements for the degree of Master of Science Marine, Earth, and Atmospheric Science Raleigh, North Carolina 2010 APPROVED BY: _______________________________ ______________________________ Dr. Nicholas Meskhidze Dr. Daniel Kamykowski Committee Chair ________________________________ Dr. Robert Reed BIOGRAPHY Alyssa Sabolis was born and raised in Reading, PA. It was at a young age that she developed an interest in the weather, specifically severe thunderstorms. She graduated from Wilson High School in the spring of 2004 and started college at Florida Institute of Technology (FIT), majoring in Meteorology. While at FIT, Alyssa was exposed to a large variety of environmental issues such as beach re-nourishment projects, estuary water quality, air quality analysis of particulate matter and a wide breadth of environmental instrumentation. She graduated in May, 2008 with a B.S. in Meteorology and began graduate school at North Carolina State University in the Department of Marine, Earth and Atmospheric Science under the advisement of Dr. Nicholas Meskhidze in the fall of 2008. ii ACKNOWLEDGEMENTS I would first like to express my gratitude to my family for their undying support and encouragement they have given over the past two years. Secondly, I would like to thank my research group members Mathew Johnson, Brett Gantt, Margaret Frey, and Mathew Wilibanks for sharing all the good times and not so good times in this whirlwind of graduate school. Thank you to all the wonderful professors at NCSU for helping give me the proper tools and knowledge to aid in my research. A special thanks to my advisor, Dr. Nicholas Meskhidze, for taking a chance with me two years ago and hiring me as part of his research group. His passion and relentless demand for the highest quality research has instilled great qualities in me that I hope to take with me for the rest of my life. I would like to thank my committee member Dr. Daniel Kamykowski for all his helpful insight on the world of ocean biology and for allowing me to use the equipment in his lab. Thank you to my other committee member, Dr. Robert Reed, for allowing me to participate in the field sampling on the Neuse River, NC and all the members of the NCSU Center for Applied Aquatic Ecology for help with water quality analysis. This research was supported by the Office of Science (BER), U.S. Department of Energy, Grant No. DE-FG02-08ER64508. iii TABLE OF CONTENTS LIST OF TABLES ................................................................................................................... vi LIST OF FIGURES ............................................................................................................... viii ACRONYMS ......................................................................................................................... xix CHAPTER 1 Marine Biogenic Volatile Organic Compound (BVOC) Production ............ 1 1.1 Introduction ................................................................................................................. 1 1.2 Objectives ..................................................................................................................
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