PART ONE. A highly sensitive and reproducible method for the determination of aliphatic amines namely monomethylamine (MMA), dimethylamine (DMA) , and trimethylamine (TMA) in marine environmental samples (water and sediments) has been developed. This involves an initial stage in which the amines are preconcentrated by microdiffusion and subsequently determined using a gas chromatograph equipped with a packed column and Nitrogen Phosphorus Selective Detector (NPSD) . The detection limit is at sub ppb level (ng/l), and the method recoveries are in the ranges of 58-68% for MMA, 55-84.3% for DMA, and 83-105.5% for TMA for the range of concentrations between 2-40 ppb. The percentage standard deviations of the chromatographic measurements are <15.1% for MMA, <11.1% for DMA, and <10% for TMA. The untreated Chromosorb 103 column packing was found to be very stable for more than a year with little deterioration in performance. Using this method, the production of methylamines by a marine phytoplankton has been studied, and has been shown to be greatly influenced by the growth conditions i.e bacteriostatic and nonbacteriostatic culture media, different levels and types of N sources, and zooplankton grazing on the phytoplankton. Maximum concentrations of methylamines were observed in the N03- enriched bacteriostatic medium. Zooplankton grazing also increases their levels. Methylamines were found to be distributed in a range of marine environments, with highest concentrations detected in marine sediments. Their levels were also higher in polluted Mersey waters than in the water off the Isle of Man (10M). MMA was found to be the dominant species in all of these samples (phytoplankton, sediment, and water) and also in the marine atmosphere. Using the same approach, l-Arninopropan-2-one, which has long been known to be a compound of urine, has been shown to be a stable indicator of raw sewage pollution. Its identity has been confirmed by GC-MS of its trifluoro acyl-derivative. Its distribution in estuarine water (Mersey Estuary) and coastal water (Port Erin, 10M) is presented. PART TWO. Volatile organic compounds (VOCs) in phytoplankton cultures, marine sediments, and Mersey Estuary water samples have been determined by a modified Grob closed-loop stripping method and GC-MS analysis. VOCs in the Mersey estuary water samples were dominated by methylated benzenes and methylated naphthalenes. In contrast, chlorinated compounds were the dominant compounds in the sediments, and methylated alkanes in the non-bacteriostatic phytoplankton culture. Some methylated benzenes were also found in the plankton sample, which might explain their observation in some of the remote unpolluted marine environment. This thesis is dedicated to my parents, my wife and children.

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Thesis (Ph. D.)--Joint Program in Marine Chemistry and Geochemistry, Massachusetts Institute of Technology/Woods Hole Oceanographic Institution, 1998. / Includes bibliographical references (p. 251-266). / by Eda Maria Hood. / Ph.D.

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This work describes efforts to improve methodologies and instrumentation for investigation of the marine CO2 system. In the first section of my thesis, a method was developed that provides simple, calibration-free measurements of seawater carbonate saturation states (Ωspec) based solely on the use of a laboratory spectrophotometer. Measurements of pH are made in paired optical cells, one with and one without added nitric acid. The amount of added nitric acid is determined through the direct proportionality between nitrate concentration and UV absorbance. After an initial calibration, the method is calibration-free and requires no volumetric or gravimetric analyses thereafter. Saturation state measurements can be obtained in twelve minutes and attain Global Ocean Acidification Observing Network accuracy goals over a wide range of conditions. This simple one-step measurement protocol is ideal for monitoring ocean acidification conditions in coastal areas, fish hatcheries and shellfish farms. The second section of my thesis outlines the development of a next-generation handheld photometer for field measurements of seawater pH. The hand-held instrument is simple to use, inexpensive, and has a pH measurement accuracy of ±0.01. Each photometer is calibrated by relating pH-indicator absorbance ratios (RB) obtained with the broadband photometer to indicator absorbance ratios (RN) obtained with a high quality, narrowband scanning spectrophotometer. The RB vs RN relationship for each photometer is entered into the instrument’s software, providing discrete, real-time pH observations from measurements of RB, salinity and temperature. Measurement accuracy is assessed through comparisons of photometer pH with pH observations obtained using standard measurement procedures and high-quality spectrophotometers. The targeted user-groups for these instruments include middle and high school students, citizen scientists, and resource managers

Thesis: Ph. D., Joint Program in Marine Chemistry and Geochemistry (Massachusetts Institute of Technology, Department of Civil and Environmental Engineering; and the Woods Hole Oceanographic Institution), 2015. / Cataloged from PDF version of thesis. / Includes bibliographical references. / Hydrophobic organic chemicals (HOCs) are a class of environmental contaminants responsible for numerous acute and chronic health effects in humans and wildlife. This thesis illustrates three applications of polyethylene (PE) passive sampling, which enhance our toolbox for estimating environmental hazards associated with HOCs. First, we present a methodology that can be used to estimate the bioaccumulation potential of numerous organic chemicals based on passive sampling and comprehensive two dimensional gas chromatography (GC x GC). Using GC x GC retention times, we show that lipid-water and samplerwater partition coefficients can be estimated within a factor of 2 and 3, respectively. The method was then applied to estimate body burdens of various HOCs in benthic organisms from GC x GC analysis of PE equilibrated with contaminated sediment. Empirical observations of accumulation in the Nereis virens polychaete were in good agreement with PE-based predictions for PCBs, but were lower by at least an order of magnitude for other classes of HOCs (such as PAHs) presumably due to metabolism. Second, we applied the same methodology to a set of contaminated sediments and estimated the cumulative baseline toxicity associated with environmental mixtures of HOCs. The predictions were compared against empirical measurements of baseline toxicity using the water flea Daphnia magna. The estimated total body burdens of HOCs were in good agreement with measured toxicity, with toxicity occurring at body burdens larger than 30 mg/gipid. In contrast, the toxicity estimated based on priority pollutants severely underestimated the observed toxicity, emphasizing the importance of cumulative effects. Lastly, to advance our understanding of the processes that affect passive sampling results in situ (when they are operating away from equilibrium), a mathematical model was developed for reactive chemicals transferring between PE and sediment beds. The reaction diffusion model was used to infer in situ degradation rates of dichlorodiphenyltrichloroethane (DDT), which in the sediments of a freshwater lake were found to be between 0.09 and 0.9 d-1. A second mathematical model describing the kinetics of exchange between passive samplers and water was also developed, which can be used in both field (infinite baths) and laboratory (finite baths) conditions. / by Alexandra Patricia Tcaciuc. / Ph. D.

Au cours de ce travail, nous nous sommes intéressés dans une première partie à la synthèse biomimétique d’alcaloïdes de type manzamines et plus particulièrement, aux manadomanzamines. Une étude de la réactivité des deux intermédiaires clés de leur biogenèse, les glutaconaldéhydes et les aminopentadiènals, a été entreprise. Ces mêmes molécules ont ensuite été utilisées comme équivalents synthétiques dans une synthèse biomimétique du squelette pentacyclique de la manadomanzamine A. Une seconde partie est consacrée à la préparation d’analogues stables de la pelletiérine en vue d’une synthèse biomimétique d’alcaloïdes du genre Lycopodium. / This work is dedicated to the biomimetic synthesis of complex polycyclic alkaloids namely the manzamine alkaloids and especially to manadomanzamine. The biogenetic hypotheses postulated for these alkaloids are reported in a first introductory chapter. A few examples of manzamine alkaloids biogenesis are described and compared. The second chapter is focused on the reactivity of reactive units (considered as simplified models of two key biosynthetic intermediates, namely glutaconaldehydes and aminopentadienals) resulting from the ring-opening of pyridinium salts, and their implication in natural products synthesis. Particularly detailed are the investigations conducted on 5-dimethylamino-2-methylpenta-2,4-dienal and the condensation of potassium glutaconaldehyde onto a pyridinium salt. The chemistry of these reactive units has been exploited to design several model studies towards the synthesis of pentacyclic indole nucleus of manadomanzamine A, isolated from an Indonesian sponge Acanthostrongylophora sp.. These biomimetic models, elaborated from a biosynthetic intermediate postulated in our biosynthesis hypothesis have culminated in the synthesis of the central pentacyclic indole nucleus. The last chapter reports the preparation of more or less oxidized analogs of pelletierine, the well known alkaloid isolated from Punica granatum. Compounds such as phenyloxazolopelletierine have been prepared and their reactivity investigated in view of the biomimetic synthesis of Lycopodium alkaloids.

Ocean uptake of anthropogenic CO2 causes ocean acidification, a secular, global-scale decline in the pH of seawater. In order to better understand the implications of contemporary acidification for marine organisms and ecosystems, there is a need to better characterise natural variability in carbonate chemistry. In this thesis, climatological seasonal variability of sea surface pH and aragonite saturation state (OmegaA) in the open ocean is indirectly derived from other parameters of the marine CO2 system, namely total alkalinity (TA) and seawater pCO2/fCO2 (pCO2sw/fCO2sw). New monthly sea surface TA, fCO2sw and temperature climatologies are developed for this purpose, utilising newly-released observational synthesis products (PACIFICA for TA and SOCAT v2 for fCO2sw). Two versions of the new SST climatology are developed, referred to as upper and lower SST (USST and LSST), to test sensitivity to the depth range of the input observations. Annual ranges are generally found to be larger for the USST climatology, derived using observations from the upper 2 m, compared to LSST (which is based on deeper observations). Further, a seasonal cycle is found in the monthly average of the differences between these climatologies north of 30 degN, perhaps partly due to seasonal variation in near-surface stratification. The USST seasonal ranges are also found to be generally larger than in two previous SST climatologies, however, difference in the depth distribution of the input measurements is unlikely the main cause. The new monthly sea surface TA climatology extends coverage into the Nordic seas, excluded from previous climatologies. TA seasonality is found to be small outside of regions with large seasonal ranges in salinity. Large seasonal ranges in salinity and TA are found beneath the Intertropical Convergence Zone, in the Antarctic seasonal sea ice zone and in the western Greenland Sea. Non-salinity driven TA seasonality is found to be large in the Gulf of Alaska, eastern equatorial Pacific and western Greenland Sea. Compared to the Lee et al. (2006) TA climatology, substantially lower annual means and seasonal ranges are found for the subarctic Pacific, a region with greatly improved coverage courtesy of PACIFICA. The pH/OmegaA climatologies derived in the final chapter suggest pH seasonality is predominantly temperature driven in the subtropics and mainly driven by variation in salinity normalised dissolved inorganic carbon (sDIC) in the subpolar north Atlantic, western subarctic Pacific and Southern Ocean. Salinity variation is found to only exert a strong influence on pH seasonality in the western Greenland Sea. Climatological seasonal pH ranges are found to be mostly small in the tropics (<0.05), moderate in the subtropics (0.05-0.10) but very large (>0.1) in parts of the Ross, Weddell, Irminger and Iceland Seas and western subarctic Pacific gyre. OmegaA seasonality is found to be predominantly sDIC-driven everywhere except in the western Greenland Sea, with temperature variation generally being of modest influence. Seasonal cycles of pH and OmegaA are found to be in anti-phase where pH is mainly thermally driven and in-phase where pH is mainly sDIC-forced (both pH and OmegaA vary inversely with DIC). Comparison is made between the primary new pH/OmegaA climatology and various open ocean carbonate chemistry time-series. The climatology captures the general form of the climatological seasonal cycles of pH and OmegaA from the time-series, although with some differences in phasing and seasonal range. Analysing the time-series for long-term trends, I find that inter-decadal anthropogenic CO2 uptake driven pH and OmegaA declines can be modulated by trends in temperature, salinity or sTA. Investigation is also conducted into how the amplitude of pH and OmegaA seasonal cycles might change by 2100 for a subpolar and subtropical time-series. Under a high CO2 emissions scenario, the seasonal range of pH is found to be strongly enhanced for the subpolar time-series and moderately reduced for the subtropical time-series, with both being due to changes in seawater buffer capacity. / Graduate / 0425 / 0415 / robdj87@hotmail.com

Carbonate geochemistry plays an important role in understanding environmental conditions during the time of precipitation. The studies for this dissertation research were focused on carbonate precipitation and crystallization in different chemical and physical environments. The first project aimed to precipitate aragonite at low oxygen levels to identify a correlation between partitioning of trace elements and anoxic and suboxic conditions. The second study focused on the precipitation of amorphous calcium carbonate in varying magnesium concentrations to determine the identity of crystalline material after transformation of ACC. Lastly, the third project was developed to understand transformation of CaCO3 polymorphs. Specifically, whether or not geochemistry is retained from one polymorph to the next. All projects could aid in development of paleoproxies to be used for determining past environmental and climatic conditions in the past.