Aspects of the biogeochemistry of carbohydrates in aquatic environments

Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution June, 1973The goal of this thesis is to examine the distribution and diagenesis of carbohydrates in aquatic environments. The following questions are studied: what is the carbohydrate composition of sediment in different environments (e.g., deep-sea oxic; shallow-sea oxic; deep-sea anoxic; fresh-water anoxic; brackish-water anoxic, etc.)? How does the environment at the sediment-water interface affect the composition of the carbohydrate input? How do sedimentary carbohydrates compare to plankton carbohydrates? How do metal-carbohydrate interactions and biological degradation affect the diagenesis of carbohydrates in recent sediments? Can fossil carbohydrates be used as a means to elucidate paleo-environments? In order to investigate these questions in a quantitative manner, a liquid chromatographic sugar analyzer sensitive to 10-10 moles was constructed. Various extraction techniques, involving acid hydrolysis and EDTA treatment, were thoroughly examined to determine lability of sugars, sources of contamination, maximum yields, and reproducibility. Furthermore, several experiments were performed to show that sugars extracted from sediment by EDTA were originally associated with in situ metal ion organic complexes. Although the carbohydrate compositions of sediment from different aquatic environments are remarkably similar, the degree of metal binding of carbohydrates varies between oxidizing and reducing sediments and appears to be related to the degree of biological degradation at the sedimentwater interface. In an oxic environment, biological degradation produces a highly metal-bound carbohydrate residue. In a reducing environment, the degree of biological activity is low (relative to oxic environments) and hence the degree of metal binding of the resulting carbohydrate residue is low. There is no evidence for further abiotic, alteration after burial in either environment. Sewage material dumped into a shallow oxic environment is degraded rapidly despite the high content of potentially toxic metals; these metals are probably tied-up in the metal bound carbohydrate residue. Metal binding appears to fix potentially soluble carbohydrates in situ, thereby inhibiting diffusion. This finding undercuts the previous belief that chromatographic separation of organic molecules along mineral surfaces is a significant diagenetic process. The relative abundances of sugars in acid extracts of sediment and plankton from different aquatic environments are similar; this similarity suggests that plankton is the main source of sedimentar carbohydrates. Carbohydrates in sediment may be used to interpret paleo-environmental fluctuations. For example, the degree of metal binding is indicative of the Eh at the sediment-water interface. The glucose and ribose contents of sediment may be used to estimate relative terrigenous and marine organic inputs, respectively. Paleo-eutrophication conditions in the surface waters also may be discerned.The research was sponsored by a grant from the Petroleum Research Fund PRF- 1943A, administered by the American Chemical Society, by grants from the National Science Foundation 20-25234 and 20-30641, and by a grant from the Woods Hole Oceanographic Institution Education Office ED-1100

Open ocean carbon monoxide photo-production

Sunlight-initiated photolysis of chromophoric dissolved organic matter (CDOM) is the dominant source of carbon monoxide (CO) in the open-ocean. A modelling study was conducted to constrain this source. Spectral solar irradiance was obtained from two models (GCSOLAR and SMARTS2). Water-column CDOM and total light absorption were modelled using spectra collected along a Meridional transect of the Atlantic ocean using a 200-cm pathlength liquid waveguide UV-visible spectrophotometer. Apparent quantum yields for the production of CO (AQYCO) from CDOM were obtained from a parameterisation describing the relationship between CDOM light absorption coefficient and AQYCO and the CDOM spectra collected. The sensitivity of predicted rates to variations in model parameters (solar irradiance, cloud cover, surface-water reflectance, CDOM and whole water light absorbance, and AQYCO was assessed. The model\u27s best estimate of open-ocean CO photoproduction was 47 +/- 7 Tg CO-C yr-1, with lower and upper limits of 38 and 84 Tg CO-C yr-1, as indicated by sensitivity analysis considering variations in AQYs, CDOM absorbance, and spectral irradiance. These results represent significant constraint of open-ocean CO photoproduction at the lower limit of previous estimates. Based on these results, and their extrapolation to total photochemical organic carbon mineralisation, we recommend a downsizing of the role of photochemistry in the open-ocean carbon cycle. (c) 2006 Elsevier Ltd. All rights reserved

Determination of Photochemically Produced Carbon Dioxide in Seawater

An analytical system was developed to determine photochemically produced carbon dioxide in marine waters. Our system was designed to measure low levels of carbon dioxide by maintaining a closed system to prevent atmospheric contamination during sample preparation, irradiation, and analysis. To detect low levels of photoproduced carbon dioxide in seawater, background dissolved inorganic carbon (DIC) was removed before irradiation. To strip out DIC, samples were acidified to pH 3.0 (converting DIC to carbon dioxide) and bubbled with low carbon dioxide air. The pH was then readjusted back to the original value, and the resulting low-DIC seawater samples were transferred pneumatically to air-tight quartz tubes for irradiation. During analysis, samples were pneumatically transferred to a sample loop, injected, and acidified. Carbon dioxide was then stripped out, dried, and carried to a nondispersive infrared carbon dioxide analyzer. Calibration was done with a series of low concentration aqueous carbonate standards (0.05 to 3 μmol L-1). The detection limit, defined as the concentration corresponding to three times the standard deviation of the experimental blank (i.e., DIC-stripped seawater), was similar to ~60 nmol L-1. Method precision was largely dependent on the agreement between multiple injections from the same tube (\u3c ± 2% relative standard deviation [RSD]) and the reproducibility between different tubes (±3% RSD). This method was used to measure carbon dioxide photoproduction in a variety of waters (e.g., estuarine, lake) including the first direct measurements in marine waters

Qualitative and Quantitative Assessment of Fatty Acids of Hazelnut by GC-TOF/MS

On the basis of gas chromatography coupled with time-of-flight mass spectrometry, we assessed the constituents and relative quantities of fatty acids extracted by supercritical carbon dioxide in seeds of hazelnut. Hazelnut seeds contain four fatty acids (palmitic, stearic, oleic, and linoleic acids). The content of unsaturated fatty acids is more than 92.9% in hazelnut seed oil. Oleic acid, which constitutes 76.1%, has a high boiling point and low volatility. Hazelnut oil has good storage stability and is recommended as senior edible oil for health and the food industry. Our study reveals the important contribution of hazelnut in the production of bioactive oils and compounds that prevent obesity, cancer, coronary disease, and many other human health as well as pharmaceutical challenges

A new micro-analytical system for reducing sugars--applications to sediment and seawater.

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Earth and Planetary Sciences, 1971.Bibliography: leaves 51-54.M.S

Estimating Hydroxyl Radical Photochemical Formation Rates in Natural Waters During Long-Term Laboratory Irradiation Experiments

In this study it was observed that, during long-term irradiations (\u3e1 day) of natural waters, the methods for measuring hydroxyl radical (˙OH) formation rates based upon sequentially determined cumulative concentrations of photoproducts from probes significantly underestimate actual ˙OH formation rates. Performing a correction using the photodegradation rates of the probe products improves the ˙OH estimation for short term irradiations (\u3c1 day), but not long term irradiations. Only the ‘instantaneous’ formation rates, which were obtained by adding probes to aliquots at each time point and irradiating these sub-samples for a short time (≤2 h), were found appropriate for accurately estimating ˙OH photochemical formation rates during long-term laboratory irradiation experiments. Our results also showed that in iron- and dissolved organic matter (DOM)-rich water samples, ˙OH appears to be mainly produced from the Fenton reaction initially, but subsequently from other sources possibly from DOM photoreactions. Pathways of ˙OH formation in long-term irradiations in relation to H2O2 and iron concentrations are discussed

Establishment success of sooty beech scale insects, Ultracoelostoma sp., on different host tree species in New Zealand

The sooty beech scale insect (Ultracoelostoma sp.) (Hemiptera: Margarodidae) exhibits a highly patchy distribution at local and regional scales. A major factor driving this common distributional phenomenon in other phloem-feeding insects is aggregation and local adaptation. The aim of this study was to determine if Ultracoelostoma was locally adapted to its natal host trees, by contrasting the establishment rates of first instar “crawlers” in reciprocal transfers to natal versus novel hosts. Although there are two closely-related species of sooty beech scale insect, the morphological characters of crawlers in this study were intermediate between those of U. assimile and U. brittini. However, all of the voucher specimens examined had consistent morphology, indicating that they belong to one species which we refer to as Ultracoelostoma sp. Reciprocal transfers of crawlers were carried out between individual red beech (Nothofagus fusca), as well as between mountain beech (N. solandri) and red beech trees, to ascertain if insects had become locally adapted to their individual host tree or to host species. In total, 480 crawlers were placed in enclosures on their natal and novel host trees, of which only 32 (6.7 %) became established. No evidence for local adaptation, either to individual host trees or to host tree species, was found. There was also no difference in crawler establishment between natal and novel hosts. However, crawlers originating from mountain beech trees had significantly higher establishment rates on both natal mountain beech and novel red beech hosts, than did crawlers originating from red beech trees. The superior ability of mountain beech crawlers to become established, even on novel red beech trees, suggests that scale insects on mountain beech trees have higher individual fitness (possibly due to maternal effects mediated by differences in host nutritional quality, defensive compounds or growth rate). This increased fitness may result in crawlers being better provisioned to search for appropriate establishment sites. The results of this study indicate that beech scale insects perform better on mountain beech at this site, although crawlers did not preferentially establish on mountain beech

Wavelength and Temperature-Dependent Apparent Quantum Yields for Photochemical Formation of Hydrogen Peroxide in Seawater

Wavelength and temperature-dependent apparent quantum yields (AQYs) were determined for the photochemical production of hydrogen peroxide using seawater obtained from coastal and oligotrophic stations in Antarctica, the Pacific Ocean at Station ALOHA, the Gulf of Mexico, and at several sites along the East Coast of the United States. For all samples, AQYs decreased exponentially with increasing wavelength at 25 °C, ranging from 4.6 × 10−4 to 10.4 × 10−4 at 290 nm to 0.17 × 10−4 to 0.97 × 10−4 at 400 nm. AQYs for different seawater samples were remarkably similar irrespective of expected differences in the composition and concentrations of metals and dissolved organic matter (DOM) and in prior light exposure histories; wavelength-dependent AQYs for individual seawater samples differed by less than a factor of two relative to respective mean AQYs. Temperature-dependent AQYs increased between 0 and 35 °C on average by a factor of 1.8 per 10 °C, consistent with a thermal reaction (e.g., superoxide dismutation) controlling H2O2 photochemical production rates in seawater. Taken together, these results suggest that the observed poleward decrease in H2O2photochemical production rates is mainly due to corresponding poleward decreases in irradiance and temperature and not spatial variations in the composition and concentrations of DOM or metals. Hydrogen peroxide photoproduction AQYs and production rates were not constant and not independent of the photon exposure as has been implicitly assumed in many published studies. Therefore, care should be taken when comparing and interpreting published H2O2AQY or photochemical production rate results. Modeled depth-integrated H2O2 photochemical production rates were in excellent agreement with measured rates obtained from in situ free-floating drifter experiments conducted during a Gulf of Maine cruise, with differences (ca. 10%) well within measurement and modeling uncertainties. Results from this study provide a comprehensive data set of wavelength and temperature-dependent AQYs to model and remotely sense hydrogen peroxide photochemical production rates globally

Measurement of Antioxidant Activity toward Superoxide in Natural Waters

Antioxidants are a class of molecules that provide a protective function against reactive oxygen species (ROS) in biological systems by out competing physiologically important molecules for ROS oxidation. In natural waters, the reactivity of antioxidants gives an estimate of oxidative stress and may determine the reactivity and distribution of reactive oxidants. We present an analytical method to measure antioxidant activity in natural waters through the competition between ascorbic acid, an antioxidant, and MCLA, a chemiluminescent probe for superoxide. A numerical kinetic model of the analytical method has been developed to optimize analytical performance. Measurements of antioxidant concentrations in pure and seawater are possible with detection limits below 0.1 nM. Surface seawater samples collected at solar noon contained over 0.4 nM of antioxidants and exhibited first-order decay with a half-life of 3-7 minutes, consistent with a reactive species capable of scavenging photochemically produced superoxide

Characterization and Photodegradation of Dissolved Organic Matter (DOM) From a Tropical Lake and Its Dominant Primary Producer, the cyanobacteria Microcystis aeruginosa

This study investigates optical and high-resolution molecular signatures and photochemical degradation of DOM from the Barra Bonita Reservoir (BB-DOM), a tropical eutrophic lake, as well as from its dominant phytoplankton species, the cyanobacteria Microcystis aeruginosa (Microcystis-DOM). Consistent with a predominantly autotrophic source, BB-DOM and Microcystis-DOM exhibited high protein-like fluorescence and contained a large number of aliphatics. Microcystis-DOM was enriched in peptide-like formulae, while BB-DOM had higher chromophoric and fluorescent DOM(CDOM and FDOM) and was enriched in moderately unsaturated formulae, indicating additions of terrigenous DOM and/or in situ processing of autochthonous material in the lake. Consistent with its higher CDOM content, BB-DOM was more photoreactive than Microcystis-DOM. For both types of DOM, photodegradation resulted in loss of CDOM, FDOM, moderately unsaturated structures, high O/C and low H/C formulae, and preservation of aliphatics. The majority of photoproducts of 0.5 d irradiation were subsequently removed by day 7, and photoproducts represented a minor fraction of the photo-irradiated DOM. For BB-DOM, molecular formula photolability increased with increasing aromaticity index values, while for Microcystis-DOM, molecular formula photolability increased with molecular mass. Photodegradation increased the proportion of molecular formulae containing N (CHO + N) in BB-DOM, while the molecular mass and the proportion of CHO + N formulae decreased upon photo-irradiation of Microcystis-DOM. In concert, these molecular shifts due to photodegradation decreased the diversity of and increased the similarity between BB-DOM and Microcystis-DOM, suggesting the selective pressure exerted by photochemistry selects for the survival of similar compounds in both samples