The effects of manipulation of sedimentary iron and organic matter on sediment biogeochemistry and seagrasses in a subtropical carbonate environment

The microbial metabolism of organic matter (OM) in seagrass beds can create sulfidic conditions detrimental to seagrass growth; iron (Fe) potentially has ameliorating effects through titration of the sulfides and the precipitation of iron-sulfide minerals into the sediment. In this study, the biogeochemical effects of Fe availability and its interplay with sulfur and OM on sulfide toxicity, phosphorous (P) availability, seagrass growth and community structure were tested. The availability of Fe and OM was manipulated in a 2 × 2 factorial experiment arranged in a Latin square, with four replicates per treatment. The treatments included the addition of Fe, the addition of OM, the addition of both Fe and OM as well as no addition. The experiment was conducted in an oligotrophic, iron-deficient seagrass bed. Fe had an 84.5% retention efficiency in the sediments with the concentration of Fe increasing in the seagrass leaves over the course of the experiment. Porewater chemistry was significantly altered with a dramatic decrease in sulfide levels in Fe addition plots while sulfide levels increased in the OM addition treatments. Phosphorus increased in seagrass leaves collected in the Fe addition plots. Decreased sulfide stress was evidenced by heavier δ34S in leaves and rhizomes from plots to which Fe was added. The OM addition negatively affected seagrass growth but increased P availability; the reduced sulfide stress in Fe added plots resulted in elevated productivity. Fe availability may be an important determinant of the impact that OM has on seagrass vitality in carbonate sediments vegetated with seagrasses.

Pyrolysis-Gas Chromatography/Mass Spectrometry of Soil Organic Matter Extracted from a Brazilian Mangrove and Spanish Salt Marshes

The soil organic matter (SOM) extracted under different vegetation types from a Brazilian mangrove (Pai Matos Island, Sao Paulo State) and from three Spanish salt marshes (Betanzos Ria and Corrubedo Natural Parks, Galicia, and the Albufera Natural Park, Valencia) was investigated by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The chemical variation was larger in SOM from the Spanish marshes than in the SOM of the Brazilian mangroves, possibly because the marshes included sites with both tidal and nontidal variation, whereas the mangrove forest underwent just tidal variation. Thus, plant-derived organic matter was better preserved under permanently anoxic environments. Moreover, given the low number of studied profiles and sedimentary-vegetation sequences in both areas, depth trends remain unclear. The chemical data also allow distinction between the contributions of woody and nonwoody vegetation inputs. Soil organic matter decomposition was found to cause: (i) a decrease in lignin contents and a relative increase in aliphatics; (ii) an increase in short-chain aliphatics at the expense of longer ones; (iii) a loss of odd-over-even dominance in alkanes and alkenes; and (iv) an increase in microbial products, including proteins, sterols, short-chain fatty acids, and alkanes. Pyrolysis-gas chromatography/mass spectrometry is a useful tool to study the behavior and composition of SOM in wetland environments such as mangroves and salt marshes. Additional profiles need to be studied for each vegetation type, however, to improve the interpretability of the chemical data.

Seasonal ramification in the biochemical composition of organic matter in Chalakudy river-estuary

The present study which is the first of its kind in this region is an attempt to generate adequate information on the relative abundances, the seasonal and spatial variations as well as on the source and fate of organic compounds found associated with the dissolved, particulate and sedimentary compartments of Chalakudy river system. The study aimed at investigating variations, the relative proportion of dissolved, particulate and sedimentary fractions of these materials as well as the pollution extent so as to be able to comment on the present condition of this river-estuarine system. This thesis focuses attention on the role of biogeoorganics in modifying the ecological and environmental condition of the dissolved, particuIate and sediment compartments with their minute variability subjected to various physical, chemical and biogeochemical processes. A scheme of study encompassing all these objectives provides the frame work for the present investigation.

Estimating the contribution of terrestrial organic matter in the South-Western margin of Baja California during the late Holocene

Universidad de Las Palmas de Gran Canaria. Facultad de Ciencias del Mar. Trabajo Fin de Título para la obtención del Graduado en Ciencias del Mar, 2013-2014

Organic matter preservation in sediments of the Peru and Oman continental margin

Detailed petrographical and bulk geochemical investigations of organic matter (OM) have been performed on sediments deposited below or close to upwelling areas offshore Peru (ODP-Leg 112; Sites 679, 681, 688) and Oman (ODP-Leg 117; Sites 720, 723, 724) in order to obtain a quantitative understanding of its accumulation and degradation. Microscopical as well as nanoscopical investigations reveal that the OM in sediments affected by upwelling mechanisms mainly (up to 98%) consists of unstructured (amorphous) organic aggregates without any apparent biological structures. In sediments which are not or to a lesser extent affected by upwelling (Site 720) terrestrial OM predominates. Organic carbon (TOC) contents are highly variable and range between 9.8% in sediments deposited below upwelling cells and 0.2% in sediments outside the upwelling zone. The TOC/sulphur ratios of the sediments scatter widely. The samples from the deep-water locations (Sites 688 and 720), show C/S-ratios of "normal" marine sediments, whereas at the other locations no correlation or even a negative correlation between sulphur and TOC concentration exists. In most of the upwelling-influenced sediments OM contains a significant amount of sulphur. The incorporation of sulphur into the OM followed microbial sulphate reduction and occurred in the upper meters of the sedimentary column. Below, OM is still present in vast amounts and relatively hydrogen-rich, but is nevertheless non-metabolizable and becomes the limiting factor for bacterial sulphate reduction. According to mass balance calculations 90-99% of the OM produced in the photic zone was remineralized and 1-3% was consumed by microbial sulphate reduction. The aerobic and anaerobic processes have greatly affected degradation and conservation of OM.

(Table 2) Chemistry of the organic matter at DSDP Leg 62 Holes

The wide distribution of sapropelic deposits in the sedimentary cover of the oceans, their Cretaceous age, and their possible oil- and gas-generating characteristics allow us to regard these deposits as a regular global stage in the history of oceanic sedimentation. So, Cretaceous sapropelic deposits are a unique object for study. Cretaceous sapropelic deposits of DSDP Sites 463, 465, and 466, as well as similar sediments of the Atlantic and Indian Oceans, are characterized by enrichment in organic matter, which sometimes reaches 33% (Cape Verde Basin, DSDP Sites 367 and 368). The objective of this study is the elucidation of genesis, paleogeographic environment of sedimentation, and oil-generating potential of Cretaceous sapropelic deposits at these sites. Attention is given to petrographic composition and distribution of the organic matter.

Organic matter preservation in turbidites on the Madeira Abyssal Plain

Oxidized intervals of five organic-rich Madeira Abyssal Plain (MAP) turbidites deposited during the Miocene, Pliocene, and Pleistocene all displayed comparable major loss of total organic carbon (TOC) (84 ± 3.1%) accompanied by a negative isotopic (d13C) shift ranging from -0.3 to -2.9 per mil. Major but significantly lower loss of total nitrogen (Ntot, 61 ± 7.1%) also occurred, leading to a decrease in TOC relative to Ntot (C/Ntot) and a +1.3 to 2.7 per mil Ntot isotopic (d15N) shift. Compound specific isotopic measurements on plant wax n-alkanes indicate the terrestrial organic component in the unoxidized deposits is 13C-enriched owing to significant C4 contribution. Selective preservation of terrestrial relative to marine organic carbon could account for the d13C behavior of TOC upon oxidation but only if a 13C-depleted component of the bulk terrestrial signal is selectively preserved in the process. Although the C/Ntot decrease and positive d15N shift seems inconsistent with selective terrestrial organic preservation, results from analysis of a Modern eolian dust sample collected in the vicinity indicate these observations are compatible. Regardless of the specific explanation for these isotopic observations, however, our findings provide evidence that paleoreconstruction of properties such as pCO2 using the d13C of TOC is a goal fraught with uncertainty whether or not the marine sedimentary record considered is 'contaminated' with significant terrestrial input. Nonetheless, despite major and selective loss of both marine and terrestrial components as a consequence of postdepositional oxidation, intensive organic geochemical proxies such as the alkenone unsaturation index, UK'37, appear resistant to change and thereby retain their paleoceanographic promise.

Terrestrial organic matter in marine sediments of the Central Equatorial Atlantic

Terrestrial organic matter (OM) in pelagic sediments is discussed with regard to depositional processes and land-sea interactions in the modern and past glacial/interglacial Equatorial Atlantic. Special emphasis is placed on a critical evaluation of different analytical approaches (C/N, Rock-Eval Pyrolysis, stable carbon isotopes, palynology, organic petrology, and selected biomarkers) which are currently used for the qualitative and quantitative assessment of terrigenous organic carbon. If binary mixing equations are used to calculate terrestrial and marine proportions of organic carbon, we consider the definition of endmember values to be most critical since these values may be biased by a great number of independent controls. A combination of geochemical methods including optical studies (organic petrology and palynology) is therefore suggested to evaluate each individual proxy. Organic geochemical analyses performed on sediments from the modern and Late Quaternary Equatorial Atlantic evidence fluctuations in eolian supply of terrigenous OM related to changes in intensity of the trade winds. Quantification of this organic fraction leads to differing proportions depending on the approach applied, i.e. the organic carbon isotopic composition or maceral analyses. Modern distribution of terrigenous OM reveals a decrease in supply towards the basin contributing less than a fifth of the total OM in pelagic areas. Organic geochemical data indicate that sedimentation in the modern northeastern Brasil Basin is affected by lateral advection of reworked OM probably from southern source areas. Glacial/interglacial deposits from the pelagic Equatorial Atlantic (ODP Site 663), covering isotopic stages 12 and 11, reveal that deposition of terrigenous OM was higher under past glacial conditions, in correspondence to generally enhanced dust fluxes. Proportions of terrigenous OM, however, never exceed 50% of the total OM according to maceral analyses. Other estimates, recently proposed by Verardo and Ruddiman (1996), are considered to be too high probably for analytical reasons. Palynological records in the Equatorial Atlantic parallel dust records. Increased portions of grass pollen suggest the admixture of C4-plant material under modern and past glacial conditions. It is therefore assumed, as one possible interpetation, that C4-plant debris has an effect on sedimentary d13Corg and might explain differences between isotopic and microscopic quantitative estimates. Using the difference between these two records, we calculate that maximum supply of C4-material remains below 20% of the total OM for the deep modern and past glacial/interglacial Equatorial Atlantic.

Hydrocarbon contents and carbon isotope composition of organic matter from holes of DSDP Legs 50 and 64

The book is devoted to fundamental problems of organic geochemistry of ocean sediments. It is based on materials of organic matter and gas studies in cores from DSDP Legs 50 and 64. Experimental results obtained in the Laboratory of Carbon Geochemistry (V.I. Vernadsky Institute of Geochemistry and Analytical Chemistry, Moscow) take the main part of the book. Evolution of organic matter in specific environment of deep ocean sediments, sources of organic matter in the ocean and methods of their identification based on isotopic analysis and other methods are under discussion. Gas geochemistry in normal conditions of diagenesis, and in conditions under intense heating is studied.

Composition of organic matter from black shales drilled in the Cape Verde Basin in DSDP Hole 41-367

Results of geochemical studies of organic matter in black shales from the Cape Verde Basin are reported. Based on these results, in combination with data of petrographic analysis, conclusions are made about sapropelic nature of their organic matter and low degree of its coalification. It corresponds to the proto-catagenetic substage of sedimentary rocks. Black shales of the Cape Verde Basin are classified as potential oil source strata.

Organic matter and sediment properties of samples from site GeoB15105 from the Black Sea

Dissolved organic matter (DOM) in marine sediments is a complex mixture of thousands of individual constituents that participate in biogeochemical reactions and serve as substrates for benthic microbes. Knowledge of the molecular composition of DOM is a prerequisite for a comprehensive understanding of the biogeochemical processes in sediments. In this study, interstitial water DOM was extracted with Rhizon samplers from a sediment core from the Black Sea and compared to the corresponding water-extractable organic matter fraction (<0.4 µm) obtained by Soxhlet extraction, which mobilizes labile particulate organic matter and DOM. After solid phase extraction (SPE) of DOM, samples were analyzed for the molecular composition by Fourier Transform Ion-Cyclotron Resonance Mass Spectrometry (FT-ICR MS) with electrospray ionization in negative ion mode. The average SPE extraction yield of the dissolved organic carbon (DOC) in interstitial water was 63%, whereas less than 30% of the DOC in Soxhlet-extracted organic matter was recovered. Nevertheless, Soxhlet extraction yielded up to 4.35% of the total sedimentary organic carbon, which is more than 30-times the organic carbon content of the interstitial water. While interstitial water DOM consisted primarily of carbon-, hydrogen- and oxygen-bearing compounds, Soxhlet extracts yielded more complex FT-ICR mass spectra with more peaks and higher abundances of nitrogen- and sulfur-bearing compounds. The molecular composition of both sample types was affected by the geochemical conditions in the sediment; elevated concentrations of HS- promoted the early diagenetic sulfurization of organic matter. The Soxhlet extracts from shallow sediment contained specific three- and four-nitrogen-bearing molecular formulas that were also detected in bacterial cell extracts and presumably represent proteinaceous molecules. These compounds decreased with increasing sediment depth while one- and two-nitrogen-bearing molecules increased, resulting in a higher similarity of both sample types in the deep sediment. In summary, Soxhlet extraction of sediments accessed a larger and more complex pool of organic matter than present in interstitial water DOM.