Provenance, Isolation and Characterisation of Organic Matter in the Cochin Estuarine Sediment-“a Diagenetic Amino Acid Marker Scenario

Cochin estuarine system is among the most productive aquatic environment along the Southwest coast of India, exhibits unique ecological features and possess greater socioeconomic relevance. Serious investigations carried out during the past decades on the hydro biogeochemical variables pointed out variations in the health and ecological functioning of this ecosystem. Characterisation of organic matter in the estuary has been attempted in many investigations. But detailed studies covering the degradation state of organic matter using molecular level approach is not attempted. The thesis entitled Provenance, Isolation and Characterisation of Organic Matter in the Cochin Estuarine Sediment-“ A Diagenetic Amino Acid Marker Scenario” is an integrated approach to evaluate the source, quantity, quality, and degradation state of the organic matter in the surface sediments of Cochin estuarine system with the combined application of bulk and molecular level tools. Sediment and water samples from nine stations situated at Cochin estuary were collected in five seasonal sampling campaigns, for the biogeochemical assessment and their distribution pattern of sedimentary organic matter. The sampling seasons were described and abbreviated as follows: April- 2009 (pre monsoon: PRM09), August-2009 (monsoon: MON09), January-2010 (post monsoon: POM09), April-2010 (pre monsoon: PRM10) and September- 2012 (monsoon: MON12). In order to evaluate the general environmental conditions of the estuary, water samples were analysed for water quality parameters, chlorophyll pigments and nutrients by standard methods. Investigations suggested the fact that hydrographical variables and nutrients in Cochin estuary supports diverse species of flora and fauna. Moreover the sedimentary variables such as pH, Eh, texture, TOC, fractions of nitrogen and phosphorous were determined to assess the general geochemical setting as well as redox status. The periodically fluctuating oxic/ anoxic conditions and texture serve as the most significant variables controlling other variables of the aquatic environment. The organic matter in estuary comprise of a complex mixture of autochthonous as well as allochthonous materials. Autochthonous input is limited or enhanced by the nutrient elements like N and P (in their various fractions), used as a tool to evaluate their bioavailability. Bulk parameter approach like biochemical composition, stoichiometric elemental ratios and stable carbon isotope ratio was also employed to assess the quality and quantity of sedimentary organic matter in the study area. Molecular level charactersation of free sugars and amino acids were carried out by liquid chromatographic techniques. Carbohydrates are the products of primary production and their occurrence in sediments as free sugars can provide information on the estuarine productivity. Amino acid biogeochemistry provided implications on the system productivity, nature of organic matter as well as degradation status of the sedimentary organic matter in the study area. The predominance of carbohydrates over protein indicated faster mineralisation of proteinaceous organic matter in sediments and the estuary behaves as a detrital trap for the accumulation of aged organic matter. The higher lipid content and LPD/CHO ratio pointed towards the better food quality that supports benthic fauna and better accumulation of lipid compounds in the sedimentary environment. Allochthonous addition of carbohydrates via terrestrial run off was responsible for the lower PRT/CHO ratio estimated in thesediments and the lower ratios also denoted a detrital heterotrophic environment. Biopolymeric carbon and the algal contribution to BPC provided important information on the better understanding the trophic state of the estuarine system and the higher values of chlorophyll-a to phaeophytin ratio indicated deposition of phytoplankton to sediment at a rapid rate. The estimated TOC/TN ratios implied the combined input of both terrestrial and autochthonous organic matter to sedimentsAmong the free sugars, depleted levels of glucose in sediments in most of the stations and abundance of mannose at station S5 was observed during the present investigation. Among aldohexoses, concentration of galactose was found to be higher in most of the stationsRelative abundance of AAs in the estuarine sediments based on seasons followed the trend: PRM09-Leucine > Phenylalanine > Argine > Lysine, MON09-Lysine > Aspartic acid > Histidine > Tyrosine > Phenylalanine, POM09-Lysine > Histadine > Phenyalanine > Leucine > Methionine > Serine > Proline > Aspartic acid, PRM10-Valine > Aspartic acid > Histidine > Phenylalanine > Serine > Proline, MON12-Lysine > Phenylalanine > Aspartic acid > Histidine > Valine > Tyrsine > MethionineThe classification of study area into three zones based on salinity was employed in the present study for the sake of simplicity and generalized interpretations. The distribution of AAs in the three zones followed the trend: Fresh water zone (S1, S2):- Phenylalanine > Lysine > Aspartic acid > Methionine > Valine ῀ Leucine > Proline > Histidine > Glycine > Serine > Glutamic acid > Tyrosine > Arginine > Alanine > Threonine > Cysteine > Isoleucine. Estuarine zone (S3, S4, S5, S6):- Lysine > Aspartic acid > Phenylalanine > Leucine > Valine > Histidine > Methionine > Tyrosine > Serine > Glutamic acid > Proline > Glycine > Arginine > Alanine > Isoleucine > Cysteine > Threonine. Riverine /Industrial zone (S7, S8, S9):- Phenylalanine > Lysine > Aspartic acid > Histidine > Serine > Arginine > Tyrosine > Leucine > Methionine > Glutamic acid > Alanine > Glycine > Cysteine > Proline > Isoleucine > Threonine > Valine. The abundance of AAs like glutamic acid, aspartic acid, isoleucine, valine, tyrosine, and phenylalanine in sediments of the study area indicated freshly derived organic matter.

Geochemistry and radionuclide content of sediment and water samples obtained from the Ob and Irtysh river, Russia

This paper reports the results of the investigations of 2006-2007 on the distribution and migration forms of artificial radionuclides and chemical elements in the Ob-Irtysh water system. Three regions were studied. One of them is a local segment of the Ob River upstream from the confluence with the Irtysh River; its investigation allowed us to estimate the general radioecological state of the aquatic environment affected by the activity of the Tomsk 7 plant. The second region is a local segment of the Irtysh River upstream from its confluence with the Ob River, where the influence of emissions from the NPO Mayak could be estimated. The third region is the water area of the Ob River after its confluence with the Irtysh River. It characterizes the real level of radioactive and chemical contamination of the middle reaches of the Ob River. In order to explain horizontal variations in the distribution of radionuclides in the upper layer of bottom sediments collected at various sites, the results of sorption-kinetic experiments with radioactive tracers in the precipitate-solution system were used. The investigation of the migration forms of trace elements and radionuclides occurring in river water was based on the method of tangential-flow membrane filtration. Chemical element contents were determined in 400-ml water samples. A set of Millipore polysulfone membranes with pore sizes of 8, 1.2, 0.45, 0.1, and 0.025 µm was employed. Taking into account the ultralow specific concentrations of radionuclides in the water, they were analyzed in 300-500 litre samples using Millipore polysulfone membranes with pore sizes of 0.45 µm and 15 kDa. This allowed us to estimate the percentages of cesium-137 and plutonium-239, 240 in the suspended particulate fraction, colloids, and dissolved species.

Eh and pH values in sediments and composition of interstitial waters from the Frolikha Bay, Baikal Lake

Redox conditions and compositions of bottom sediments and sedimentary pore waters in the area of the hydrothermal vent in the Frolikha Bay (Baikal Lake) are under discussion. According to obtained results, the submarine vent and its companion spring nearby on the land originate from a common source. The most convincing evidence for their relation comes from proximity of stable oxygen and hydrogen isotope compositions in the pore waters and spring water. The isotope composition indicates meteoric origin of the pore waters, but their major- and minor element compositions have influence of deep water, which may seep through the permeable faulted crust. Although the pore waters near the submarine vent have specific enrichment in major and minor constituents, hydrothermal discharge at the Baikal bottom causes minor influence on water composition of the Baikal Lake, unlike freshwater lakes in rifts of the East Africa and North America.

Geochemical analysis of bulk sediment and interstitial water of sediment cores from the North-West African continental margin

Molybdenum and vanadium were analysed in 9 scediment cores recovered from the continental slope and rise off NW Africa. Additionall chemical and sedimentological parameters as well as isotope stage boundaries were available for the same core profiles from other investigations. Molybdenum, ranging between <1 and 10 ppm, occurs in two associateions, either with organic carbon and sulphides in sediments with reducing conditions or with Mn oxides in oxidized near-surface core sections. Highest values (between 4 and 10 ppm Mo) are found in sulphide-rich core sections deposited during glacial times in a core from 200 m water depth. The possibility of anoxic near-bottom water conditions prevailing at thhis site during certain glacial intervals is discussed. In oxidized near-surface core sections, the diagenetic mobility of Mo becomes evident from strong Mo enrichment together with Mn oxides (values up to 4 ppm Mo). This enrichment is probably due to coprecipitation and/or adsorption of Mo from interstitial water to the diagenetically forming Mn oxides. The close relation between Mo and Corg results in strongly covarying sedimentation rates in both components reaching up to 10 times the rates in glacial compared to interglacial core sections. Vanadium (values between 20 and 100 ppm) does not show clear relations to climate and near-bottom or sediment milieu. It occurs mainly bound to the fine grained terrigenous fraction, associated with aluminium silicates (clay minerals) and iron oxides. Additionally positive covariation of vanadium with phosphorus in most core profiles suggest that some V may be bound to phosphates.

Ikaite of sediment cores from the Zaire deep-sea fan

Most concentration profiles of sulfate in continental margin sediments show constant or continuously increasing gradients from the benthic boundary layer down to the deep sulfate reduction zone. However, a very marked change in this gradient has been observed several meters below the surface at many locations, which has been attributed to anoxic sulfide oxidation or to non-local transport mechanisms of pore waters. The subject of this study is to investigate whether this feature could be better explained by non-steady state conditions in the pore-water system. To this end, data are presented from two gravity cores recovered from the Zaire deep-sea fan. The sediments at this location can be subdivided into two sections. The upper layer, about 10 m thick, consists of stratified pelagic deposits representing a period of continuous sedimentation over the last 190 kyr. It is underlain by a turbidite sequence measuring several meters in thickness, which contains large crystals of authigenic calcium carbonate (ikaite: CaCO3·6H2O). Ikaite delta13C values are indicative of a methane carbon contribution to the CO2 pool. Radiocarbon ages of these minerals, as well as of the adjacent bulk sediments, provide strong evidence that the pelagic sediments have overthrust the lower section as a coherent block. Therefore, the emplacement of a relatively undisturbed sediment package is postulated. Pore-water profiles show the depth of the sulfate-methane transition zone within the turbiditic sediments. By the adaptation of a simple transport-reaction model, it is shown that the change in the geochemical environmental conditions, resulting from this slide emplacement, and the development towards a new steady state are fully sufficient to explain all features related to the pore-water profiles, particularly, [SO4]2- and dissolved inorganic carbon (DIC). The model shows that the downslope transport took place about 300 yr ago.

Compositions of branched glycerol dialkyl glycerol tetraethers (GDGTs) in sediment samples from Bullenmoor peat bog, Northern Germany

Two types of intact branched glycerol dialkyl glycerol tetraethers (GDGTs) were detected in peat bog samples from Bullenmoor, Northern Germany. Glucuronosyl and glucosyl branched GDGTs comprise on average ca. 4% of the microbial intact polar lipids in the anoxic, acidic peat layer ca. 20 cm below the surface of the bog, suggesting an important ecological role for the source microorganisms. No corresponding phospholipids were detected. Notably, glycosidic branched GDGTs are 5-10 times less abundant than their intact isoprenoid counterparts derived from Archaea, while branched GDGT core lipids exceed their isoprenoid analogues by about an order of magnitude. These contrasting relationships may reflect lower standing stocks of the biomass of producers of branched GDGTs, combined with higher population growth rates relative to soil Archaea. Search strategies for the microbial producers of these conspicuous orphan lipids should benefit from the discovery of their intact polar precursors.

Sediment biogeochemistry at CO2 vents off Papua-New Guinea (2013, 2014)

Measurement of biogeochemical parameters in coral reef sediments at carbon dioxide vents off Upa-Upasina (Normandy Island, Papua-New Guinea). The data includes in-situ micro/minisensor profiles, sediment characteristics, microbial and meiofauna abundances of vent sediments and reference sites without vent influence.

Pore water chemistry of sediment core GeoB15101-7 and water chemistry of CTD casts GeoB15101-1 and GeoB15101-6

Submarine brine lakes feature sharp and persistent concentration gradients between seawater and brine, though these should be smoothed out by free diffusion in open ocean settings. The anoxic Urania basin of the Eastern Mediterranean contains an ultra sulfidic, hypersaline brine of Messinian origin above a thick layer of suspended sediments. With a dual modeling approach we reconstruct its contemporary stratification by geochemical solute transport fundamentals, and show that thermal convection is required to maintain mixing in the brine and mud layer. The origin of the Urania basin stratification was dated to 1650 years before present, which may be linked to a major earthquake in the region. The persistence of the chemoclines may be key to the development of diverse and specialized microbial communities. Ongoing thermal convection in the fluid mud layer may have important, yet unresolved consequences for sedimentological and geochemical processes, also in similar environments.

Sediment and porewater geochemistry of core GIK13725, Wester Baltic Sea

Based on chemical-thermodynamical balances the species distributions and mineral stabilities of the chemical compositions of the pressed pore solutions taken from a Baltic Sea mudsediment are evualuated by means of the computer program WATEQF (PLUMMER et al., 1976). According to these evaluations calcite and aragonite are to be found in supersaturation throughout the whole profile. The SiO2 concentration of the pore solutions is mainly controlled by the dissolutions of amorphous silica present in minimal undersaturation. By means of SEM pictures idiomorph quartzcrystals as well as presumptive clay minerals transformation and reformations could be proved as stable transformation phases of the dissolved SiO2 species. The stability of the solid phases containing Al-components as of feldspars and clayminerals decreases with increasing dept and is mainly controlled by AIF3 complexes higher concentrated with increasing depth.