Determination of Organochlorine Pesticides in Sediments from Authie Bay Using Microwave Assisted Solvent Extraction

The aim of this study was to develop an analytical method to determine the organochlorine concentrations in sediments. Combination of Microwave assisted Solvent Extraction (MASE) and capillary gas chromatography with specific detection (electron capture detector) was a viable approach for the determination of pesticides in solid matrixes. In this study, MASE development was focused on the selection of a suitable extraction solvent for all the target analytes. MASE procedure was validated by comparison with conventional methods such as Soxhlet and sonication extraction. The proposed method was then applied to determine the organochlorine insecticides concentrations in samples from Authie Bay (France). Environmental water samples were analysed and five target analytes were detected in concentrations from 0.03 to 0.56 ng/g of dry sediment. These investigations showed the accumulation and the persistency of these products in sediments in spite of the fact they were banned a few decades ago.     

Investigation of the origin and sedimentary environment of marine sediments from coastal areas of western Japan by INAA

Trace elements such as Sc, lanthanoids, Th and U were determined by means of instrumental neutron activation analysis (INAA) in marine sediment core samples collected from 5 coastal areas in western Japan mainly facing the Pacific. The origin of the coastal sediments and the sedimentary environment are discussed in terms of such parameters as the La*/Lu* and Ce*/La* ratios, the Th/Sc ratios and the Th/U-Ce/U plot obtained from the analytical data. In particular, it was confirmed that the Th/U-Ce/U plot introduced in this work is extremely useful for estimating the sedimentary environment, including redox conditions.     

Adsorption and kinetic behavior of uranium and thorium in seawater-sediment system

The adsorption and kinetic mechanism of uranium (U) and thorium (Th) in seawater-sediments system of Mumbai Harbour Bay (MHB) has been studied by K _d values of two sets of experimental determinations using a batch experiment. After equilibrium time (7 days), under static conditions, K _d for U and Th ranged from 25,030 to 55,662 mL/g (mean: 42,140 mL/g) and 24,926 to 38,561 mL/g (mean: 34,256 L/kg), respectively. Extraction studies showed that both U and Th were strongly bound to sediment components due to insignificant difference in their mean concentration in equilibrium solution. Rate constants (k) for transfer between seawater and the exchangeable fraction were found to be similar for the sediments as 1.02 ± 0.03 day^?1 for uptake of U and Th. The resulting adsorption data were fitted to Freundlich, linear and Langmuir isotherm models. All the three models showed a significant correlation (R ² >0.9), indicating that there is more complex relationships with adsorption behavior of U and Th on sediment surface. Since, the Freundlich constant (n) for U and Th was found to be closer to unity. Therefore linear model was observed to be highly suitable. Based on the linear model, the distribution coefficient (k _d) of Th was about 1.5 times higher than U. According to Freundlich model, sorption of U in sediments observed to be higher than Th. However, Langmuir model considered in opposite to Freundlich and showed a higher value of K _L constant for Th than U. The pH (water) of the sediments ranged from 7.8 to 8.2 and the estimated total carbon (determined by C H N S–O elemental analyser) ranged from 1.7 to 3.4 %.     

Sorption/desorption of radioruthenium on the surface sediments of Daya Bay,China

The sorption/desorption of radioruthenium was investigated by the batch method in sea water system at ambient temperature on the surface sediments obtained around the Daya Bay of Guangdong Province, where the first nuclear power station of China has been running from 1994. It was found that the sorption percentage was obtained to be around 40% for all the surface sediments in 60 minutes. Then, the sorption percentage goes up slowly. The sorption percentage of radioruthenium reached around 80% in 113 days (2713 hours). The distribution coefficients decreased from 3.16·10⁴ to 1.35·10³ ml/g with the increasing of sediment concentration in the range of 4–10000 mg/l. The results of the desorption experiments suggest that the sorption of radioruthenium is irreversible with 81.5% relative hysteresis coefficient.     

A Study on the Engineering Geological Properties of Fine-grained Marine Sediments

Through studies on the engineering geological properties of fine marine sediments, this article fully verified that the sedimentary environment is an important factor which determines the engineering geological properties of fine marine sediments. Meanwhile, these properties are controlled and affected by factors such as composition, physico-chemical nature, micro-textures, etc. of fine soils.     

Effect of alteration processes on the distribution of radionuclides in uraniferous sedimentary rocks and their environmental impact, southwestern Sinai, Egypt

The contents of natural radionuclides in various types of sedimentary rocks in Um Bogma Formation and base of El Hashash Formation were determined by gamma-ray spectrometry. Three types of lower Carboniferous sedimentary rocks were investigated; sandstone (El Hashash Formation), dolostone and argillaceous sediments (Um Bogma Formation). The alteration processes are dolomitization, dedolomitization, karstification and lateritization. The specific radioactivity of ²³⁸U, ²²⁶Ra, ²³²Th and ⁴⁰K determined in different samples, indicate that ²³⁸U and its decay products contribute primarily to the high natural radioactivity of rocks. The maximum concentration of ²³⁸U reached up to 2129.36 ppm in argillaceous sediments. The average concentrations of determined radionuclides (²³⁸U, ²²⁶Ra, ²³²Th and ⁴⁰K) are 8.34 ppm, 7.88 ppm, 4.68 ppm and 0.3%, respectively in sandstone. In dolostones the average concentrations are 418.69 ppm, 808.75 ppm, 3.14 ppm and 0.29%, respectively. For argillaceous sediments are 276.88 ppm, 419.49 ppm, 11.47 ppm and 0.93%, respectively. The ²³⁸U/²²⁶Ra ratio in sandstone ranges between 0.89 and 1.25, while in dolostones and argillaceous sediments are 0.27–2.63 and 0.27–1.83, respectively. These variations in the concentrations of radioelements and their ratios are due to the action of the alteration processes affected these different sedimentary rocks in different times. Environmentally, the Ra_eq in dolostones and argillaceous sediments exceeds the permitted limits, while in the sandstone samples; it is within the permissible levels.     

Polycyclic aromatic hydrocarbons (PAHs) in surface sediments of Monastir Bay (Tunisia,Central Mediterranean): distribution,origin and seasonal variations

To assess PAH contamination state of Monastir Bay, surface sediments were collected and analysed for 17 selected parent PAHs by GC/MS. Sediments were sampled from five sites in wet and dry seasons. Total PAH concentrations were in the range of 25.6 to 576.8?ng/g d.wt in winter and 44.9–395.8?ng/g d.wt in summer. Comparison of results with Sediment Quality Guidelines suggested no eco-toxicological risk for benthic organisms. The use of molecular indices has shown that PAHs in surface sediments originate mainly from pyrolytic sources. Total PAH concentrations in surface sediments showed no significant correlations with organic matter content and pelite fraction. The analysis of spatial and seasonal variations of PAHs in surface sediments has demonstrated that final distribution of PAHs in surface sediments is mainly governed by hydrological conditions.     

Energy dispersive X-ray fluorescence and neutron activation analysis of surficial sediments of the Sea of Marmara and the Black Sea around Istanbul

Surficial sediment samples, collected from 27 sampling sites of the Sea of Marmara and the Black Sea nearby Istanbul area in 1996 and 1999 years, were analyzed quantitatively for some heavy metals and some other elements by using radioisotope excited energy dispersive X-ray fluorescence (EDXRF). The U and Th concentrations of the samples were determined by instrumental neutron activation (INAA). The results were compared with those from other contaminated and uncontaminated sedimentary materials. It is found that some elemental concentrations of the Sea of Marmara and the Black Sea sediments are comparable with those in most other sea sediments in the vicinity of densely populated regions.     

Developing a methodology for carbon isotope analysis of lacustrine diatoms

Stable isotope analysis of sedimentary carbon in lakes can help reveal changes in terrestrial and aquatic carbon cycles. A method based on a single, photosynthetic organism, where host effects are minimised, should offer more precision than carbon isotope studies of bulk lake sediments. Here we report the development of a systematic method for use on fossil lacustrine diatom frustules, adapted from previous studies in marine environments. A step-wise cleaning experiment on diatomaceous lake sediments from Lake Challa, near Mount Kilimanjaro, was made to demonstrate the necessary treatment stages to remove external sedimentary carbon. Changes in soluble carbon compounds during these cleaning experiments were measured using gas chromatography/mass spectrometry (GC/MS). The mass spectrometry methods were refined to measure the small percentage of carbon in these samples and details of these methods are presented. Samples of cleaned diatoms containing <1% carbon yielded robust results. Carbon isotope analyses of diatom samples containing different species mixtures were performed and suggested that differences existed, although the effects lay within current experimental error and require further work. Unlike what was found in work on oxygen and silicon isotopes from diatom frustules, mineral contamination had no discernible impact on the diatom carbon isotope ratios from these sediments. The range of values found in the lakes investigated thus far can be interpreted with reference to the supply and nature of carbon from the catchment as well as to the demand generated from lake primary productivity.     

Geochemistry of marine sediments from inner Ría de Vigo (NW Spain)

Two sediment cores were recovered in San Simón Bay (NW Spain) in order to establish sediment accumulation rates by ²¹⁰Pb and ¹³⁷Cs dating and to reconstruct metal pollution history. Sediment composition was determined by X-ray Fluorescence. A main lithogenic origin was shown up. Grain size conditions radionuclide activities and element concentrations. Fine grained sediments concentrate pollutants and showed higher activities. Radionuclide profiles are affected by diagenetic processes and sedimentary disturbances, but a temporal framework could be obtained for the intertidal area, where the anthropogenic inputs of Cu, Pb and Zn started several decades ago.     

New information about the U/Th sediment contamination provided by the neutron-induced fission activation analysis

The possibility to obtain new information about the U/Th contamination using the patterns of the fission track micromapping is put into evidence. For the investigated samples, bed load sediments sampled from Danube river and Delta, fission track micromappings were obtained using the neutron-induced fission of the U and Th elements and the track registration of their fission fragments in muscovite track detectors. Utilising the optical microscopy, these micromappings were used both for U and Th content measurements and for studies of U/Th atom distributions. Considering the track micromapping pattern as a characteristic of the U/Th atom distribution in the analysed sample, and basing on the micromapping patterns that were previously obtained for the samples contaminated in the specific conditions, the authors were able to establish: (1) the presence of the contamination of the sediments in spite of the fact that the U/Th concentration values did not exceed the natural background values, (2) the solubility of the U/Th chemical compounds in the initial waste and (3) the presence of a succession of U/Th contaminations as well as the presence of the transported contamination.     

Geochemical variability of copper and iron in Oman Margin sediments

An analysis of the geochemical distribution of selected trace metals among various geochemical phases of the sediments in the Oman Margin was carried out using a sequential extraction technique. The present study showed that most Cu in abyssal sediment is associated with only oxidisable mainly organic and sulphide bound metals with insignificant bound to exchangeable, carbonates, easily/moderately reducible fraction. The preservation of Cu in the sediments indicates the importance of primary production and upwelling in the overlying waters and an organic flux in the sedimentary deposition of open-ocean environments. The early diagenetically formed oxidisable mainly organic and sulphide fraction are not degraded and results in a pronounced association of Cu with organic fraction in the sediments of the Oman continental margin. The strong correlation between Cu, TOC and Fe oxides associated with the oxidisable fraction in one of the core indicates that it is likely to be the presence of sulphides.     

Mössbauer Investigation of Characteristic Distribution of Iron Oxides in Sediments from the Antarctica

Sediments from the Admiralty Bay, King George Island, Antarctica, were investigated by ⁵⁷Fe Mössbauer spectroscopy, X-ray diffractometry, and radiometry. Quartz, feldspar, chlorite, calcite, dolomite, mica, kaolinite, hematite and magnetite were identified as constituent minerals in the sediment samples. The phase composition and the iron distribution among the crystallographic sites of iron-bearing minerals (silicates, magnetite and hematite) of samples from different location have been derived from the complex Mössbauer spectra. At different locations sediments had significant characteristic differences in the mineral composition, in the iron distribution among the crystallographic site of silicates, and in the specific radioactivity of Cs radionuclides. These results indicate differences in the rock formation and alteration by the sediments in this maritime part of Antarctica. There is a much higher amount of iron oxides in the sediments from south part of the geological fault across the Admiralty Bay than in the north part. This can be associated with much more alteration in the rocks in the south part compared to the northern one. This finding can contribute to the question of the history of the formation and alteration of volcanic rocks in the border of Antarctica.     

Intact polar membrane lipids in prokaryotes and sediments deciphered by high-performance liquid chromatography/electrospray ionization multistage mass spectrometry--new biomarkers for biogeochemistry and microbial ecology

Lipids from prokaryotic cell membranes can serve as sources of information on the biogeochemistry and microbial ecology of natural ecosystems. Traditionally, apolar derivatives of the intact polar membrane molecules, e.g., fatty acids, have been the major target of lipid-based biogeochemical studies. However, when still intact, i.e., as glycerol esters and ethers with attached polar headgroups, membrane lipids are diagnostic for living prokaryotes, which makes them excellent biomarkers for the study of in situ microbial processes in geological systems such as sediments or soils. Intact polar lipids (IPLs) are attractive analytical targets because they are taxonomically more specific than their apolar derivatives and avoid exclusion of signals from prokaryotes that primarily build their membranes with ether-bound lipids such as archaea and some bacteria. Here we report results from analyses of IPLs in pure cultures of biogeochemically relevant prokaryotes and marine sediments by high-performance liquid chromatography/electrospray ionization ion-trap mass spectrometry (HPLC/ESI-IT-MSn). This technique is suitable for screening of biomass and environmental samples for distinctive taxonomic structural features such as distribution of polar lipid headgroups, types of bonds between alkyl moiety and glycerol backbone, and the chain length and degree of unsaturation in the alkyl moieties. We present analytical protocols to decipher structural information from mass spectral data. The IPL contents in selected archaeal and bacterial species are diverse and qualify as molecular fingerprints. Applied to marine sediments, the approach provided detailed information on the dominant microbial groups. The IPLs from bacterial members of anaerobic methanotrophic communities in surface sediments at Hydrate Ridge resemble those found in Desulfosarcina variabilis. The presence of dietherglycerophospholipids, however, suggests the presence of other bacteria possibly affiliated with the deepest phylogenetic branches in the tree of life. Sediments from approximately 90 m below the seafloor on the Peruvian continental margin are dominated by intact archaeal tetraethers with glycosidically bound hexoses as headgroups, consistent with a significant fraction of the community being archaea. Additional calditol-based tetraethers imply that the sedimentary archaea are taxonomically linked to the crenarchaeal Sulfolobales.     

Tributyltin determination in marine sediments: A comparative study of methods

Two independent speciation methods have been applied to the determination of tributyltin (TBT) in marine sediments: (1) acetic acid leaching/hydride generation/cold trapping/GC/quartz furnace AA; and (2) toluene–tropolone extraction/HPLC/GFAA. TBT determines in a typically moderately polluted sediment (Porto Vecchio Bay, Corsica, France) are in very good agreement, as also are the determination of total recoverable tin by the first method and by a direct one using strong acid leaching followed by GFAA. These cross-verifications lead one to conclude that both speciation methods are convenient and allow for valid determination of TBT in marine sediments, with no loss of TBT. Method-induced modification of tin speciation has not been observed.     

Concentrations of some elements in the coastal sea sediments: Bays with marinas

Summary Surface sediments and sediment cores from two bays in the Adriatic sea (Punat Bay and Soline Bay, Croatia) have been analyzed for a number of elements, in particular: Ti, V, Mn, Fe, Cu, Zn, As and Pb, by using XRF. Maps of elemental distribution in surface sediments show increased concentrations for some elements present in antifouling paints (Cu, Zn, Pb) near the service areas in the villages or marinas. Core profiles for these elements were used to evaluate the environmental impact of newly constructed marinas. Source partition indicates the influence of other sources located in near by villages. The critical factor in these considerations was shown to be water exchange with the open sea.     

Distribution of uranium in sediment of creek ecosystem

The present study was carried on distribution of uranium isotopes and Thorium in marine sediment from creek of Mumbai Harbour Bay (MHB) using radiochemical separation followed by alpha spectrometry. The activity concentration of uranium and thorium in sediment of MHB has ranged between 1–4 and 1.8–4.5 ppm respectively. The activity ratio of ²³⁴U/²³⁸U in sediment was found close to unity at most of the locations of creek suggesting a conservative behaviour. The observed Th/U ratio (0.9) in comparison to global Th/U ratio (?3.5) in the creek sediment indicates that it receives low radiogenic nature of terronenous input.     

Seasonal Changes in Methylarsenic Distribution in Tosa Bay and Uranouchi Inlet

The distribution of arsenic species, including trivalent methylarsenicals, was observed in coastal seawater of Tosa Bay and Uranouchi Inlet Japan. In Tosa Bay, most arsenic was dissolved in the inorganic form throughout the year and the concentration of total dissolved arsenic was higher than that in Uranouchi Inlet. The sum of methylarsenicals found in surface waters comprised 2–25% and 10–82% of the total dissolved arsenic in Tosa Bay and Uranouchi Inlet, respectively. In Uranouchi Inlet, seasonal variations in the concentrations of arsenicals were observed both in the water column and in surface sediments. The maximum concentrations of methylarsenicals appeared during summer, and became comparable to those of inorganic arsenicals in surface water. The concentration of trivalent methylarsenicals was usually low, and their seasonal changes seemed to be independent of those of the pentavalent species. The variations in methylarsenic(V) concentration did not coincide with those of chlorophyll a in either Tosa Bay or Uranouchi Inlet. These results suggested that methylarsenic(V) in natural waters was produced not directly by the activity of phytoplankton but through decomposition of organic matter by bacteria.