Chemical analyses of heavy metal contamination in sediments of the Venice Lagoon and toxicological implications

Heavy metals are extracted from sediments using 1 M HCl; then, solutions are neutralised with 1 M NaOH, to fit the conditions suitable for the Vibrio Fischeri test. In the neutralised solutions different percentages of initial metal concentration are present, depending on the individual solubilities. The chemical investigation of the metal fraction extracted from the sediment with this procedure and the different metal bioavailability depending on the presence of natural complexing agents are the subject of this work. The results obtained confirm the good agreement between heavy metal fraction extracted using 1 M HCl and the anthropogenic component in the sediment. The use of voltammetric techniques, and the addition of low molecular weight humic acids into extracts show the ability of natural complexing agents in affecting heavy metal bioavailability and toxicity.     

Reassessment and comparison of natural radioactivity levels in relation to granulometric contents of recently excavated major river sediments

River sediment depositions on the bottom of rivers most frequently consist of sand and gravel particles, which make them particularly valuable for the building construction. Knowledge of radioactivity present in building material enables one to assess any possible radiological hazard to mankind by the use of such materials. The natural radionuclide (²³⁸U, ²³²Th and ⁴⁰K) contents have been analyzed for the recently excavated sediment samples of Cauvery, Vellar, Ponnaiyar and Palaru rivers with an aim of evaluating the radiation hazard nature. To know the radiological characteristics of the sediment, the different radiological parameters are calculated. Natural radioactivity level is higher in Palaru river and it is lower in Vellar river sediments. In all the rivers, concentration of ²³⁸U is decreased, and concentrations of ²³²Th and ⁴⁰K are increased towards the river mouth. Granulometric analysis shows that the sand is the main constituent in all the river sediment samples. Content of sand is gradually decreased, and contents of silt and clay are gradually increased towards the river mouth. Cluster analysis was carried out to find the similarity level between the radioactivity and granulometric measurements. The radioactivity level of all the four river sediments mainly depends upon the contents of silt and clay. Averages of the all calculated radiation hazard indices are lower than recommended level in Cauvery, Vellar and Ponnaiyar river sediments. Therefore, the sediment of the above rivers does not pose any significant radiological threat to the population when it is used as a building construction material.     

Sediment transport investigation near Sagar Island in Hooghly Estuary,Kolkata Port,Kolkata

A radiotracer investigation was carried out in Hooghly Estuary at Kolkata Port Trust, Kolkata to examine the suitability of a dumping site for dredged sediment located at south of shipping channel. Scandium-46 (300 GBq) as scandium glass powder having the particle size distribution ranging from 40 to 100 μm was used as a radiotracer. The tracer was injected onto the seabed at the site using a remotely operated injection system and its movement was tracked using waterproof scintillation detector. The tracer concentration curves were plotted for different trackings. From the tracer concentration curves iso-activity contours were plotted and parameters such as general direction of movement on seabed, transport velocity, transport thickness and bed load movement rate were determined. The analysis of data indicated that the sediment predominantly moves towards north-east direction during the period of the study and coming in the shipping channel. Based on the investigations, it was found that the proposed site is not suitable for dumping the dredged material, as the movement of sediment is towards the shipping channel.     

Adsorption — Desorption equilibria of some radionuclides in sediment — Sea water system

Chemical and physical properties of Suez Canal bottom sediments (SCBS) and sea water at port Tawfeek area, the south entrance of Suez canal, have been studied. The SCBS was separated into its size fractions (natural sediment, sand, silt and clay). These different sediment fractions were allwed to be in equilibrium with⁸⁹Sr,⁶⁰Co and¹³⁴Cs solutions. Desorption studies were carried out on these contaminated sediments.     

Distribution of uranium and thorium in fractionated sediment samples obtained from different locations across Thane Creek area (Mumbai,India)

Uranium concentration varies from 9.01 to 12.7, 8.03 to 11.5, 9.1 to 14.0 and 10.1 to 14.2 mg/kg in grab sediment, coarse sand fraction, fine sand fraction, silt and clay fraction respectively. Thorium concentration varies from 20.0 to 29.4, 17.3 to 28.6, 19.6 to 30.4 and 21.1 to 35.9 in grab sediment, coarse sand fraction, fine sand fraction, silt and clay fraction respectively. Uranium and thorium concentrations vary in different size fractionated sediment samples like silt and clay fraction > fine sand fraction > coarse sand fraction.     

A comparative study of the adsorption of uranium on commercial and natural (Cypriot) sea sand samples

The adsorption of hexavalent uranium on two different types of sea sand [e.g. a local, Cypriot (N_SS) and a commercially available marine sediment (C_SS)] has been investigated as a function of pH, initial metal concentration, ionic strength and contact time under normal atmospheric conditions. Before carrying out the adsorption experiments, the sea sand samples have been characterized by XRD, XRF, N₂-adsorption, acid/base titrations and FTIR spectroscopy. Sample characterization showed clearly that the two sea sand types differ significantly in their composition, particularly in their calcite and FeOOH content. According to experimental data obtained from acid/base titrations and adsorption batch experiments sea sand composition affects the acid/base and the adsorption properties of the adsorbents. The extraordinary high affinity of N_SS for hexavalent uranium in the alkaline pH region can be attributed to the formation of mixed U(VI)–carbonato surface species on the FeOOH crystall phases present in N_SS, which effectively compete the formation of U(VI)–carbonato complexes in solution. On the other hand, data obtained by adsorption experiments carried out in solution of different ionic strengths don’t differ significantly from one another indicating the formation of inner-sphere complexes. Finally, the adsorption on sea sands is a relatively fast two-step process.     

Behavior of long-lived radionuclides in the Danube river ecosystem in Serbia

Summary Radioactivity of water and sediments from the Danube river in its course through Serbia during 2001-2003 years has been tested by alpha- and gamma-ray spectrometry. Except for cesium originating from Chernobyl, the radioactivity level of water and sediment coincide with the content of natural radionuclides in the environment of rivers basin. No increase in the radioactivity of sediments, due to slowing down of the water flow, was observed. The obtained results were analyzed in accordance with the model which considers only naturally occurring radionuclides originating in river sediment. The distribution coefficients for natural radionuclides are determined.     

Identification of N,N-dimethyltryptamine and beta-carbolines in psychotropic ayahuasca beverage

Recently many people have shown great interest in traditional indigenous practices and popular medicine, involving the ingestion of natural psychotropic drugs. We received a request to analyze and determine the nature of a dark green liquid with a dark brown plant sediment, which the police had seized at an airport and inside the home of a person belonging to the 'Santo Daime' religious movement. Gas chromatography/mass spectrometry analysis of the extract identified N,N-dimethyltryptamine, a potent hallucinogen, and the beta-carboline alkaloids harmine and harmaline, revealing monoamine oxidase A-inhibiting properties. These substances are typical components of Ayahuasca, a South American psychotropic beverage obtained by boiling the bark of the liana Banisteriopsis caapi together with the leaves of various admixture plants, principally Psychotria viridis.     

Investigation of U(VI) desorption behavior from natural sediment,Oak Ridge

Investigation of U(VI) desorption from the natural sediment of Oak Ridge Field Research Center saprolite is of great importance to predict the fate and transport of U(VI) in the subsurface environment. After treatment by the dithonite- citrate-bicarbonate method, only 20% of U(VI) was extracted by 0.1 mol/L HNO₃ solution, indicating that the predominate adsorbed carrier of U(VI) in natural sediment was iron (hydr)oxides. Further evidence collected through a high resolution TEM investigation such as goethite observed in clay minerals. The desorption of U(VI) from PRFRC saprolite was satisfactorily fitted by surface complexation modeling at a low NaHCO₃ concentration starting from 0.001 to 0.1 mol/L, whereas appreciable over-estimation was observed at high concentrations of NaHCO₃. The uncertainty analysis method used in this study was an expanded uncertainty analysis method, and estimates with a 95% confidence interval (c) were obtained for these test data points. These observations revealed that the goethite with clay minerals played the vital role in U(VI) sorption and desorption behaviors in subsurface sediments.     

µ-X-ray fluorescence and µ-X-ray diffraction investigations of sediment from the Ruprechtov nuclear waste disposal natural analog site

Results from combined µ-XRF and µ-XRD investigations of a uranium-rich tertiary sediment from a nuclear repository natural analog site in Ruprechtov, Czech Republic, are reported. The goal of the investigations is to identify arsenopyrite from diffraction patterns obtained in As-rich areas of the sample. Arsenopyrite has been revealed to be present in the sediment as thin coatings on the surface of Fe nodules from previous µ-XANES results and observed linear dependencies between Fe and As(0) distributions obtained from µ-XRF measurements. In thin sections of the sediment investigated here we find, however, neither diffraction reflections expected for arsenopyrite nor for other As-sulfides. The As(0) phase is likely present in the form of very small grains, or it is amorphous. Statistical analysis of the µ-XRD data using unsupervised classification and principle component analysis from selected sample areas also indicate that pyrite and siderite, but no arsenopyrite, are the sole diffracting phases. That pyrite and siderite are found in the same sample is an indication that the pH of the sediment environment during diagenesis must have been neutral. This allows us to refine our hypothesis for the mechanism of uranium immobilization.     

Radiological responses of different types of Egyptian Mediterranean coastal sediments

The aim of this study was to identify gamma self-absorption correction factors for different types of Egyptian Mediterranean coastal sediments. Self-absorption corrections based on direct transmission through different thicknesses of the most dominant sediment species have been tested against point sources with gamma-ray energies of ²⁴¹Am, ¹³⁷Cs and ⁶⁰Co with 2% uncertainties. Black sand samples from the Rashid branch of the Nile River quantitatively absorbed the low energy of ²⁴¹Am through a thickness of 5 cm. In decreasing order of gamma energy self-absorption of ²⁴¹Am, the samples under investigation ranked black sand, Matrouh sand, Sidi Gaber sand, shells, Salloum sand, and clay. Empirical self-absorption correction formulas were also deduced. Chemical analyses such as pH, CaCO₃, total dissolved solids, Ca²⁺, Mg²⁺, CO₃^2?, HCO₃^? and total Fe²⁺ have been carried out for the sediments. The relationships between self absorption corrections and the other chemical parameters of the sediments were also examined.     

Sorption interaction of phenanthrene with soil and sediment of different particle sizes and in various CaCl2 solutions

The objective of this investigation is to evaluate the influences of natural sorbent particle size and system Ca(2+) concentration on sorption of low-polarity organic chemicals. The physicochemical properties of the different particle size soil and sediment subsamples and the surface characters of the soil and sediment samples in various CaCl(2) concentrations were determined. The sorption behavior of phenanthrene (PHN) on the subsamples of different particle size and to the samples in various CaCl(2) solutions was examined. Batch experiments demonstrate that the sorption capacities increase with decreased particle size for both soil and sediment. It is presumably due to the higher total organic carbon (TOC) content for the finer particles. But the enhancements in sorption coefficients are not met with the equal increases in TOC contents. The effect of Ca(2+) on PHN uptake is strong in short contact time but slight in long contact time. With increasing Ca(2+) concentration, the sorption capacities for Beizhai soil increase first in the low Ca(2+) concentration range, and then decline. Nevertheless, the increase of Ca(2+) concentration greatly reduces the uptake of phenanthrene on Guanting sediment over the overall measured range. The different physicochemical properties, such as dissolved organic carbon (DOC) content, mineral and element composition, and surface characters, between soil and sediment may result in this discrepancy.     

Modified superheated water extraction of pesticides from spiked sediment and soil

In this study a laboratory-made superheated water system was applied in order to extract some pesticides from sand, sediment and soil samples. Extraction efficiencies were investigated at different time intervals with regard to temperature, type and amount of organic modifier. Pesticides were removed from the aqueous extract using dichloromethane as a trapping solvent. The optimal extraction temperature from sand specimens for malathion, heptachlor, aldrin, dieldrin, butachlor, metalaxyl and propiconazole was found to be 160 °C, while those for chlordane and thiobencarb were 120 °C and 180 °C, respectively. The static extraction time for heptachlor, aldrin, dieldrin, butachlor and metalaxyl was found to be 15 min, whereas for malathion and thiobencarb it was 5 min, and for chlordane and propiconazole it was 10 and 20 min, respectively. Recoveries for the extractions of the pesticides from sand under optimized extraction conditions ranged between 96 and 101%. Those obtained from sediment under such conditions were unsatisfactory, and were consequently improved by adding an organic modifier to the superheated water, and sodium chloride to the extract during liquid-liquid extraction. These procedures were optimized further for the parameters described and recoveries exceeded 91%, with the exception of butachlor. The extraction technique was also applied to soil samples at a reduced water flow rate of 0.5 mL min⁻¹, yielding recoveries of 82–105%, and 76% for dieldrin. The reproducibilities, expressed as relative standard deviations (RSDs), ranged between 2 and 13%.     

EPXMA survey of shelf sediments (Southern Bight, North Sea): A glance beyond the XRD-invisible

Shelf sediments of the southern North Sea, were studied with a microanalytical [electron probe X-ray microanalysis (EPXMA)] and two bulk [X-ray diffraction (XRD) and X-ray fluorescence (XRF)] techniques. The investigation proved that the promptness of the microanalytical method is combined with a reasonable analytical reliability. XRD studies of such a type of sediments with monotonous mineral composition are not able to provide mineralogical information beyond the main well-crystalline minerals and the mineralogical quantitative characteristic of the sediment based on XRD estimations are incorrect. The EPXMA mineralogical interpretations are based on the statistical evaluation of a huge data set (thousands of mineral particles) and provide a rather correct quantitative determination of the main minerals. The comparative EPXMA-XRF study revealed that the Al, Si, K, Ca, Fe and to some extent Ti contents estimated by EPXMA are fairly reliable. In this respect the accuracy of the EPXMA-based mineral identification of the pure silicates, pure aluminosilicates, and Al-, Ca-, Fe- and Ti-containing minerals with simple composition is very high. Mg-calcite, augite and apatite determinations are assessed to be correct. The supposed accuracy of the clay mineral determinations is slightly lower (70-80%) than that of the other main minerals due to the complex and varying composition of the clays. The identification of XRD-invisible accessory minerals and quantification of their presence in the sediments is an essential advantage of the EPXMA, which makes it a useful approach in tracing the origin of the sediments, the pathways of their transport and the geochemical processes they have undergone.However, the EPXMA has several flaws, which need to be solved in the future sediment investigations: (1) calibration with natural standards is needed in order to provide a higher accuracy of the mineral determinations; (2) any EPXMA study of sediments needs to be secured with XRF examinations of selected samples since EPXMA gives only semi-quantitative information about the abundance of the elements; (3) ultra-thin window EPXMA of low-Z elements has to be used since some of them (O, C) are always present in the main sediment components: silicates, aluminosilicates, carbonates and metal oxyhydroxides; (4) the interpretations of the clay fraction have to be supported with detailed XRD investigations of selected samples, while the mineralogy of the silt and sand fractions needs to be backed up with optical microscopy studies. The information from different analytical techniques (EPXMA with XRF-XRD-optical microscopy of selected samples) combined with the knowledge about the most possible minerals in a given environment, would give the most reliable results in studying mineralogical composition of shelf sediments.     

Multivariate Observations of the Distribution of Polychlorinated Biphenyls in Environmental Compartments of Two Harbours

Abstract

The objectives of this study were to identify, classify and categorize polychlorinated biphenyl (PCB) residues in samples collected from the Hamilton and Wheatley Harbour environmental compartments. The study is built around the use of a principal components analysis method, namely the soft independent modelling of class analogy (SIMCA) technique. This multivariate method is widely used for evaluating differences and observing similarities among multiple objects. The results obtained from this work confirm that the gas chromatographic data sets obtained with the samples provide a good approximation of the pattern derived from a determination of the composition of commercial Aroclors in water, sediment and biota samples. The data analysis technique provides insight into the origin of PCB contamination in environmental samples and indicates pathways for the environmental degradation or bioaccumulation of PCBs. This investigation contributes some evidence that multivariate reduction techniques are suitable for the investigation of complex data sets in environmental studies.     

Determination of U isotope ratios in sediments using ICP-QMS after sample cleanup with anion-exchange and extraction chromatography

The determination of uranium is important for environmental radioactivity monitoring, which investigates the releases of uranium from nuclear facilities and of naturally occurring radioactive materials by the coal, oil, natural gas, mineral, ore refining and phosphate fertilizer industries, and it is also important for studies on the biogeochemical behavior of uranium in the environment. In this paper, we describe a quadrupole ICP-MS (ICP-QMS)-based analytical procedure for the accurate determination of U isotope ratios (²³⁵U/²³⁸U atom ratio and ²³⁴U/²³⁸U activity ratio) in sediment samples. A two-stage sample cleanup using anion-exchange and TEVA extraction chromatography was employed in order to obtain accurate and precise ²³⁴U/²³⁸U activity ratios. The factors that affect the accuracy and precision of U isotope ratio analysis, such as detector dead time, abundance sensitivity, dwell time and mass bias were carefully evaluated and corrected. With natural U, a precision lower than 0.5% R.S.D. for ²³⁵U/²³⁸U atom ratio and lower than 2.0% R.S.D. for ²³⁴U/²³⁸U activity ratio was obtained with less than 90 ng uranium. The developed analytical method was validated using an ocean sediment reference material and applied to an investigation into the uranium isotopic compositions in a sediment core in a brackish lake in the vicinity of U-related nuclear facilities in Japan.     

Rate of sedimentation in the Yamuna river around Delhi using the226Ra−210Pb method

For six sediment cores collected from Yamuna river (tributary of Ganges) around Delhi, rate of sedimentation was determined by the²²⁶Ra–²¹⁰Pb method. While an average rate of 42 mm/y is obtained, there are variations core to core. A clear-cut downstream increase in the rate, from 5 mm/y when the river enters Delhi, to 80 mm/y when it leaves Delhi, indicates solid waste contribution from the urban areas. The sediment flux of 4000 mg/cm²/y is not balanced by the calculated rate of erosion (40 tonnes/km²/y) in the river. Thus, much of the sediment flux is of local origin.     

Trace elements distribution in Antarctic sediments by neutron activation analysis

In the present investigation iron and trace elements were determined by instrumental neutron activation analysis in a number of sea bottom sediment samples, collected in the Ross Sea and close to the Italian Station at Terra Nova Bay in Antarctica. Full listing of results is presented and discussed as well as the evaluation of precision and accuracy. In order to find correlations and similarities among the sediment samples, the analytical data were submitted to statistical treatment. In addition rare earth element patterns were obtained. Typical trends were observed with no evident Eu negative anomaly and a depletion of heavy rare earth elements.     

Determination of oxytetracycline residues in matrixes from a freshwater recirculating aquaculture system

This paper describes related procedures to determine the amount of oxytetracycline (OTC) present in trout tissue (muscle with skin attached), biofilter sand, sediment, and tank water from a recirculating aquaculture system. OTC was extracted from the matrixes by different techniques, depending on complexity of the matrix and desired OTC detection level in that matrix. Listed in order of increasing complexity, OTC was extracted from tank water by dilution with acidic buffer containing ethylenediaminetetraacetic acid (EDTA); from biofilter sand by shaking with 0.1 N HCl; from sediment by homogenization and shaking with buffer/EDTA; and from ground trout by homogenization and shaking with buffer/EDTA (twice), with further cleanup and concentration of the extract on a polymeric solid-phase extraction cartridge. The 4 procedures all used the same reversed-phase gradient chromatography on a polymeric column with UV detection at 350 nm. The lower limit of detection (estimated) and upper limit of validation for each of these 4 matrixes were 0.04-4.0 microg/g (ppm; trout), 0.03-20 ppm (biofilter sand), 1-6000 ppm (sediment), and 0.003-10 ppm (water). Recoveries ranged from 82 to 108%, with relative standard deviation <20% over the applicable concentration ranges. These procedures were used to monitor OTC residues resulting from medicated feed administered to rainbow trout in a recirculating aquaculture system.