137Cs in Biota and Sediment Samples from Turkish Coast of the Black Sea, 1997–1998

During the periods of 1997–1998, macroalgae, sea snail, mussel, fish and sediment samples were collected from different stations at Turkish Black Sea coast in order to determine activity levels of ¹³⁷Cs radionuclide. ¹³⁷Cs activity in the tested algae species and in soft parts of mussel and sea snail, were found to be below the lower limit of detection. On the other hand, the ¹³⁷Cs concentration in muscle tissue of the sea snail samples were found from 6±2 to 19±7 Bq·kg^–1 dry weight. The range of the ¹³⁷Cs concentration in anchovy fish muscles were found between 4±2 – 10±5 Bq·kg^–1 dry weight. The ¹³⁷Cs concentration in the whiting fish muscle was found below the lower limit of detection. However, this activity found in shad fish muscle to be 25±10 Bq·kg^–1 dry weight. The concentrationsof the ¹³⁷Cs activity in the sediment samples proved that the eastern region of the Black Sea was affected by Chernobyl at a very high degree compared with the western part. The measured ²³⁸U, ²³²Th and ⁴⁰K concentrations in sediment samples are within the range of the cited values in the previous works at the Turkish Black Sea coast.     

Polychlorobiphenyls in Antarctica

The presence and the distribution of polychlorobiphenyls (PCBs) in Antarctic environmental components and the effect of the seasonal formation/melting process of pack ice on the pollution level of seawater were investigated. Seawater, marine, and lake sediment and soil samples were collected in a large area of the Ross Sea and Victoria Land during the 1988–1989, 1989–1990, 1990–1991, and 1991–1992 Italian expeditions. The results obtained highlighted a low and quite homogeneous PCB contamination of the studied area. Surface seawater samples from Gerlache Inlet and Wood Bay showed a typical PCB concentration of 130 pg/liter, and an increase after pack ice melting of about 30–40%. Marine sediment, lake sediment, and soil samples showed normalized mean PCB contents of 150, 240, and 130 (pg/g)/(m²/cm³), respectively.     

Plutonium concentration distribution in bed load sediment samples along the Romanian sector of the Danube river and the Black Sea coast

The concentrations of²³⁸Pu and^{239, 240}Pu were determined in 12 sediment samples collected from the bed of the Romanian Danube river and Black Sea coast during June–September 1994. After the sample material has been properly prepared and²⁴²Pu tracer added, plutonium was separated from americium and curium by anion exchange. After electrodeposition on stainless steel discs the elements were counted with an -spectrometry system with silicon surface-barrier detectors. The^{239, 240}Pu concentrations range between 150 and 800 mBq kg^–1 dry, while the²³⁸Pu concentrations rise up to max 150 mBq kg^–1 dry. Although the chemical yields are rather low (51%) we appreciate the results as valuable since they report for the first time the distribution of the plutonium contamination along the Danube river and the Black Sea coast-Romanian sector.     

Dietary intake of zinc and selenium in Turkey

It is known that in the Turkish soil Se and Zn concentrations are somewhatlower than in other countries. Lower zinc intake causes significant healthproblems mostly at rural areas. Six different population groups, total of55 subjects, consisting of children, people from rural areas, university studentsand staff members were selected and diet samples were collected by duplicateportion technique. Bread and flour samples were collected from six differentbakeries in Ankara. Zinc, selenium and other trace elements in these sampleswere analyzed mostly by INAA. Daily dietary zinc intake differs among differentgroups, ranging 5–13 mg Zn/day, and for all cases, it is lower thanRDA value of 15 mg Zn/day. Similarly, selenium daily intake is around 20–53µg Se/day, which is also lower than RDA value of 55–70 µgSe/day.     

Diffuse and internal reflectance spectroscopy for the determination of trace metals in powdered solids: cobalt and copper collected with zinc tetrathio-cyanatomercurate

Small amounts of cobalt and copper can be determined directly, after coprecipitation with zinc tetrathiocyanatomercurate, by diffuse reflectance spectroscopy. The limits or detection are about 1 μg of metal per 40 mg of collector; if 100–200-ml sample volumes are available, 5–10 ng of metal ion per ml can be determined, but these limits are improved by about 50 % if the powdered solid samples are wetted before measurement.     

Use of atomic absorption spectrometry for the determination of metals in sediments in south-west Louisiana

The relatively recent introduction of atomic absorption spectrometry has produced a rapid and relatively inexpensive method for the determination of metal concentrations in a wide variety of samples. One such application is in the determination of metal concentrations in soils and sediments. Soils and sediments represent concentrated reservoirs for these metals that serve as sinks for introduced trace metals or can become environmental sources. The coastal zone of Louisiana provides a ‘living laboratory’ to investigate the mechanisms of transport, deposition, and dissolution of trace metals into this fragile environment. Investigations done in the coastal zone have found trace metals tend to concentrate near pollution inputs and sources and have not migrated to or significantly impacted the coastal zone of Louisiana. Common trace metals determined and their range of concentrations in coastal soil and sediments are chromium (10–30 ppm), copper (10–25 ppm), iron (0.6–2.1%), manganese (200–600 ppm), nickel (6–20 ppm), lead (8–20 ppm), and zinc (30–55 ppm).     

Polonium concentration distribution in bed load sediment samples along the Romanian sector of the Danube river and the Black Sea coast

The concentrations of²¹⁰Po have been determined in 12 sediment samples collected from the bed of the Romanian Danube river and the Black Sea coast during June–September 1994. After the sample preparation and the addition of the²⁰⁸Po tracer, polonium was coprecipitated with manganese dioxide, the precipitate was dissolved in hydrochloric acid and the polonium isotopes deposited on silver planchettes were counted by -spectrometry. The resolution of the subsequent -spectra was typically 40 to 60 keV full-width-half-maximum with 450 mm² silicon surface-barrier detectors at 30% counting efficiency. The procedure is quite fast, giving chemical yields between 60 and 80%. The²¹⁰Po concentrations range between 5 and 73 Bq kg^–1 dry, showing for the first time the polonium contamination distribution along the Romanian sector of the Danube river and the Black Sea coast.     

Examination of the modified monostandard method in neutron activation analysis

The reproducibility, the small scale as well as the large scale variability of¹³⁷Cs extracted sequentially from the soil by using a modified Tessier procedure was investigated at several grassland sites in Bavaria/Germany and in the Chemobyl area. Because undisturbed grassland soils are never homogeneous with respect to their soil properties, all sequential extractions at the German sites were carried out at each plot separately for different soil layers (e.g., 0–2, 2–5, 5–10, 10–15, 15–20 and 20–30 cm). The results show that the coefficients of variation (CV) for the reproducibility of the extraction procedure for¹³⁷Cs was (with some exceptions) around 10–20% for all fractions. For the small scale variability of¹³⁷Cs (samples within an area of 10×10m²) the values for theCV were (again with a few exceptions) in the same range. Compared to that, the large scale variability of extractable¹³⁷Cs (random soil samples within an area of 100×200 km²) was higher for all fractions, even though only moderately. The implications of these results with respect to a sampling design are discussed.     

Assessment of heavy metals pollution in Sudanese harbours along the Red Sea Coast

The levels of some heavy metals in sediments of two harbours along the Sudanese Coast of the Red Sea were examined and reported for the first time. A total of thirty-six surface sediment samples were collected from Port-Sudan and Sawakin harbours. Part of each sample was partitioned into five fractions with grain-size ranges of 1000–500, 500–250, 250–125, 125–63 and less than 63 μm. The Mn, Fe, Ni, Cu, Zn and Pb concentration in bulk samples and sub-samples were determined by atomic absorption spectrophotometry. The spatial distribution pattern of heavy metal content of crustal origin in the sediments is more uniform in Port-Sudan harbour than in Sawakin harbour. The granulometric normalization revealed that some sites in Port-Sudan harbour and one site in Sawakin harbour have been exposed to different levels of heavy metal contamination, which probably originated from ships, industrial and domestic activities.     

A test method for determining palladium in chloride solutions on the solid phase of a fibrous anion exchanger

The sorption of palladium(II) from chloride solutions on polyacrylonitrile fiber filled with the AV-17 anion exchanger (PANF-AV-17) and its subsequent determination with p-nitrosodiethylaniline on the solid phase were studied. The results of determining palladium with this reagent on the solid phase of polyacrylonitrile fiber filled with the KU-2 cation exchanger and the AV-17 anion exchanger were compared. A test method was developed for determining palladium on the PANF-AV-17 solid phase. Sorption was performed in the batch mode; the analytical signal was estimated by measuring the diffuse reflection coefficient or visually using a color scale. The detection limit was 0.005 µg/mL; the range of the calibration scale was 0–0.2 µg/mL at the volume of the test solution 10–20 mL. The accuracy of the procedure was verified by the added-found method in the analysis of tap water and a standard reference sample of natural sodium chloride water. The relative standard deviation was no more than 25%; the time of the analysis of 5 or 6 samples was 25–30 min.Translated from Zhurnal Analiticheskoi Khimii, Vol. 60, No. 1, 2005, pp. 85–90.Original Russian Text Copyright © 2005 by Dedkova, Shvoeva, Savvin.     

Material transport between the atmosphere and sediment of the Lake Balaton

A monitoring system was developed to gain information on the present level of pollutants in the Lake Balaton, Hungary. Determination of 13 polycyclic aromatic hydrocarbons (PAHs) and inorganic pollutants (mostly toxic metals) in aerosol, precipitation and sediment samples was carried out. The aim of collecting aerosol and precipitate samples in the same site at the same period was to determine the distribution of elements in two depositions. For the fractionation by particle size, aerosols were sampled by a cascade impactor. A simple three-stage sequential leaching procedure was applied to establish the distribution of metals among environmentally mobile, bound to carbonates and oxides, and environmentally immobile, (bound to silicates) fractions in aerosols. Sediment samples were collected from 17 different sites inside of the lake and 10 sites at harbors at 30–70 cm in depth. Core samples were cut to 10-cm pieces, dried at room temperature, and finally passed through a 63-μm sieve. Total concentrations of elements were determined by atomic absorption spectrometry (AAS) after an acidic digestion. The concentrations of PAHs were determined by HPLC method with fluorescence detection.In aerosol samples collected from September 6, 2002 to January 26, 2003, concentration of Cd was <0.1 μg/m³, and the majority of Cd has been found in the mobile fraction. Cadmium was associated to particles between 0.25 and 2 μm indicating the anthropogenic origin. Similar distribution of Pb was obtained in all seasons, and the highest concentration of Pb was found as 8.6 ng/m³ in particle size of 0.7 and 1.4 μm. Results of total concentration of elements of bottom sediments of the Lake Balaton and harbors were compared to Interim Sediment Quality Guideline (ISQG) values and the Probable Effect Level (PEL) values. Data showed that the average concentrations of elements were usually less than those of ISQGs and other background data for soils and geochemical values. The sediment is not polluted and its disposal is feasible. There is no direct correlation between the concentration of elements deposited onto the surface of the lake from dry and wet deposition and the upper part of the sediment. So, from the budget of the deposition, the concentration of elements in the upper layer of the sediment cannot be predicted.Seasonal changes of the concentration of PAHs in aerosol was observed, samples collected at winter contained the highest values. In December–January 2002/2003, the wet deposition was found as 64 μg/m² period. Among the individual compounds, the wet deposition rate of phenantrane, fluoranthene and pyrene was dominant, while for dry deposition, these compounds were fluoranthene and pyrene. The concentrations of ∑PAHs found for all sites and depth of sediment samples ranged from 11 to 1734 μg/kg dry weight with an average of 132 μg/kg. These values represent a quite low pollution level compared to other sediment with anthropogenic influence. Based on the results, it can be definitely confirmed that the chemical quality of the water and sediment of the Lake Balaton is satisfactory.     

Determination of mineral constituents in duplicate portion diets of two university student groups by instrumental neutron activation

Concentrations of 15 elements were determined simultaneously in duplicateportion diets of two university student groups from So Paulo Universityconsisting of nine women (20–23 years) and ten men (20–24 years).Thediet samples were prepared by either freeze-drying or drying in a ventilatedoven. About 100–200 mg of diets were irradiated for 2 minutes and 8hours in the IEA-R1m research reactor and Br, Ca, Cl, Co, Cr, Cs, K, Fe, Mn,Mg, Mo, Na, Rb, Se, and Zn were determined by instrumental neutron activationanalysis (INAA). The average daily intakes found in the women and men groupswere: 2.1 and 4.3 mg of Br, 501 and 707 mg of Ca; 3.1 and 6.0 g of Cl; 12and 25 mg of Co; 15 and 36 µg of Cs; 53 and 63 µg of Cr; 5.1 and10.8 mg of Fe; 1.3 and 2.8 g of K; 134 and 306 mg of Mg; 1.3 and 4.1 mg ofMn; 134 and 302 mg of Mo, 2.0 and 4.1 g of Na; 2.4 and 4.6 mg of Rb; 29 and41 µg of Se; 6.2 and 10.6 mg of Zn, respectively. The daily intakesof Ca, Se and Zn in both groups and Fe in the women groups appeared to bebelow the U.S. RDA recommendations. For the elements Na and Cl the daily intakeswere higher than the recommended values by RDA.     

Comparison of GC/MSD and GC/AED for the determination of organotin compounds in the environment

Summary Methods are described for the analysis of environmental samples like water, sediment and suspended matter for the determination of all organotin compounds (OTs) that are currently used as biocides: tributyltin (TBT), triphenyltin (TPT), tricyclohexyltin (TCT) and fenbutatin oxide (FBTO). In water also five degradation products (di and mono substituted analogs) can be determined. Alkylation using a Grignard reagent was used to obtain OT derivatives amenable to gas chromatography (GC). Both methylation and pentylation have been employed for derivatization prior to GC analysis. The present results show that derivatization efficiencies for TPT, TCT and FBTO at trace levels are higher using methylation than pentylation. Detection limits for each type of sample matrix were determined using GC/Mass Selective Detection (GC/MSD) and GC/Atomic Emission Detection (AED). In sediment and suspended matter only tri-substituted OTs (i.e. the parent compounds) could be determined. Detection limits ranged from 0.2 to 10 ng/g dry weight. FBTO, not previously detected in environmental samples, was found at levels of 4 and 11 ng/g in a suspended matter sample and a sediment sample, respectively. In water the OTs and their degradation products were determined at levels of 1–10 ng/l (as tin) using 200 ml water samples.     

Anomalously high237Np in intertidal sediments from the Ribble Estuary in the Irish Sea

Depth profiles and inventories of²³⁷Np in sediment cores from the Ribble Estuary in the Irish Sea have been studied along with those of Pu isotopes,²⁴¹Am and¹³⁷Cs, to allow a more detailed look of anomalously high²³⁷Np content observed in this estuary previously. The comprehensive data obtained showed that the depth profiles of both²³⁷Np contents and²³⁷Np/^239,240Pu activity ratios were clearly different from those of^239,240Pu,²⁴¹Am, and¹³⁷Cs and their activity ratios. As much as 80–90% of²³⁷Np inventories (0.32–1.06 kBq/m²), found in three cores, were estimated to be derived from a source other than Sellafield, on the basis of comparison of the²³⁷Np/^239,240Pu inventory ratio (0.65–1.74%) found in the Ribble Estuary cores with those (0.10–0.16%) in the Ravenglass Estuary cores.     

Trace and minor elements in four commercial honey brands

Instrumental neutron activation analysis was used to measure the concentrations of 24 elements in four honey brands commercially available in Austin, Texas (USA). The measured elements (and concentration) were: As, (<30 ng/g); Ba, (<2 g/g); Br, (0.24–0.49 g/g); Ce, (<20 ng/g); Co, (9–180 ng/g); Cr, (37–64 ng/g); Cs, (<3–45 ng/g); Fe, (<4–15.9 g/g); Hf, (<3 ng/g); Hg, (1 ng/g); K, (91–230 g/g); La, (<4 ng/g); Na, (20.3–25.3 g/g); Ni, (0.39–0.77 g/g); Rb, (68–340 ng/g); Sb, (13–61 ng/g); Sc, (<0.3–200 ng/g); Se, (<20 ng/g); Sm, (<9 ng/g); Sr, (<2 ng/g); Th, (<4 ng/g); U, (<30 ng/g); Zn, (3.36–4.61 g/g); and Zr, (<0.5–0.84 g/g). The results obtained were compared to the concentration of the same elements in honey produced or commercially available in Turkey, Mexico, El-Salvador, China, Czechoslovakia and Yugoslavia.     

Determination of 5-fluorouracil in hospital effluents

Cytostatic anticancer drugs are an increasingly important issue in the environmental debate, mainly due to the lack of knowledge about the fate of these toxic substances. Over the last decades, 5-fluorouracil (5-FU) has been one of the most frequently used antineoplastic agents and may, therefore, be regarded as one of the pilot substances for environmental contamination. As a prerequisite for these investigations, a method for the determination of 5-FU in hospital effluents has been developed. Waste water samples were enriched by solid-phase extraction on ENV⁺ columns (concentration factor 500) and analysed by capillary electrophoresis using a buffer containing 80% 160 mM sodium borate buffer (pH 9.5) and 20% acetonitrile (v/v). This method is applicable within the range 5–500 g 5-FU L^–1. The standard curve (correlation coefficient >0.99) was linear with recovery rates from 80 to 96% and an accuracy from 9.0 to 20% (intra-assay standard deviation 0.7–8.9%; inter-assay standard deviation 2.2–9.5%). Based on the consumption of 5-FU in oncologic departments and the detection limit of 1.7 g L^–1, this method covers the range necessary to evaluate 5-FU in hospital effluents. The applicability of the method was proven by chemical analysis of real hospital waste water samples. Obtained over a time period of 1 month (range 20–122 g 5-FU L^–1), the results were similar to those calculated by an input–output model. The presented method provides an analytical tool necessary to face the monitoring of environmental contamination problems.Abbreviations 5-FU 5-Fluorouracil - OECD Organization for economic cooperation and development     

Quality control in the analysis of lead and cadmium in blood

Summary An extensive quality control programme has been developed within a global UNEP/WHO project on Assessment of Exposure to Lead and Cadmium through Biological Monitoring. This project was coordinated by the Karolinska Institute (Department of Environmental Hygiene) and the National (Swedish) Institute of Environmental Medicine. The project was carried out within the framework of UNEP's Global Environmental Monitoring System (GEMS) and was initiated in 1978 on the basis of recommendations from a UNEP/WHO meeting of a Government Expert Group on Health-Related Monitoring.On termination of the project in 1981 it was decided to extend the analytical QC assurance programme on a periodic basis in order to maintain the analytical capability of the participating laboratories. A QC programme was conducted by our Institute in a follow-up study of the above mentioned UNEP/WHO programme and for a National Swedish Board of Occupational Safety and Health project, as well as for a recently concluded project in which a decrease in bloodlead levels in residents of Stockholm for the period 1980–1984 was established.In the latter project decreased blood-lead levels of about 20% were found in samples stored frozen (–20 ° C) for 4 years. This finding stimulated a study of the long-term stability of our QC samples. Results of lead and cadmium analyses performed for each QC sample during 1980–1985 were computerized. The results showed that the QC samples appeared to be stable for 2–3 years when stored at –20 °C. The losses of cadmium were 5 –10% in 5–6 years of storage at –20 ° C and seem to be less than those of lead (7–15%). Analysis of several QC sets, prepared on different occasions, but analyzed on the same day, confirmed that losses occur.     

Simultaneous determination of copper,mercury and lead by first-order derivative spectrophotometry using dithizone as reagent

A first-order derivative spectrophotometric method has been developed for the simultaneous determination of copper, mercury and lead at g/L levels using dithizone as reagent. The procedure involves the simultaneous extraction of these elements by dithizone in chloroform from weakly alkaline solutions. Linear calibration curves were obtained in the ranges 0.5–10 (Cu), 1–10 (Hg) and 1–10 (Pb) g present in 40 ml of aqueous phase with detection limits of 5 g/L (Cu) and 20 g/L (Hg and Pb). The R.S.D.s for 100 g/L of copper, mercury and lead were 2.5, 2.6 and 3.1% respectively, for 5 determinations. The method is applicable for the determination of copper and lead in marine sediment samples with good precision and accuracy.     

Efficient radiochemical separation for the determination of plutonium in environmental samples,using a supported,highly specific extractant

A radiochemical separation procedure has been developed for a very efficient isolation of plutonium from environmental samples. Essentially, the method involves the following steps: ashing of the sample and preparation of the load solution; separation of plutonium by a column containing a commercially available, highly specific, supported extractant; electrodeposition of Pu and subsequent -spectrometry. Detailed procedures are reported for liver samples and for soil. The modifications necessary for sample sizes above 5 g dry weight and up to 200 g are also given. Recoveries of added tracers are 60–70%. The precision of the method is <10% (RSD). The accuracy was examined by analyzing also certified standard reference materials. Due to the very efficient isolation of Pu, the resulting -spectrum is virtually free of interfering -emitters of Th and U.     

Natural depuration rate and concentration of cesium-137 radionuclide in Black Sea macro algae

Cesium-137 concentrations in red, brown and green algae have been studied for the calculation of natural depuration rates. The algae species were collected from the same population of the Black Sea stations during the period of 1986–1995. The natural depuration rates are estimated as biological half-lives. The pattern of depuration results represented by a single component for each algae division. The biological half-lives of¹³⁷Cs in red (Phyllophora nervosa), green (Chaetomorpha linum) and brown (Cystoceira barbata) algae are estimated to be 18.5, 21.6 and 29.3 months, respectively.¹³⁷Cs and⁴⁰K activity levels and their ratios in algae species in two stations in Black Sea region of Turkey have been determined during the period of 1990–1995. The results showed that the Sinop region was more contaminated than the ile region on the Black Sea coast of Turkey from the Chernobyl accident.