210Pb fluxes in sediment layers sampled from Northern Patagonia lakes

Unsupported ²¹⁰Pb fluxes were determined from sediment core inventories in lakes located in Northern Patagonia, Argentina. Total ²¹⁰Pb, ²²⁶Ra, associated with supported ²¹⁰Pb, and ¹³⁷Cs specific activity profiles were measured by gamma-ray spectrometry. Unsupported ²¹⁰Pb fluxes showed very low values when compared to other regions, with a 12 fold variation, ranging from 4 to 48 Bq m^–2.y^–1. The linear correlation observed between the ²¹⁰Pb fluxes and¹³⁷Cs cumulative fluxes in sediment cores sampled from water bodies within a zone with similar precipitation demonstrated that both radioisotopes behave in the same manner in these systems concerning the processes occurred from fallout to sediment deposition, and that there are no appreciable local or regional sources of unsupported ²¹⁰Pb. Positive correlation of ²¹⁰Pb fluxes with organic matter contents of the uppermost sediment core layers was also observed.     

Mercury, zinc, manganese, and iron accumulation in leachate pond sediments from a refuse tip in Southeastern Brazil

This work evaluates Hg, Zn, Fe and Mn transfer from the leachate of a refuse tip based on their accumulation in a sediment core of 17 cm collected in a leachate pond of a small refuse tip ageing approximately 10 years. Sediment samples were digested with an acid mixture (50% acqua regia solution), heated at 70 °C during 1 h, in a thermal-kinetic reactor “cold finger”. The extract was analysed to obtain Hg content by cold vapour absorption atomic spectrometry (CVAAS). Fe, Mn and Zn contents were obtained by flame atomic absorption spectrometry (FAAS) after total decomposition of the samples. Concentration ranges along the core varied from 0.16 to 0.58 μg g^− 1; 7.3 to 145 μg g^− 1; 11.7 to 116 μg g^− 1 and 0.21% to 1.82% for Hg, Zn, Mn and Fe, respectively. All metals showed enrichment in the upper layers (above 6 cm) which probably correspond to the year 1996. Results indicated that Hg transfer is one order of magnitude higher than Zn and suggest that metals accumulation in sediments probably reduce their migration to groundwater.     

Fluorimetric determination of uranium in certain refractory minerals,environmental samples and industrial waste materials

Summary A simple sample decomposition and laser fluorimetric determination of uranium at trace level is reported in certain refractory minerals, like ilmenite, rutile, zircon and monazite; environmental samples viz. soil and sediments; industrial waste materials, such as, coal fly ash and red mud. Ilmenite sample is decomposed by heating with ammonium fluoride. Rutile, zircon and monazite minerals are decomposed by fusion using a mixture of potassium bifluoride and sodium fluoride. Environmental and industrial waste materials are brought into solution by treating with a mixture of hydrofluoric and nitric acids. The laser induced fluorimetric determination of uranium is carried out directly in rutile, zircon and in monazite minerals and after separation in other samples. The determination limit was 1 μg ^. g^-1 for ilmenite, soil, sediment, coal fly ash and red mud samples, and it is 5 μg ^. g^-1 for rutile, zircon and monazite. The method is also developed for the optical fluorimetric determination of uranium (determination limit 10 μg ^. g^-1) in ilmenite, rutile, zircon and monazite minerals. The methods are simple, accurate, and precise and they require small quantity of sample and can be applied for the routine analysis.     

Selective separation of gold from iron ore samples using ion exchange resin

Gold in iron ore samples is separated from iron (major matrix cation), antimony and vanadium using anion exchange resin in (0.2 M) HBr, potassium peroxodisulfate and acetone:water:nitric acid media. The exchangeable anion Cl⁻ of the ion exchanger Dowex 1X 4 is replaced by Br⁻ using (6 M) HBr solution. Certified reference material DGP-M1, spiked ferric magnetic oxide, gold radioactive tracer ¹⁹⁸Au and gold standard solutions are used to study the adsorption efficiency and the yield recovery of tetrabromoaurate AuBr₄⁻ from the resin. Ten eluents have been tried to elute gold from the column, and it has been found that a 10 ml potassium peroxodisulfate and 240 ml acetone:water:nitric acid [125:5:5] solution fulfills the objective. The set up of the separation procedure allows quantitative adsorption of gold by the resin, while the major matrix cation (Fe) and others (Cd, Ag, Cu, V, Sb, Ti) have been passed through the column with the feeding solution (0.2 M) HBr. The resin selectivity coefficient (K) of separating Au from Fe has been found to be K_Fe^Au≈6.4×10¹¹. The eluted Au is treated with K₂S₂O₈ and H₂O₂ for spectrophotometric determination as rhodamine-B complex at 555.6 nm. The linearity, detection limit, precision, and accuracy of the determination method have been found to be up to 2.0 μg g⁻¹, 0.018 μg g⁻¹, 0.009 μg g⁻¹ and 3%, respectively.     

Slurry-based procedures to determine chromium, nickel and vanadium in complex matrices by ETAAS

Two slurry-based ETAAS methodologies are compared to determine directly Cr, Ni and V in coal fly ash, soils and sediments: current slurry analysis (USS) and ‘slurry extraction’ (SE). Slurries for USS-ETAAS were prepared in 0.5% HNO₃. HF and HNO₃ were evaluated as chemical modifiers. HF was the extractant for the SE-ETAAS approach.A unique slurry-based procedure to measure Cr, Ni and V could not be established. Cr concentrations up to 100 μg g^{− 1} were accurately determined by USS (0.5% HNO₃; λ = 429.0 nm; LOD = 0.35 μg g^{− 1}) whereas higher contents required the SE procedure (sample grinding, 30% HF; LOD = 0.02 μg g^{− 1}). Both methods were appropriate to determine Ni (LOD = 0.11 and 0.08 μg g^{− 1}, for USS and SE, respectively). V was satisfactorily quantified only with the USS approach (LOD = 0.80 μg g^{− 1}).     

Indirect atomic absorption spectrometry (IAAS) as a tool for the determination of iodide in infant formulas by precipitation of AgI and redissolution with cyanide

A method to determine iodide in infant formula samples by indirect atomic absorption spectrometry (IAAS) was developed. The iodide in solution resulting from an alkaline digestion (Na₂CO₃–NaOH) of the sample is precipitated with silver; the precipitate is redissolved by adding cyanide solution, and this solution is subjected to GF-AAS. Temperatures of 1000 and 2100°C were selected for the ashing and atomization steps, respectively, using a mixture of Pd and Mg(NO₃)₂ as a matrix modifier (at concentrations of 36 and 16 μg ml⁻¹, respectively). The sensitivity, LOD, LOQ and characteristic mass obtained were, respectively, 1.12×10⁻² l μg⁻¹, 3.1 μg g⁻¹ and 10.4 μg g⁻¹ and 7.3 pg, referred to sample. The linear interval of concentrations extends up to 10 μg l⁻¹ of iodide, with no need to use the standard addition method; the mean R.S.D. of data within this range is 3.4%, with 2.9% over the whole procedure. No interfering effects were observed among the foreign ions studied, and 100.0% was the mean analytical recovery achieved within the linear range of concentrations. The application of the method to seven real samples gave a mean content of 12.8 μg g⁻¹ of iodide, as well as less than 3.1 μg g⁻¹ in eight other samples.     

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.     

Depth distribution of137cesium,90strontium and210lead in sediments of lake Mondsee,Austria

¹³⁷Cs,⁹⁰Sr and²¹⁰Pb were determined in sediment cores from lake Mondsee /Austria/. The depth profiles show that¹³⁷Cs remains undisturbed, i.e. its distribution corresponds to the fallout deposition pattern.⁹⁰Sr, however, has been transported into the upper sediment layers. In this upper zone nearly constant levels of⁹⁰Sr and also of²¹⁰Pb/²¹⁰Po/were found. Comparison of the⁹⁰Sr and¹³⁷Cs profiles indicates that chemical processes must be responsible for the translocation of⁹⁰Sr as well as²¹⁰Pb, and not bioturbation, i.e. mixing of upper sediment layers by benthic organisms.Dedicated to Prof. Dr. Karl Schlögl, University of Vienna, for his 60th birthday.     

Speciation analysis of selenium enriched green onions (Allium fistulosum) by HPLC-ICP-MS

Green onions (Allium fistulosum) enriched with 10 or 100 μg mL^− 1 Se(IV) or SeMet were analyzed for total selenium and species distribution. Anion and cation exchange chromatographies were applied for the separation of selenium species with mass spectrometric detection. Two different sample preparation methods (NaOH and enzymatic) were compared from the Se extraction efficiency point of view. Total selenium concentration accumulated by the onions reached the 200 μg g^− 1 level expressed for dry weight when applying SeMet at a concentration of 100 μg mL^− 1 as the source of Se. Speciation studies revealed that both in onion bulbs and leaves the predominant form of organic selenium is Se-methyl-selenocysteine (MeSeCys). When Se(IV) was applied for Se-enrichment at a concentration level of 100 μg mL^− 1 both onion leaf and bulb contained a significant amount of inorganic selenium. An unknown compound was also detected.     

Radionuclides in a sediment trap and bottom sediment samples from the eastern Turkish coast of the Black Sea

Summary Radionuclide (¹³⁷Cs, ²³⁸U, ²³²Th and ⁴⁰K) concentrations were determined in a sediment trap and bottom sediment samples collected from a station at the eastern Turkish coast of the Black Sea. The specific activity of the ¹³⁷Cs radionuclide in the settling particles ranged from 0.04±0.01 to 0.10±0.02 Bq^. g^-1dry weight. The calculated flux rate of the ¹³⁷Cs was between 0.37 and 2.59 Bq^. m^-2. d^-1in the sampling periods of 2002 and 2003. The ¹³⁷Cs concentration in the bottom sediment profile were between 0.039±0.013-9.083±0.017 Bq^. g^-1dry weight in the same station. The vertical profile of the radionuclides suggests that they have little mobility during the 17 years after the Chernobyl accident.     

Heavy metals in selected soils of the semi-arid region of Nigeria

Eight soil profiles developed on crystalline basement complex rocks in the semi-arid region of Nigeria were analyzed for total contents of cesium (Cs), chromium (Cr), cobalt (Co), hafnium (Hf), iron (Fe), lanthanum (La), lutetium (Lu), scandium (Sc), thorium (Th), uranium (U) and ytterbium (Yb). The contents range from 50.3–95.4 Cs, 16.1–58.1 Cr, 0.6–9.0 Co, 9.0–34.8 g g^–1 Hf, 0.31–3.69% Fe, 17.2–60.7 La, 60.4–90.6 Lu, 2.6–12.6 Sc, 8.3–21.5 Th, 4.7–9.2 U and 3.6–92 g g^–1, Yb. Their corresponding means were 68.4, 35.1, 4.0, 19.9 g g^–1, 1.70%, 37.1, 79.4, 6.5, 14.7, 6.7 and 5.0 g g^–1. In general, total Cs, Co, Fe, La, U and Yb increased with further increase with depth. On the other hand, Lu, Sc and Th showed no distinct vertical distribution within the profiles. All eleven elements were correlated with the amounts of clay present in the soils, the correlation being stronger for Cs, Th, Yb, Cr and Lu.     

Determination of131I,134Cs,137Cs in grass and cheese after Chernobyl accident in Austria

Various samples from Styria /grass/ and Salzburg /cheese/ were analyzed for¹³¹I,¹³⁴Cs and¹³⁷Cs concentration during April–July 1986 by -ray spectrometry. The concentrations are reported in nCi kg^–1 wet weight. The concentration values found for¹³¹I 0.2–17.2 nCi kg^–1 /grass/, 0.1–0.5 nCi kg^–1 /cheese/, for¹³⁴Cs 1.1–6.2 nCi kg^–1 /grass/, 0.2–1.3 nCi kg^–1 /cheese/, for¹³⁷Cs 1.6–15.7 nCi kg^–1 /grass/, 0.3–2.2 nCi kg^–1 /cheese/. While radioactivity of¹³¹I,¹³⁴Cs and¹³⁷Cs in cheese samples increases from May to June, it decreases in grass samples from May to July 1986.     

The210Pb and137Cs profiles in sediment cores from Bay of Quinte,Lake Ontario

²¹⁰Pb,²²⁶Ra and¹³⁷Cs profiles have been measured for sediment cores from three locations in Bay of Quinte, Lake Ontario, Canada. Compaction of the sediment with depth of burial is taken into account in calculating recent sedimentation rates and age profiles at these locations from the excess²¹⁰Pb profiles. The rates are 1.803+0.592 cm·y^–1 (0.254±0.083 g·cm^–2·y^–1), 0.101±0.017 cm·y^–1 (0.036+0.006 g·cm^–2·y^–1), and 0.795±0.218 cm·y^–1 (0.076±0.021 g·cm^–2·y^–1). The corresponding fluxes of excess²¹⁰Pb to sediment/water interface are determined to be 1.652, 0.253, and 1.123 pCi·cm^–2·y^–1, respectively. The anomalies observed in the radionuclide concentration profiles are attributed to physical mixing. It is postulated that the significantly higher flux of²¹⁰Pb observed at one of the locations is due to inputs from Trent River which joins the Bay near this location.     

Radiochronology of sediments from the Mediterranean Sea using natural210Pb and fallout137Cs

The²¹⁰Pb and¹³⁷Cs profiles of sediment cores from two locations in southern Spain, three locations in southern Turkey and two locations in northern Cyprus were determined by direct -ray spectroscopy. Sedimentation rates were derived for all locations using the²¹⁰Pb data. The rates range from 1.39±0.12 cm · y^–1 (0.50±0.04 g · cm^–2 · y^–1) to 0.08±0.01 cm · y^–1 (0.039±0.003 g · cm^–2 · y^–1). Except for one core, the¹³⁷Cs profiles were also used to compute sedimentation rates. The results are in good agreement with those of²¹⁰Pb values. The results of the Constant Initial Concenration and Constant Rate of Supply dating models are in good agreement with each other. The flux of unsupported²¹⁰Pb varies between 0.11±0.03 to 0.74±0.01 pCi · cm^–2. The average depositional flux was found to be considerably lower for cores from the Eastern Mediterranean.     

Cationic and Anionic Effects on the Glass Transition Temperature for Aqueous Electrolyte Solutions

Glass-forming composition regions of aqueous CH₃COOM (M = Li, Na, K, Rb, Cs, and Tl), CF₃COOM (M = Li, Na, K, Rb, and Cs), and Et₄NX (Et₄ = C₂H₅, X = OH, CH₃COO, Cl, Br, NO₃, and SCN) solutions are reported as a function of water concentration R (R = moles of water per moles of salt). Glass transition temperatures (T _g) were measured by a simple differential thermal analysis (DTA) method with a cooling rate of about 600 K-min^–1. The T _g of all solutions decrease with increasing R (decreasing salt concentration). It is found that T _g at the same R value decrease in the order Na⁺ > Li⁺ > K⁺ > Rb⁺ > Cs⁺ in all glass-forming composition regions of the alkali acetate salt and alkali trifluoroacetate salt solutions. T _g for Et₄NX solutions decrease in the order CH₃COO^– ~OH^– > Cl^– > Br^– > NO ₃ ^– > SCN^–. The effects of the cation and anion on the glass-forming behavior in these aqueous solutions are discussed.     

Mechanisms of Tebuconazole Adsorption in Profiles of Mineral Soils

The study attempted to identify the soil components and the principal adsorption mechanisms that bind tebuconazole in mineral soils. The K_F values of the Freundlich isotherm determined in 18 soils from six soil profiles in batch experiments after 96 h of shaking ranged from 1.11 to 16.85 μg^1−1/n (mL)^1/n g⁻¹, and the exponent 1/n values from 0.74 to 1.04. The adsorption of tebuconazole was inversely correlated with the soil pH. Both neutral and protonated forms of this organic base were adsorbed mainly on the fraction of humins. The adsorption of the protonated form increased in the presence of hydrogen cations adsorbed in the soil sorption sites. Fourier transform infrared spectroscopy coupled with the molecular modeling studies and partial least squares regression analysis indicated that the tebuconazole molecule is bound in the organic matter through the formation of hydrogen bonds as well as hydrophobic and π–π interactions. Ion exchange was one of the adsorption mechanisms of the protonated form of this fungicide. The created mathematical model, assuming that both forms of tebuconazole are adsorbed on the organic matter and adsorption of the protonated form is affected by the potential acidity, described its adsorption in soils well.     

Chitosan–magnetite nanocomposites (CMNs) as magnetic carrier particles for removal of Fe(III) from aqueous solutions

This research focuses on removal of Fe(III) from aqueous solution using chitosan–magnetite nanocomposites as potential sorbent. The presence of nanosized magnetic particles within the nanocomposites was confirmed by TEM and SAED analysis. The particles with diameter 508 μm and 84 μm, follow Frendlich sorption isotherm at 30 °C, and the Frendlich constants (K_F, 1/n) have been found to be 5.974 mg g⁻¹, 2.66 and 35.98 mg g⁻¹, 1.385, respectively. Out of various kinetic models, the experimental data for dynamic uptake of Fe(III) is best fitted on ‘pseudo-second order’ kinetic model. The linear nature of plots between log (% sorption) and log (time) is indicative of intra-particle diffusion. For the particles with diameters 508 μm and 84 μm, the value of k_id was found to be 1.78 mg l⁻¹ min^−0.5 and 2.13 mg l⁻¹ min^−0.5. The sorption mean free energy from the Dubinin–Radushkevic isotherm was found to be 7.04 kJ mol⁻¹ indicating chemical nature of sorption. The increase in chitosan content in sorbent particles is found to enhance the Fe(III) uptake. The various thermodynamic parameters have also been evaluated. Finally, the presence of Cu²⁺ ions in the sorbate is found to decrease the uptake of Fe(III).     

Comparison of GC-ICP-MS and HPLC-ICP-MS for species-specific isotope dilution analysis of tributyltin in sediment after accelerated solvent extraction

This study describes a direct comparison of GC and HPLC hyphenated to ICP–MS determination of tributyltin (TBT) in sediment by species-specific isotope dilution analysis (SS-IDMS). The certified reference sediment PACS-2 (NRC, Canada) and a candidate reference sediment (P-18/HIPA-1) were extracted using an accelerated solvent extraction (ASE) procedure. For comparison of GC and LC methods an older bottle of PACS-2 was used, whilst a fresh bottle was taken for demonstration of the accuracy of the methods. The data obtained show good agreement between both methods for both the PACS-2 sediment (LC–ICP–IDMS 828±87 ng g^–1 TBT as Sn, GC–ICP–IDMS 848±39 ng g^–1 TBT as Sn) and the P-18/ HIPA-1 sediment (LC–ICP–IDMS 78.0±9.7 ng g^–1 TBT as Sn, GC–ICP–IDMS 79.2±3.8 ng g^–1 TBT as Sn). The analysis by GC–ICP–IDMS offers a greater signal-to-noise ratio and hence a superior detection limit of 0.03 pg TBT as Sn, in the sediment extracts compared to HPLC–ICP–IDMS (3 pg TBT as Sn). A comparison of the uncertainties associated with both methods indicates superior precision of the GC approach. This is related to the better reproducibility of the peak integration, which affects the isotope ratio measurements used for IDMS. The accuracy of the ASE method combined with HPLC–ICP–IDMS was demonstrated during the international interlaboratory comparison P-18 organised by the Comité Consultatif pour la Quantité de Matière (CCQM). The results obtained by GC–ICP–IDMS for a newly opened bottle of PACS-2 were 1087±77 ng g^–1 Sn for DBT and 876±51 ng g^–1 Sn for TBT (expanded uncertainties with a coverage factor of 2), which are in good agreement with the certified values of 1090±150 ng g^–1 Sn and 980±130 ng g^–1 Sn, respectively.     

Investigation on Distribution and Risk Assessment of Volatile Organic Compounds in Surface Water,Sediment, and Soil in a Chemical Industrial Park and Adjacent Area

The occurrences, distributions, and risks of 55 target volatile organic compounds (VOCs) in water, sediment, sludge, and soil samples taken from a chemical industrial park and the adjacent area were investigated in this study. The Σ₅₅-VOCs concentrations in the water, sediment, sludge, and soil samples were 1.22–5449.21 μg L⁻¹, ND–52.20 ng g⁻¹, 21.53 ng g⁻¹, and ND–11.58 ng g⁻¹, respectively. The main products in this park are medicines, pesticides, and novel materials. As for the species of VOCs, aromatic hydrocarbons were the dominant VOCs in the soil samples, whereas halogenated aliphatic hydrocarbons were the dominant VOCs in the water samples. The VOCs concentrations in water samples collected at different locations varied by 1–3 orders of magnitude, and the average concentration in river water inside the park was obviously higher than that in river water outside the park. However, the risk quotients for most of the VOCs indicated a low risk to the relevant, sensitive aquatic organisms in the river water. The average VOCs concentration in soil from the park was slightly higher than that from the adjacent area. This result showed that the chemical industrial park had a limited impact on the surrounding soil, while the use of pesticides, incomplete combustion of coal and biomass, and automobile exhaust emissions are all potential sources of the VOCs in the environmental soil. The results of this study could be used to evaluate the effects of VOCs emitted from chemical production and transportation in the park on the surrounding environment.     

Natural radionuclides and 137Cs activity concentration in the bottom sediment cores from Kuwait Bay

Summary The activity concentration of natural radionuclides and ¹³⁷Cs in the bottom sediments cores from Kuwait Bay have been determined by γ-ray spectrometry. Particular attention was devoted to the exact determination of two uranium isotopes: ²³⁵U and ²³⁸U in order to find any presence of depleted uranium dispersed during the 1991 Gulf War. The calculated ²³⁸U/²³⁵U activity ratios for all the surface (15 cm) as well as the core profile (up to 70 cm in depth) samples were within the limit of one standard deviation close to the value of 21.5 for natural uranium. Simultaneous instrumental determination of the unsupported ²¹⁰Pb and ²²⁶Ra in a few sediment core profiles was used for quantification of sediment accumulation rates. The calculated sedimentation rates (for the constant atmospheric ²¹⁰Pb flux rate - CRS model) ranged from 0.2 to 0.6 cm ^. y^-1 and were close to the data calculated by the Weibull distribution of ¹³⁷Cs in undisturbed sediment cores.