A biomonitoring study: 210Po and heavy metals in marine organisms from the Adriatic Sea (Italy)

In various samples of marine organisms from the central Adriatic Sea ²¹⁰Po was determined by alpha spectrometry and thirteen heavy metals (Mn, Fe, Co, Cr, V, Ni, Cu, Zn, Cd, As, Sn, Hg and Pb) by energy dispersive, polarised X ray fluorescence spectrometry (EDPXRF). ²¹⁰Po activity concentration ranged between 0.3 and 44.6 Bq kg⁻¹ fresh weight. The data obtained depend upon the type of the marine organism; among the pelagic species, anchovy displayed the highest polonium concentration. Typical concentration ( \upmu \textg·\textg_(\textfresh) ^{- 1} ) \left( {\upmu {\text{g}}\cdot{\text{g}}_{{({\text{fresh}})}}^{ - 1} } \right) ranges were as follows: Mn: <1.32–1.73; Fe: 4.11–94.27; Co < 0.13–0.23; Ni: <0.13–0.52; Cu: 0.37–145.31; Zn: 0.46–16.46; Cd: <0.10–0.25; As: 0.36–60.52; Hg: <0.13–0.70; Pb: <0.13–0.35, Sn: <0.20–12.67; V and Cr were always <1.32. The data obtained are also compared with those obtained by other authors for the same organism coming from other Italian seas.     

Atmospheric deposition fluxes of <Superscript>7</Superscript>Be, <Superscript>210</Superscript>Pb and <Superscript>210</Superscript>Po at Xiamen,China

The atmospheric deposition fluxes of ⁷Be, ²¹⁰Pb and ²¹⁰Po at Xiamen were measured. The samples were collected from March 2004 to April 2005 and the sampling period was one month. The ⁷Be and ²¹⁰Pb activity were measured using HPGe γ-spectrometer after concentration using Fe(OH)₃ co-precipitation method. The ²¹⁰Po was counted with an α-spectrometer after the sample was digested and spontaneous plated onto a silver planchet. At Xiamen, the atmospheric deposition fluxes of ⁷Be varied between 0.11 and 2.93 Bq·m⁻²·d⁻¹ and the average was 1.64 Bq·m⁻²·d⁻¹; ²¹⁰Pb fluxes varied between 0.04 and 0.85 Bq·m⁻²·d⁻¹, and the average was 0.51 Bq·m⁻²·d⁻¹; ²¹⁰Po fluxes varied between 0.002 and 0.133 Bq·m⁻²·d⁻¹, and the average was 0.061 Bq·m⁻²·d⁻¹. There were positive correlations between the deposition fluxes of ⁷Be, ²¹⁰Pb or ²¹⁰Po and the amount of precipitation. The residence time of aerosols varied between 6.0 and 54.0 days with a mean of 27.1 days, which were calculated by ²¹⁰Po/²¹⁰Pb fluxes ratios.     

Assessment of <Superscript>210</Superscript>Po in foodstuffs consumed in Korea

²¹⁰Po in the daily diet in Korea was analyzed and the ingestion dose from an intake of ²¹⁰Po was estimated by considering the dietary habit of a Korean person. The ²¹⁰Po concentrations of a leafy vegetable (0.36 Bq·kg⁻¹ for lettuce) in the terrestrial food were higher than those of grain, whereas Chinese cabbage had a lesser ²¹⁰Po concentration (0.019 Bq·kg⁻¹). The ²¹⁰Po concentration of the animal product was similar to those detected in the grain and vegetable. The ²¹⁰Po concentrations in the shell and crustaceous were high from 19.1 to 33.0 Bq·kg⁻¹, however, its value fell in the overall range of the reported values. The effective dose from ²¹⁰Po for an adult from the Korean population was about 269.4 μSv·y⁻¹. Nearly 80% of the ingestion dose from the intake of ²¹⁰Po was attributed to the consumption of seafood. It suggests that the marine food ingestion is a critical pathway for natural ²¹⁰Po to the Korean population.     

Vertical distribution of <Superscript>210</Superscript>Pb and <Superscript>226</Superscript>Ra and their activity ratio in marine sediment core of the East Malaysia coastal waters

Marine sediment cores were collected from two stations at East Malaysia coastal waters on June 2004. Activity concentrations of ²¹⁰Pb in sediment core were ranged from 11 Bqkg⁻¹ to 84 Bqkg⁻¹ dry wt. for SR 01 and 4 Bqkg⁻¹ to 66 Bqkg⁻¹ dry wt. for SB 03. Meanwhile, activity concentrations of ²²⁶Ra in sediment core were varied significantly depending on the sampling location of SR 01 and SB 03 with ranged 17–26 Bqkg⁻¹ dry wt. and 8–11 Bqkg⁻¹ dry wt., respectively. The activity ratios of ²¹⁰Pb/²²⁶Ra were no significantly different at all sampling stations with an average of 1.78. Refer to the entire results; the activities of ²¹⁰Pb and ²²⁶Ra were higher at station SR 01 than station SB 03, but contrast with ratio of ²¹⁰Pb/²²⁶Ra. The reasons of different ²¹⁰Pb and ²²⁶Ra activity concentration and distribution of their ratios were strictly related to their half lives, environment origin, potential sources and behavior.     

Trace metals in mussel shells and corresponding soft tissue samples: a validation experiment for the use of <Emphasis Type="Italic">Perna perna</Emphasis> shells in pollution monitoring

The uptake of Cr, Mn, Ni, Cu, Zn, Cd and Pb in soft tissue of Perna perna mussels and their shells has been studied in aquarium experiments in which mussels were exposed for 30 or 60 days to seawater spiked with different concentrations of these contaminants (125 and 500 μg L⁻¹). Tissue samples were analyzed after acid digestion by conventional solution nebulization ICP–MS. Laser ablation ICP–MS was used for the quantitative determination of trace elements in different areas of the corresponding shells. With the exception of Mn and Zn, all other elements studied showed a significant concentration enhancements in soft tissue, with the magnitude of this enhancement following the order: Cr > Ni > Cd > Cu > Pb. A corresponding increase in most contaminants, although less pronounced, was also observed in the newly formed growth rings of mussel shells, contributing to the validation of Perna perna mussel shell as a bioindicator of toxic elements.     

<Superscript>210</Superscript>Pb and <Superscript>137</Superscript>Cs dating of sediments from Zigetang Lake,Tibetan Plateau

Zigetang Lake located in the central Tibetan Plateau was selected for the purpose of understanding of recent sedimentation rates. Based on ¹³⁷Cs dating marker, the sediment rate was 0.077 cm·yr⁻¹. The sedimentation rate was calculated to be 0.071 cm·yr⁻¹ and 0.029 g·cm⁻²·yr⁻¹ on the basis of ²¹⁰Pb CIC model. ²¹⁰Pb CRS model was also used for understanding of recent sedimentation change. The sediment accumulation rates for the CRS model ranged from 0.022 to 0.038 g·cm⁻²·yr⁻¹ with an irregular high value of 0.12 g·cm⁻²·yr⁻¹ around 1932 at Zigetang Lake core in the past eighty years.     

Vertical inventories and fluxes of <Superscript>210</Superscript>Pb, <Superscript>228</Superscript>Ra and <Superscript>226</Superscript>Ra at southern South China Sea and Malacca Straits

Inventories and fluxes of ²¹⁰Pb, ²²⁸Ra and ²²⁶Ra were determined in sediment cores collected at nine stations covering of the southern South China Sea and Malacca Straits with the thickness of water column between 42 and 83 m depth. The inventories of ²¹⁰Pb, ²²⁸Ra and ²²⁶Ra were calculated range from 0.15–2.55 Bq cm⁻², 0.05–0.40 Bq cm⁻² and 6.83–83.63 Bq cm⁻², meanwhile the fluxes ranged from 0.005–0.079 Bq cm⁻² yr⁻¹, 0.009–0.048 Bq cm⁻² yr⁻¹ and 0.003–0.037 Bq cm⁻² yr⁻¹, respectively. The results show that the highest inventories and fluxes for ²¹⁰Pb, ²²⁸Ra and ²²⁶Ra were found at station WC 01 and EC 05. Because there are additional sources of ²¹⁰Pb, ²²⁸Ra and ²²⁶Ra, where water transport will brings more dissolved isotopes, influence of the transportation and deposition of suspended particles, fast rate of regeneration and greater production of those radionuclides and others.     

Distributions of <Superscript>210</Superscript>Po and <Superscript>210</Superscript>Pb radioactivity in the intermediate layer of the northwestern North Pacific

The distributions of ²¹⁰Po and ²¹⁰Pb in the intermediate layer (400–2000 m) of the northwestern North Pacific were determined to elucidate the export flux of particulate matter. ²¹⁰Po generally showed depletion relative to ²¹⁰Pb in the intermediate layer, suggesting that ²¹⁰Po was scavenged by particles. Because the removal rate constants of ²¹⁰Po in the western region were higher than those in the eastern region and this trend coincided with that of the particle fluxes in the surface layer, the export production in the surface layer was assumed to influence the particle flux in the intermediate layer of the northwestern North Pacific.     

Contamination assessment of heavy metal in surface sediments of the Wuding River, northern China

The heavy metal contents and the contamination levels of the surface sediments of the Wuding River, northern China, were investigated. Heavy metal concentration ranged in μg g⁻¹: 50.15–71.91 for Cr, 408.1–442.9 for Mn, 20.11–43.59 for Ni, 17.51–20.1 for Cu, 68.32–89.57 for Zn, 0.2–0.38 for Cd and 15.08–16.14 for Pb in the Wuding River sediments. The enrichment factor (EF) and the geo-accumulation index (Igeo) demonstrated that the sediments of the Wuding River had been polluted by Cd, Cr and Ni, which mainly originated from anthropogenic sources, whereas the sediments had not been polluted by Zn, Pb, Cu and Mn, which were derived from the crust. In addition, the assessment results of EF and Igeo suggested that the sediments of the Wuding River was “moderately” polluted by Cd and “unpolluted to moderately” polluted by Cr and Ni. The elevated urban sewage discharges and agriculture fertilizers usage in river basin are the anthropogenic sources of these heavy metals in river.     

Dependence of <Superscript>210</Superscript>Po activity on organic matter in the reverine environs of coastal Kerala

This paper deals with the distribution of ²¹⁰Po in the river bank soil samples of three major rivers namely Bharathapuzha, Periyar and Kallada river of Kerala. The dependence of ²¹⁰Po activity on organic matter content in the samples was also studied. The soil samples were collected and analyzed for ²¹⁰Po radionuclide using standard radiochemical analytical method. Activity of ²¹⁰Po increases with increase in organic matter content in samples. Along the Bharathapuzha river bank the ²¹⁰Po activity ranges from 2.96 to 12.48 Bq kg⁻¹ with mean 5.62 Bq kg⁻¹. The organic matter percentage in the samples ranges from 0.4 to 2.8 and a good correlation with correlation coefficient 0.9 was found between activity and organic matter percentage. In the Periyar river environs ²¹⁰Po activity ranges from 3.47 to 13.39 Bq kg⁻¹ with mean value 9.27 Bq kg⁻¹. Organic matter percentage in these samples ranges from 1.20 to 4.10 and the correlation coefficient between ²¹⁰Po activity and organic matter percentage was found to be 0.8 In the Kallada river bank soil samples ²¹⁰Po activity ranges from 4.46 to 6.45 Bq kg⁻¹. The organic matter percentage ranges from 1.4 to 3. The correlation coefficient between ²¹⁰Po activity and organic matter percentage in the samples was found to be 0.9.     

A preliminary study on the effect of mineralization parameters on determination of metals in <Emphasis Type="Italic">Viscum album</Emphasis> species

An increasing interest in determination of various macro- and microelements in medicinal plants has been observed. The majority of studies are carried out using one mineralization method without any optimization. The present study demonstrates that changes in mineralization parameters can significantly affect the recovery of the elements determined. In the study, the dried plant material was mineralized in 12 ways and iron (Fe), copper (Cu), zinc (Zn), nickel (Ni) and manganese (Mn) levels were determined. The samples were mineralized in the dry or open microwave mode as well as 10 closed microwave modes. The influence of acid amounts, irradiation power and time, addition of hydrogen peroxide and perfluoric acid was examined. All parameters were shown to be critical — good efficiency was observed with larger amounts of acid. The determined content varied significantly in the same sample and were in the ranges (ug g⁻¹): 46–136 (Fe), 1.4–11.8 (Cu), 4.0–11.3 (Ni), 15.4–53.8 (Zn) and 9.5–67.6 (Mn). Increased irradiation resulted in the loss of copper and zinc and better recovery of nickel. The results demonstrate that such determinations should include the mineralization optimization step.      

A pilot study for the preparation of a new Reference Material based on antarctic krill

The preparation of new Certified Reference Materials (CRMs) of antarctic matrices forms the backbone of an ongoing project in the framework of the Italian National Program for Antarctic Research. The first CRM of this kind (MURST-ISS-A1 Antarctic Marine Sediment) is already available. The second phase focuses on the certification of antarctic krill, a small shrimp extremely abundant in the Southern Ocean. The total mass of krill available for this purpose is approximately 44 kg and results from the combination of three different catches (Ross Sea, Marguerite Bay and Livingston Island, respectively). The quantification of the following elements in the raw mass appears to be affordable by current analytical techniques, values being in the range of (in μg/g) 0.11–0.30 for As, 0.03–0.12 for Cd, 0.06–0.23 for Cr, 6.1–21 for Cu, 5.7–7.6 for Fe, 0.005–0.008 for Hg, 0.7–1.2 for Mn, 0.013– 0.077 for Ni, 0.04–0.57 for Pb and 12–16 for Zn. On the other hand, the average values ascertained in freeze-dried krill are as a rule one order of magnitude higher, i.e., (in μg/g), 3.2 for As, 0.6 for Cd, 1.8 for Cr, 75 for Cu, 61 for Fe, 0.025 for Hg, 4.6 for Mn, 0.7 for Ni, 2.1 for Pb and 81 for Zn. Information on the pretreatment of krill and details on the planned certification campaign are also given. Received: 10 June 1997 / Revised: 24 September 1997 / Accepted: 28 September 1997     

Improvements on the method for determining of <Superscript>210</Superscript>Pb and <Superscript>210</Superscript>Po in lead

An improved method is proposed to determine the content of ²¹⁰Pb in lead using ²¹⁰Po measured by alpha-ray spectrometry. This improved method, which is based on radiochemical separation by DDTC–toluene extraction, employs EDTA and citrate as masking reagents for the lead ions. To selectively extract polonium from an alkaline solution, the pH dependency was examined using a liquid scintillation counting method. And pH 9 was chosen as an extraction condition. Then ²¹⁰Po was electrodeposited on a stainless steel disk, and the chemical recovery was followed by ²⁰⁹Po tracer. The effectiveness of the new method was validated by the agreement with the analytical results from five samples as determined by gamma-ray spectrometry.     

Certification of the contents of some heavy metals (Cd, Cu, Hg, Ni, Pb and Zn) in three types of soils

Summary The element contents of Cd, Cu, Hg, Ni, Pb and Zn of three types of soil were certified. The preparation, homogeneity and stability are reported. The certified contents as well as values for Co, Cr, Mn and Se and for the aqua regia soluble contents Cd, Cr, Cu, Mn, Ni, Pb and Zn are given.

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Zertifizierung von Schwermetallspuren (Cd, Cu, Hg, Ni, Pb und Zn) in drei Bodenproben

Zusammenfassung In drei verschiedenen Bodenproben wurden die Elementgehalte an Cd, Cu, Hg, Ni, Pb und Zn zertifiziert. Es wird berichtet über die Bereitung, Homogenität und Stabilität. Die zertifizierten Gehalte sowie der Gehalt an Cr, Co, Mn und Se und der Gehalt an königswasserlöslichem Cd, Cr, Cu, Mn, Ni, Pb und Zn werden angegeben.

     

Measurements of <Superscript>210</Superscript>Po and <Superscript>210</Superscript>Pb in total diet samples: Estimate of dietary intakes of <Superscript>210</Superscript>Po and <Superscript>210</Superscript>Pb for Japanese

To estimate the dietary intakes of ²¹⁰Pb and ²¹⁰Po for the Japanese adults and their annual effective doses, ²¹⁰Pb and ²¹⁰Po were measured for 240 daily diet samples collected at two locations of Ishikawa Prefecture in Japan over three years by duplicate portion studies. No appreciable differences in intake rates of ²¹⁰Pb and ²¹⁰Po and their ²¹⁰Po/²¹⁰Pb ratios were seen among the years in each district, and between the two districts. The intake rates evaluated using 240 diet samples were 0.20 Bq/d/p for ²¹⁰Pb and 0.61 Bq/d/p for ²¹⁰Po as a median, respectively. Annual effective doses of ²¹⁰Pb and ²¹⁰Po for Japanese adults were estimated to be 0.050 and 0.053 mSv/y, respectively.     

Disequilibrium of dissolved <Superscript>234</Superscript>U/<Superscript>238</Superscript>U and <Superscript>210</Superscript>Po/<Superscript>210</Superscript>Pb in Greek rivers

For the first time, a radiological study for the dissolved ²³⁸U, ²³⁴U, ²¹⁰Pb and ²¹⁰Po was held in major Greek rivers across the country. ²³⁴U/²³⁸U activity ratios are above one in all samples and ²¹⁰Po/²¹⁰Pb activity ratios are respectively below the unit indicating the disequilibrium in the samples. Quite satisfactory correlations were observed among ²³⁴U and ²³⁸U as well as among ²¹⁰Po and ²¹⁰Pb values. Uranium isotopes were separated by ion exchange and electroplated on stainless steel plates. ²¹⁰Po was spontaneously deposited on nickel plates, while ²¹⁰Pb was indirectly determined through the ingrowth of ²¹⁰Po. The sources were measured by a-spectrometry.     

Certification of the contents of some heavy metals (Cd, Co, Cu, Mn, Hg, Ni, Pb and Zn) in three types of sewage sludge

Summary The element contents of Cd, Co, Cu, Mn, Hg, Ni, Pb and Zn of three different types of sewage sludge were certified. The preparation, the homogeneity and the stability are reported. The certified contents as well as values for Cr and Se and for the aqua regia soluble contents of Cd, Cr, Co, Cu, Mn, Ni, Pb and Zn are given.

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Zertifizierung von Schwermetallspuren (Cd, Co, Cu, Mn, Hg, Ni, Pb und Zn) in drei Klärschlammproben

Zusammenfassung In drei verschiedenen Klärschlammproben wurden die Elementgehalte an Cd, Co, Cu, Mn, Hg, Ni, Pb und Zn zertifiziert. Es wird berichtet über die Herstellung, Homogenität und Stabilität. Die zertifizierten Gehalte sowie der Gehalt von Cr, Se und der Gehalt an königswasserlöslichem Cd, Cr, Co, Cu, Mn, Ni, Pb und Zn werden angegeben.

     

Anreicherung und spektrochemische Bestimmung von Spurenelementen in reinsten Thalliumpr?paraten

Zusammenfassung Zur Anreicherung von Spurenelementen aus Lösungen reinster Thalliumpräparate wird die Matrix Thallium als TlJ ausgefällt. Dabei bleiben die Spuren Mg, Zn, Al, Ga, In, Fe, Co, Ni, Mn, Sn, La, Ce, Th und U quantitativ in Lösung, während Bi, Cu, Pb und Cd sowie die Edelmetalle Ag, Hg, Pd, Au und Pt vom Niederschlag mitgerissen werden. Die Adsorption der für die Reinheitsprüfung des Thalliums wichtigen Elemente Bi, Cu, Pb und Cd kann verhindert werden, wenn sie mit Hilfe von ÄDTA in Komplexanionen übergeführt werden. Als Fällungsmittel wird NaJ verwendet. Zur spektrochemischen Bestimmung werden Pb, Cd, Bi, Ni, Co und In als DDTC-Komplexe mit Chloroform extrahiert. Nach Zusatz einer Mischung von Lithiumcarbonat-Kohle und den Referenzelementen Sn und Pd wird der Eindampfrückstand im Gleichstrombogen analysiert. Cu und Fe werden photometrisch bestimmt.

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Enrichment and spectrochemical determination of trace elements in high-purity thallium preparations

For the enrichment of trace elements in solutions of high-purity thallium samples, thallium is precipitated in form of TlI. In this process the noble metals Ag, Hg, Pd, Au, Pt and also Bi, Cu, Pb and Cd will be co-precipitated, whereas many other elements (Mg, Zn, Al, Ga, In, Fe, Co, Ni, Mn, Sn, La, Ce, Th, U) will remain completely in solution. The adsorption of the four elements Bi, Cu, Pb, Cd, which are important for the purity control of thallium compounds, can be prevented, if they are complexed with EDTA to form complex anions. The precipitating reagent is NaI. For the spectrochemical determination of Pb, Cd, Bi, Ni, Co, and In, the trace elements are extracted as DDTC complexes with chloroform. After the addition of a mixture of Li₂CO₃, carbon, and the reference elements Sn and Pd, the sample is analysed, using the d.c. arc. Cu and Fe are determined spectrophotometrically.

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Wir danken dem Fonds der chemischen Industrie für die finanzielle Unterstützung dieser Arbeit.     

Spectral and Thermal Studies of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) Complexes with 3-methylglutaric Acid

Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) 3-methylglutarates were prepared as solids with general formula MC₆ H₈ O₄ ×n H₂ O, where n =0–8. Their solubilities in water at 293 K were determined (7.0×10⁻² −4.2×10⁻³ mol dm⁻³ ). The IR spectra were recorded and thermal decomposition in air was investigated. The IR spectra suggest that the carboxylate groups are mono- or bidentate. During heating the hydrated complexes lose some water molecules in one (Mn, Co, Ni, Cu) or two steps (Cd) and then mono- (Cu) or dihydrates (Mn, Co, Ni) decompose to oxides directly (Mn, Cu, Co) or with intermediate formation of free metals (Co, Ni). Anhydrous Zn(II) complex decomposes directly to the oxide ZnO. This revised version was published online in July 2006 with corrections to the Cover Date.     

Aqueous Equilibrium and Solution Structural Studies of the Interaction of N,N′-bis(4-imidazolymethyl)etylenediamine with Ca(II), Cd(II), Co(II), Cu(II), Mg(II), Mn(II), Ni(II), Pb(II) and Zn(II) Metal Ions

Divalent metal complexes of N,N′-bis(4-imidazolymethyl)etylenediamine (EMI) have been studied using potentiometric and spectroscopic techniques (UV-Vis and NMR methods) in aqueous 0.1 mol⋅L⁻¹ KCl supporting electrolyte at 25 °C. Final models and overall stability constants for the complexes of Ca(II), Cd(II), Co(II), Cu(II), Mg(II), Mn(II), Ni(II), Pb(II) and Zn(II) have been established by potentiometry for all M(II)–EMI systems, except for Co(II)–EMI. The data revealed that EMI forms ML complexes with all M(II)–EMI systems, which is the dominant species over a wide range of pH except for the Ca(II)–EMI and Mg(II)–EMI systems. Formation of the MnHL complex was also found for Mn(II)–EMI solutions. In addition, the UV-Vis and ¹H NMR results allowed us establish the coordination modes for the metal complexes between EMI with Cd(II), Cu(II), Ni(II) and Zn(II).