Distribution of 210Pb and 137Cs in Snow and Soil Samples from Antarctica

Abstract

This paper reports some results on natural and artificial radionuclide distribution in snow samples collected at the Priestly Nevé—Plateau (inland, 1998 m a.s.l.) and the Vegetation Island (near the coast, 200 m a.s.l.) stations, and in a soil sample from Wood Bay station, both near the Italian Base at Terranova Bay in Antarctica. Data on Pb-210 and Cs-137 in snow samples from an 80 cm deep trench and in granulometric fractions of a soil core are discussed.     

Quantification of measurement uncertainty in the sequential determination of <Superscript>210</Superscript>Pb and <Superscript>210</Superscript>Po by liquid scintillation counting and alpha-particle spectrometry

Methodologies for the quantification of measurement uncertainties associated with the determination of ²¹⁰Pb- and ²¹⁰Po-specific activities by liquid scintillation counting (LSC) and alpha-particle spectrometry are presented, and are demonstrated using the soil reference material IAEA-326. Major contributors to the combined uncertainty associated with the measurement result of ²¹⁰Pb were the uncertainties of net count rates in the ²¹⁰Pb energy region of the sample spectrum and in the ²¹⁰Bi energy region of the blank spectrum. The predominant sources of uncertainty in the measurement of ²¹⁰Po were the uncertainties of net count rates in the regions of interest of ²⁰⁹Po and ²¹⁰Po. The relative standard uncertainty of ²¹⁰Po exponentially increases with the time interval between the sampling date and the separation date of Po, and this effect is strongly dependent on the ²¹⁰Po/²¹⁰Pb activity ratio. When the specific activity of ²¹⁰Pb is much higher than that of ²¹⁰Po in the sample, the relative standard uncertainty of the ²¹⁰Po determination increases significantly within a short time interval between the sampling date (or reference date) and the separation date of Po in samples.     

Estimation of the Annual Effective Dose Due to the Ingestion of 210Pb and 210Po in Crops from a Site of Coal Mining and Processing in Southwest China

The exploitation of mineral resources may cause the environmental release of radionuclides and their introduction in the human trophic chain, affecting public health in the short and long term. A case study of the environmental radiation impact from coal mining and germanium processing was carried out in southwest China. The coal mines contain germanium and uranium and have been exploited for more than 40 years. The farmlands around the site of the coal mining and germanium processing have been contaminated by the solid waste and mine water to some extent since then. Samples of crops were collected from contaminated farmlands in the research area. The research area covers a radius of 5 km, in which there are two coal mines. ²¹⁰Pb and ²¹⁰Po were analyzed as the key radionuclides during the monitoring program. The average activity concentrations of ²¹⁰Pb and ²¹⁰Po in the crops were 1.38 and 1.32 Bq/kg in cereals, 4.07 and 2.19 Bq/kg in leafy vegetables and 1.63 and 1.32 Bq/kg in root vegetables. The annual effective doses due to the ingestion of ²¹⁰Pb and ²¹⁰Po in consumed crops were estimated for adult residents living in the research area. The average annual effective dose was 0.336 mSv/a, the minimum was 0.171 mSv/a and the maximum was 0.948 mSv/a. The results show that the crops grown on contaminated farmland contained an enhanced level of radioactivity concentration. The ingestion doses of local residents in the research area were significantly higher than the average level of 0.112 mSv/a in China, and the world average level of 0.042 mSv/a through ²¹⁰Pb and ²¹⁰Po in crop intake, respectively.     

Vertical Distribution of137 Cs in The Lacustrine Areas and Preliminary Results of 7Be Activity in Snow Samples at Terra Nova Bay (ANTARCTICA)

Abstract

¹³⁷ Cs activity in samples from lacustrine areas around the Italian base in Antarctica is reported as an integration of a previous work. Preliminary data of cosmogenic ⁷ Be activity determined in snowfalls, total atmospheric depositions, soil and air particulate collected during the 1990–91 and 1991–92 Italian expeditions in Antarctica is presented. The results obtained point out the efficiency of snow in the processes of air particulate scavenging and provide useful information for the development of research in Antarctica in the study of air/snow transfer processes by means of natural radionuclides.     

Trace metal speciation in coastal and off-shore sediments from Ross Sea (Antarctica)

The information on total metal concentration in sediments is not sufficient to assess the metal behaviour in the environment, while speciation studies are more effective in estimating environmental impact of contaminated sediments. Concerning metal distribution in Antarctic marine sediments, several studies reported total or extractable (by means of a unique reagent) content, but only few publications dealt with metal speciation.This work presents the total content and speciation pattern of Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn in 12 cm sediment cores, sampled both in coastal and off-shore sites of the Ross Sea shelf area, within the framework of the Italian National Antarctic Programme (PNRA). The total content results of metals are comparable with the background values and the speciation highlights good environmental quality of the studied areas. Only Cd and Pb, in fact, are present in significative amount in non residual phases (acid-extractable and reducible, respectively).     

Halocarbons in Aqueous matrices from the Rennick Glacier and the Ross Sea (Antarctica)

Aqueous matrices from Antarctica were analysed for three volatile chlorinated hydrocarbons (VCHCs): tetrachloromethane (CCl₄), trichloroethylene (C₂HCl₃) and tetrachloroethylene (C₂Cl₄). The matrices analysed were snow from Rennick Nèvè and Rennick Glacier sampled during the Italian Expeditions of 1995/96 and 1996/97, respectively, and seawater, pack ice, sea-microlayer, subsuperficial water and freshwater, collected during the Italian Expedition of 1997/98. Extractions from the aqueous matrices were carried out in Antarctica (the laboratories of the Italian Base, Terra Nova Bay). Because of the critical space–time conditions in these laboratories, an extraction procedure was developed, suitable for large volumes of water (10?L), in order to combine the extraction of other classes of organic compounds (polychlorinated biphenyls, polycyclic aromatic hydrocarbons and chlorinated pesticides) with those of our direct interest. The VCHC organic extracts were analysed in Italy by GC-ECD and GC-MS. The analyses confirmed the presence of the three halocarbons in Antarctica in quantities ranging from units to some dozens of nanograms per kilogram. The results were evaluated with respect to the local distribution of these compounds and their diffusion on a global scale.     

The fractionation and determination procedures for the speciation of Pb and Po in soil samples

A method for speciation and determination of ²¹⁰Pb and ²¹⁰Po in soil samples was developed. The speciation was carried out by fractionating the soil samples into five fractions which are water soluble or exchangeable, bound to carbonates, bound to Fe-Mn oxides, bound to organic matter and bound to residue. After mineralisation, 10% solution of each fraction was used to spontaneously deposit polonium on a silver disk at 85-90 °C and pH 1.5, and ²¹⁰Po was measured by α-spectrometry; the remain solution was used to separate lead by anion-exchange resin and purified by precipitation as PbS and PbSO₄, and ²¹⁰Pb was determined by a low background β-counter. The IAEA-327 reference material (soil) was studied for ²¹⁰Pb and ²¹⁰Po speciation. The results show that: (1) the average yields are 88.7 ± 6.4% for ²¹⁰Pb and 93.8 ± 8.2% for ²¹⁰Po; (2) if compared to the total ²¹⁰Pb activity in the sample, ²¹⁰Pb fractions are 0.95% in exchangeable form, 10.6% bound to carbonates, 14.3% bound to Fe-Mn oxides, 7.0% bound to organic matter and 67.2% bound to residue or acid soluble, and the corresponding values for ²¹⁰Po are 0.17%, 0.97%, 21.0%, 0.47% and 77.4%, respectively; and (3) the obtained ²¹⁰Pb concentration is in good agreement with the recommended value given by the IAEA.     

Optimization of Pb determination via spontaneous deposition of Po on a silver disk

The accuracy of ²¹⁰Pb determination via spontaneous deposition of ²¹⁰Po on a silver disk and alpha spectrometric measurement was examined. The study focused on the storage conditions of the polonium-containing solutions, the tracer used in polonium analysis and the effect of storage time and acid concentration on ²¹⁰Po deposition. The intermediate precision and repeatability associated with the improved ²¹⁰Pb analysis of fresh groundwater samples was 5 and 14%, respectively. These improved values were achieved by using glass bottles as storage containers for the solution remaining from the first ²¹⁰Po deposition, by rinsing the sample container with concentrated hydrochloric acid after storage and by using different isotopes of polonium as the yield determinant tracer in the first and the second deposition. Less polonium adsorption onto the storage container walls occurred with HCl than with HNO₃. The overall uncertainty in ²¹⁰Pb analysis was (11 ± 7)% at the 95% confidence level. The minimum detectable activity concentration was 0.1 mBq l⁻¹ calculated from blank samples and 0.05 mBq l⁻¹ using the background counts of the alpha spectrometer.     

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

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

Sedimentary process inferences from Humic substances analysis and deposition rates (Western Ross Sea,Antarctica)

The first 40?cm of sediment of three basins in the Ross Sea were sampled using a box corer. Site Y1 was located close to the coast in Terra Nova Bay; the sediment of site Y3 was collected in a more distal basin in the central sector of the Ross Sea; finally site Y5 was sampled in the deepest zone of the Joides Basin.

Sediment cores were sliced and analysed with a depth resolution of 2–4.5?cm. The distribution of humic substances and their structural features along the cores were determined and related to the pattern of Total Organic Carbon (TOC) and sedimentological data. The grain size distribution and the ²¹⁰Pb inventories allow the sediment of the study sites to be characterised.

The humic substance content in the sediment decreases, with a change in slope between 23 and 26?cm at Y1, between 12 and 15?cm at Y3 and constant values with further depth. At Y5 the depth profile of humic substance content shows constant values in the upper 17?cm and values decrease with further depth. The pattern of humic substance yield is similar to that found for TOC. The analysis of the elemental composition of the humic acids extracted from different sediment depths shows an increasing C/N atomic ratio at sites Y1 and Y3 and constant values along the Y5 core. The depth profile of the C/N atomic ratio is confirmed by the changes observed in the structural characterisation and indicates a shift from the freshly deposited organic matter on the sediment surface to more humified material (humin). The results obtained highlight a different sedimentation rate at the three sites as deduced from sedimentological analysis.     

Horizontal and vertical distributions of Biogenic and Anthropogenic Organic compounds in the Ross Sea (Antarctica)

Horizontal and vertical distributions of organic compounds extractable with n-hexane were investigated at five sampling stations (Ross Sea) during the Italian Antarctic Expedition 1997/98. Samples were collected from seven depths under pack ice and from two or three depths at the other stations located at different distances from the coast. The lowest concentrations of biogenic and anthropogenic compounds were found at station Y3, the furthest from the coast, while the highest concentrations were observed under pack ice (B2-2 station) or in the Polynya zone (Y1 station). The levels of organic compounds in the particulate phase were higher than those in the dissolved phase for all the investigated samples. Concentrations of biogenic organic compounds (long-chain aldehydes and alcohols, fatty acid esters and n-alkanes) were well related to fluorescence intensity, which is usually reported as a biological activity index. The odd-to-even carbon-number ratio for n-alkanes was lower than 1 at stations B2-2, Y1, Y5 and Y6 (located less than 150?km far from the coast) with the predominance of n-C16, n-C24 and n-C28, indicative of autochthonous pelagic species. An odd-to-even ratio higher than unity and a different n-alkane profile were observed at station Y3 (about 300?km from the Ross Ice Shelf and 600?km from Terra Nova Bay). Low levels of pollutants (i.e. phthalates) were found, mainly in the particulate phase up to a depth of 50?m, confirming a local source of the phthalates found at significant concentrations during previous expeditions.     

Natural Products Produced in Culture by Biosynthetically Talented Salinispora arenicola Strains Isolated from Northeastern and South Pacific Marine Sediments

Laboratory cultures of two ‘biosynthetically talented’ bacterial strains harvested from tropical and temperate Pacific Ocean sediment habitats were examined for the production of new natural products. Cultures of the tropical Salinispora arenicola strain RJA3005, harvested from a PNG marine sediment, produced salinorcinol (3) and salinacetamide (4), which had previously been reported as products of engineered and mutated strains of Amycolatopsis mediterranei, but had not been found before as natural products. An S. arenicola strain RJA4486, harvested from marine sediment collected in the temperate ocean waters off British Columbia, produced the new aminoquinone polyketide salinisporamine (5). Natural products 3, 4, and 5 are putative shunt products of the widely distributed rifamycin biosynthetic pathway.     

水合Pb(OH)~+在高岭石(001)晶面的吸附机理(英文)

采用密度泛函理论广义梯度近似平面波赝势法,结合周期平板模型,探讨了水体环境中Pb(OH)+在高岭石铝氧八面体(001)晶面的吸附行为和机理,确定了吸附配合物的结构、配位数、优势吸附位和吸附类型.结果表明,Pb(II)与高岭石铝氧(001)面的氧原子形成单齿或双齿配合物,其配位数为3-5,均为半方位构型.高岭石表面存在含"平伏"氢原子的表面氧(Ol)位和含"直立"氢原子的氧(Ou)位,后者更易与Pb(OH)+单齿配位,该吸附配合物具有较高的结合能(-182.60 kJ·mol-1),为优势吸附物种;高岭石表面位于同一个Al原子上的"OuOl"位可形成双齿配合物.表面Ol与水分子配体形成氢键,对配合物的稳定性起到关键作用.Mulliken布居和态密度分析表明,高岭石单齿配合物中Pb―O成键机理主要为Pb 6p轨道与Pb 6s―O 2p反键轨道进行耦合,电子转移到反键轨道.双齿配合物"Pb―Ol―H"共配位结构中,受配位氢原子影响,Pb―Ol成键过程成键态电子填充占主导地位.     

Solid-phase extraction of Pb2+ ion from environmental samples onto L-AC-Ag-NP by flame atomic absorption spectrometry (FAAS)

The development of a solid-phase extraction (SPE) procedure for the pre-concentration of trace amounts of Pb²⁺ ion on 2-furan-2-yl-1-furan-2-ylmethyl-1H-benzoimidazole loaded on activated carbon modified with silver nanoparticles (L-AC-Ag-NP) was presented. The metal ion retained on the sorbent was quantitatively determined via complexation with the ligand. The complexed metal ion was efficiently eluted using 10 mL of 4 mol L^?1 sulphuric acid in 10 w/v% acetone. The influences of the analytical parameters, including pH, amounts of the ligand and the solid phase, eluent conditions and sample volume, on the recoveries of the metal ion were optimised. Using the optimised parameters, the linear response of the SPE method for Pb²⁺ ion were in the ranges of 0.2–160 µg L^?1, and the detection limit for Pb²⁺ ion was 0.034 µg L^?1. The proposed method exhibits a pre-concentration factor (PF) of 80 and an enhancement factor of 30 for Pb²⁺ ion. The presented results demonstrate the successful application of the proposed method for the determination of Pb²⁺ ion in some real samples with high recoveries (>93%) and reasonable relative standard deviation (RSD < 2%).     

Trace,Alkaline and Alkaline-Earth Elements in Sea Water Samples from Terra Nova Bay - Ross Sea (ANTARCTICA): A Three-Year Period of Observation

Abstract

This report concerns the correlation of the analytical results relevant to some elements obtained in filtered sea water samples collected in Terra Nova Bay and the Ross Sea (Antarctica) during three Italian expeditions. The following ranges of variability of the medians of total concentrations (ng/l) - which include time effect among expeditions and bias effect among participant groups - were found for trace elements (single values refer to elements which were only determined once by one laboratory): Sb (260), As (1.2 10³), Cd (5–50), Cr (120), Co (4), Cu (110–230), Fe (435–445), Pb (6–52), Mn (15–88), Hg (3), Ni (185–580), Se (30) and Zn (242–265). Speciation studies pointed out that 10–40% of Cd, 15–60% of Cu and 20–50% of Pb were present in the samples as an ASV-labile fraction.

As for alkaline and alkaline-earth elements, the following concentration ranges in surface sea waters, expressed in mM, were found: Li ([1.4–3.0] 10^?2), Na (394–480), K(5.1–9.9), Ca (6.4–14.7), Mg (46.2–59.0) and Sr ([7.6–10] 10^?2).

Inter- and intra-laboratory data comparison, incorrect results, local variations of concentration, including pollution effects and pack melting effect, are discussed in detail.     

Synthesis and characterization of Pb(II) compounds constructed from N-tosyl-L-glutamic acid

{[Pb(tsgluo)]?·?H₂O} _n (1), [Pb₂(tsgluo)₂(phen)₂] (2), and [Pb₂(tsgluo)₂(bipy)₂] (3) (H₂tsgluo?=?N-p-tolylsulfonyl-L-glutamate, phen?=?1,10-phenanthroline, bipy?=?2,2′-pyridine) have been synthesized in the absence or presence of phen or 2,2′-bipy and structurally characterized by elemental analysis, IR, and X-ray crystallography. Single-crystal X-ray analyses reveal that tsgluo exhibits two coordination modes to link lead ions. Complex 1 gives a 2-D layer structure while 2 and 3 exhibit monomolecular structures; 3 is further connected into a double-chain structure by hydrogen bonds. Phen and 2,2′-bipy are very important for the crystal structure. Fluorescence of the compounds is also discussed.     

Magnetic Nitrogen-Doped Porous Carbon Nanocomposite for Pb(II) Adsorption from Aqueous Solution

We report in the present study the in situ formation of magnetic nanoparticles (Fe₃O₄ or Fe) within porous N-doped carbon (Fe₃O₄/N@C) via simple impregnation, polymerization, and calcination sequentially. The synthesized nanocomposite structural properties were investigated using different techniques showing its good construction. The formed nanocomposite showed a saturation magnetization (M_s) of 23.0 emu g⁻¹ due to the implanted magnetic nanoparticles and high surface area from the porous N-doped carbon. The nanocomposite was formed as graphite-type layers. The well-synthesized nanocomposite showed a high adsorption affinity toward Pb²⁺ toxic ions. The nanosorbent showed a maximum adsorption capacity of 250.0 mg/g toward the Pb²⁺ metallic ions at pH of 5.5, initial Pb²⁺ concentration of 180.0 mg/L, and room temperature. Due to its superparamagnetic characteristics, an external magnet was used for the fast separation of the nanocomposite. This enabled the study of the nanocomposite reusability toward Pb²⁺ ions, showing good chemical stability even after six cycles. Subsequently, Fe₃O₄/N@C nanocomposite was shown to have excellent efficiency for the removal of toxic Pb²⁺ ions from water.     

Compositional Study of Phospholipids from the Dried Big Head and Opossum Shrimp,Mussel, and Sea Cucumber Using 31P NMR Spectroscopy: Content and Fatty Acid Composition of Plasmalogen

Herein, we present a qualitative and quantitative analysis of the compositions of plasmalogens and phospholipids (PLs) in dried big head shrimp (Solenocera melantho), opossum shrimp (Neomysis awatschensis), mussel (Mytilus galloprovincialis), and sea cucumber (Apostichopus japonicus). We also analyze the fatty acid composition of the extracted lipids, phosphatidyl choline (PtdCho), and plasmalogen choline (PlsCho) from each sample. In big head shrimp, opossum shrimp, and mussel, phosphatidyl choline (PtdCho) was the most abundant PL at 1677.9, 1603, and 1661.6 mg/100 g of dried sample, respectively, whereas the most abundant PL in sea cucumber was PlsCho (206.9 mg/100 g of dried sample). In all four samples, plasmalogen ethanolamine (PlsEtn) was higher than phosphatidyl ethanolamine (PtdEtn). The content (mg/100 g of dried sample) of PlsCho was highest in mussel (379.0), and it was higher in big head shrimp (262.3) and opossum shrimp (245.6) than sea cucumber (206.9). The contents (mg/100 g of dried sample) of PlsEtn were in the order of mussel (675.4) > big head shrimp (629.5) > opossum shrimp (217.9) > sea cucumber (51.5). For analyzing the fatty acids at the sn-2 position of PlsCho, the consecutive treatment with phospholipase A₁, solid phase extraction, thin-layer chromatography (TLC), and GC-FID were applied. The most abundant fatty acid was eicosapentaenoic acid (EPA, C20:5, n-3) in big head shrimp and sea cucumber, palmitoleic acid (C16:1, n-7) in opossum shrimp, and docosadienoic acid (C22:2, n-6) in mussel.     

Diphenyllead(IV) thiosemicarbazonates and pyrazolonates: Synthesis and characterization

Cyclization of thiosemicarbazones derived from β-keto esters and β-keto amides (HTSC) in the presence of diphenyllead(IV) acetate was explored in methanol solution at room temperature and under reflux. All β-keto ester TSCs underwent cyclization to give the corresponding pyrazolone (HL), which, except in one case, deprotonated and coordinated the PbPh₂²⁺ moiety to form homoleptic [PbPh₂(L)₂] or heteroleptic [PbPh₂(OAc)(L)] derivatives. Cyclization did not occur with β-keto amide TSCs and only [PbPh₂(TSC)₂] or [PbPh₂(OAc)(TSC)] thiosemicarbazonates were isolated. The complexes were characterized by IR spectroscopy in the solid state and by ¹H, ¹³C and ²⁰⁷Pb NMR spectroscopy in DMSO–d₆ solution, in which they evolve and decompose with time. Additionally, crystals of p-acetoacetanisidide thiosemicarbazone (HTSC¹⁰), [PbPh₂(OAc)(L⁵)] · MeOH (HL⁵ = 2,5-dihydro-3,4-dimethyl-5-oxo-1H-pyrazolone-1-carbothioamide), [PbPh₂Cl(L²)] (HL² = 2,5-dihydro-5-oxo-3-phenyl-1H-pyrazolone-1-carbothioamide), [PbPh₂(OAc)(TSC⁸)] · 2MeOH (HTSC⁸ = acetoacetanilide thiosemicarbazone), [PbPh₂(OAc)(TSC¹⁰)] · H₂O and [PbPh₂(OAc)(TSC¹¹)] · 0.75MeOH (HTSC¹¹ = o-acetoacetotoluidide) were studied by X-ray crystallography. The complexes, monomers or dimers with almost linear C–Pb–C moieties, are compared with the corresponding derivatives of Pb(II).     

Removal of Cd(II) and Pb(II) from aqueous solution by modified attapulgite clay

Three low-cost adsorbents (purified raw attapulgite (A-ATP), high-temperature-calcined attapulgite (T-ATP), and hydrothermal loading of MgO (MgO-ATP)) were prepared as adsorbents for the removal of Cd(II) and Pb(II). By evaluating the effect of the initial solution pH, contact time, initial solution concentration, temperature and coexistence of metal ions on Cd(II) and Pb(II) adsorption, the experimental results showed that MgO-ATP was successfully prepared by hydrothermal reaction and calcination as well as appearing to be a promising excellent adsorbent. At an initial pH of 5.0, A-ATP, T-ATP and MgO-ATP reached maximum adsorption amounts of 43.5, 53.9 and 127.6 mg/g for Pb(II) and 10.9, 11.2, and 25.3 mg/g for Cd(II) at 298 K, respectively. The Cd(II) adsorption on A-ATP was fitted by the Freundlich model, while the adsorption of Pb(II) and Cd(II) on T-ATP and MgO-ATP as well as Pb(II) adsorption on A-ATP agreed with the Langmuir model. All kinetic experimental data favored pseudo second-order model. The calculated thermodynamic parameters suggested that Pb(II) adsorption onto MgO-ATP was spontaneous and exothermic. When considering foreign metal ions, the three adsorbents all presented preferential adsorption for Pb (II). Chemical adsorption had a high contribution to the removal of Cd(II) and Pb(II) by modified attapulgite. In summary, the adsorption was greatly enhanced by the hydrothermal loading of MgO. It aimed to provide insights into the MgO-ATP, which could be able to efficiently remove Cd(II) and Pb(II) and serve as an economic and promising adsorbent for heavy metal-contaminated environmental remediation.