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.     

中国燃油大气铅排放量估算

依据不同时期车用汽油铅含量国家标准及汽油消费量数据,估算了我国1980—2006年的全国燃油大气铅排放量及2001—2005年分地区燃油大气铅排放量。结果表明,27年间我国因汽油燃烧共计向大气排放了约20万t铅。汽油无铅化后,燃油大气铅年排放量比从前降低了98%。     

Determination of lead concentrations and isotope ratios in recent snow samples from high alpine sites with a double focusing ICP-MS

A double focusing ICP-MS, equipped with a Micro Concentric Nebulizer, has been used to determine concentrations and isotopic ratios of lead in recent snow samples (1993–1996) from high alpine sites in Switzerland. Concentrations varied between 0.02 ± 0.002 and 5.5 ± 0.15 ng/g and are slightly lower than concentrations reported by Atteia [1], by Batifol et al. [2], and by Wagenbach et al. [3] for precipitation samples from similar remote sites in Europe. Since concentrations of lead in the fresh snow samples were mainly in the lower pg/g range, the method to determine the isotopic ratios ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb had to be optimized. They could finally be determined with an average standard error of 0.14% within 12 min and a total sample consumption of 0.8 mL. The average ratios ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb were 0.875 and 2.117, respectively. These values are comparable to isotopic compositions of lead in aerosols collected in Western Europe [4] and are less radiogenic than predicted by Grousset et al. [5]. Our data indicate that, although lead emissions from traffic have decreased largely during the last 10 years, the contribution from this source in modern snow is still detectable and seems to be equal to the lead input from other anthropogenic sources (e.g. waste incineration, industry).     

Determination of heavy metals at the pg/g level in Antarctic snow with DPASV and IDMS

Summary Differential pulse anodic stripping voltammetry (DPASV) and isotope dilution mass spectrometry (IDMS) were used to analyse heavy metals in Antarctic snow samples. It was possible to determine Pb and Cd with DPASV at the German Antarctic station Georg-von-Neumayer whereas the analyses of Pb, Cd, Tl, Cr, Ni, Cu, Zn, and Fe with IDMS were carried out at the University of Regensburg. 80% of the elemental concentrations in surface snow samples analysed with IDMS lay in the following ranges: Pb=3–40 pg/g, Cd<0.2–3 pg/g, Tl<0.2 pg/g, Cr<0.8–15 pg/g, Ni<4.8–40 pg/g, Cu<11–30 pg/g, Zn=30–500 pg/g, and Fe=(0.5–1.5)×10³ pg/g. In most cases an acceptable agreement between the DPASV and IDMS results was obtained for Pb and Cd. More than 50% of all Pb analyses agreed within a deviation of 0–10 pg/g. The Cd results between both methods usually deviated by less than 1 pg/g. Slightly higher Pb concentrations were analysed in the average with IDMS compared with DPASV. This effect was not observed for the Cd data. A possible explanation for this fact are non-ionic Pb species in the melted snow samples, which cannot be analysed by DPASV. One particular investigation of Pb concentrations showed that the analysed data with DPASV decreased with the increasing length of sun-shine after a snowfall when samples of the same origin were determined. Blank control is the major requirement for accurate analysis results of heavy metals in this low concentration range. On the other hand, accuracy must always be tested by independent analytical methods. In this work it is shown that Pb and Cd can be analysed directly in the Antarctica with DPASV and that the result of this method is in acceptable agreement with the definitive method IDMS.

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Bestimmung von Schwermetallen im pg/g Bereich in antarktischen Schneeproben durch differentielle Pulsinversvoltammetrie und massenspektrometrische Isotopenverdünnungsanalyse

     

Preliminary study of HCHO spatial and temporal distribution from Coastal to Plateau areas in Antarctica

Formaldehyde concentrations were determined in over 1800 snow samples (snowpit, firn cores and superficial snow) from Antarctica by a sensitive spectrofluorimetric Flow Injection Analysis method. The method performances (detection limit: 55?ng/L; reproducibility: 2.5% at 1?µg/L level; linear range: 0.1–3000?µg/L) allowed a reliable determination of formaldehyde content in all the collected samples. The range of determined concentrations was 0–70?µg/L with a mean concentration of 7.7?µg/L and a median concentration of 5.8?µg/L. The formaldehyde background level was estimated at a few micrograms per liter in coastal and plateau areas of Northern Victoria Land. In some stations the background values are modulated by HCHO deposition events recurring over relatively large time periods.     

Analysis of Organic Compounds in Antarctic Snow and Their Origin

Abstract

Organic compounds extractable with n-hexane were identified and quantitatively determined in pack, surface and deep snow samples taken at different depths and collected at several altitudes above sea level from Antarctica during the 1993/94 Italian expedition. The comparison between the composition of organic compounds in snow and the ones in pack and sea-water samples pointed out that the three matrices substantially contain the same biogenic and anthropogenic organic compounds. The contribution of marine aerosol to organic content in the snow is confirmed by the enrichment ratios calculated for the more representative classes of identified compounds (n-alkanes, phthalates and low molecular weight alkylbenzenes). The changes in the composition of organic compounds in snow as the altitude increases seem to depend on the dimensional spectrum of the aerosol. Thus, smallest particles, richest in surfactant material, reach the highest altitudes.     

Organic Compounds in Surface and Deep Antarctic Snow

Abstract

Eight surface snow samples taken during the 1987/88, 1988/89 and 1990/91 Italian Antarctic Expeditions and six samples collected at different depths from two dissimilar sites during the 1990/91 Expedition, were analyzed for the non-chlorinated organic content using the GC capillary columns technique and GC-MS. Several biogenic and anthropogenic classes of organic compounds were identified and quantitatively determined. The data obtained give a more complete picture of the pollution level in Antarctica.     

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.     

Determination of trace elements in automotive fuels by filter furnace atomic absorption spectrometry

The determination of Cd, Cr, Cu, Pb and Ni was performed in gasoline and diesel fuel samples by electrothermal atomic absorption spectrometry using the Transverse Heated Filter Atomizer (THFA). Thermal conditions were experimentally defined for the investigated elements. The elements were analyzed without addition of chemical modifiers, using organometallic standards for the calibration. Forty-microliter samples were injected into the THFA. Gasoline samples were analyzed directly, while diesel fuel samples were diluted 1:4 with n-heptane. The following characteristic masses were obtained: 0.8 pg Cd, 6.4 pg Cr, 12 pg Cu, 17 pg Pb and 27 pg Ni. The limits of determination for gasoline samples were 0.13 μg/kg Cd, 0.4 μg/kg Cr, 0.9 μg/kg Cu, 1.5 μg/kg Pb and 2.5 μg/kg Ni. The corresponding limit of determination for diesel fuel samples was approximately four times higher for all elements. The element recovery was performed using the addition of organometallic compounds to gasoline and diesel fuel samples and was between 85 and 105% for all elements investigated.     

Thallium and cadmium in recent snow and firn layers in the Canadian Arctic by atomic fluorescence and absorption spectrometries

Compared to the Antarctic and Greenland, the Canadian Arctic has seen extremely few trace metal studies on snow and ice. Surface, subsurface and depth samples of snow and firns were collected from the Agassiz Ice Cap, Ellesmere Island, Canada using clean room practices. Results for Tl (directly determined by LEAFS) and Cd (determined by GFAAS) are reported. To our knowledge, the thallium depth profile presented here is the first one so far reported for both polar systems, Greenland or other places. Tl concentrations peak in the winter-spring periods, when the Arctic atmosphere is loaded with foreign pollutants and suspended particulates which sometime severely reduce the visibility, creating a phenomenon commonly known as the Arctic haze. These results are in general accordance with the historical Arctic air pollution and acidity/conductivity data on ice cores. Surface concentrations of Tl range from 0.3 to 0.9 pg/g, which is a few times higher than those found in Antarctica. Cadmium shows seasonal characteristics similar to Tl although there is not a definite correlation between the two. However, there could be two predominant origins of metals which were deposited in the snow: Eurasian origin in January–April corresponding to high level metals (main deposition), and a less definite origin in May–December corresponding to low level metals.     

Determination of Thallium in Antarctic Snow by Means of Laser Induced Atomic Fluorescence and High Resolution Inductively Coupled Plasma Mass Spectrometry

Abstract

Measurements of thallium levels in Antarctic snow samples collected in an area surrounding the Italian Station at Terra Nova Bay in different campaigns have been performed without preconcentration by means of Laser Induced Atomic Fluorescence Spectroscopy (LIAF) as well as by High Resolution Inductively Coupled Plasma Mass Spectrometry (HR ICP-MS).

The data obtained by both methods compare favourably and are of the order of tenths of pg/g. The data is discussed taking into account the effect of the marine aerosol and the crustal contribution to the thallium content in samples.     

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.     

Micrometeorites in Antarctic ice detected by Ir: estimation of 120k year old accretion rate

The accretion rate of micrometeorites (MMs) was estimated from Ir contents in snow around Dome Fuji Station and ice shards obtained during ice core drilling at Dome Fuji Station, Antarctica. The snow and ice shards were melted and filtered from the residues. Although MMs were not found on filters, we tried to detect them from the residues as Ir peaks determined by instrumental neutron activation analysis (INAA). Although Ir is very rare in the earth’s crust, its concentration is high in extraterrestrial matter (e.g., chondrites). Trace amounts of Ir can be easily detected by INAA, because the cross section of Ir is relatively large (e.g., 309 barn). The accretion rates were estimated for 120k year ago, 5k year ago and at present, as (3.2 ± 0.9) × 10² t/year (8.6 ± 0.18) × 10³ t/year and (1.3 ± 0.10) × 10³ t/year, respectively. These estimates were comparable to those of previous studies, however the rate of 120k year ago was approximately an order of magnitudes lower than the others.     

Determination of methylcyclopentadienylmanganese tricarbonyl (MMT) in gasoline and environmental samples by gas chromatography with helium microwave plasma atomic emission detection

A highly sensitive and specific method is described for the determination of methylcyclopentadienylmanganese tricarbonyl (MMT) in gasoline and environmental samples by gas chromatography–plasma atomic emission detection (GC–AED). The procedure is simple, rapid and free from interferences. The absolute limit of detection is 0.5 fg of MMT (0.5×10⁻¹⁵ g) expressed as Mn. The precision for replicate injections ( n =5) of an MMT solution (10 pg Mn) was 2.8% relative standard deviation (RSD ). Applications of the method to analysis of gasoline (petrol), and preliminary results of the analyses of environmental samples such as air and roadside dirt, are given. © 1997 by John Wiley & Sons, Ltd.     

Determination of nitrate at the ng/g level in Antarctic snow samples with ion chromatography and isotope dilution mass spectrometry

Summary Nitrate traces in Antarctic snow and hoar-frost samples, which were collected on the Ekström ice shelf during January and February, 1987, were determined with ion chromatography at the German Antarctic station Georg-von-Neumayer. For comparison, sample preparations for isotope dilution mass spectrometry were also carried out at the German station whereas the mass spectrometric measurements took place in Regensburg. Comparable reproducibilities of 1%–5% were found for both methods of analysing nitrate concentrations in the range of 40–190 ng/g. An excellent agreement of the results of both methods with an average deviation of 0.1% was found in three sets of firn core samples. The average relative deviation of the ion chromatographic values from those of isotope dilution mass spectrometry was –10% for eleven hoar-frost and surface snow samples. The highest nitrate concentrations were analysed in hoar-frost samples with an average value of 548 ng/g. The following order, which corresponds to the age of nitrate depositions, was: new snow (206 ng/g), old surface snow (146 ng/g), and snow from firn cores (61 ng/g). The decreasing concentration with the age of samples is the result of re-emission of nitrate into the atmosphere after its deposition by snow. A seasonal variation of the nitrate concentration with a summer maximum and a winter minimum was observed for firn core samples. Accurate results of analytical data, which are published from all parts of Antarctica today, can only be guaranteed by the application of independent methods, e.g., by ion chromatography and isotope dilution mass spectrometry as it is shown in this work.

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Bestimmung von Nitrat im ng/g Bereich in antarktischen Schneeproben durch Ionen-Chromatographie und massenspektrometrische Isotopenverdünnungsanalyse

     

Anodic Stripping Potentiometric Determination of Cu,Pb, Cd and Zn In Natural Waters on a Novel Combined Electrode System

Abstract

A method is described for the reliable determination of copper, lead, cadmium and zinc in natural waters by anodic stripping potentiometry with the use of a novel combined electrode. The method involves two stripping cycles during which copper is initially determined on its own, followed by simultaneous determination of lead, cadmium and zinc after addition of gallium (III) ions. The optimum conditions include 0.01 M HCl as supporting electrolyte, 10 mg/L Hg (II) as chemical oxidant; E_dep(Cu) -700 mV vs Ag/AgCl; E_{dep(Pb,Cd,Zn)} -1200 mV vs Ag/AgCl; t_dep 10s; 150 μg/L Ga (III); sample rotation rate 5 and rest period 30s. Under these conditions, as low as 0.06 μg/L Cu (0.7% RSD); 0.2 μg/L Pb (13% RSD); 0.04 μg/L Cd (7.8% RSD) and 0.06 μg/L Zn (5.5% RSD) can be determined reliably. A linear concentration range of 0–110 μg/L was obtained for the four metals. The successful application of the method to reference fresh water, creek water and tap water is demonstrated.     

Ultrasensitive determination of heavy metals at the sub-picogram per gram level in ultraclean Antarctic snow samples by inductively coupled plasma sector field mass spectrometry

Assessing changes in heavy metals concentrations in Antarctic snow dated from the last century is of high interest to determine to which extent the most remote regions of our planet are contaminated for these metals, and to have a better understanding into their long-range transport from the different natural and anthropogenic source areas to the Antarctic continent. Such investigations are unfortunately very difficult because the concentrations to be measured are exceedingly low, down to the sub-picogram per gram level. They require a strict control of contamination problems from field sampling to laboratory analysis, and the use of ultrasensitive analytical techniques.

We present here important advances in the analytical protocols for obtaining reliable data on the occurrence of heavy metals in Antarctic snow. Utmost precautions were taken to obtain a series of large size ultraclean snow blocks from the wall of a 8.3 m clean hand-dug pit at a remote site in Coats Land, Antarctica. These blocks were then sub-sampled inside a laminar flow clean bench in a cold room, using ultraclean protocols, to provide high-resolution heavy metal times series. V, Cr, Mn, Cu, Ag, Ba, Pb, Bi and U were then determined directly, without any pre-concentration step, by the ultrasensitive inductively coupled plasma sector field mass spectrometry (ICP-SFMS) technique in clean room conditions. Calibration of the instrument was performed using ultralow concentrations standards, and extreme precautions were taken to ensure the cleanliness of the instrument and its introduction system. The results show that it is possible to accurately measure a variety of heavy metals in Antarctic snow, down to the sub-picogram per gram level, using this approach. Examples of the data obtained for the Coats Land site are finally presented. For U, the observed concentrations range from 0.004 to 0.21 pg/g; they are the first data ever obtained for this metal for Antarctic snow and ice.     

Determination of ethyl glucuronide and fatty acid ethyl esters in hair samples

Hair testing for alcohol biomarkers is an important tool for monitoring alcohol consumption. We propose two methods for assessing alcohol exposure through combined analysis of ethyl glucuronide (EtG) and fatty acid ethyl esters (FAEEs) species (ethyl myristate, palmitate, stearate and oleate) in hair (30 mg). EtG was analysed by liquid chromatography–tandem mass spectrometry, while FAEEs were analysed by gas chromatography–tandem mass spectrometry using electron impact ionization. Both methods were validated according to internationally accepted guidelines. Linearity was proven between 3 and 500 pg/mg for EtG and 30–5000 pg/mg for FAEEs, and the limits of quantification were 3 pg/mg for EtG and 30 pg/mg for each of the four FAEEs. Precision and accuracy were considered adequate, processed EtG samples were found to be stable for up to 96 h left in the injector and processed FAEEs samples for up to 24 h. Matrix effects were not significant. Both methods were applied to the analysis of 15 authentic samples, using the cut‐off values proposed by the Society of Hair Testing for interpretation. The results agreed well with the self‐reported alcohol consumption in most cases, and demonstrated the suitability of the methods to be applied in routine analysis of alcohol biomarkers, allowing monitoring consumption using low sample amounts.     

Neutron activation analysis of snow and ice in Antarctica

In order minimize the possible contamination during storing and pre-treatment of such pure samples as ice and snow collected in Antarctica, trace elements in experimental tools such as bottles, beakers, tubings and filters were determined by neutron activation analysis. By using well certified tools, ice and snow samples from Antarctica and high mountains in China and in Japan were analyzed. Relative concentrations of volatile elements such as Zn, Cd, As, Sb or Ag to Al or Fe which are major components in the earth crust were found to be 10 to 1000 times higher than in the ordinary soil for the samples from Antarctica and Mt. Naimonanyi in China.     

Industrial contaminants in Antarctic biota

A critical review of the levels and patterns of industrial contaminants in biota from Antarctica and the Southern Ocean revealed that concentrations are low with respect to other regions of the world, although in some specimens/species (e.g. leopard seal, some invertebrates) they are occasionally high and comparable to those found in regions with a strong human impact; the highest levels of persistent organic pollutants (POPs) were detected in the vicinity of scientific stations. Bioconcentration prevails at the lower trophic levels of pelagic food webs, while biomagnification can become the main route of contamination at higher levels. In a benthic food web, biomagnification poses a major risk for organisms that accumulate lipids to overwinter, compared to those that accumulate glycogen. Hexachlorobenzene, DDTs and chlordanes showed similar concentrations and patterns in the 1980s-1990s period in organisms from Western and Eastern Antarctica, while the polychlorinated biphenyls time trend was different in a variety of species from the two regions.