Winter evolution of DMS and DMSP in Venice lagoon water and sediment

The evolution of dimethylsulphide (DMS) and dimethylsulphoniopropionate (DMSP) concentrations in the water and sediment of the Venice lagoon were studied together with the concentration of chlorophyll a, temperature and the composition and density of phytoplankton to understand the role of the sediment as a source of DMS during the winter period. The temporal trend of water DMS concentration in this period showed a maximum concentration in February (75.7 nmol S l-1) related to low DMSP and chlorophyll a concentrations but to high phytoplanktonic abundance. The DMS and DMSP concentrations were greater in the sediment than in the water. The temporal trend of DMS concentration in sediment showed a maximum in February (1155 nmol S l-1) related to the maximum of DMS concentration in surface water. These observations suggested that in the winter period DMS could be produced by the conversion of the DMSP present in the bulk water but principally by that present in the sediment (microbiological degradation of DMSP or other sulphur-containing compounds) that subsequently diffuse in water.     

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.     

Determination of Trace Metals in Antarctic Sediments from Terra Nova Bay - Ross Sea

Abstract

Trace metals (Cu, Pb, Zn, Cd, Cr, Ni, Co, Mn) and iron concentration were determined in several sediments collected in the Antarctica (Terra Nova Bay—Ross Sea). Samples were analyzed by inductively coupled plasma (ICP-AES) after selective and total extraction. The results are in good agreement with the data previously collected in the same area.     

Distribution of humic substances dissolved and particulated in water column in Ross Sea, Antarctica

Dissolved (DFA) and particulate (PFA) fulvic acids were studied in some areas of the Ross Sea (Antarctica) characterised by different water masses. Our interest was focused on their distribution in the water column. Moreover, their correlation with fluorescence data and structural characterisation in relation to the water masses was also studied. We found that PFA concentration was mainly influenced by the primary production in surface layers and by stratification of water masses along the water column. Conversely, the DFA are less influenced by primary production and by the stratification of the water masses. An early stage of the humification process can be hypothesised for PFA related to DFA as shown by elemental analyses and spectroscopic data. PFA collected in the bottom depths of the water column showed a relationship with age of water mass (the highest concentration was found for the oldest circulating water mass (CDW)). This relationship was not observed for DFA. Moreover, any significant difference in structure was found in the DFA and PFA extracted from samples collected at bottom depths.     

Precise measurement of Fe isotopes in marine samples by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS)

A novel analytical technique for isotopic analysis of dissolved and particulate iron (Fe) from various marine environments is presented in this paper. It combines coprecipitation of dissolved Fe (DFe) samples with Mg(OH)₂, and acid digestion of particulate Fe (PFe) samples with double pass chromatographic separation. Isotopic data were obtained using a Nu Plasma MC-ICP-MS in dry plasma mode, applying a combination of standard-sample bracketing and external normalization by Cu doping. Argon interferences were determined prior to each analysis and automatically subtracted during analysis. Sample size can be varied between 200 and 600 ng of Fe per measurement and total procedural blanks are better than 10 ng of Fe. Typical external precision of replicate analyses (1S.D.) is ±0.07‰ on δ⁵⁶Fe and ±0.09‰ on δ⁵⁷Fe while typical internal precision of a measurement (1S.E.) is ±0.03‰ on δ⁵⁶Fe and ±0.04‰ on δ⁵⁷Fe. Accuracy and precision were assured by the analysis of reference material IRMM-014, an in-house pure Fe standard, an in-house rock standard, as well as by inter-laboratory comparison using a hematite standard from ETH (Zürich). The lowest amount of Fe (200 ng) at which a reliable isotopic measurement could still be performed corresponds to a DFe or PFe concentration of ∼2 nmol L⁻¹ for a 2 L sample size. To show the versatility of the method, results are presented from contrasting environments characterized by a wide range of Fe concentrations as well as varying salt content: the Scheldt estuary, the North Sea, and Antarctic pack ice. The range of DFe and PFe concentrations encountered in this investigation falls between 2 and 2000 nmol L⁻¹ Fe. The distinct isotopic compositions detected in these environments cover the whole range reported in previous studies of natural Fe isotopic fractionation in the marine environment, i.e. δ⁵⁶Fe varies between −3.5‰ and +1.5‰. The largest fractionations were observed in environments characterized by redox changes and/or strong Fe cycling. This demonstrates the potential use of Fe isotopes as a tool to trace marine biogeochemical processes involving Fe.     

First Systematic Voltammetric Measurements of Cd,Pb, and Cu in Hydrofluoric Acid-Dissolved Siliceous Spicules of Marine Sponges: Application to Antarctic Specimens

Ultrasensitive Square Wave Anodic Stripping Voltammetry is used for the first time for the systematic determination of Cd, Pb, and Cu in siliceous spicules of marine sponges; the procedure is performed directly in hydrofluoric acid solution, according to a procedure previously established in our laboratory, with the aim of demonstrating the feasibility of such measurements and to improve knowledge of heavy metal distribution in Porifera. The following Demospongiae species are considered: Sphaerotylus antarcticus, Haliclona sp., Kirkpatrickia coulmani, and Inflatella belli from the Ross Sea, Antarctica, and Petrosia ficiformis from the Mediterranean Sea, Italy. The method shows a good accuracy; the analytical variability is approximately ±10% for all the metals studied and for all the measurements performed, showing a good repeatability of the method in consideration of low metal concentrations (order of tenths of µg g^?1 dry weight, i.e., of hundreds of ng L^?1 in the HF solution). In particular, the concentrations of heavy metals in the body of the sponge vary in the range 0.038–0.93 µg g^?1 dry weight (d.w.) for Cd, 0.024–0.52 µg g^?1 d.w. for Pb, and 0.32–1.3 µg g^?1 d.w. for Cu. Similar ranges of concentration were recorded in the oscula of S. antarcticus and I. belli. Heavy metal concentration in the spicules can vary within and between specimens and, in particular, siliceous spicules of Antarctic sponges show higher concentrations of Cd and Pb and lower concentrations of Cu than those from the Mediterranean.     

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.     

高时空分辨率研究海盐液滴快速风化过程

以高速摄像仪与显微拉曼光谱联用研究聚四氟(疏水)乙烯基底和石英(亲水)基底上的单个海水液滴的快速风化过程.海水液滴风化的形貌图像达到毫秒时间分辨率和微米空间分辨率.通入干氮气后海水液滴在石英基底上发生快速风化过程,首先析出Na2Ca5(SO4)6·3H2O和Na2xCa8-x(SO4)6·3H2O(0＜x＜1)晶体,然后析出NaCI晶体,最后析出KMgCl3·6H2O晶体.我们发现在快速降低湿度的过程中析出钙钠复盐,在缓慢降低湿度的过程中析出CaSO4·2H2O,并已经确定各种结晶产物的位置以及Na2Ca5(SO4)6·3H2O和CaSO4· 2H2O两种晶体的生长速率,并在聚四氟乙烯基底上观察到中空结构的海盐颗粒.     

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.     

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.     

Levels of essential and potentially toxic trace metals in Antarctic macro algae

Eleven species of Antarctic algae were examined for their accumulation ability in the uptake of different metals and metalloids from the Antarctic aquatic environment. Macro algae were collected during the 2000 austral summer season at Jubany Station (Argentinean base) around Potter Cove, King George Island. The elements quantified were: As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Se, Sr, V, and Zn. An optimized microwave-assisted digestion procedure was used to digest the samples and the elements were determined by inductively coupled plasma optical emission spectrometry. A wide range of metal retention capacity among the different species was observed. The highest levels of trace elements were found in Monostroma hariotii and Phaeurus antarcticus, with concentrations up to 3095 μg g⁻¹ for Fe. On the basis of the levels of trace elements observed in Monostroma hariotii and its wide distribution in the Antarctic Peninsula, this organism accomplishes a number of prerequisites to be considered as an adequate biomonitor for future studies.     

Study of organic sulphur compounds (DMS,DMSP and CS2) in lagoon ecosystems: the case of the Venice lagoon

This study of the origin and fate of dimethyl sulphide (DMS) in a particular and complex lagoon ecosystem such as that of the Venice lagoon focuses on the temporal evolutions of DMS concentrations in surface water together with those of dimethylsulphoniopropionate (DMSP), carbon disulphide (CS2), nutrients (nitrate, nitrite, ammonium, phosphate, silicate), sulphate, chlorophyll a, chlorinity, water temperature and phytoplankton (composition and density). Measurements were made from 3 March 1997 to 23 July 1998 at three stations in the central part of the Venice lagoon. The temporal trends of DMS concentration showed an absolute maximum concentration in winter (65 nmol S/l, 19/2/1998, Stn. 1; 119 nmol S/l, 19/2/1998, Stn. 2; 29 nmol S/l, 17/2/1998, Stn. 3) and two relative maxima in the spring-summer period. The spring-summer secondary maxima of DMS concentration were related to the maxima of DMSP and chlorophyll a concentrations and consequently to phytoplanktonic abundance while the winter DMS maximum showed no relation to DMSP or to chlorophyll a suggesting that the production and the fate of DMS could be different for the two periods. According to previous studies the CS2 concentration increased in the spring, achieved its maximum in summer, decreased in autumn and fell to its minimum in winter.     

南极冰雪样品中超痕量重金属的分析测定进展

本文全面阐述了南极冰雪样品中重金属分析测定的发展概况和极地样品分析中出现的困难，评述了各种分析方法（包括富集技术、超灵敏的分析技术）的优缺点，并指出其发展方向。引用文献４７篇。     

Simultaneous determination of chlorophyll a and chlorophyll b by derivative spectrophotometry

Chlorophyll a (Chl a) and chlorophyll b (Chl b) plant pigments, which are important in the food industry and are beneficial as environmental pollution indicators, have been extracted with a novel solvent mixture (1:1 v/v acetone–propanol) not containing chloroform and simultaneously determined by first-derivative spectrophotometry. The results were statistically compared to those obtained by the ordinary absorption spectrophotometric reference utilizing the principle of additivity of absorbances. The testing of the developed method in synthetic mixtures of Chl a and Chl b and in real plant material samples (grass, spinach, chard, purslane, black cabbage, crisp lettuce, rocket, dill and seaweed) proved successful in that the developed extractive derivative spectrophotometric method was both rapid and precise, and was not dependent on the Chl a/b ratio in contrast to the reference method which was adversely affected by the latter parameter.     

Temporal evolution of lead isotope ratios and metal concentrations in sediments of the north Aegean Sea,in Turkish coast

In present research, fifteen surficial and two profile sediment samples were studied in terms of sediment chronology and pollution degree on the ground of pollution indexes such as enrichment factor (EF), contamination factor (CF), Pollution Load Index (PLI) and lead isotope ratios (²⁰⁶Pb/²⁰⁷Pb, ²⁰⁸Pb/²⁰⁶Pb). Lead-210 (polonium-210) activity concentrations were measured by utilizing alpha spectrometry. Sediment chronology was determined via modified CRS mathematical model. Average mass accumulation rates are 0.301 and 0.227 g cm^?2 year^?1 in Bak?rçay River mouth and Ayval?k offshore stations respectively. Mass accumulation rates do not display the systematic increases along the cores from bottom layers to top layers. In Bak?rçay River mouth station ²¹⁰Pb flux is higher than the range of global atmospheric ²¹⁰Pb flux value. Due to the high CF and EF values of Sr both of stations have hydrothermal features. Ayval?k offshore station has displayed Na, Cd pollution since 1945, but Na, Cd, As, Mo, Ag pollutions have existed in Bak?rçay River mouth station since 1983 in terms of CF and EF values. According to PLI index, Bak?rçay River mouth station has “starting level pollution” degree and it displayed an “acute corruption” in 1981. ²⁰⁶Pb/²⁰⁷Pb ratios range from 1.17 to 1.25, ²⁰⁸Pb/²⁰⁶Pb ratios range from 1.99 to 2.16 in study area. When ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb ratios are evaluated with together, it is seen that both of the stations have had the natural (geologic) sediments since 2011.     

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.     

‘Extreme Mass Spectrometry’: the role of mass spectrometry in the study of the Antarctic Environment

A focus on the studies of the Antarctic environment that have been performed by mass spectrometry is presented herein; our aim is to give evidence of the essential role of this instrumental technique in the framework of the scientific research in Antarctica, with a comprehensive review on the main literature of the last two decades. Due to the wideness of the topic, the present review is limited to the determination of organic pollutants, natural molecules and biomarkers in Antarctica, thus excluding elemental analysis and studies on inorganic species. The work has been divided into five sections, on the basis of the considered environmental compartment: air; ice and snow; seawater, pack ice and lakes; soil and sediments; and organisms and biomarkers. Copyright © 2014 John Wiley & Sons, Ltd.     

Metabolomic Profiling,Antioxidant and Enzyme Inhibition Properties and Molecular Docking Analysis of Antarctic Lichens

The lichen species Lecania brialmontii, Pseudephebe pubescens, and Sphaerophorus globosus are part of the prominent lichenoflora of the Antarctic territory. In this work, we report the metabolomic identification of ethanolic extracts of these species, their antioxidant and cholinesterase enzyme inhibitory activity, and conduct a molecular docking analysis with typical compounds. Eighteen compounds were identified by UHPLC-ESI-QTOF-MS in L. brialmontii, 18 compounds in P. pubescens, and 14 compounds in S. globosus. The content of phenolic compounds was variable among the species, ranging from 0.279 to 2.821 mg AG/g, and all three species showed high inhibition potential on the cholinesterase enzymes. Molecular docking showed important interactions between AChE and BChE with the selected compounds. This study evidences the chemical fingerprint of three species of the order Lecanorales that support the continuation of the study of other biological activities and their potential for medical research.     

Spatial and temporal distribution of environmental markers from Coastal to Plateau areas in Antarctica by firn core chemical analysis

The chemical analysis of shallow firn cores sampled in coastal and plateau areas in Northern Victoria Land and along a transect from Talos Dome to Dome C (East Antarctica, Pacific Ocean sector) allowed a global view of spatial and temporal changes in chemical composition of snow depositions over the last 100 years. Variations in concentration of primary (sea spray) and secondary (biogenic emission, atmospheric inputs) source markers were observed and discussed as a function of distance from the sea and altitude.

In the stations characterized by relatively high snow accumulation rates, the sub-sampling resolution was sufficient to obtain a stratigraphic dating by using the periodical variations of seasonal markers. In these stations, a subdivision in “summer” and “winter” samples was carried out in order to study the seasonal changes of the contributions of the measured compounds to the snow composition as elevation and distance from the sea increase.

Some evidence of post-depositional effects which are able to change the original deposition of chloride and nitrate, was observed at stations with low accumulation rates. The reliability of the depth/concentration profile of these substances for reconstructing past deposition was also discussed.     

Development of a sampling and flow injection analysis technique for iron determination in the sea ice environment

A trace metal clean method for sampling and analysis of iron is set up and applied to sea ice and its associated snow, brine, and underlying seawater sampled during the Antarctic expedition “ARISE in the East” (Antarctic Remote Ice Sensing Experiment, AA03-V1, September-October 2003, 64-65°S/112-119°E, RV Aurora Australis). For clean sampling, a non-contaminating electropolished stainless steel ice corer is designed in conjunction with a polyethylene lathe equipped with Ti chisels to remove possibly contaminated outer layers of ice cores. A portable peristaltic pump with clean tubing is used on the ice to sample the underlying seawater (interface ice-water = 0, 1 and 30 m) and sea ice brine from access holes. Considering the extreme range of salinities (1-100) and Fe concentrations (0.1-100 nM) previously observed in similar environments, it is of paramount importance to set up a simple and sensitive Fe analyser adapted to such gradients. We use a flow injection analysis (FIA) technique and successfully demonstrate its capability to measure Fe concentrations directly in the sample without an on-line preconcentration/matrix separation step. We test the sensitivity, accuracy, precision and long-term stability of the analytical procedure. Also we explore and remediate interferences from a suite of other trace elements, such as Ni, Cd, Cr, Mn, Cu, Zn and Co. Analysis of reference materials NASS-5 and CASS-3 gives a good agreement with the certified values. Repeated measurements over a period of 5 months of an “in-house” Antarctic seawater standard yields a concentration of 1.02 ± 0.07 nM (n = 17, 1σ). The detection limit (3σ of the blank) is on average 0.12 nM. We report here results of the Fe distribution in sea ice that are in good agreement with previously published data. To our knowledge, this work provides the first complete profiles of total dissolvable and dissolved Fe in sea ice.