The distribution of dissolved thallium in the different water masses of the western sector of the Ross Sea (Antarctica) during the austral summer

Vertical profiles for total dissolved thallium were obtained at five sites in the western sector of the Ross Sea (Southern Ocean), Antarctica. Thallium is estimated to have a natural mean seawater concentration between 50 and 65 pmol L^{− 1} with higher values in the North Pacific (65 ± 5 pmol L^{− 1}) and lower in the Bay of Biscay and Irish Sea (49 ± 3 pmol L^{− 1}). Our samples show a concentration varying from 22 to 55 pmol L^{− 1} with a mean value of 46 pmol L^{− 1}, depending on depth, dissolved oxygen, salinity and local topographic characteristics. The analyses were performed using an ICP-SFMS that has enabled us to obtain reliable Tl concentration measurements with a relative standard deviation of better than 2.5% and a detection limit, calculated as three times the standard deviation of the “blank signal” of 0.69 pmol L^{− 1} (1.60 pmol L^{− 1}, obtained analysing four blank solutions (n = 5) prepared with the same water and acid used for the dilution/acidification steps). Thallium appears to have a nearly conservative distribution in seawater as highlighted also from the comparison with the profiles of two seawater conservative elements: molybdenum and uranium; however it also highlights the presence of a reactive component of thallium, which is more influenced by the presence of particulate matter, oxygen content and fluorescence.     

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.     

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.     

Evaluation of volatile chlorinated hydrocarbons distribution along depth profiles in the Ross Sea, Antarctica

The presence and the distribution along depth profiles of volatile chlorinated hydrocarbons (VCHCs) were evaluated in seawater samples collected in the Ross Sea (Southern Ocean, Antarctica) during the 2002-2003 Italian expedition. Sampling areas were located where the Circumpolar Deep Water interacts with the shelf waters that supply the Ross Sea.The VCHCs investigated were: 1,1,1-trichloroethane (C₂H₃Cl₃), tetrachloromethane (CCl₄), trichloroethylene (C₂HCl₃), tetrachloroethylene (C₂Cl₄). The analytical procedure consisted of a liquid-liquid extraction carried out with n-hexane directly in Antarctica, followed by gas chromatographic analysis with electron capture detection carried out in Italy.Concentration levels for the VCHCs analysed ranged from digits to hundreds of ng/L according to the station, depth and substance considered. Important differences in concentration levels between the three stations near the Ross Ice Shelf and the two stations located in the Cape Adare area were observed. In particular the stations situated in the Cape Adare zone, at certain depths, showed a thermal inversion due to the mixing of the Circumpolar Deep Water with the waters generated inside the Ross Sea Basin. The lowest concentration levels were recorded at this temperature increase.     

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).     

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.     

Use of radioactive kryptonate of thallium in the determination of oxygen dissolved in water or other liquids

Radioactive kryptonate of thallium is placed in the liquid sample. Oxygen dissolved in the sample reacts with the surface layer of radioactive kryptonate of thallium, and releases radioactive krypton in amount proportional to the amount of oxygen.     

The application of redox and induced reactions to the determination of thallium(III) in the presence of thallium(I)

Summary A new method of the determination of thallic ions [Tl(III)] in the presence of thallous [Tl(I)] ones, based on the oxidizing properties of Tl(III) towards cysteine was proposed. Cysteine was employed as an initiator in the iodineazide reaction and the oxidized part of the initiator was eliminated from the induced reaction medium by the respective redox reaction; the reaction products do not affect the above reaction. The contents of thallic ions (50–500 ng) in the sample can be determined from the progress in the induced reaction by measuring the unreacted iodine. The relative experimental error of the determination does not exceed 6%.     

Square-wave anodic-stripping voltammetric determination of Cd, Pb, and Cu in a hydrofluoric acid solution of siliceous spicules of marine sponges (from the Ligurian Sea, Italy, and the Ross Sea, Antarctica)

Square-wave anodic-stripping voltammetry (SWASV) was set up and optimized for simultaneous determination of cadmium, lead, and copper in siliceous spicules of marine sponges, directly in the hydrofluoric acid solution (approximately 0.55 mol L(-1) HF, pH approximately 1.9). A thin mercury-film electrode (TMFE) plated on to an HF-resistant epoxy-impregnated graphite rotating-disc support was used. The optimum experimental conditions, evaluated also in terms of the signal-to-noise ratio, were as follows: deposition potential -1100 mV vs. Ag/AgCl, KCl 3 mol L(-1), deposition time 3-10 min, electrode rotation 3000 rpm, SW scan from -1100 mV to +100 mV, SW pulse amplitude 25 mV, frequency 100 Hz, DeltaE(step) 8 mV, t(step) 100 ms, t(wait) 60 ms, t(delay) 2 ms, t(meas) 3 ms. Under these conditions the metal peak potentials were Cd -654 +/- 1 mV, Pb -458 +/- 1 mV, Cu -198 +/- 1 mV. The electrochemical behaviour was reversible for Pb, quasi-reversible for Cd, and kinetically controlled (possibly following chemical reaction) for Cu. The linearity of the response with concentration was verified up to approximately 4 microg L(-1) for Cd and Pb and approximately 20 microg L(-1) for Cu. The detection limits were 5.8 ng L(-1), 3.6 ng L(-1), and 4.3 ng L(-1) for Cd, Pb, and Cu, respectively, with t(d) = 5 min. The method was applied for determination of the metals in spicules of two specimens of marine sponges (Demosponges) from the Portofino natural reserve (Ligurian Sea, Italy, Petrosia ficiformis) and Terra Nova Bay (Ross Sea, Antarctica, Sphaerotylus antarcticus). The metal contents varied from tens of ng g(-1) to approximately 1 microg g(-1), depending on the metal considered and with significant differences between the two sponge species.     

234Th-based measurements of particle flux in surface water of the Bransfield Strait, western Antarctica

Measurements of particulate and dissolved ²³⁴Th were carried out in March 2002 in the Bransfield Strait located between the Antarctic Peninsula and the South Shetland Islands. The ²³⁴Th/²³⁸U disequilibrium found in the upper water column has allowed evaluation of downward particle fluxes across a frontal zone, which divides water masses coming from the Bellingshausen Sea and the Weddell Sea. The highest particle flux has been found in this mixing zone, where it was 3–5 times greater than in the adjacent waters. Total mass fluxes in the upper 150-m water column were estimated as about 2.2 g m^?2 day^?1 in the eastern part of the Strait and 3.1 g m^?2 day^?1 in the western area.     

Fulvic acid enrichment in the microlayer of the Gerlache Inlet Sea (Antarctica): preliminary results

The aim of this work was to study the presence of fulvic acids in Antarctic waters, as they appear to be principal film-forming components in the surface microlayer. We obtained a series of samples during two Antarctic Italian Expeditions in 1998/99 and 2000/01 and studied the distribution and the structural differences between fulvic acids extracted from both microlayer and subsurface waters.

Fulvic acids are concentrated in the microlayer and the enrichment factor between microlayer and subsurface water differs between samples. The enrichment factor values for fulvic acids lie between those found for dissolved organic carbon (DOC) and particulate organic carbon (POC) in the literature. Fulvic acids extracted from the microlayer were found to be different in structure from those present in the subsurface layer and enriched in sulphur content. We hypothesised that sulphur-containing compounds are slightly bound and/or occluded in fulvic acid structures. The sulphur-containing compounds analysed in the microlayer could be dimethylsulfide (DMS) and/or its products stemming from photochemical and biological oxidation reactions.     

Assessing the dynamics of chromophoric dissolved organic matter (CDOM) in the Yellow Sea and the East China Sea in autumn by EEMs-PARAFAC

In this study we have successfully characterized the fluorescent components of chromophoric dissolved organic matter(CDOM) in the Yellow Sea and the East China Sea in autumn using excitation-emission matrix fluorescence spectroscopy(EEMs) combined with parallel factor analysis(PARAFAC).PARAFAC aids the characterization of fluorescence CDOM by decomposing the fluorescence matrices into individual components.Four humic-like components(C1,C2,C3,and C4),one marine biological production component(C6),and two protein-like components(C5 and C7) were identified by PARAFAC.We researched the distributional patterns of fluorescence intensity,regression analyses between salinity,chlorophyll a concentration and fluorescence intensities of individual fluorophore,and regression analysis between salinity and fluorescence intensities percent of individual fluorophore.The results revealed that C2 and C4 showed conservative mixing behavior,while C1 and C3 possessed conservative mixing behavior in high salinity region and additional behavior in low and middle salinity region,which were considered to be derived from riverine and degradation of organic matter from resuspended and/or sinking particles and show non-conservative mixing behavior.In addition to riverine sources,the tryptophan-like C5 may receive widespread addition(likely from photo-degradation or biodegradation),while the most likely sources for the one marine humic-like C6 and tyrosine-like C7 were biological activity and microbial processing of plankton-derived CDOM,which were suggested to be of autochthonous origin and biologically labile.The application of EEM-PARAFAC modeling presents a unique opportunity to observe compositional changes,different mixing behavior and temporal variability in CDOM in the Yellow Sea and the East China Sea.     

A multinuclear NMR study in the solid state and in solution of thallium(I) tris-(pyrazol-1-yl)borates (thallium scorpionates)

The ¹H, ¹³C and ¹⁵N NMR spectroscopic properties of six thallium tris-(pyrazol-1-yl)borates, including a tetrakis derivative, were determined. The results in solution were necessary to understand those, more complicated, in the solid state. A collection of ²⁰⁵Tl-¹⁵N and ²⁰⁵Tl-¹³C couplings was measured in the latter state. Among those, a very large coupling constant (between 194 and 282 Hz) has been measured on the carbon at the position 4 of the pyrazole ring in several compounds and particularly for the cyclobutyl derivative [Tl(Tp^Cbu)]. It has been assigned to a direct interaction of the 4-C-H ? Tl type and related to the X-ray structures, when available.     

The behaviour of copper and thallium hexafluoromolybdates(V) in acetonitrile

Copper(I), copper(II), and thallium(III) hexafluoromolybdates(V), prepared by the oxidation of the metals in acetonitrile with molybdenum hexafluoride (A. Prescott, D.W.A.Sharp, and J.M. Winfield, $\text{J. Chem. Soc., Dalton Trans.}$, 1975, 963) have been investigated by cyclic voltametry. Half wave potentials, E_{$\text{1}\text{2}$} V vs. Ag^p+/Ag were obtained using a evacuable cell equipped with anexternal Ag^p+/Ag electrode, enabling strict anerobic conditions to be maintained. A number of reversible or quasi-reversible electron transfer processes have been observed, enabling comparison with synthetic work to be made. Results for Cu^I and Cu^II hexafluoromolybdates(V) are in accord with preparative experience. MoF₆. Mo^VI/Mo^VE_{$\text{1}\text{2}$} +1.600V, oxidises Cu metal to Cu^II in MeCN, and Cu^II is reduced by Cu^O to Cu^I , Cu^lI/Cu^IE_{$\text{1}\text{2}$} = +0.750 or +0.710V for Cu^I and Cu^II solutes respectively, Cu^I/Cu^OE$\text{1}\text{2}$ = ?0.720V not reversible. A wave at E_{$\text{1}\text{2}$} = ?0.350V is assigned to Mo^V/Mo^IV by analogy with Ag^I hexafluoromolybdate (D.W.A. Sharp, unpublished work). E_{$\text{1}\text{2}$} data for I₂ in MeCN, I₂/I₃^- = 0.280, I₃^?/I^? = -0.116V, suggest that reduction of MoF₆^? by I is not likely, in contrast to the situation in SO₂ (A.J. Edwards and R.D. Peacock, $\text{Chem. Ind.}$, 1960, 1441). Reduction of MoF₆^? by Cu^o in MeCN should be feasible, but appears to be very slow. Pure Tλ^III hexafluoromolybdate(V) is obtained from Tλ^o and MoF₆ only when the mole ratio MoF₆:Tλ>5:1. Smaller ratios produce yellow solids in which Mo:Tλ is $\text{ca}$. 2:1. Tλ^III is a stronger oxidising agent than Cu^II in MeCN, as oxidation of Cu^I by Tλ^III is rapid and quantitative. However a reversible electron transfer wave assignable to Tλ^III/Tλ^I is not observed in the expected fange +1.600 to +0.710V possibly because of solute-electrode interactions.     

Volume change of ion pair formation: Rubidium nitrate and thallium(I) nitrate in water

Density data for dilute aqueous solutions of RbNO ₃ and TlNO ₃ at 25°C lead to the following equations for the apparent molal volumes: RbNO₃: Φ_V = 43.0₇ + 2.46c ^1/2 + 0.15c (0?0.41M) TINO₃: Φ_V = 39.5₀ + 10.83c ^1/2 ? 25.46c + 26.0c ^3/2 (0.03?0.25M) From these expressions and a semiempirical equation for Φ_v of a completely dissociated 1:1 electrolyte, values of ΔΦ_v for ion pair formation at c=0.10 are calculated to be+5 ml-mole^?1 for RbNO ₃ and+12 ml-mole^?1 for TlNO ₃ . Comparison of ΔΦ_v with the electrostriction volume effect suggests that virtually all of the electrostriction is removed in the formation of the TlNO ₃ ion pair but only about half with RbNO ₃ . Values of ΔΦ_v are in poor agreement with those estimated from electrostatic theories of ion pair formation.     

Sea water contamination in underground waters of salento (Southern Italy)

In the present work, a study of a physico-chemical characterisation of underground waters, utilised for agriculture and human use in the Lecce district (Southern Italy) has been reported. The aim of the work has been to define the quality of underground waters in the different areas and to value salt contamination due to seawater intrusion. Statistical techniques, such as Principal Component Analysis (PCA) and Cluster Analysis (CA), have been utilised to examine the correlations among the different parameters and to define contamination areas. The results have shown a high salt contamination in artesian wells of the Ionian Sea coast.     

The determination of thallium(III) with the 2,2'-bipyridyl-iron(II) chelate

A spectrophotometric determination of thallium (III), based on solvent extraction of an ion-association pair formed between the cationic 2,2'-bipyridyl-iron(II) chelate and the anionic thallium(III) bromide complex is described. The best extractant is 1,2-dichloroethane and extraction is possible over the pH range 2.5–6.7. The composition of the extracted species was confirmed, and conditions were established for the extraction over the concentration range 7.9·10^-6–3.5·10^-5M of thallium in aqueous solution.