Geospeciation, toxicological evaluation, and hazard assessment of trace elements in superficial and deep sediments.

To evaluate the hazard assessment of dredging and disposal of sediments, an in-depth chemical and toxicological characterization of sediments was carried out in Venice Lagoon. The bioaccessible and mobile concentration of trace elements in superficial and deep sediments (in the Holocene-Pleistocene limit) can deeply affect the quality of the aquatic ecosystem. Geospeciation and total concentration of trace elements in sediment cores were assessed and several toxicological tests were carried out.

The use of cation exchange matrix separation coupled with ICP-MS to directly determine platinum group element (PGE) and other trace element emissions from passenger cars equipped with diesel particulate filters (DPF).

Inductively coupled plasma-mass spectrometry coupled with cation exchange matrix separation has been optimised for the direct determination of platinum group element (PGE) and trace element emissions from a diesel engine car. After matrix separation method detection limits of 1.6 ng g(-1) for Pd, 0.

Plasma selenoproteins concentrations in type 2 diabetes mellitus--a pilot study.

The association between the concentration/activity of selenium/selenoproteins in plasma and type 2 diabetes mellitus is still a matter of debate. This cross-sectional pilot study evaluates whether patients with diabetes present a different plasma selenoproteins status than a healthy control group and examines whether the introduction of clinical parameters allows the detection of correlations and further grouping criteria. For this purpose, the levels of plasma glutathione peroxidase (GPx), selenoprotein P (SelP), and seleno-albumin (SeAlb) present in 40 patients affected by type 2 diabetes mellitus were determined simultaneously and accurately by a newly developed analytical method.

Post 17th-century changes of European PAH emissions recorded in high-altitude Alpine snow and ice.

The occurrence of organic pollutants in European Alpine snow/ice has been reconstructed over the past three centuries using a new online extraction method for polycyclic aromatic hydrocarbons (PAH) followed by liquid chromatographic determination. The meltwater flow from a continuous ice core melting system was split into two aliquots, with one aliquot directed to an inductively coupled plasma quadrupole mass spectrometer for continuous trace elements determinations and the second introduced into a solid phase C18 (SPE) cartridge for semicontinuous PAH extraction. The depth resolution for PAH extractions ranged from 40 to 70 cm, and corresponds to 0.

Organic micropollutants in wet and dry depositions in the Venice Lagoon.

Atmospheric transport is an important route by which pollutants are conveyed from the continents to both coastal and open sea. The role of aerosol deposition in the transport of polycyclic aromatic hydrocarbons (PAHs), polychlorobiphenyls (PCBs) and polybromodiphenyls ethers (PBDEs) to water and soil systems has been evaluated by measuring their concentrations in wet and dry depositions to the Venice Lagoon. The organic micropollutant flux data indicate that they contribute to the total deposition flux in different ways through wet and dry deposition, showing that the prevalent contribution derives from wet deposition.

Assessment of a procedure to determine trace and major elements in atmospheric aerosol.

The determination of trace elements in atmospheric particulate is affected by a number of problems that arise from some critical points such as the blank of the filters, sample heterogeneity and pre-analytical treatments. In the framework of a monitoring campaign conducted in the Venice Lagoon the analytical methodology for the determination of 20 trace elements (Al, As, Ca, Cd, Co, Cr, Cs, Cu, Fe, K, Li, Mg, Mn, Na, Ni, Pb, Rb, Sr, V, Zn) in atmospheric particulate samples by inductively coupled plasma quadrupole mass spectroscopy (ICP-QMS) has been optimized taking into account the individual critical points. Tests were carried out to estimate the blank contributions, and minimize the detection limit (LOD), measurements were also carried out to evaluate the accuracy and the repeatability.

Simultaneous speciation analysis of glutathione peroxidase, selenoprotein P and selenoalbumin in human serum by tandem anion exchange-affinity HPLC and on-line isotope dilution ICP-quadrupole MS.

A method based on anion exchange (AE) and affinity (AF)-HPLC (AE-AF-HPLC) hyphenated to inductively coupled plasma-(quadrupole) mass spectrometry (ICP-QMS) was developed for the speciation analysis of selenoprotein P (SelP), glutathione peroxidase (GPx) and selenoalbumin (SeAlb) in human serum. AE-HPLC is proposed here for the on-line alleviation of Cl and Br spectral interferences on (77)Se ((40)Ar(37)Cl) and (82)Se ((81)Br(1)H). Separation of GPx, SelP and SeAlb by AE-AF-HPLC was obtained within a total chromatographic runtime of <20 min.

Atmospheric mercury depletion event study in Ny-Alesund (Svalbard) in spring 2005. Deposition and transformation of Hg in surface snow during springtime.

A field campaign was conducted in Ny-Alesund (78 degrees 54'N, 11 degrees 53'E), Svalbard (Norway) during April and May 2005. An Atmospheric Mercury (Hg) Depletion Event (AMDE) was observed from the morning of April 24 until the evening of April 27. Transport of already Hg and ozone (O3) depleted air masses could explain this observed depletion.

Direct determination of levoglucosan at the picogram per milliliter level in Antarctic ice by high-performance liquid chromatography/electrospray ionization triple quadrupole mass spectrometry.

A method for the direct determination of levoglucosan at the picogram per milliliter level in less than 1 mL of Antarctic ice has been developed. Chemical analysis is performed by high-performance liquid chromatography with triple quadrupole tandem mass spectrometric detection. Levoglucosan, a specific molecular marker for biomass burning, is identified by negative ion electrospray mass spectrometry using m/z 161/113, 161/101, 161/85, and 161/71 as monitoring ion transitions.

Pahs and trace elements in PM(2.5) at the Venice Lagoon.

The results of an experimental analysis carried out to investigate PM(2.5) concentration levels and the content of polycyclic aromatic hydrocarbons, as well as inorganic trace elements in the atmospheric particles are presented. Measurements were taken with a micrometeorological station equipped with an optical PM(2.

Direct determination of rare earth elements at the subpicogram per gram level in antarctic ice by ICP-SFMS using a desolvation system.

A method, based on inductively coupled plasma sector field mass spectrometry coupled with a microflow nebulizer and a desolvation system, has been developed for the direct determination of rare earth elements (REE) (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) down to the subpicogram per gram level (1 pg/g = 10(-12) g g(-1)) in approximately 1 mL of molten Antarctic ice. Contamination problems were carefully taken into account by adopting ultraclean procedures during the sample pretreatment phases. The use of a desolvation system for sample introduction during the analysis greatly reduced spectral interferences from oxide formation; the residual interfering contributions were calculated and subtracted whenever necessary.

Atmospheric PCB concentrations at Terra Nova Bay, Antarctica.

Concentrations of gas-phase polychlorobiphenyls (PCBs) were studied over an austral summer at a site in Terra Nova Bay, Antarctica. Gas-phase concentrations of individual PCB congeners in the atmosphere of Terra Nova Bay ranged from below the detection limit to 0.25 pg m(-3), with a mean concentration of sigmaPCB of 1.

Seasonal evolution of gas-phase PCB concentrations in the Venice Lagoon area.

The concentrations of gas-phase PCBs were measured from March 2002 to June 2003 at two sites of the Venice Lagoon and at one site of the Euganei hills. The aims of this study were to evaluate the various gas-phase PCB sources, the spatial and temporal variability of PCB concentrations in the gas-phase that enter the Venice Lagoon atmosphere and the influence of the air temperature on PCB trends. The highest annual average concentration of summation PCBs was observed at the station directly influenced by "urban" sources with values about 3 and 1.

Meteoric smoke fallout over the Holocene epoch revealed by iridium and platinum in Greenland ice.

An iridium anomaly at the Cretaceous/Tertiary boundary layer has been attributed to an extraterrestrial body that struck the Earth some 65 million years ago. It has been suggested that, during this event, the carrier of iridium was probably a micrometre-sized silicate-enclosed aggregate or the nanophase material of the vaporized impactor. But the fate of platinum-group elements (such as iridium) that regularly enter the atmosphere via ablating meteoroids remains largely unknown.

Transport of gas-phase polycyclic aromatic hydrocarbons to the Venice lagoon.

Concentrations of gas-phase polycyclic aromatic hydrocarbons (PAHs) were studied over one year at two sites of the Venice lagoon (designated Marine and Industrial) and at a mainland station (designated Rural) in Italy. Average sigmaPAH concentrations, calculated as sum of 16 PAHs, at Marine are about three and five times lower than those at Industrial and Rural, respectively. The seasonal trends, the temperature-PAH relationship, and principal component analysis indicate that at Industrial and Marine sites several local sources (vehicle and industrial emissions, etc.

Historical record of European emissions of heavy metals to the atmosphere since the 1650s from alpine snow/ice cores drilled near Monte Rosa.

Cr, Cu, Zn, Co, Ni, Mo, Rh, Pd, Ag, Cd, Sb, Pt, Au, and U have been determined in clean room conditions by inductively coupled plasma sector field mass spectrometry and other analytical techniques, in various sections of two dated snow/ice cores from the high-altitude (4450 m asl) glacier saddle Colle Gnifetti, Monte Rosa massif, located in the Swiss-Italian Alps. These cores cover a 350-year time period, from 1650 to 1994. The results show highly enhanced concentrations for most metals in snow/ice dated from the second half of the 20th century, compared with concentrations in ancient ice dated from the 17th and 18th centuries.

Trace element determination in seawater by ICP-SFMS coupled with a microflow nebulization/desolvation system.

Direct and simultaneous determination of Al, Ag, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Pb, Sb, U, V and Zn in diluted (1:10 v:v) seawater from the Antarctic Ocean and the Venice Lagoon at the ng mL(-1) and pg mL(-1) level has been performed by using an inductively coupled plasma sector field mass spectrometer (ICP-SFMS). Samples were analysed by using a PFA microflow nebulizer coupled with a desolvation system or a PFA microflow nebulizer coupled with a Teflon spray chamber, respectively. Measurements were carried out at low (LR, m/Delta m=300), medium (MR, m/Delta m=3,000) and high (HR, m/Delta m=7,500) resolutions depending on the studied isotope.

Atmospheric heavy metals in tropical South America during the past 22,000 years recorded in a high altitude ice core from Sajama, Bolivia.

V, Co, Cu, Zn, As, Rb, Sr, Ag, Cd, Ba, Pb, Bi and U have been analysed by inductively coupled plasma sector field mass spectrometry in various sections of a dated snow/ice core drilled at an altitude of 6542 m on the Sajama ice cap in Bolivia. The analysed sections were dated from the Last Glacial Stage ( approximately 22,000 years ago), the Mid-Holocene and the last centuries. The observed variations of crustal enrichment factors (EFc) for the various metals show contrasting situations.

Post-17th-century changes of European lead emissions recorded in high-altitude alpine snow and ice.

Lead concentrations and lead isotope ratios were analyzed in two firn/ice cores covering the period from 1650 to 1994, which were obtained from the 4450 m high glacier saddle Colle Gnifetti located in the Monte Rosa massif at the Swiss-Italian border. This study presents the first glaciochemical time series with annual resolution, spanning several centuries of lead concentrations and lead isotopic compositions in precipitation in Europe. Lead concentrations in firn dated from the 1970s are approximately 25 times higher than in ice dated from the 17th century, confirming the massive rise in lead pollution in Europe during the last few centuries.

Determination of polychlorobiphenyls and polycyclic aromatic hydrocarbons in the atmospheric aerosol of the Venice Lagoon.

An analytical method for simultaneous determination of "particle"-associated and "gaseous"-phase concentrations of polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH) in atmospheric aerosol samples obtained by high-volume samplers using polyurethane foam adsorbent (PUF) and quartz fibber filters (QFF) has been investigated. Quality control of the analytical procedure was carried out by blank control and by evaluating limits of detection, recoveries, accuracy, and repeatability. The proposed method was subsequently used to determine PAH and PCB in the "gaseous" and "particulate" phases of the aerosols that enter the Venice Lagoon atmosphere.

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.

Seasonal variations of heavy metals in central Greenland snow deposited from 1991 to 1995.

To better assess the seasonality in the fallout of heavy metals to central Greenland, a continuous series of 68 snow samples has been collected at a remote site in the Summit area from a 2.7 m pit using ultraclean sampling procedures. This covers a continuous four year time period from spring 1991 to spring 1995.

Short-term variations in the occurrence of heavy metals in Antarctic snow from Coats Land since the 1920s.

Short-term variations in heavy metals concentrations in Antarctic snow have been investigated by analysing 13 metals (Al, V, Cr, Mn, Co, Cu, Zn, Ag, Cd, Ba, Pb, Bi and U) in a series of ultraclean samples collected from two snow pits in Coats Land in the Atlantic sector of Antarctica. The samples covered a approximately 70 years time period from the 1920s to 1990. They were analysed by inductively coupled plasma sector field mass spectrometry and graphite furnace atomic absorption spectrometry.

Seasonal variations in nickel and vanadium in Mont Blanc snow and ice dated from the 1960s and 1990s.

Ni and V have been determined in snow and ice collected at a high altitude location (Col du Dôme) near the summit of Mont Blanc on the French-Italian border; dated from the 1960s and 1990s. Ni and V were simultaneously determined by inductively coupled plasma sector field mass spectrometry. Measured concentrations range from 6 to 700 pg g(-1) and 4 to 1,100 pg g(-1) for Ni and V, respectively.

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.