Bromine, iodine and sodium along the EAIIST traverse: Bulk and surface snow latitudinal variability.

During the East Antarctic International Ice Sheet Traverse (Eaiist, december 2019), in an unexplored part of the East Antarctic Plateau, snow samples were collected to expand our knowledge of the latitudinal variability of iodine, bromine and sodium as well as their relation in connection with emission processes and photochemical activation in this unexplored area. A total of 32 surface (0-5 cm) and 32 bulk (average of 1 m depth) samples were taken and analysed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Our results show that there is no relevant latitudinal trend for bromine and sodium. For bromine they also show that it has no significant post-depositional mechanisms while its inland surface snow concentration is influenced by spring coastal bromine explosions. Iodine concentrations are several orders of magnitude lower than bromine and sodium and they show a decreasing trend in the surface samples concentration moving southward. This suggests that other processes affect its accumulation in surface snow, probably related to the radial reduction in the ozone layer moving towards central Antarctica. Even though all iodine, bromine and sodium present similar long-range transport from the dominant coastal Antarctic sources, the annual seasonal cycle of the ozone hole over Antarctica increases the amount of UV radiation (in the 280-320 nm range) reaching the surface, thereby affecting the surface snow photoactivation of iodine. A comparison between the bulk and surface samples supports the conclusion that iodine undergoes spring and summer snow recycling that increases its atmospheric lifetime, while it tends to accumulate during the winter months when photochemistry ceases.

Domoic acid at trace levels in lagoon waters: assessment of a method using internal standard quantification.

Domoic acid (DA) is a neurotoxin produced by different algae, including pennate diatoms, principally from the genus Pseudo-nitzschia, and it is the main cause of amnesic shellfish poisoning. Determination of this toxin in seawater samples is fundamental to define the real contamination risks for aquatic species. We have developed two very sensitive instrumental methods using hydrophilic interaction liquid chromatography coupled using tandem mass spectrometry in positive and negative polarity modes. Instrumental detection limits were 9 pg mL(-1) for positive and 19 pg mL(-1) for negative ionisation. A procedural method based on solid-phase extraction for the determination of dissolved DA present in seawater has been developed, and an extraction procedure was employed for the determination of the toxin in the particulate fraction. DA quantification was performed using the internal standard method to account for signals fluctuations and random errors during sample treatment. To our knowledge, this is the first study to use this quantification method for DA determination. Trueness, extraction yield, matrix effects, repeatability and procedural detection limits were evaluated during method validation. Procedural detection limits of 0.3 pg mL(-1) (positive mode) and 0.6 pg mL(-1) (negative mode) were found for the dissolved fraction, and absolute limits of 0.4 pg (positive mode) and 6.0 pg (negative mode) for particulate samples were obtained. The most sensitive method in positive mode was applied to define DA occurrence in the Venice Lagoon. Trace concentrations of domoic acid ranging from 1.5 to 16.2 pg mL(-1) were found for the first time in the Venetian environment.

The direct influence of ship traffic on atmospheric PM2.5, PM10 and PAH in Venice.

The direct influence of ship traffic on atmospheric levels of coarse and fine particulate matter (PM(2.5), PM(10)) and fifteen polycyclic aromatic hydrocarbons (PAHs) has been estimated in the urban area of Venice. Data analysis has been performed on results collected at three sites over the summer, when ship traffic is at a maximum. Results indicate that monitoring of the PM daily concentrations is not sufficiently detailed for the evaluation of this contribution, even though it could be useful for specific markers such as PAHs. Therefore a new methodology, based on high temporal resolution measurements coupled with wind direction information and the database of ship passages of the Harbour Authority of Venice has been developed. The sampling sites were monitored with optical detectors (DustTrack(®) and Mie pDR-1200) operating at a high temporal resolution (20s and 1s respectively) for PM(2.5) and PM(10). PAH in the particulate and gas phases were recovered from quartz fibre filters and polyurethane foam plugs using pressurised solvent extraction, the extracts were then analysed by gas chromatography- high-resolution mass spectrometry. Our results shows that the direct contribution of ships traffic to PAHs in the gas phase is 10% while the contribution to PM(2.5) and to PM(10) is from 1% up to 8%.

Elemental labeling for the identification of proteinaceous-binding media in art works by ICP-MS.

In the history of art, artists have used many different organic compounds to dissolve pigments and apply them onto a support to obtain a paint layer. Proteins were used with success from the Middle Ages up to the Renaissance, and the traditional protein sources were animal parts (skins, tendons and bones) or milk and eggs. Moreover, some of these materials are commonly used as adhesive. In this paper, the first application of the metallomic analytical technique to the identification of proteins in artworks is reported. Samples were derivatized with DTPA/Eu and the derivatization procedure was evaluated by matrix-assisted laser desorption/ionization time-of-flight before high performance liquid chromatography inductively coupled plasma MS analysis. This study has been carried out on laboratory models prepared in-house for method development, resulting in the correct identification of the different classes of proteinaceous binders typically used. In addition, some unknown paint layer samples have been analyzed demonstrating that the method is applicable to very small sample amounts (0.6 mg), which are compatible with the amount normally available for this kind of analysis. The results obtained demonstrate the effectiveness of the method, suggesting the potential future use as novel diagnostic tool in the scientific study of artworks.

Speciation analysis of mercury in seawater from the lagoon of Venice by on-line pre-concentration HPLC-ICP-MS.

A method based on the coupling of HPLC with ICP-MS with an on-line pre-concentration micro-column has been developed for the analysis of inorganic and methyl mercury in the dissolved phase of natural waters. This method allows the rapid pre-concentration and matrix removal of interferences in complex matrices such as seawater with minimal sampling handling. Detection limits of 0.07 ng L(-1) for inorganic mercury and 0.02 ng L(-1) for methyl mercury have been achieved allowing the determination of inorganic mercury and methyl mercury in filtered seawater from the Venice lagoon. Good accuracy and reproducibility was demonstrated by the repeat analysis of the certified reference material BCR-579 coastal seawater. The developed HPLC separation was shown to be also suitable for the determination of methyl mercury in extracts of the particulate phase.

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 1.5 times higher compared to the concentrations found at the stations where "marine" sources and "not subjected to direct local sources" were respectively sampled from. The temporal trends of summation PCBs concentrations were similar at the three sampling stations corresponding to seasonal temperature changes. Greater concentrations occurred in the summer and first autumn months while the lower ones occurred in late autumn and winter. The temperature dependences were investigated using plots of the natural logarithm of the summation PCBs concentrations vs. reciprocal mean temperatures.

Development of an ombrotrophic peat bog (low ash) reference material for the determination of elemental concentrations.

Given the increasing interest in using peat bogs as archives of atmospheric metal deposition, the lack of validated sample preparation methods and suitable certified reference materials has hindered not only the quality assurance of the generated analytical data but also the interpretation and comparison of peat core metal profiles from different laboratories in the international community. Reference materials play an important role in the evaluation of the accuracy of analytical results and are essential parts of good laboratory practice. An ombrotrophic peat bog reference material has been developed by 14 laboratories from nine countries in an inter-laboratory comparison between February and October 2002. The material has been characterised for both acid-extractable and total concentrations of a range of elements, including Al, As, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Na, Ni, P, Pb, Ti, V and Zn. The steps involved in the production of the reference material (i.e. collection and preparation, homogeneity and stability studies, and certification) are described in detail.