Carmela Ianni

Distribution of polycyclic aromatic hydrocarbons in the sediments of the Adriatic Sea

Distribution of the sixteen polycyclic aromatic hydrocarbons (PAHs) indicated from USEPA as priority pollutants was studied in surface sediments of two coastal areas of the Adriatic Sea. PAHs were recovered from the sediments by solvent extraction and then analyzed by means of gas chromatography-mass spectrometry. Total concentrations of the analytes in the range 24.1-501.1 ng/g were detected. The observed distribution has been discussed taking into account different aspects, such as the fluvial inputs and the grain size of the sediments. By using a molecular marker approach and characteristic compositional patterns it was possible to ascribe to combustion processes the main source of PAHs. Furthermore a good correlation between benzo[a]pyrene and the total concentration of PAHs (r=0.953) has been pointed out.

Trace metals distributions in coastal sea ice of Terra Nova Bay, Ross Sea, Antarctica

In an attempt to clarify the release of trace elements from the seasonal coastal sea ice, samples were periodically collected in a nearshore station inside the Gerlache Inlet (Terra Nova Bay, Western Ross Sea), during the summer 2000/01 and analysed for dissolved and particulate cadmium, copper, iron, manganese and lead, as well as salinity, suspended particulate matter, nutrients and phytoplankton pigments. In order to provide insight on the metal association with the particles included in the sea ice, the metal solid speciation was also investigated. Both vertical distributions within the ice cores and temporal variations at the seawater interface were studied, in an effort to fully characterize the system and correlation among the considered parameters. Concentrations and speciation patterns clearly indicate metal incorporation within the annual sea ice due to resuspension of sediments, followed by release of particulate metals during melting as a primary process affecting trace metal availability in the Antarctic coastal waters.

An optimum multiparameter mixing analysis of the shelf waters in the Ross Sea

The analysis of the mixing processes involving water masses on the Ross Sea continental shelf is one of the goals of the CLIMA project (Climatic Long-term Interactions for the Mass balance in Antarctica). This paper uses extended Optimum MultiParameter analysis (OMP), which is applied to four datasets collected during the cruises of 1994/95, 1995/96, 1997/98 and 2000/01 in the Ross Sea (Antarctica). Data include both hydrological, (temperature, salinity, and pressure; T, S, and P, respectively) and chemical parameters (O2, Si(OH)4, PO4, and NO3+NO2). The OMP analysis is based on the assumption that the mixing is a linear process which affects all parameters equally so that each sample shows physical/chemical properties that are the result of the mixing of some properly selected Source Water Types (SWTs). OMP thus evaluates the best set of contributions by all SWTs to each sample, and allows the spatial distribution and structure of the water masses in a basin to be evaluated. Ocean circulation may subsequently be inferred by means of a deeper analysis of the spreading of the water mass. In this study, the “real” Redfield ratios observed in the Ross Sea were used to correct the equations referring to the chemical parameters in accordance with the extended version of OMP. The solutions include some physically realistic constraints. The results allow a detailed description of the water mass distribution, validated through comparison with some “canonical” thermohaline characteristics of the Ross Sea hydrology. In particular our results verify the spreading of the HSSW over the entire continental shelf and emphasize the key role it plays in the ventilation of the deep waters outside the Ross Sea. In addition a description is given of the intrusion of relatively warm waters coming from the open ocean and flowing at some specific locations at the continental shelf break.

Trace metals in Adriatic coastal sediments: Distribution and speciation pattern

Abstract In the framework of the Italian National Project for the safeguard of Adriatic Sea (PRISMA 2), distribution of trace metals in surface coastal sediments of two areas influenced by river Po freshwaters (Ancona and Chioggia) was studied. A sequential extraction technique was used to determine the chemical association of heavy metals (Pb, Cu, Cd, Fe, Hg, Sn, Co and Zn) with major sedimentary phases (exchangeable ions and carbonates, Mn and Fe oxides, sulphides and organic matter and residual minerals). The relationship between the metals content and the grain‐size composition of the sediments was studied: all the elements resulted associated principally with the fine fraction. The considered sediments are not particularly polluted and speciation revealed that the major part of the heavy metals present are not easily mobilizable and bioavailable.

Effects of Ice Melting on Cu, Cd and Pb Profiles in Ross Sea Waters (Antarctica)

Abstract In the framework of the Italian Research Programme in Antarctica, evolution of dissolved and particulate Cu, Cd and Pb profiles in the coastal waters of Gerlache Inlet (Terra Nova Bay, Western Ross Sea) was studied during the Austral Summer 1997/98. In order to relate the distributions of trace metals with the physical and biological processes, a series of temperature and salinity measures were made, and water samples were collected to determine nutrients and chlorophyll. Samples of pack ice and marine microlayer (50–150 μm) were also collected and analysed. Concerning the surface layer, it was found that metal concentrations are mainly affected by the dynamic of the pack ice melting and phytoplankton activity. The first process influences both the input of metals from meltwaters and the covering of the seawater surface, allowing atmospheric dust input only when all ice has been melt or removed. Direct release of particulate Cu from ice was clearly shown by surface maxima and by the high concentrations of suspended particulate matter and particulate metals found in the ice core section interfaced with the seawater. Differently, the high amount of Cd in the particulate included in the pack ice seems not to affect the concentration in surface particulate; on the contrary, the corresponding increase of dissolved Cd indicates that it isreleased in dissolved form when the pack ice melts. Surface distribution is further complicated by the effect of phytoplankton activity, which removes Cu and Cd from water, incorporating them into organic particulate. Finally, in absence of pack ice, there is evidence of inputs of Pb and Cu due to atmospheric dust brought into the column water through marine microlayer. In intermediate and deep waters, the vertical distribution of Pb and Cd was characterised by substantially constant profiles, while Cu shown, during the end of the summer and in absence of a well-defined water column stratification, a “scavenging-type” distribution which overlaps its “nutrient-type” behaviour.

Biogeochemistry, grain size and mineralogy of the central and southern Adriatic Sea sediments: a review

This review aims to present the current status of studies on geochemical (major minor and trace elements), biochemical (total organic carbon, total nitrogen, isotopic carbon composition, Bacteria, Archaea, phytopigments, proteins, carbohydrates, lipids, humic and fulvic acids), mineralogical (light and heavy minerals, clay minerals) and pollutant (trace metals, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, pesticides, organic stannic compounds) parameters, grain-size composition and sediment–water interactions (early diagenesis and benthic fluxes) for the bottom sediments of the central and southern Adriatic Sea. The review highlighted gaps in or completeness of the parameters needed for research, of areas in which the parameters were investigated, as well as the interdisciplinary nature of the studies. In general, biogeochemical, mineralogical, grain-size and pollutant studies in the central and southern Adriatic Sea are restricted to limited areas, consider only single parameters without an interdisciplinary approach and, except for some more recent projects, are predominatly out of date. On the whole, there is a lack of an organised study concerning the various parameters for the entire central and southern Adriatic Sea and their evolution over time.

Bioavailability of trace elements in surface sediments from Kongsfjorden, Svalbard

The bioavailability of trace elements in marine sediments from Kongsfjorden (Svalbard Islands, Norwegian Arctic) was assessed and discussed. Total concentrations of several elements were determined in two granulometric fractions and their bioavailability evaluated by both applying a sequential-selective extraction procedure and using a biomimetic approach based on proteolytic enzymes. Total concentration values and solid speciation patterns indicated overall that the anthropogenic impact of trace elements in the investigated area is negligible, although a minor enrichment with respect to crustal values was found for As, Cd, Cr, Ni, and V. Enrichment of trace elements in the <63-μm fraction compared to the coarser one was evident for As, Cd, Cr, and Ni. The evaluation of the bioavailable fractions showed that a large part of the total content of trace elements cannot enter the aquatic food chain and emphasised the risk of overestimating the environmental impact of heavy metals if the assessment is only based on total concentrations.

Heavy metals distribution in the Eolian Basin (South Tyrrhenian Sea)

The concentration and distribution of heavy metals in the Eolian Basin are discussed. The data concern sediment and particulate matter samples and are correlated with the environmental parameters. In the sediments the measurements indicate that the elements (Zn, Pb, Co, Ni, Cr, Cu, Cd, Mn, Fe) display characteristics which seem not to be influenced by the various water masses circulating in the archipelago. In the particulate matter, the distribution of heavy metals (Pb, Cd, Cu, Mn, Fe) shows interesting correlations with the environmental characteristics of the zone.

Heavy metals in albanian coastal sediments

Heavy metals (Fe, Mn, Cr, Ni, Cu, Cd, Pb, Sn) concentration has been determined on 39 coastal sediment samples collected in Albania. The relationship between the heavy metals content and the grain size has been considered. All metals, except Cu and Cd, resulted accumulated in the finest fraction, which constituted up to 95% of most of the considered sediments. A good correlation has been found for Ni, Cr, Fe, Zn, Cu in the entire area, indicating a common origin for these metals in the analyzed sediments. Concentration values fall in the range reported for Dinaric chain derived sediments, revealing, generally, a natural origin of the metal contents. Though in some selected areas such as the Drin and the Skumbin Bay, an antropogenic input of Cr, Fe, Ni and Cu can be observed, as the result of discharging of mines and smelter activities.

Inductively coupled plasma optical emission spectrometric determination of trace elements in sediments after sequential selective extraction: effects of reagents and major elements on the analytical signal

The interfering effects due to the reagents and matrix elements associated with a four step sequential extraction procedure on ICPOES determination of trace elements were investigated in a systematic way. The emission lines were selected in order to include the most interesting elements for environmental studies (Zn, Pb, Ni, Cr, V and Cu) and the concentrations ranged according with the values occurring in the real samples. In order to distinguish between chemical and physical interfering effects, the Mg 280.270-Mg 285.213 line intensity ratio was measured, in each condition. Both pneumatic and ultrasonic nebulization were considered for comparison. It was found that both the elements which constitute the sample and the reagents which are added during the sample preparation steps significantly influence the emission intensity of all the analytes, depending on the analytical concentration and the nebulization system. Generally, the signal variations were higher with ultrasonic nebulization. Concerning the interference mechanism, it was found that the effect of the major elements (Na, K, Mg, Ca, Al and Fe) is essentially related to a change of the aerosol generation and transport processes. Differently, acetic acid, ammonium acetate and hydroxylamine hydrochloride significantly improved the plasma excitation conditions, depending on their concentration. A change of the sample introduction efficiency due to the presence of these reagents was also evident. On the contrary, the effect of hydrochloric and nitric acid emerged to be related only to the processes occurring in the sample introduction system.