Trace Element Analyses in an Epiphytic Lichen and its Bark Substrate to Assess Suitability for Air Biomonitoring

Total concentrations of Cd, Cr, Fe, Ni, Pb and Zn were compared from October 1996 to April 1998 in Physcia biziana (Massal.) Zhalbr. v. leptophylla Vezda and in the bark of Quercus ilex L. sampled from the same trees at an urban park. Trace metal concentrations were also measured in the bark covered by the lichen thalli. The lichens showed significantly higher Cr, Fe, Ni and Zn concentrations than both uncovered and covered barks. By contrast, both types of barks had higher concentrations of Cd and Pb than lichens. Trace elements showed a wide temporal variation of concentrations both in the lichens and barks. No relationship was found between the analysed matrices as regards the time course of trace element concentrations.     

Statistical analysis of heavy metals in Cerastoderma edule glaucum and Venerupis aurea laeta from Ganzirri Lake, Messina (Italy)

Our study was carried out on two species of clams, Venerupis aurea laeta and Cerastoderma edule glaucum, from Ganzirri Lake considered as “environmental biomarkers” for their changes in physiology, morphology or distribution under the influence of substances in the environment. The aim of the present study was to conduct a statistical analysis on Venerupis and Cerastoderma to investigate the difference between the two autochthonous clams according to the presence of metals, and to link metal concentrations to the reproductive cycle of clam during 2009–2010. Metal analysis was carried out with inductively coupled plasma mass spectrometry (ICP-MS). Accuracy and precision were assessed by analyzing the certified standard matrix: mussel tissue NIST SRM 2976. The multivariate analysis was made using the SPSS 13.0 software package for Windows (SPSS Inc., Chicago, IL). In this study, the concentrations of some metals found in clam tissues showed seasonal cycles with higher values in summer than in winter. The significances of metal concentrations differences between Venerupis and Cerastoderma samples were estimated with Mann–Whitney U-test. The concentrations of Ag, As, Cd, Mn, Se and Zn show a significant p-level that suggests a difference between the two group samples. Statistical analysis showed that the link of metal concentrations to the reproductive cycles of Venerupis and Cerastoderma was not evident.     

Simultaneous determination of Cd(II), Cu(II), Pb(II) and Zn(II) by derivative stripping chronopotentiometry in Pittosporum tobira leaves: a measurement of local atmospheric pollution in Messina (Sicily, Italy)

The purpose of this study is to investigate the bio-accumulation of Cd(II), Cu(II), Pb(II) and Zn(II) in Pittosporum tobira (Thunb.) Aiton leaves sampled in different zones of Messina, in order to assess the level of atmospheric metal deposition in correlation with the traffic volume. Derivative stripping chronopotentiometry was used as a practical, precise and sensitive technique to determine simultaneously Cd, Cu, Pb and Zn levels in Pittosporum leaves. In the optimised electro-chemical conditions, detection limits lower than 0.05 microg kg(-1) were achieved, whereas the accuracy, expressed as obtained recoveries from certified materials, was in the range 93.5-102.7%. The obtained data provided evidence that Cd and Pb levels significantly decreased from high to low traffic density zones (p < 0.005, ANOVA), whereas Cu and Zn are accumulated by plants particularly from the soil and their contents is not related to the traffic volume.     

Acute toxicity of heavy metals towards freshwater ciliated protists

The acute toxicity of five heavy metals to four species of freshwater ciliates (Colpidium colpoda, Dexiotricha granulosa, Euplotes aediculatus, and Halteria grandinella) was examined in laboratory tests. After exposing the ciliates to soluble compound of cadmium, copper, chromium, lead, and nickel at several selected concentrations, the mortality rate was registered and the LC50 values (with 95% confidence intervals) were calculated. Large differences appeared in sensitivities of the four species to the metals. H. grandinella showed the highest sensitivity for cadmium (0.07 mg l(-1), LC50) and lead (0.12 mg l(-1), LC50), whilst E. aediculatus showed the highest sensitivity for nickel (0.03 mg l(-1), LC50). The comparison with data obtained with other species indicate that Halteria grandinella and Euplotes aediculatus are excellent and convenient bioindicator for evaluating the toxicity of waters and wastewaters polluted by heavy metals. The short time (24 h) and simplicity of the test procedure enable this test to be used in laboratory studies.     

Interannual fluctuations in acoustic biomass estimates and in landings of small pelagic fish populations in relation to hydrology in the Strait of Sicily

The main results of research work carried out since 1998 with regard to the application of hydro-acoustic technologies for the evaluation of biomass and distribution of small pelagic fish species off the southern coast of Sicily are presented, taking into account information from hydrology and from ecology of the fish populations targeted. The biomass estimates and the population‐density charts presented concern the two main species, i.e. sardine Sardina pilchardus (Walbaum, 1792) and anchovy Engraulis encrasicolus (Linnaeus, 1758). Both the sardine and anchovy populations experienced large inter-annual fluctuations, with biomass estimates ranging from 6000 to over 36,000 tonnes (t) (sardine) and from about 7000 to 23,000 t (anchovy). Acoustic estimates are largely consistent with landings recorded in Sciacca (the main fishing port for small pelagic species in the study area) during the year following the evaluation surveys. In addition, trends in sardine and anchovy biomass estimates appears to be negatively correlated with the mean sea surface temperature calculated over the time intervals January–September (sardine) and June–November (anchovy) of the preceding year, which correspond to larval and juvenile growth periods of target species. Observed patterns would suggest the importance of enrichment processes relevant to the survival of early stages, so determining recruitment success and finally higher population sizes.     

Phototransformation of <Emphasis Type="SmallCaps">l</Emphasis>-tryptophan and formation of humic substances in water

Humic substances are poorly known, though they represent a major pool of non-biotic organic carbon on earth. In particular, there is little knowledge on the formation of humic substances by irradiation of organic matter dissolved in waters. Specifically, it is known that humic substances can be formed from proteins by photochemical processes in surface waters, but the role of single amino acids and their transformation pathways are not yet known. Therefore, here we studied the phototransformation of aqueous l-tryptophan under simulated sunlight. Irradiated l-tryptophan solutions were analyzed by absorption, fluorescence, nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopies, chromatography, potentiometry and mass spectrometry (MS). The solutions appeared turbid after irradiation; therefore, nephelometry and dynamic laser light scattering were used to characterize the suspended particles. Results show that about 95% of l-tryptophan was degraded in 8-h irradiation, undergoing deamination and decarboxylation of the amino acidic moieties to release ammonium and formate. The MS signal at m/z 146 suggests the formation of 3-ethylindole, while pH-metric and NMR data revealed the presence of hydroxylated compounds. The phototransformation intermediates of l-tryptophan had fluorescence and absorption spectra similar to those of humic substances, they were able to produce ^·OH upon irradiation and tended to aggregate by both ionic and hydrophobic interactions. Overall, our findings reveal for the first time the nature of products formed upon phototransformation of l-tryptophan. Interestingly, the transformation of l-tryptophan is quite different from that of the previously studied l-tyrosine, although both compounds produce humic-like materials under irradiation.     

Organochlorine pesticides,PCBs and heavy metals in tissues of the mullet Liza aurata in lake Ganzirri and Straits of Messina (Sicily,Italy)

The aim of this research was to investigate the presence of organochlorine pesticides, PCBs and heavy metals (Cd, Cr, Cu, Ni, Pb and Zn) in fish living in lake Ganzirri and the Straits of Messina, using the mullet Liza aurata as a "biological indicator". Different tissues of Liza aurata, which include the muscle, gill and vertebral column, were taken for analyses. Quantitative determination of the organochlorine compounds was performed by GC-ECD and confirmed with GC-MS. The concentrations of "essential" and "toxic" heavy metals were determined by Atomic Absorption Spectrophotometry. For the mullets of lake Ganzirri, the study showed DDE in three samples of gills and one of muscle, at concentrations below the MRL; no appreciable residues of PCBs (Aroclor 1232 series) were found. The concentrations of Zn and Cu were much higher than those of the "toxic" metals. No traces of organochlorine pesticides and PCBs were found in the individuals from the Straits of Messina. Therefore, these results indicate that these two environments are not at toxicological risk.     

Speciation of inorganic arsenic in coastal seawater from Ionian and Tyrrhenian Seas (Sicily, Italy) using derivative anodic stripping chronopotentiometry

The purpose of this paper was to use derivative anodic stripping chronopotentiometry (dASCP) as a sensitive and accurate technique, to determine the concentrations of dissolved As (III) and As (V) in coastal seawater samples from the Straits of Messina, the Ionian and the Tyrrhenian seas, and to investigate the relationship between the anthropogenic activities on the coastal areas and the concentration of dissolved inorganic arsenic in seawaters. The obtained data indicated that As (V) was the most abundant species, with concentration ranging from 26.7 to 307 nM, whereas As (III) levels were lower than 48 nM in all the samples. In particular, As (III) and As (V) levels significantly decreased from high to low anthropogenic activities zones (p < 0.00001, ANOVA), with the reference samples, from a wildlife reserve, showing the lowest values. Furthermore it was observed that human activities influenced inorganic arsenic speciation, since the zones that received high human input presented the highest As(V)/As (III) ratio.     

Interannual fluctuations in acoustic biomass estimates and in landings of small pelagic fish populations in relation to hydrology in the Strait of Sicily

The main results of research work carried out since 1998 with regard to the application of hydro-acoustic technologies for the evaluation of biomass and distribution of small pelagic fish species off the southern coast of Sicily are presented, taking into account information from hydrology and from ecology of the fish populations targeted. The biomass estimates and the population-density charts presented concern the two main species, i.e. sardine Sardina pilchardus (Walbaum, 1792) and anchovy Engraulis encrasicolus (Linnaeus, 1758). Both the sardine and anchovy populations experienced large inter-annual fluctuations, with biomass estimates ranging from 6000 to over 36,000 tonnes (t) (sardine) and from about 7000 to 23,000 t (anchovy). Acoustic estimates are largely consistent with landings recorded in Sciacca (the main fishing port for small pelagic species in the study area) during the year following the evaluation surveys. In addition, trends in sardine and anchovy biomass estimates appears to be negatively correlated with the mean sea surface temperature calculated over the time intervals January-September (sardine) and June-November (anchovy) of the preceding year, which correspond to larval and juvenile growth periods of target species. Observed patterns would suggest the importance of enrichment processes relevant to the survival of early stages, so determining recruitment success and finally higher population sizes.     

Trace elements and vanadium in tissues and organs of five species of cetaceans from Italian coasts

Trace element concentrations (chromium, copper, zinc, iron, manganese and vanadium) were determined in organs of five species of cetaceans (Stenella coeruleoalba, Tursiops truncatus, Grampus griseus, Physeter macrocephalus, Ziphius cavirostris) that were found stranded along Italian coasts in the period 2000–2009. This dataset represents an important opportunity to verify and assess (particularly for V) patterns of incorporation of trace elements in different organs of cetaceans in a wide spectrum of species and related specimens distributed in all the age classes, and consequently determine the physiological and metabolic effects on the distribution modes of the same chemicals. In particular, Cu, Zn, and Fe accumulate preferentially in the liver of all studied specimens, while Mn and Cr values are found to be nearly constant in the analysed organs and tissues regardless of species. Comparable concentrations of trace elements, in different age classes, were measured for both specimens of S. coeruleoalba and T. truncatus (the most abundant dolphin species in the Mediterranean sea) in all analysed organs. On the other hand, unprecedented reported concentrations of V in tissues and organs of cetaceans from the Mediterranean show higher values when compared to levels measured in other marine mammals from the Atlantic Ocean.