Seasonal, spatial and inter-annual variations of trace metals in mussels from the Adriatic sea: a regional gradient for arsenic and implications for monitoring the impact of off-shore activities

Mussels are widely used as bioindicator organisms for monitoring chemical pollutants including trace metals. These elements are natural constituents in the marine environment and their basal concentrations in the organisms can be influenced by several environmental and biological factors. The aim of this work was to extend our knowledge on the natural variability of trace metals in mussels tissues, focusing on seasonal and inter-annual fluctuations in a coastal reference site of the Adriatic coast (Portonovo); a total of 39 samplings were performed during 5 years, providing an extended data-set for tissue levels of As, Ba, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, V and Zn. Concentrations of trace metals in mussels tissues revealed marked seasonal fluctuations with significant differences between various sampling years. Such fluctuations appeared mostly related to phytoplanctonic blooms and especially to reproductive cycle which exhibited a certain inter-annual shift of the gametogenesis period. Lower concentrations were measured in summer months for the majority of elements while a different seasonal cycle was observed for arsenic, not correlated with gonadic development, neither with other elements. Chemical speciation of arsenic was characterized to distinguish compounds of natural origin from those potentially reflecting an anthropogenic impact. Arsenobetaine and arsenocholine were always the predominant forms (up to 85% of total arsenic), while a significant increase of dimethylarsine and trimethylarsine oxide in spring (24% of total arsenic) might reflect the effect of phytoplanctonic bloom on both geochemistry and trophic transfer of this element. A significant inter-annual variability was observed for both the seasonal cycle and the range of values measured for all the elements, with particularly marked differences for arsenic, ranging from less than 10 to more than 40 microg/g in summer periods of different years. Data obtained on reference mussels were used to assess the impact of 41 off-shore platforms distributed along 5 nautical districts in the Northern and Central Adriatic Sea. Organisms sampled on these structures from 2001 to 2005 exhibited a certain enrichment of cadmium and zinc, probably associated to the use of anodic electrodes. Marked annual and geographical variations were measured for concentrations of arsenic in mussels of different platforms. However, the comparison with results of Portonovo, allowed to exclude the anthropogenic impact of exploitation activities and revealed a natural regional gradient of arsenic levels in mussels tissues associated to the changing influence of the Po river runoff on seawater salinity. In particular the higher concentrations measured in organisms sampled from platforms in the Central compared to Northern Adriatic confirmed a significant relationship between salinity and arsenic bioaccumulation, consistent with a role of arsenobetaine as an acquired osmolyte for mussels. The overall results confirmed the importance of natural variability when assessing the potential impact of anthropogenic activities.     

Species-dependent chromium accumulation, lipid peroxidation, and glutathione levels in germinating kiwifruit pollen under Cr(III) and Cr(VI) stress

The accumulation of chromium by germinating kiwifruit pollen appears to be significantly affected by Cr species, Cr concentration and calcium availability. Cr(III) accumulation always occurred in a linear manner while Cr(VI) uptake followed a logarithmic model. In the absence of exogenous calcium, Cr(III) accumulation was much higher than that of Cr(VI). It was observed that, as the Cr(III) concentration increased, there was a significant decrease in the endogenous calcium content of pollen, ultimately leading to complete calcium depletion after 90 min of incubation at 150 microM Cr(III). This loss of calcium could be responsible for the strong inhibition of tube emergence and growth following exposure of pollen to Cr(III). Indeed, when exogenous calcium was added to the kiwifruit pollen culture medium, significant growth recovery and reduced Cr(III) uptake occurred; the opposite was true in Cr(VI)-treatments. A significant rise in lipid peroxide production occurs in the presence of both Cr species; the effect was more pronounced following Cr(VI) exposure. Finally, glutathione pool dynamics appears to be differentially affected by chromium species and concentrations. In conclusion, results of the present study have provided important information regarding the different activity profiles of Cr(III) and Cr(VI) in relation to kiwifruit pollen performance, and have also demonstrated differences in some biochemical responses of pollen to metal stress.     

Possible effects of persistent organochlorinated pollutants cocktail on thyroid hormone levels and pituitary-thyroid interrelations

In polluted district of Michalovce in East Slovakia (POLL) and two districts with background pollution (BCGR) 2046 adults (834 males and 1212 females aged 20-75 years) were examined. Serum levels of thyrotropin (TSH), free thyroxine (FT4), total triiodothyronine (TT3) and antithyroperoxidase antibodies (TPOab) were estimated by electrochemiluminiscent assay and also these of 15 polychlorinated biphenyl congeners (PCBs), p,p'-DDE, p,p'-DDT, hexachlorobenzene (HCB) and hexachlorocyclohexane were measured by high resolution gas chromatography/mass spectrometry. In addition, also dioxins, furans, coplanar- and mono-ortho-PCBs as well as selected hydroxylated and methylsulphonated PCBs and DDE metabolites were measured by appropriate methods based on gas chromatography/mass spectrometry principle. In POLL significantly higher levels of all organochlorines were found than these in BCGR. When pooled values from both areas were stratified in terms of PCBs level and treated as continuous variables, positive association of PCBs with FT4 and TT3 was found, the latter two being also mutually associated. However, within the category of PCBs level <530 ng/glipid (n=232) the association between PCBs and both the FT4 (p<0.09) and TT3 (p<0.03) was negative and any association of these was not found within the category of PCBs level of 531-1000 ng/g (n=691). In contrast, in the category of 531-2000 ng/g (n=1307) positive association appeared between PCBs and FT4 (p<0.001) as well as TT3 (p<0.05). Highly significant association of PCBs with FT4 (p<0.001) was further found in the categories with PCBs level of 1001-101414 ng/g (n=1307) and 2001-101414 (n=1123), while significant association with TT3 was observed only in the category of 531-2000 ng/g. Such findings suggest possible threshold level in positive effect of PCBs on FT4 and TT3 level which seems to be individual and located somewhere around the PCBs level of 1000 ng/g. However, highly significant negative association of both FT4 and TT3 with TSH was found in each of above indicated PCBs categories. Considerable difference in FT4 and TT3 level between large groups of subjects with the same range of PCBs level was also found suggesting different individual susceptibility to the effects of organochlorines. Among a total of 26 cases from POLL with very low TSH level (<0.5 mU l(-1)) 13 cases showed very high level of PCBs, FT4 and TT3, thus supporting a hypothesis on a novel sporadic form of high PCBs related peripheral subclinical hyperthyroidism possibly resulting from the long-term disruption of equilibrium between bound and free thyroxine in plasma by high PCBs level followed by a striking inhibition of TSH release from the pituitary.     

Environmental sustainability and the integration of different methods for its assessment

The aim of this paper is to propose a research framework, based on the joint use of three widely used methods: EMergy Evaluation (EME), Ecological Footprint Analysis (EFA) and Greenhouse Gas Inventory (GHGI), that are applied to assess the environmental sustainability of a region. The results of application of these methods to several Italian Provinces enabled us to compare their sustainability, and to test the methods with respect to sustainability requirements at local and global level. The outcomes suggest that the proposed framework provides an organic evaluation of regional systems based on key aspects, such as resources depletion, consumption patterns, waste production and absorption.     

Magnetic susceptibility measurements as proxy method to monitor soil pollution: development of experimental protocols for field surveys

In the framework of the development of new methods for measuring and monitoring soil pollution, this paper deals with the use of magnetic methodologies to monitor the heavy metals presence in soils. In particular it shows a procedure for collecting magnetic susceptibility measurements in order to interpret them as proxy variable for monitoring heavy metals in soils. Magnetic measurements are carried out using a magnetic susceptibility meter with two different probes for in situ field surveys. The experimental procedure is divided in two parts. In the first part we carry out laboratory tests aimed to evaluate, for both the probes, the effective investigation depth for soil, the measurement reproducibility under different conditions, and the influence of water content. We complete this part comparing in situ measurements obtained by means of two probes with different characteristics. In the second part we carry out tests to evaluate the relationships between heavy metal levels and magnetic susceptibility values of soil samples. We investigate the variability of the magnetic susceptibility measurements contaminating different soil samples with well known concentration of heavy metals. Moreover we study the correlation between magnetic susceptibility values and metal concentrations, determined by means of AAS, in soil samples collected during a field survey. Results suggest that a careful check of the experimental procedure play a crucial role for using magnetic susceptibility measurements for heavy metals in situ monitoring. This is very helpful both for improving the quality of data and for making simpler data interpretation.     

The environmental behaviour of polychlorinated phenols and its relevance to cork forest ecosystems: a review

Pentachlorophenol (PCP) has been used as a herbicide, biocide and preservative worldwide since the 1930s and as a result, extensive and prolonged contamination exists. The environmental impact increases when its many degradation products are taken into consideration. A number of chloroanisols and their related chlorophenols have been found in cork slabs collected from Portuguese oak tree forests before stopper manufacturing, and contamination by PCP and polychlorinated anisole (PCA) has been detected in Canadian forests. It is suggested that the use of polychlorinated phenols, in particular PCP, is thought to be a cause of the cork taint problem in wine, a major socio-economic impact not only for industry but on sensitive and highly biodiverse ecosystems. It also highlights particular issues relating to the regional regulation of potentially toxic chemicals and global economics world wide. To fully understand the impact of contamination sources, the mechanisms responsible for the fate and transport of PCP and its degradation products and assessment of their environmental behaviour is required. This review looks at the current state of knowledge of soil sorption, fate and bioavailability and identifies the challenges of degradation product identification and the contradictory evidence from field and laboratory observations. The need for a systematic evaluation of PCP contamination in relation to cork forest ecosystems and transfer of PCP between trophic levels is emphasised by discrepancies in bioaccumulation and toxicity. This is essential to enable long term management of not only transboundary contaminants, but also the sustainable management of socially and economically important forest ecosystems.     

Post-traumatic stress disorder and comorbid depression among survivors of the 1999 earthquake in Turkey

This study examined the prevalence of post-traumatic stress disorder (PTSD) and comorbid depression some three years after the August 1999 earthquake in Turkey among a sample of 769 survivors relocated to a permanent housing site built for homeless survivors in the epicentre region. Time since trauma was 3.1 years for 81 per cent of the participants and 3.9 years for the remainder. Survivors were assessed using the Screening Instrument for Traumatic Stress in Earthquake Survivors, an easily administered self-rating scale with demonstrated validity. The estimated rates of PTSD and comorbid depression were 40 per cent and 18 per cent, respectively. Linear regression analyses showed that PTSD strongly related to fear during the earthquake, while depression related to loss of family members. These results suggest that catastrophic earthquakes have long-term psychological consequences and highlight the need for a cost-effective mental health care model for earthquake survivors.     

Distribution of polycyclic aromatic hydrocarbons (PAHs) and tributyltin (TBT) in Barcelona harbour sediments and their impact on benthic communities

Sediments have long been recognised as a sink for many contaminants like polycyclic aromatic hydrocarbons (PAHs) and tributyltin (TBT), which by virtue of their nature can strongly adsorb onto sediments affecting the benthic community inhabiting them. Using geographical information systems, this study reports and combines the results of several already existing studies along Barcelona harbour in order to assess the potential ecological impacts of these contaminants on the benthos of the harbour ecosystem. Chemical analysis indicated low to moderate contents of PAHs and high contents of TBT in sediments in Barcelona harbour. Comparison against existing sediment quality guidelines (SQGs) indicated that acutely toxic effects would not be expected for PAHs but for TBT, which represents a serious environmental threat for the benthic community. Benthos surveys revealed a deterioration of the benthic community throughout the harbour, especially in the inner port.     

Minimization of the environmental impact of chrome tanning: a new process with high chrome exhaustion

In all tanning technology operations wastes are generated. These reach the environment as residual waters, solid and liquid waste as well as atmospheric emissions and odours.

This study tests an alternative method to the traditional tanning method at an industrial level. The new method is based on tanning without float and by significantly increasing the temperature at the end of the tanning process. The properties of the leathers obtained using the two methods have been compared and the results indicate that those leathers have similar physical, chemical, and organoleptic properties. However, the differences existing from the environmental point of view are significant. It is not necessary to use clean water for this tanning. Moreover, there is a 75% reduction of the residual float, a 91% reduction of the chrome discharged, and a 94% reduction of the chlorides discharged. A financial assessment was carried out to demonstrate that the newly proposed system is 32% more economic than the traditional one.     

Fate of cadmium in Elodea canadensis

Elodea canadensis is a submersed macrophytes, widely distributed in stormwater treatment ponds and able to remove heavy metals from water. This study examines the Cd uptake, translocation, and efflux patterns in Elodea. Several experiments were set up in a climate chamber. To study the root and shoot Cd uptake, living and dead roots and shoots were treated with (109)Cd in one- and two-compartment systems. Furthermore, to examine Cd translocation and distribution, either roots or shoots were treated with (109)Cd. Finally, the efflux of Cd from roots and shoots, respectively, to the external solution was studied after loading whole plants with (109)Cd. Results from the two compartment studies show that Cd is accumulated via direct uptake by both roots and shoots of Elodea. The Cd accumulation proved not to be metabolically dependent in Elodea, and the apoplastic uptake in particular was decreased by Cd pretreatment. In one week, up to 23% of the root uptake was translocated to the shoots, while about 2% of the Cd accumulated by shoots was translocated to the roots. Thus, slight dispersion of Cd is possible, while metal immobilization will not be directly mediated via the Elodea plant. The efflux experiment proved that both shoots of dead plants and roots of living plants had a faster efflux than did shoots of living plants. This information is relevant for an understanding of the fate of Cd in stormwater treatment ponds with Elodea.