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.     

Dioxin mass balance in a municipal waste incinerator

A dioxin mass balance in an Spanish municipal waste incinerator (MWI) is presented. Input and output inventories from two sampling collection episodes including the analysis of PCDD/PCDF in urban solid waste (USW), stack gas emissions, fly ash and slag are reported. In one collection the levels of USW were around 8 pg I-TEQ/g and non-thermal destruction was observed overall. In the other collection the levels of USW were higher (around 64 pg I-TEQ/g) and the dioxin balance revealed a thermal destruction. Analysis of the different waste materials (textile, organic, plastic, wood and paper) was performed separately and the textile samples presented the highest levels.     

Analysis of dioxins and furans in environmental samples by GC-ion-trap MS/MS

The work aims to characterise PCDDs/Fs in environmental matrices by high resolution gas chromatography coupled to low resolution quadrupole ion-trap mass spectrometry (GC-QITMS/MS). In particular, the study was mainly focused in different environmental samples such as sewage sludge, soils, and sediments and in combustion residues as fly ashes. Previous experiences have already detected and quantified PCDDs/PCDFs in all matrices studied. Moreover, isomer-specific analysis of 2,3,7,8-PCDDs/Fs compounds corroborated good correlation between GC-QITMS/MS and a well-established technique such as high resolution mass spectrometry (HRMS). Finally, QC measures included the participation in intercalibration exercises. Successful results were achieved using GC-QITMS/MS in the analysis of fly ashes, soils and sediment materials. In general, GC-QITMS/MS constitutes an interesting alternative for routine analysis of dioxins in such as matrices.     

Detection of mutagens in unconcentrated and concentrated drinking water supplies before and after treatment using a microscale fluctuation test

The aim of this work was to study three different concentration methods coupled with the microscale fluctuation test for routine screening of different drinking water supplies before and after treatment. Unconcentrated samples were also tested. The results showed the formation of direct-acting mutagens in drinking water from surface sources after chlorination.     

Surveillance programme on dioxin levels in soils in the Campo de Gibraltar (southwest Spain)

The results of an epidemiologic study undertaken by the Spanish Council for Scientific Research (CSIC) after commission by the Spanish Parliament indicated that Huelva and Cádiz were the zones in Andalusia with elevated risk of cancer. A 6% (women) and 10% (men) cancer mortality excess was observed with respect to the other six Andalusian provinces. Huelva and Cádiz are located in the south-western region of Spain, and are characterized by a strong industrial activity concentrated in several industrial sites. This situation led to two environmental surveys in these areas, in which the presence of dioxins was studied among other parameters. A PCDD/F assessment in soils of the Campo de Gibraltar (Cádiz) was carried out from June 2003 to June 2004. A total of 20 samples were collected in this study divided in two sampling campaigns. The first 10 samples were taken in locations affected by high industrial activity zones as well as in landfills (hotspots). The rest of the samples were collected in areas that were not expected to be contaminated, such as agricultural zones and forests. I-TEQ values of the samples ranged from 0.26 to 15.08 ng/kg dm. In all, 85% of the samples were below the limit of 5 ng I-TEQ/kg I-TEQ concentrations of three samples only surpassed this limit. These zones corresponded to a landfill, a quarry used for dumping chemical product containers and a sample from the sewage system of the industrial site. These sites were used neither for agricultural nor for public purposes.     

Dioxin like compounds from municipal waste incinerator emissions: assessment of the presence of polychlorinated naphthalenes

Polychloronaphthalenes (PCN) were identified and quantified in emission samples collected from five different municipal waste incinerators (MWI). Polychlorodibenzo-p-dioxins (PCDD) and polychlorodibenzofurans (PCDF) were also determined to find a possible relationship between these classes of organochlorinated compounds. The analyses of PCDD/PCDF and PCN were carried out by high resolution gas chromatography coupled with high resolution mass spectrometry using a positive electron ionization source and operating in the selected ion monitoring analyzer mode (HRGC-HRMS/EI(+)-SIM). The total levels of PCN varied from 1.08 up to 21.36 ng/Nm3 (mono- to octachlorinated) and 0.33 to 5.72 ng/Nm3 (tetra- to octachlorinated), whereas the levels of PCDD/PCDF ranged between 1.14 and 276.26 ng/Nm3 (0.01 and 5 ng I-TEQ/Nm3), depending on the type of the MWI. These findings do not corroborate a PCN and PCDD/PCDF correlation.     

Ostracoda and foraminifera as short-term tracers of environmental changes in very polluted areas: the Odiel Estuary (SW Spain)

The analysis of 17 cores collected in the Odiel Estuary (SW Spain) permits delimiting the recent evolution of this zone during the past decades and the influence of natural and anthropogenic factors on the distribution of Ostracoda and Foraminifera. In the upper estuary, the coincidence of acid waters, prolonged subaerial exposure, and coarse sediments may explain the absence or the disappearance of these microorganisms during the industrial period (1966-1985) in the major part of this area. In the lower estuary, sedimentary evolution and industrial wastes are the main factors influencing both the distribution and trends of the populations of these two groups. Finally, the main changes observed in the marine estuary are due to the sedimentary effects of the construction of two banks and the dredging of the main estuarine channel.     

Assessment of polychlorinated dibenzo-p-dioxins and dibenzofurans in sludges according to the European environmental policy

The amount of sewage sludge generated in Europe is expected to surpass the 10 million tons/year in 2006 as a result of the waste water treatment process according to the Water Policy in European Union. Sewage sludge is what is left behind after water is cleaned in waste treatment plants and is characterized for this high content in nitrogen and phosphorous that could be of great importance in agriculture as fertilizer or soil conditioner. On the other hand, pollutants like metals and organic contaminants are usually removed from water and are accumulated in the sewage sludge, reaching the food chain if their concentrations are not below the safe limits established by the European legislation. The latter issue is of great concern nowadays and in this sense, different works alert against the use of the sewage sludge in agriculture arguing that serious illnesses, even resulting in death as well as adverse environmental impacts are associated to the application of sewage sludge. This work is a continuation of a former comprehensive survey on of priority organic pollutant in sludges for agricultural purposes carried out by our group in Catalonia and this time is focused on the polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F), one of the most toxic group of organic compounds listed in the Work Document on Sludge which is the reference tool in this field in Europe and is also included in the Stockholm Convention. Eighty eight samples were collected from the end of 2003 to April 2006 and the concentrations detected were lower than the 100 ng/kg I-TEQ limit recommended by the European legislation (EC, 2000). Thus, sewage sludges generated in Catalonia do not represent a threat to human health if they are used as fertilizers in agriculture.     

PFAS profiles in three North Sea top predators: metabolic differences among species?

Profiles of seven compounds of perfluoro-alkyl substances (PFASs) were compared among three species of top predators from the Danish North Sea: the white-beaked dolphin (Lagenorhynchus albirostris), the harbor porpoise (Phocoena phocoena), and the harbor seal (Phoca vitulina). The seals had higher total burdens (757.8 ng g^?1 ww) than the dolphins (439.9 ng g^?1 ww) and the porpoises (355.8 ng g^?1 ww), probably a reflection of feeding closer to the shore and thus contamination sources. The most striking difference among the species was the relative contribution of perfluorooctanesulfonamide (PFOSA) to the profiles; the seals (0.1 %) had much lower levels than porpoises (8.3 %) and dolphins (26.0 %). In combination with the values obtained from the literature, this result indicates that Carnivora species including Pinnipedia have a much higher capacity of transforming PFOSA to perfluorooctane sulfonic acid (PFOS) than cetacean species. Another notable difference among the species was that the two smaller species (seals and porpoises) with supposedly higher metabolic rates had lower concentrations of the perfluorinated carboxylic acids, which are generally more easily excreted than perfluorinated sulfonamides. Species-specific characteristics should be recognized when PFAS contamination in marine mammals is investigated, for example, several previous studies of PFASs in cetaceans have not quantified PFOSA.