Chemometric data analysis application to Sparus aurata samples from two offshore farming plants along the Apulian (Italy) coastline

The levels of polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs), dioxin-like polychlorobiphenyls (DL-PCBs), non-dioxin-like polychlorobiphenyls (NDL-PCBs), and polybromodiphenyl ethers (PBDEs) in fish collected from two marine offshore farming plants were determined. Each sample was constituted by specimens of the same size collected at the same time in four different seasons along the farming year. The feeds given were of industrial origin and the plants were positioned in two different sites respectively exposed to different environmental characteristics. A chemometric approach was applied to interpret the subtle differences observed in fish body burdens across the three chemical groups taken into consideration. The approach consisted in a stepwise multivariate process including a hierarchical cluster analysis (CA) and a linear discriminant analysis (DA). The two main clusters determined by CA were subjected to the canonical DA, backward and forward selection procedures to select the best discriminative functions. A clear temporal and spatial discrimination was found among the samples. Across the three chemical groups, the monthly separation seemed to depend on the growth process and the main exposure was due to the feed. In addition, the two plants differed significantly from the environmental point of view and the most important discriminating group of chemicals were the NDL-PCBs. The approach resulted really effective in discriminating the subtle differences and in individuating suggestions to improve the quality of culturing conditions.     

Rapid determination of residues of pesticides in honey by µGC-ECD and GC-MS/MS: Method validation and estimation of measurement uncertainty according to document No. SANCO/12571/2013

A simple and straightforward method for simultaneous determination of residues of 13 pesticides in honey samples (acrinathrin, bifenthrin, bromopropylate, cyhalothrin-lambda, cypermethrin, chlorfenvinphos, chlorpyrifos, coumaphos, deltamethrin, fluvalinate-tau, malathion, permethrin and tetradifon) from different pesticide classes has been developed and validated. The analytical method provides dissolution of honey in water and an extraction of pesticide residues by n-Hexane followed by clean-up on a Florisil SPE column. The extract was evaporated and taken up by a solution of an injection internal standard (I-IS), ethion, and finally analyzed by capillary gas chromatography with electron capture detection (GC-µECD). Identification for qualitative purpose was conducted by gas chromatography with triple quadrupole mass spectrometer (GC-MS/MS). A matrix-matched calibration curve was performed for quantitative purposes by plotting the area ratio (analyte/I-IS) against concentration using a GC-µECD instrument. According to document No. SANCO/12571/2013, the method was validated by testing the following parameters: linearity, matrix effect, specificity, precision, trueness (bias) and measurement uncertainty. The analytical process was validated analyzing blank honey samples spiked at levels equal to and greater than 0.010 mg/kg (limit of quantification). All parameters were satisfactorily compared with the values established by document No. SANCO/12571/2013. The analytical performance was verified by participating in eight multi-residue proficiency tests organized by BIPEA, obtaining satisfactory z-scores in all 70 determinations. Measurement uncertainty was estimated according to the top-down approaches described in Appendix C of the SANCO document using the within-laboratory reproducibility relative standard deviation combined with laboratory bias using the proficiency test data.     

Proximity to wood industries and respiratory symptoms in children: a sensitivity analysis

Increased prevalence of respiratory and irritation symptoms was found in children who live near a large wood industrial park. Proximity to the wood industries was used as indicator of exposure. This study describes a sensitivity analysis for the results of the survey. All the children (3-14 years) living in the area were surveyed through a parental questionnaire (n = 3854) and their addresses were geocoded. The distances from each child's home and school to the closest industry were combined, weighted and used as an indicator of exposure. A sensitivity analysis was performed to check 1) the robustness of the results to the choice of weights used for defining the exposure indicator, 2) the effect of outliers on risk estimates and 3) the sensitivity on the functional form used for modeling the dose-response function. The choice of the weights did not influence the association between proximity to the industries and respiratory symptoms. Excluding the subjects who lived far away from the industries showed that in a radius of 5 km from the industries the study did not had enough power to estimate a gradient in the dose-response function. Besides, results were sensitive to the choice of the functional form used for modeling the minimum distance. The sensitivity analyses confirmed the overall increasing trend of respiratory symptoms with proximity to the industries and pointed out that all the assumptions made for defining a proxy of exposure need to be carefully checked.     

Changes in Genetic Structure of Posidonia oceanica at Monterosso al Mare (Ligurian Sea) and Its Resilience Over a Decade (1998–2009)

Genetic differences in the Posidonia oceanica meadow of Monterosso al Mare (NW Mediterranean, Marine Protected Areas (MPAs) "Cinque Terre") were compared in three stations, at an increasing distance from a source of impact (beach nourishment) in the recent decade. Random amplified polymorphic DNA analysis showed a higher genetic variability (>20?%) in the area directly subjected to the stress, increasing with time. Clone integration, confirmed by phenotypic analysis, showed increases both in shoot density and leaf length connected to genetic differences observed in DNA fingerprints of new shoots. Analysis of molecular variance (AMOVA) showed 45?% individual differences within populations and 54?% among the populations. The fixation index (F (ST)?=?0.54), of the genetic differentiation, showed a marked difference between the populations at different temporal scales. Over a decade AMOVA indicated genetic variations from 28?% (1998) to 54?% (2009). These results make it clear that in the P. oceanica population examined the environment had, in ten years, selected those clones which were more resistant to the anthropogenic impact, despite being subjected to the effects of the resuspension of fine sediments. These findings could help to explain both the survival of the regressed Mediterranean P. oceanica meadows in areas subjected to moderate impacts and the extreme variability in success of revegetation experiments. Management of the ecological disturbance here described indicates also the timescale in population response to stress and its increased resilience in MPAs.     

Reduced activity of alkaline phosphatase due to host–guest interactions with humic superstructures

Nuclear Magnetic Resonance (NMR) spectroscopy was applied to directly study the interactions between the alkaline phosphatase enzyme (AP) and two different humic acids from a volcanic soil (HA-V) and a Lignite deposit (HA-L). Addition of humic matter to enzyme solutions caused signals broadening in ¹H-NMR spectra, and progressive decrease and increase of enzyme relaxation (T₁ and T₂) and correlation (τ_C) times, respectively. Spectroscopic changes were explained with formation of ever larger weakly-bound humic–enzyme complexes, whose translational and rotational motion was increasingly restricted. NMR diffusion experiments also showed that the AP diffusive properties were progressively reduced with formation of large humic–enzyme complexes. The more hydrophobic HA-L affected spectral changes more than the more hydrophilic HA-V. ¹H-NMR spectra also showed the effect of progressively greater humic–enzyme complexes on the hydrolysis of an enzyme substrate, the 4-nitrophenyl phosphate disodium salt hexahydrate (p-NPP). While AP catalysis concomitantly decreased NMR signals of p-NPP and increased those of nitrophenol, addition of humic matter progressively and significantly slowed down the rate of change for these signals. In agreement with the observed spectral changes, the AP catalytic activity was more largely inhibited by HA-L than by HA-V. Contrary to previous studies, in which humic–enzyme interactions were only indirectly assumed from changes in spectrophotometric behavior of enzyme substrates, the direct measurements of AP behavior by NMR spectroscopy indicated that humic materials formed weakly-bound host–guest complexes with alkaline phosphatase, and the enzyme catalytic activity was thereby significantly inhibited. These results suggest that the role of extracellular enzymes in soils may be considerably reduced when they come in contact with organic matter dissolved in the soil solution.     

An international comparative study of end-of-life vehicle (ELV) recycling systems

End-of-life vehicles (ELV) have become a global concern as automobiles have become popular worldwide. An international workshop was held to gather data and to discuss 3R policies and ELV recycling systems, their background and present situation, outcomes of related policies and programs, the framework of recycling and waste management, and case studies on related topics in several countries and regions, as well as the essential points of the comparison. Legislative ELV recycling systems are established in the EU, Japan, Korea, and China, while in the US, ELV recycling is managed under existing laws on environmental protection. Since automobile shredding residue (ASR) has a high calorific value and ash content, and includes heavy metals as well as a mass of unclassified fine particles, recycling ASR is considered highly difficult. Countries with a legislative ELV system commonly set a target for recovery rates, with many aiming for more than 95 % recovery. In order to reach this target, higher efficiency in ASR recovery is needed, in addition to material recycling of collectable components and metals. Environmentally friendly design was considered necessary at the planning and manufacturing stages, and the development of recycling systems and techniques in line with these changes are required for sound ELV management.     

Integration of geophysical,geochemical and microbiological data for a comprehensive small-scale characterizationof an aged LNAPL-contaminated site

Characterization of aged hydrocarbon-contaminated sites is often a challenge due to the heterogeneity of subsurface conditions. Geoelectrical methods can aid in the characterization of such sites due to their non-invasive nature, but need to be supported by geochemical and microbiological data. In this study, a combination of respective methods was used to characterize an aged light non-aqueous phase liquid-contaminated site, which was the scene of a crude oil blow-out in 1994. As a consequence, a significant amount of crude oil was released into the subsurface. Complex resistivity has been acquired, both along single boreholes and in cross-hole configuration, in a two-borehole test site addressed with electrodes, to observe the electrical behaviour at the site over a two-year period (2010–2011). Geoelectrical response has been compared to results of the analysis of hydrocarbon contamination in soil and groundwater samples. Geochemical parameters of groundwater have been observed by collecting samples in a continuous multi-channel tubing (CMT) piezometer system. We have also performed a biological characterization on soil samples by drilling new boreholes close to the monitoring wells. Particular attention has been given to the characterization of the smear zone that is the sub-soil zone affected by the seasonal groundwater fluctuations. In the smear zone, trapped hydrocarbons were present, serving as organic substrate for chemical and biological degradation, as was indicated by an increase of microbial biomass and activity as well as ferrogenic-sulfidogenic conditions in the smear zone. The results show a good agreement between the intense electrical anomaly and the peaks of total organic matter and degradation by-products, particularly enhanced in the smear zone.     

Enzyme and fungal treatments and a combination thereof reduce olive mill wastewater phytotoxicity on Zea mays L. seeds

The phytotoxicity of olive-mill wastewater (OMW) has been suggested to be mainly due to its phenolic components. This study investigated the impact of three different low-cost dephenolization treatments on the wastewater phytotoxicity. To this aim, germinability of maize (Zea mays L.) seeds sown on a sandy-loamy soil which had been spread with different volumes (from 40 to 160m(3)ha(-1)) of either biologically-treated OMW or relative incubation control was determined. Biological treatments included either Panus tigrinus liquid cultures or incubation with commercial laccase (1UIml(-1)) or an innovative sequential combination of laccase and P. tigrinus cultures. All treatments markedly reduced phytotoxicity and promising results were obtained with commercial laccase. In fact, germinability and mean germination times in soil spread with laccase-treated OMW, did not significantly differ from those observed in soil irrigated with tap water (control) up to OMW volumes of 120m(3)ha(-1). Although the highest phenol reduction (ca. 81%) was obtained by the sequential use of laccase and P. tigrinus, the feasibility of the enzyme treatment is undoubtedly more convincing under the technological point of view.     

Polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in milk from Italian women living in Rome and Venice

The levels of selected polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were measured in human milk samples from the areas of Venice and Rome, primarily in order to characterize the current levels of infant exposure to PCBs and PBDEs due to breast feeding in Italy. Sixteen non-dioxin-like PCBs, including the traditional indicator congeners, and 11 PBDEs, comprising the relevant PBDE-47, PBDE-99, and PBDE-153, were determined. Congeners were selected for analysis according to their relative abundance in human tissues, toxicological relevance, and diffusion in the environment. Dietary habits of the milk donors were recorded by questionnaires; mothers of the Venice area were classified into three groups according to their consumption of local fish, molluscs, and other fishery products. Sigma(16)(PCBs) and Sigma(11)(PBDEs) (ng g(-1) fat) for the areas of Venice and Rome were respectively, 250-390 and 240, and 1.6-2.8 and 4.1. An increase of fish and fishery product consumption could not be associated with an increase of PCB and PBDE levels in milk.     

Platinum,palladium, and rhodium deposition to the <Emphasis Type="Italic">Prunus laurus cerasus</Emphasis> leaf surface as an indicator of the vehicular traffic pollution in the city of Varese area

Background, aim, and scope  

The widespread use of some platinum group elements as catalysts to minimize emission of pollutants from combustion engines produced a constantly growing increase of the concentration of these elements in the environment; their potential toxicological properties explain the increasing interest in routine easy monitoring. We have found that leaves of Prunus laurus cerasus are efficient collectors of particulate with a dimension <60–80 μm, and a simple and reliable procedure was developed to reveal traces of platinum, palladium, and rhodium released from automotive catalysts. The analysis of the dust deposited on the foliage is a direct indicator of traffic pollution.