Heavy Metals in Liver and Muscle of Bluefin Tuna (Thunnus thynnus) Caught in the Straits of Messina (Sicily, Italy)

The present investigation was carried out on the bluefin tuna (Thunnus thynnus) collected during the month of April 2003 from the Straits of Messina. The aim of this study is to determine heavy metal levels (Cd, Cu, Hg, Mn, Pb and Zn) in liver and muscle tissues of 14 Thunnus thynnus of different age and sex and to investigate the relationships between fish sex and size (length and weight and metal concentrations in the tissues. The concentrations of the various metals were determined by a Varian atomic absorption spectroscopy instrument. The results showsignificant variations (p < 0.01) for Hg and Zn concentrations in muscle than in liver samples. Concentrations of Cd and Pb are below the instrumental detection limits in almost all muscle samples. Levels of Hg (3.03 + 0.55 μg/g) are above the MRLs only in muscle (1μg/g) establishing toxicological risks for the consumer. Regression analysis shows a negative correlation between mercury level and weight and length in samples from both female and male. No significant difference between mean heavy metals concentrations and male or female tuna is seen. For greater food safety, it would be advisable to reduce the mercury intake by selecting safer fish, species and size and by the avoidance of tuna fish consumption by pregnant women, young children and old people, who are more sensitive to mercury exposure.     

Effects of water temperature and mixed layer depth on zooplankton body size

Ecological consequences of global warming include shifts of species ranges toward higher altitudes and latitudes as well as temporal shifts in phenology and life-cycle events. Evidence is accumulating that increasing temperature is also linked to reduced body size of ectotherms. While temperature can act directly on body size, it may also act indirectly by affecting the timing of life-cycle events and the resulting population age and size structure, especially in seasonal environments. Population structure may, in turn, be influenced by temperature-driven changes in resource availability. In a field mesocosm experiment, we investigated how water temperature and mixed surface layer depth (a temperature-dependent determinant of light availability to phytoplankton) affected population dynamics, population age and size structure, and individual size at stage (size at first reproduction) of Daphnia hyalina during and after a phytoplankton spring bloom. Mixed layer depth was inversely related to the magnitudes of the phytoplankton spring bloom and the subsequent Daphnia peak, but had no effect on the body size of Daphnia. Conversely, temperature had no effects on abundance peaks but strongly affected the timing of these events. This resulted in at times positive, at other times negative, transient effects of temperature on mean body size, caused by asynchronous changes in population size structure in cold versus warm treatments. In contrast to mean body size, individual size at stage consistently decreased with increasing temperature. We suggest that size at stage could be used as an unbiased response parameter to temperature that is unaffected by transient, demographically driven changes in population size structure.     

A multivariate approach for a comparison of big data matrices. Case study: thermo-hygrometric monitoring inside the Carcer Tullianum (Rome) in the absence and in the presence of visitors

In the last decades, the very fast improvement of the analytical instrumentation has led to the possibility of quickly and easily getting a lot of data; in turn, the need of advanced statistical methods suitable to extract the full information furnished by instruments has increased. Such kind of data treatments is particularly important in any case of continuous monitoring of one or more parameters, so the microclimate monitoring is a typical example for this application. Microclimate control is essential in the conservation of Cultural Heritage (CH), but decisions on optimal conservation parameters cannot base only on existing norms that do not take into account the environment’s history. Often CH has survived for many centuries in conditions that must be considered risky but also a stable state (equilibrium) resulting from a long adaptation process during which a more or less heavy damage occurred to the materials. Any successive change of microclimate parameters has interrupted this equilibrium conditions and has induced further damage to material until a new equilibrium is reached; dimension and frequency of changes are proportional to the expected damage. This thermodynamic consideration provides the background for a CH conservation project based on microclimate control and highlights the importance of environmental monitoring for the identification of equilibrium parameters to be maintained. In 2010, we monitored the microclimate of an important historical building in Rome, the Mamertino Carcer, before its opening to visitors. One year later, we repeated the monitoring in the presence of visitors, and here, we present a careful choice of multivariate data treatments adopted for an enough, simple and immediate evaluation of the microclimatic changes; this allows an easier understanding also for persons with not too deep scientific background, such as Superintendents and, in turn, really useful information to provide suggestions for a conservation project. Results evidenced the expected loss of isolation of the site that occurred by opening to visitors; this led to wider excursions of both temperature and relative humidity and, in turn, to a worsening of the conservative conditions. Surely, a monitoring of particulate matter, correlated to air fluxes and, in turn, to microclimate, is of fundamental importance for the conservation of frescoes and will be object of one of our future diagnostic interventions in the site.     

Evaluation of Direct-Oxidative DNA Damage on Human Lung Epithelial Cells Exposed to Urban Airborne Particulate Matter

Airborne particulate matter (PM) extracts were investigated for their content of organic compounds and for the direct and oxidative DNA damage induced on lung epithelial cells A549. PM₁₀ was seasonally collected at two monitoring sites (Stations 1 and 2), characterized by different traffic loads. The cells were exposed for 30 min to extracts of PM₁₀ diluted at 0.025%, 0.05%, and 0.1% for summer samples, and at 0.05%, 0.1%, and 0.15% for winter samples. Oxidative and direct DNA damage were evaluated by formamidopyrimidine glycosylase (fpg) comet assay analyzing tail moment (TM) values from fpg-enzyme-treated cells (TMenz) and enzyme untreated cells (TM) respectively and by comet percentage analysis. Measurements relating to Station 2 showed higher levels of polycyclic aromatic hydrocarbons (PAHs), and their methyl-(methyl-PAHs) and nitro-(nitro-PAHs) derivatives in both the seasons. Nitro-PAH concentrations were higher in summer than in winter at both the stations. We found a significant increase of comet percentages at the highest dose of extract from both stations in summer and from Station 2 in winter. The TM and TMenz values relative to the summer sampling showed an early oxidative DNA damage induction also followed by direct DNA damage more evident at Station 2, that seems to correlate with the presence of higher nitro-PAH concentrations during the warm season. At both monitoring stations, the results from winter sampling campaign showed a direct DNA damage induction at 0.1% of extract and oxidative-direct DNA damage at the highest dose (0.15%).     

Solid-phase extraction for multi-residue analysis of pesticides in honey

A fast and simple multi-residue method for the analysis of 15 organophosphorus (OP), 17 organochlorine (OC), 8 pyrethroids (PYR), 12 N-methyl-carbamate (NMC) pesticide residues and bromopropylate in honey is presented. Ready-to-use EXtrelutNT 20 column, eluted with dichloromethane, was used to extract the pesticide residues from the aqueous-acetone honey sample, obtaining a clean extract directly analyzable. Determination was carried out by gas chromatography (GC) coupled with flame photometric detector (FPD) for OP compounds and by GC coupled with mass spectrometry detector (MSD) for OC and PYR pesticides and bromopropylate. The NMC pesticides were analysed by liquid chromatography-double derivatization coupled with spectrofluorimetric detector (LC/DD/Fl). This method allows the determination of the 53 pesticide residues at low concentrations (0.0005-0.074 mg/kg) and can be used to assess the compliance with the Maximum Residues Levels (MRLs) set by the European Union. The performance of the method was evaluated and specificity, linearity, recovery, repeatability, reproducibility, limit of quantification (LOQ) and limit of detection (LOD) were determined. A good linearity (r(2)≥ 0.99) was found in the range 0.0005-0.074 mg/kg for the majority of the compounds studied. Most of the pesticides had recoveries in the range 70-103 % and values of relative standard deviation (RSD) < 20 for repeatability and reproducibility, showing good accuracy and precision of the method. Aldicarb partially degraded in aldicarb sulphoxide during the analytical procedure, giving anomalous values. The LOQ for all pesticides investigated was from 0.0005 to 0.025 mg/kg while the LOD ranged from 0.0002 to 0.008 mg/kg.     

Determination of acidic herbicides in cereals by QuEChERS extraction and LC/MS/MS

A simple and rapid method has been studied for the determination of acidic herbicides (2,4-D, Dichlorprop, Dichlorprop-p, Fluazifop, Fluroxypyr, MCPA, Mecoprop and Mecoprop-p) on cereals (rye). The method involves an alkaline hydrolysis with sodium hydroxide in order to release covalently bound compounds, prior to QuEChERS extraction, followed by neutralization and analysis via liquid chromatography-double mass spectrometry LC/MS/MS. The performance of the method either with or without alkaline hydrolysis was studied in terms of recovery rates and limit of quantification (LOQ). In either case, recoveries were determined at four spiking levels (0.02 mg/kg, 0.05 mg/kg, 0.1 mg/kg and 0.5 mg/kg) with 5 replicates for each level. Mean recoveries ranged from 90 to 120 %, whereas relative standard deviations (RSD %) proved to be less than 20 %. Quantitative analysis was carried out by the internal standard (Nicarbazin) and the LC/MS/MS analysis was performed in electrospray ionisation (ESI) negative mode using a Zorbax XCB Eclipse column. The developed method was applied to the analysis of several cereals commercially available like as rye flour, oat meal, oat flakes and dehusked oat. Residue levels were found below the limit of quantification (LOQ) of the method. The method has been tested in EU Proficiency Tests for cereals with good results.     

Air pollutants and the characterization of the organic content of aerosol particles in a mixed industrial/semi-rural area in central Italy

Both regulated and unregulated air pollutants were detected during an intensive seasonal sampling campaign in a mixed industrial/semi-rural area on the outskirts of Rome, Italy, at two sites located opposite a hospital waste incinerator, downwind according to the direction of the prevailing local winds. Concentrations of pollutants were significantly lower than in urban atmospheres. The composition of particulate organic material indicated a heavy biogenic impact, accompanied by a lower contribution from petroleum-related processes. Both PAH and nitro-PAH group compositions of particulates were used to assess the nature and relative importance of sources. Both sites showed that different and diffuse sources contributed to local pollution with a significant contribution from traffic, proving that the hospital waste incinerator was not the main pollution source in this area. Among unregulated compounds, a series of positional isomers of nitro-PAHs and other organic compounds associated with particulate matter were investigated. In particular, 1- and 3-nitrophenanthrene identification was carried out, and they proved to be the most abundant nitro-PAHs.