Temporal and spatial changes of PAH concentrations in Mytilus galloprovincialis from Ria de Vigo (NW Spain)

The aim of this study was to establish the temporal trends and spatial distribution of Polycyclic Aromatic Hydrocarbons (PAHs) in Ria de Vigo by means of studying the PAH burden in wild mussels. The samples were collected in eight sites along the margins of the Ria de Vigo during November from 1998 to 2008 and Polycyclic Aromatic Hydrocarbon contents were determined using high performance liquid chromatography–fluorescence derivatization (HPLC–FLD). Quality of chemical analysis was guaranteed by participation in QUASIMEME intercalibration exercises carried out during the period of analysis. The concentrations for the sum of 13 PAHs were in the range 24–480 μg/kg dw, typical of an urban and industrialized area (50–500 μg/kg dw) except for a punctual input in La Guía in 1998 that led to a concentration above 1,000 μg/kg dw. In general, the sites in the outermost section of the estuary (ría) showed the lowest values, with an increasing gradient in the medium and inner parts of the ría. Temporal patterns show, in general, a downward trend. The relative proportion of 3 and 4 ring PAHs also varies with the site, the former being predominant in the outermost area and the latter in the medium and inner parts of the ría. This is consistently related with the sources and processes taking place in different areas of the estuary.     

A flux-based assessment of the effects of ozone on foliar injury, photosynthesis, and yield of bean (Phaseolus vulgaris L. cv. Borlotto Nano Lingua di Fuoco) in open-top chambers

Stomatal ozone uptake, determined with the Jarvis' approach, was related to photosynthetic efficiency assessed by chlorophyll fluorescence and reflectance measurements in open-top chamber experiments on Phaseolus vulgaris. The effects of O₃ exposure were also evaluated in terms of visible and microscopical leaf injury and plant productivity. Results showed that microscopical leaf symptoms, assessed as cell death and H₂O₂ accumulation, preceded by 3-4 days the appearance of visible symptoms. An effective dose of ozone stomatal flux for visible leaf damages was found around 1.33 mmol O₃ m⁻². Significant linear dose-response relationships were obtained between accumulated fluxes and optical indices (PRI, NDI, ΔF/F_m^′). The negative effects on photosynthesis reduced plant productivity, affecting the number of pods and seeds, but not seed weight. These results, besides contributing to the development of a flux-based ozone risk assessment for crops in Europe, highlight the potentiality of reflectance measurements for the early detection of ozone stress.     

PTR-MS measurements and analysis of models for the calculation of Henry's law constants of monosulfides and disulfides

Sulfides are known for their strong odor impact even at very low concentrations. Here, we report Henry’s law constants (HLCs) measured at the nanomolar concentration range in water for monosulfides (dimethylsulfide, ethylmethylsulfide, diethylsulfide, allylmethylsulfide) and disulfides (dimethyldisulfide, diethylsulfide, dipropylsulfide) using a dynamic stripping technique coupled to Proton Transfer Reaction-Mass Spectrometry (PTR-MS). The experimental data were compared with literature values and to vapor/solubility calculations and their consistency was confirmed employing the extra-thermodynamic enthalpy-entropy compensation effect. Our experimental data are compatible with reported literature values, and they are typically lower than averaged experimental literature values by about 10%. Critical comparison with other freely available models (modeled vapor/solubility; group and bond additivity methods; Linear Solvation Energy Relationship; SPARC) was performed to validate their applicability to monosulfides and disulfides. Evaluation of theoretical models reveals a large deviation from our measured values by up to four times (in units of M atm⁻¹). Two group contribution models were adjusted in view of the new data, and HLCs for a list of sulfur compounds were calculated. Based on our findings we recommend the evaluation and adaption of theoretical models for monosulfides and disulfides to lower values of solubility and higher values of fugacity.     

One-Year Study of the Elemental Composition and Source Apportionment of PM10 Aerosols in Florence,Italy

Abstract

An extensive investigation was carried out for the characterisation of the air particulate composition in Florence. The aim was to determine the aerosol elemental concentrations, as well as to identify pollution sources. For our investigation, the external Particle-Induced X-Ray Emission–Particle-Induced γ-Ray Emission beam facility of the Istituto Nazionale di Fisica Nucleare, Van de Graaff accelerator at the Physics Department of the Florence University was used. We report the results of the analysis of a long temporal series (approximately 1 yr) of PM₁₀ particulate samples, collected on Millipore filters on a daily basis in three different sites (characterised by different urban settings). Daily concentrations of more than 20 elements were detected. The long sampling period (approximately 1 yr) allowed a comparison with the air quality recommended values and the identification of seasonal variations. Four main sources (traffic, oil-combustion, soil-dust, and wind transported sea-salt) were extracted with the help of Principal Component Analysis (PCA). An absolute PCA showed traffic to be the major source both in the high traffic site and in the urban background site.     

Outbreak of fatal nitrate toxicosis associated with consumption of fennels (Foeniculum vulgare) in cattle farmed in Campania region (southern Italy)

Nitrate and nitrite are toxicants that have become increasingly significant environmental chemicals. Increase in environmental distribution of nitrogenous compounds, especially in surface and ground water, has been attributed to the intensive use of nitrate as agricultural fertilizers and to increasing amounts of nitrogenous wastes produced by municipalities, industries, and feedlots. The purpose of this study is to illustrate a fatal nitrate toxicosis in cattle associated with the consumption of fennels (Foeniculum vulgare). Fifteen cows from the same farm suddenly developed weakness, muscular tremors, respiratory distress, and finally convulsions. The affected animals died within 24 to 48 h from the onset of the clinical signs. Five cows underwent a complete post-mortem examination. In all examined animals, gross lesions included presence of dark unclotted blood around the nostrils and the anal region, moderate inflammation of the gastrointestinal mucosa, and brown discoloration of the skeletal muscles and kidneys. The histological examination showed tubular degeneration and congestion of glomerular vessels in the kidney. Toxicological analysis detected nitrates at 4 672.2 ppm in the fennels used to feed the animals. The source of exposure to nitrates was identified in the fennels. The fennels were grown in a polluted area of the Campania region in southern Italy and distributed in a public market for human consumption. The waste from the sale of the fennels was fed to the cows. The accumulation of nitrates in some vegetables poses a risk not only for animal health but also for human and environmental safety.     

Assessment of ambient air quality in the port of Naples

Two experimental monitoring campaigns were carried out in 2012 to investigate the air quality in the port of Naples, the most important in southern Italy for traffic of passengers and one of the most important for goods. Therefore, it represents an important air pollution source located close to the city of Naples. The concentrations of sulfur dioxide (SO₂), nitrogen dioxide (NO₂), and BTEX (benzene, toluene, ethylbenzene, and xylenes) in the air were measured at 15 points inside the Naples port area through the use of passive samplers. In addition, a mobile laboratory was positioned in a fixed point inside the port area to measure continuous concentration of pollutants together with particulate matter, ambient parameters, and wind direction and intensity. The pollution levels monitored were compared with those observed in the urban area of Naples and in other Mediterranean ports. Even though the observation time was limited, measured concentrations were also compared with limit values established by European legislation. All the measured pollutants were below the limits with the exception of nitrogen dioxide: its average concentration during the exposition time exceeded the yearly limit value. A spatial analysis of data, according to the measured wind direction and intensity, provided information about the effects that ship emissions have on ambient air quality in the port area. The main evidence indicates that ship emissions influence sulfur dioxide concentration more than any other pollutants analyzed.

Implications: Two monitoring campaigns were carried out to measure BTEX, SO₂, NO₂, and PM₁₀ (particulate matter with an aerodynamic diameter <10 μm) air concentrations in the port of Naples. NO₂ hourly average and PM₁₀ daily average comply with European legislative standards. Spatial variation of pollutants long the axis corresponding to the prevailing wind direction seems to indicate a certain influence of ship emissions for SO₂. For NO₂ and PM₁₀, a correlation between concentrations in the harbor and those measured by the air quality monitoring stations sited in the urban area of Naples was observed, indicating a possible contribution of the near road traffic to the air pollution in the port of Naples.     

Spatial and temporal trends of polycyclic aromatic hydrocarbons in wild mussels from the Cantabrian coast (N Spain) after the Prestige oil spill

Polycyclic aromatic hydrocarbon (PAH) levels were determined in tissues of wild mussels (Mytilus galloprovincialis) collected at 17 stations along the Cantabrian coast (N Spain), from Navia (Asturias) to Fuenterrabía (Basque Country), in order to assess the extent of the environmental impact caused by the Prestige oil spill (November 13, 2002). Six sampling campaigns were carried out in April, June and November in 2003 and 2004. The comparison of PAH data with those obtained earlier in 2000 showed a widespread pyrolytic and petrogenic contamination and allowed an estimation, for the first time, of the background pollution in the region and identification of the chronic hotspots. The spatial distribution found in the first samples after the oil spill revealed the eastern area as the most affected due to the continuous arrival of fuel slicks since early summer 2003. Several stations in this area showed increased total PAH concentrations of up to 15 times the pre-spill levels, which did not recover until April 2004, more than one year after the accident. Molecular parameters within the aliphatic and aromatic fractions were determined to assess the presence of Prestige oil in these samples.     

Organic and inorganic diffuse contamination in urban soils: the case of Torino (Italy)

Soils in urban parks are useful tracers of diffuse contamination and could represent a potential health risk for citizens. Soils in the parks of Torino, Italy, were sampled and analysed for a broad range of organic and inorganic contaminants. Concentrations of potentially toxic elements, PAHs, PCBs and polychlorinated dibenzo-p-dioxins and dibenzofurans were often above national legislation limits, and higher than surrounding rural areas or than other cities. Mean concentrations were 233 mg kg(-1) for Cr, 164 mg kg(-1) for Ni, 124 mg kg(-1) for Pb and 170 mg kg(-1) for Zn. Other inorganic contaminants such as Cd, As, and Hg showed high concentrations in some soils. Organic contaminants were also found to be enriched in the sampled parks (e.g. maximum concentrations of PCDDs/DFs and PCBs were 12.6 ng kg(-1) and 0.310 mg kg(-1), respectively). Data from this study reveal an important enrichment of parks for some contaminants, reflecting the intensity of phenomena of diffuse contamination. Historical parks presented the highest degree of contamination, suggesting that the age of soils rather than their proximity to sources of emissions is a key factor in determining soil contamination. Data obtained in this study could be of help in the investigation and remediation practices of urban contaminated sites within large cities.     

The direct influence of ship traffic on atmospheric PM2.5, PM10 and PAH in Venice

The direct influence of ship traffic on atmospheric levels of coarse and fine particulate matter (PM_2.5, PM₁₀) and fifteen polycyclic aromatic hydrocarbons (PAHs) has been estimated in the urban area of Venice. Data analysis has been performed on results collected at three sites over the summer, when ship traffic is at a maximum. Results indicate that monitoring of the PM daily concentrations is not sufficiently detailed for the evaluation of this contribution, even though it could be useful for specific markers such as PAHs. Therefore a new methodology, based on high temporal resolution measurements coupled with wind direction information and the database of ship passages of the Harbour Authority of Venice has been developed. The sampling sites were monitored with optical detectors (DustTrack^® and Mie pDR-1200) operating at a high temporal resolution (20s and 1s respectively) for PM_2.5 and PM₁₀. PAH in the particulate and gas phases were recovered from quartz fibre filters and polyurethane foam plugs using pressurised solvent extraction, the extracts were then analysed by gas chromatography- high-resolution mass spectrometry. Our results shows that the direct contribution of ships traffic to PAHs in the gas phase is 10% while the contribution to PM_2.5 and to PM₁₀ is from 1% up to 8%.     

Life cycle of the jellyfish <Emphasis Type="Italic">Rhizostoma pulmo</Emphasis> (Scyphozoa: Rhizostomeae) and its distribution,seasonality and inter-annual variability along the Catalan coast and the Mar Menor (Spain,NW Mediterranean)

Rhizostoma pulmo is one of the most abundant scyphomedusae along the Mediterranean coasts. To understand changes in the population densities of the medusa stage and its relationship with the benthic stage, we describe all developmental stages from the life cycle of R. pulmo, from the scyphistoma stage to young medusae reared in the laboratory. Mature scyphistomae showed a mean total body length of 1.7 mm and the average tentacle number was 16. Asexual reproduction occurred by lateral budding, podocyst and pedalocyst production. Each strobila released up to 8 ephyrae that had a mean total body diameter of 3.5 mm. Moreover, we also present data on the temporal and spatial distribution of the species in the Catalan Sea and the coastal lagoon on Mar Menor (NW Mediterranean) during the years 2007–2009. In the Catalan Sea, the presence of adult R. pulmo was recorded as extended along the whole coast, but most of the observation was concentrated in the central area; the highest abundances were recorded during the months of July and August. The highest number of observations was detected in 2008 in coincidence with the inter-annual variation observed in the Mar Menor lagoon.