Monitoring of marine mucilage formation in Italian seas investigated by infrared spectroscopy and independent component analysis

The aim of this study is to present and to discuss some characteristics of recalcitrant organic matter mechanism and formation. These aggregates called mucilages that are produced by the degradation reactions of several algae, have been investigated by infrared (FTIR) spectroscopy. FTIR spectra of macroaggregates produced by different algal samples have been daily collected in order to investigate the steps of aggregation. Afterwards, they have been elaborated by means of Independent Component Analysis (ICA). ICA investigation of FTIR spectra showed that the global aggregation process of marine mucilage always consisted of two different phases or independent components (ICs). One IC is related to the first degradation step of algal cells leading to the production of mono and oligosaccharides with aminoacids and oligopeptides. The second IC is related to the polymerization of oligosaccharides with aminoacids and oligopeptides and to their interaction with less polar compounds such as lipids thus producing supramolecular structures. The emerging mechanisms of anomalous size aggregates of organic matter match those of natural organic matter aggregation. The approach we suggest is to use synthetic mucilages which allows to monitor the macroaggregates formation because it can hardly be performed by means of natural marine macroaggregates.     

Heavy metal distribution and speciation in the Northern Adriatic Sea

In the present study the concentrations of cobalt, copper, iron, manganese, zinc were analysed and the speciation of copper and zinc performed, with a summer and winter sampling, for two areas in the Northern Adriatic Sea and crossing at the farthest zones of the Po river-sea water interface. Results show that when salinity increases the concentrations of all investigated metals (with the exception of cobalt) present some degree of biogeochemical cycling. Copper is the element whose dissolved phase has the highest importance in metal transport across the salinity gradient. Results of speciation analysis demonstrate that the presence of excess amounts (5-8 fold) of unbound ligands confers a buffering capacity for potential inputs of dissolved metals into the Northern Adriatic Sea. The speciation of both copper and zinc in the dissolved phase was dominated by organic complexation.     

Influence of tobacco smoke on carcinogenic PAH composition in indoor PM10 and PM2.5

Because of the mutagenic and/or carcinogenic properties, Polycyclic Aromatic Hydrocarbons (PAH), have a direct impact on human population. Consequently, there is a widespread interest in analysing and evaluating the exposure to PAH in different indoor environments, influenced by different emission sources. The information on indoor PAH is still limited, mainly in terms of PAH distribution in indoor particles of different sizes; thus, this study evaluated the influence of tobacco smoke on PM₁₀ and PM_2.5 characteristics, namely on their PAH compositions, with further aim to understand the negative impact of tobacco smoke on human health. Samples were collected at one site influenced by tobacco smoke and at one reference (non-smoking) site using low-volume samplers; the analyses of 17 PAH were performed by Microwave Assisted Extraction combined with Liquid Chromatography (MAE–LC). At the site influenced by tobacco smoke PM concentrations were higher 650% for PM₁₀, and 720% for PM_2.5. When influenced by smoking, 4 ring PAH (fluoranthene, pyrene, and chrysene) were the most abundant PAH, with concentrations 4600–21 000% and 5100–20 800% higher than at the reference site for PM₁₀ and PM_2.5, respectively, accounting for 49% of total PAH (Σ_PAH). Higher molecular weight PAH (5–6 rings) reached concentrations 300–1300% and 140–1700% higher for PM₁₀ and PM_2.5, respectively, at the site influenced by tobacco smoke. Considering 9 carcinogenic PAH this increase was 780% and 760% in PM₁₀ and PM_2.5, respectively, indicating the strong potential risk for human health. As different composition profiles of PAH in indoor PM were obtained for reference and smoking sites, those 9 carcinogens represented at the reference site 84% and 86% of Σ_PAH in PM₁₀ and PM_2.5, respectively, and at the smoking site 56% and 55% of Σ_PAH in PM₁₀ and PM_2.5, respectively. All PAH (including the carcinogenic ones) were mainly present in fine particles, which corresponds to a strong risk for cardiopulmonary disease and lung cancer; thus, these conclusions are relevant for the development of strategies to protect public health.     

The adaptive response of lichens to mercury exposure involves changes in the photosynthetic machinery

Lichens are an excellent model to study the bioaccumulation of heavy metals but limited information is available on the molecular mechanisms occurring during bioaccumulation. We investigated the changes of the lichen proteome during exposure to constant concentrations of mercury. We found that most of changes involves proteins of the photosynthetic pathway, such as the chloroplastic photosystem I reaction center subunit II, the oxygen-evolving protein and the chloroplastic ATP synthase β-subunit. This suggests that photosynthesis is a target of the toxic effects of mercury. These findings are also supported by changes in the content of photosynthetic pigments (chlorophyll a and b, and β-carotene). Alterations to the photosynthetic machinery also reflect on the structure of thylakoid membranes of algal cells. Response of lichens to mercury also involves stress-related proteins (such as Hsp70) but not cytoskeletal proteins. Results suggest that lichens adapt to mercury exposure by changing the metabolic production of energy.     

PAH air pollution at a Portuguese urban area: carcinogenic risks and sources identification

This study aimed to characterize air pollution and the associated carcinogenic risks of polycyclic aromatic hydrocarbon (PAHs) at an urban site, to identify possible emission sources of PAHs using several statistical methodologies, and to analyze the influence of other air pollutants and meteorological variables on PAH concentrations.The air quality and meteorological data were collected in Oporto, the second largest city of Portugal. Eighteen PAHs (the 16 PAHs considered by United States Environment Protection Agency (USEPA) as priority pollutants, dibenzo[a,l]pyrene, and benzo[j]fluoranthene) were collected daily for 24 h in air (gas phase and in particles) during 40 consecutive days in November and December 2008 by constant low-flow samplers and using polytetrafluoroethylene (PTFE) membrane filters for particulate (PM₁₀ and PM_2.5 bound) PAHs and pre-cleaned polyurethane foam plugs for gaseous compounds. The other monitored air pollutants were SO₂, PM₁₀, NO₂, CO, and O₃; the meteorological variables were temperature, relative humidity, wind speed, total precipitation, and solar radiation. Benzo[a]pyrene reached a mean concentration of 2.02 ng?m^?3, surpassing the EU annual limit value. The target carcinogenic risks were equal than the health-based guideline level set by USEPA (10^?6) at the studied site, with the cancer risks of eight PAHs reaching senior levels of 9.98?×?10^?7 in PM₁₀ and 1.06?×?10^?6 in air. The applied statistical methods, correlation matrix, cluster analysis, and principal component analysis, were in agreement in the grouping of the PAHs. The groups were formed according to their chemical structure (number of rings), phase distribution, and emission sources. PAH diagnostic ratios were also calculated to evaluate the main emission sources. Diesel vehicular emissions were the major source of PAHs at the studied site. Besides that source, emissions from residential heating and oil refinery were identified to contribute to PAH levels at the respective area. Additionally, principal component regression indicated that SO₂, NO₂, PM₁₀, CO, and solar radiation had positive correlation with PAHs concentrations, while O₃, temperature, relative humidity, and wind speed were negatively correlated.     

Precision and Accuracy in the Determination of Sulfur Oxides,Fluoride, and Spherical Aluminosilicate Fly Ash Particles in Project MOHAVE

The precision and accuracy of the determination of particu-late sulfate and fluoride, and gas phase SO₂ and HF are estimated from the results obtained from collocated replicate samples and from collocated comparison samples for high-and low-volume filter pack and annular diffusion denuder samplers. The results of replicate analysis of collocated samples and replicate analyses of a given sample for the determination of spherical aluminosilicate fly ash particles have also been compared. Each of these species is being used in the chemical mass balance source apportionment of sulfur oxides in the Grand Canyon region as part of Project MOHAVE, and the precision and accuracy analyses given in this paper provide input to that analysis. The precision of the various measurements reported here is ±1.8 nmol/m³ and ±2.5 nmol/m³ for the determination of SO₂ and sulfate, respectively, with an annular denuder. The precision is ±0.5 nmol/m³ and ±2.0 nmol/m³ for the determination of the same species with a high-volume or low-volume filter pack. The precision for the determination of the sum of HF(g) and fine particulate fluoride is ±0.3 nmol/m³. The precision for the determination of aluminosilicate fly ash particles is ±100 particles/m³. At high concentrations of the various species, reproducibility of the various measurements is ±10% to ±14% of the measured concentration. The concentrations of sulfate determined using filter pack samplers are frequently higher than those determined using diffusion denuder sampling systems. The magnitude of the difference (e.g., 2-10 nmol sulfate/m³) is small, but important relative to the precision of the data and the concentrations of particulate sul-fate present (typically 5-20 nmol sulfate/m³). The concentrations of SO₂(g) determined using a high-volume cascade impactor filter pack sampler are correspondingly lower than those obtained with diffusion denuder samplers. The concentrations of SO_x (SO₂(g) plus particulate sulfate) determined using the two samplers during Project MOHAVE at the Spirit Mountain, NV, and Hopi Point, AZ, sampling sites were in agreement. However, for samples collected at Painted Desert, AZ, and Meadview, AZ, the concentrations of SO_x and SO₂(g) determined with a high-volume cascade impactor filter pack sampler were frequently lower than those determined using a diffusion denuder sampling system. These two sites had very low ambient relative humidity, an average of 25%. Possible causes of observed differences in the SO₂(g) and sulfate results obtained from different types of samplers are given.     

Material and energy recovery in integrated waste management systems. An evaluation based on life cycle assessment

This paper reports the environmental results, integrated with those arising from mass and energy balances, of a research project on the comparative analysis of strategies for material and energy recovery from waste, funded by the Italian Ministry of Education, University and Research. The project, involving the cooperation of five University research groups, was devoted to the optimisation of material and energy recovery activities within integrated municipal solid waste (MSW) management systems. Four scenarios of separate collection (overall value of 35%, 50% without the collection of food waste, 50% including the collection of food waste, 65%) were defined for the implementation of energetic, environmental and economic balances. Two sizes of integrated MSW management system (IWMS) were considered: a metropolitan area, with a gross MSW production of 750,000 t/year and an average province, with a gross MSW production of 150,000 t/year. The environmental analysis was conducted using Life Cycle Assessment methodology (LCA), for both material and energy recovery activities. In order to avoid allocation we have used the technique of the expansion of the system boundaries. This means taking into consideration the impact on the environment related to the waste management activities in comparison with the avoided impacts related to the saving of raw materials and primary energy. Under the hypotheses of the study, both for the large and for the small IWMS, the energetic and environmental benefits are higher than the energetic and environmental impacts for all the scenarios analysed in terms of all the indicators considered: the scenario with 50% separate collection in a drop-off scheme excluding food waste shows the most promising perspectives, mainly arising from the highest collection (and recycling) of all the packaging materials, which is the activity giving the biggest energetic and environmental benefits. Main conclusions of the study in the general field of the assessment of the environmental performance of any integrated waste management scheme address the importance of properly defining, beyond the design value assumed for the separate collection as a whole, also the yields of each material recovered; particular significance is finally related to the amount of residues deriving from material recovery activities, resulting on average in the order of 20% of the collected materials.