Rossano Piazza

Development of a method for simultaneous analysis of PCDDs, PCDFs, PCBs, PBDEs, PCNs and PAHs in Antarctic air

The development of a unique analytical method for the determination of five classes of persistent organic pollutants (POPs) in atmospheric gas and the particle phase through gas chromatography coupled to high-resolution mass spectrometry is presented. Every step of the pre-analytical and analytical optimization process is described. Great effort was put into simplifying the traditional techniques, with reference to EPA and literature methods. Automated instruments were used for sample extraction and cleanup in order to enhance repeatability and reduce contamination risks. Unlike most common approaches, no separation of the analytes was performed before the GC analysis in order to avoid sample fractionation and to save time and materials. This allowed low instrumental and method detection limits (pg to sub-pg) to be achieved. Accuracy and precision were tested by fortifying the matrix and analysing standard reference materials (NIST SRM 1649b Urban Dust and 2585 Organic Contaminants in House Dust). The method was applied to five samples from Terra Nova Bay, Antarctica. Concentrations of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), polybrominated diphenyl ethers (PBDEs) and polycyclic aromatic hydrocarbons (PAHs) are presented. Lighter compounds dominate the distribution and are mainly present in the gaseous phase. The observed pattern may be attributable to long-range transport. Results are in general agreement with literature data, where available.

Gas-particle distributions, sources and health effects of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) in Venice aerosols.

Air samples were collected in Venice during summer 2009 and 2012 to measure gas and particulate concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs). PCB-11, considered a marker for non-Aroclor contamination of the environment, was found for the first time in the Venetian lagoon and in Europe. An investigation on sources has been conducted, evidencing traffic as the major source of PAHs, whereas PCBs have a similar composition to Aroclor 1248 and 1254; in 2009 a release of PCN-42 has been hypothesized. Toxicological evaluation by TCA and TEQ methods, conducted for the first time in Venice air samples, identified BaP, PCB-126 and PCB-169 as the most important contributors to the total carcinogenic activity of PAHs and the total dioxin-like activity of PCBs and PCNs.

Determination of polychlorobiphenyls in Venice Lagoon sediments

Polychlorinated biphenyl (PCBs) congeners were measured in 14 sediment samples collected at five sites in the Venice Lagoon selected on the basis of a supposed diversity of inputs and of pollution levels. The PCBs were determined after a sonication assisted extraction by gas chromatography mass spectrometry (GCMS). The sum of the congener concentrations determined in the samples range from 4.05 to 239.15 ng/g on a dry weight basis. The concentration values are very variable both comparing the sites and comparing different samples from the same site and can be connected to the sand percentage in the sediment samples. The correlation matrix obtained from data matrix using the congener concentrations as variables shows high values, mostly between 0.964 and 1, suggesting that the pattern of the PCB congeners and the ratios among the concentrations in Venice Lagoon sediments are more or less constant; the samples differ only in the concentration level.

PBDEs and PCBs in sediments of the Thi Nai Lagoon (Central Vietnam) and soils from its mainland.

Concentration and distribution of PCBs, PCB 11, and PBDEs in both surficial sediment and soil samples, taken from a zone subject to recent accelerated development, were investigated to assess the environmental quality and understand both natural and anthropogenic processes that influence contaminant behaviors. Values of PCB and PBDE are in the lower range of those reported in literature, typical of low impacted coastal zones. This could be due to efficient processes of resuspension and removal. Contaminants in the lagoon showed higher concentrations in sediments from sites close to the city and the outfalls of the industrial area, while soils showed maximum values in the northern samples. In addition, congener patterns and statistical analyses suggest the presence of effective degradation processes, especially for PBDEs, with the exception of the most concentrated samples that may indicate a direct input. PCB 11 is a significant component (up to 18%) in most lagoon sediments. Its presence is strongly associated with fine particles, thus the distribution seems to be driven mainly by the system hydrodynamic and does not trace the sources. Due to evaporation, only flooded agricultural soils show a similar relative abundance of this congener.

Organic micropollutants in wet and dry depositions in the Venice Lagoon.

Atmospheric transport is an important route by which pollutants are conveyed from the continents to both coastal and open sea. The role of aerosol deposition in the transport of polycyclic aromatic hydrocarbons (PAHs), polychlorobiphenyls (PCBs) and polybromodiphenyls ethers (PBDEs) to water and soil systems has been evaluated by measuring their concentrations in wet and dry depositions to the Venice Lagoon. The organic micropollutant flux data indicate that they contribute to the total deposition flux in different ways through wet and dry deposition, showing that the prevalent contribution derives from wet deposition. The fluxes calculated for PBDEs, showed the prevalence of 47, 99, 100 and 183 congeners, both in dry and wet fluxes. With regard to PCBs, the flux of summation operatorPCB for wet deposition is in the same order of magnitude of the diffusive flux at the air-water interface. The PAH fluxes obtained in the present study are similar to those obtained in previous studies on the atmospheric bulk deposition to the Venice Lagoon. The ratios between Phe/Ant and Fl/Py indicate that the pollutants sources are pyrolytic, deriving from combustion fuels.

Quantitative determination of un-derivatised amino acids in artistic mural paintings using high-performance liquid chromatography/electrospray ionization triple quadrupole mass spectrometry

The tempera painting technique is one of the most common methods used throughout art history. Tempera is defined by the type of binders used and in this work we study protein-based temperas. Proteinaceous binders can be characterized by the chromatographic determination of the amino acids present where techniques are either based on gas chromatography or high-performance liquid chromatography (HPLC) coupled to mass spectrometry. The objective of this work was to develop a derivatisation-free HPLC method with triple quadrupole tandem mass spectrometric detection (HPLC/ESI-MS/MS) of 21 amino acids contained in the protein-based binders of tempera paints. The analytical method identifies the painting techniques of two contemporary artists: Sironi and DeLuigi. The sample data are compared to painting material standards. The results show that the samples from works by DeLuigi contain mainly animal glue binders, while the samples from Sironi paintings contain binders that are an amino acid mixture with an overall composition between that of eggs and casein.

Recognizing different impacts of human and natural sources on the spatial distribution and temporal trends of PAHs and PCBs (including PCB-11) in sediments of the Nador Lagoon (Morocco).

The Nador Lagoon holds a major interest in present-day Moroccan socioeconomic development. This environment is exposed to a number of potential polluting sources, such as mine tailings, urban and industrial dumping, and untreated wastewater inputs from surrounding cities. The aim of this study was to assess concentrations and trends of persistent contaminants such as PCBs and PAHs and to identify their origin. The non-Aroclor PCB-11 was determined for the first time in the lagoon sediments. Chronology and source assessment helped identifying the timing and nature of inputs and post-depositional processes controlling the two classes of contaminants: PAHs present a typical mixed petrogenic signature, with the exception of sediments deposited in the period 1930-1960 near the city of Nador, when pyrogenic inputs prevailed; PCBs show signs of microbial anaerobic degradation from 1950 to 1990, probably linked to changing hydrodynamic conditions in the South-Western part of the lagoon where agricultural inputs are dominant. The presence of PCB-11 is linked to specific productions and might be affected by degradation processes. Presently, different land uses (e.g., urban and agricultural areas) appear to be the key factors in controlling the level and composition of PAHs and PCBs in lagoon sediments. Total PAH and PCB levels are low (from 21.6 to 108 ng g(-1) and from 2.50 to 20.7 ng g(-1), respectively) but recent increasing values and the potential threat to humans and biota require continuous and constant monitoring.

Polychlorinated biphenyls in sediments of selected coastal environments in northern Morocco

disturb them, e.g., typhoons, storm surges, dredging activities etc. Their movement into biotic communities within this area predominantly occurs via the sediment ingester-suspension feeder-carnivore route rather than through primary producers and secondary trophic level consumers. From a human health standpoint, lead was identified as the element of greatest concern with advisory excedences noted in bivalves from the dump (Site 2) northwards to Lower Base Channel (Site 6). With the exception of copper in Q. palatum from Site 2, trace metal levels in all other biotic representatives were well below critical threshold levels of concern when weighed against existing USA advisories (USEPA, 1986; USFDA, 1998) and food standards of other countries (Nauen, 1983).

Historical PCB fluxes in the Mexico City Metropolitan Zone as evidenced by a sedimentary record from the Espejo de los Lirios lake

The accumulation of PCBs over time was studied in a sediment core collected from Espejo de los Lirios, an ecological reserve located within the heart of Cuatitlan Izcalli, in the Northern part of Mexico City Metropolitan Zone. A (210)Pb-derived chronology, was used to reconstruct the historical PCB fluxes to the site during approximately 84 yr (1911-95). The highest input fluxes occurred in the 1977, after a significant increase after the late 1940s. This trend is clearly the consequence of the increasing emissions that are related to the onset of industrial activities starting from early 1970s. A phase of decrease, after the ban of the use in open systems, ended in 1989 and in 1995, at the time of sampling, the trend was toward a new increase to the highest levels. A reconstruction of PCB atmospheric concentration from sedimentary fluxes is attempted; and the estimate suggests that PCBs concentrations in the air of the Cuautitlán Izcalli seem not of concern. Nonetheless, the contamination levels found in the sediments are relatively high, reaching values above the threshold effect level (TEL) guidelines and, in two cases, close to the probable effect level (PEL) which mean that some adverse effects on the fauna may have occurred all over the time interval represented by the core.

PCBs in Central Vietnam coastal lagoons: levels and trends in dynamic environments

PCBs were analysed in surficial sediments and selected sediment cores collected between 2002 and 2008 in Central Vietnam coastal lagoons. The aim was to determine contamination levels and trends, and to evaluate the effects of anthropogenic pressures and natural events. Samples were mostly fine-grained with low total PCB concentrations (0.367-44.7 μg kg(-1)). Atmospheric transport and post depositional processes modify to some degree the fingerprint of PCB inputs to the environment favouring the predominance of 3, 4 and 5 chlorinated congeners. The similarity of congener distributions in contemporary surficial samples also suggests the presence of a unique source over the entire study area, probably connected to mobilisation and long range transports from land-based stocks. The removal of consistent sediment layers is hypothesised based on repeated samplings of the same area. Natural meteorological events (such as typhoons) are suspected to be responsible for these sediment losses.