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.     

Genotoxicity of sediment extracts of the Berre lagoon (France)

To evaluate the genotoxic risk that contaminated sediment could constitute for benthic organisms, three contaminated (VA, VC and VN) and one uncontaminated (RN) sediment samples were collected in the Berre lagoon (France). Potentially bioavailable contaminants in sediments were obtained using sediment extraction with synthetic seawater adjusted to pH 4 or pH 6, simulating the range of pH prevailing in the digestive tract of benthic organisms. The genotoxic activities of these extracts were evaluated by three short-term bioassays: the Salmonella mutagenicity test using the Salmonella typhimurium strain TA102, the alkaline comet assay and the micronucleus assay on the Chinese Hamster Ovary cells CHO-K1. Results of the Salmonella mutagenicity assay detected a mutagenic response for RN extract at pH 6, and for VA extract at pH 4. Results of the comet and micronucleus assays detected low genotoxic/clastogenic activities for VA and VC extracts at pH 6 and higher activities for RN, VA and VC extracts at pH 4. To identify if metals (Al, Fe, Mn, As, Cd, Co, Cr, Cu, Hg, Ni, Pb and Zn) were involved in these genotoxic activities, their concentrations were determined in the extracts, and their speciation was assessed by thermodynamic calculations. Results showed that extracts from sites VA, VC and VN generally presented the highest trace metal contents for both extractants, while the site RN presented lower trace metal contents but the highest Fe and Mn contents. Thermodynamic calculations indicated that Fe, Mn, As and in a lower extend Co, Ni and Zn were mainly present under free forms in extracts, and were consequently, more likely able to induce a genotoxic effect. Results globally showed no correspondence between free metal contents and genotoxic activities. They suggested that these positive results could be due to uncharacterized compounds, acting as direct genotoxic agents or enhancing the genotoxic properties of analyzed metals.     

Risk assessment of linear alkylbenzene sulphonates, LAS, in agricultural soil revisited: robust chronic toxicity tests for Folsomia candida (Collembola), Aporrectodea caliginosa (Oligochaeta) and Enchytraeus crypticus (Enchytraeidae)

To obtain robust data on the toxicity of LAS, tests with the collembolan Folsomia candida L., the oligochaetes Aporrectodea caliginosa Savigny (earthworm) and Enchytraeus crypticus Westheide and Graefe (enchytraeid) were performed in a sandy loam soil. Additionally limited tests with LAS spiked to sewage sludge, and subsequently mixed into soil, were performed. For the endpoint of interest, reproduction in soil, we found an EC10 of 205 mg LAS kg(-1) soil [8.6-401] [95% confidence limits] for F. candida and an EC10 of 46 mg LAS kg(-1) soil [13-80] for A. caliginosa after 28 days. E. crypticus was not affected by concentrations up to 120 mg LAS kg(-1) soil. When adding (low contaminated) non-spiked sludge to soil, high stimulation of reproduction was observed for E. crypticus and A. caliginosa but not for F. candida. We argue that this difference in stimulative response between the tested species is related to the difference in feeding behaviour. Sludge spiked with LAS did not significantly affect the reproduction of F. candida (fertility: number of juvenile offspring) and A. caliginosa (fecundity: number of cocoons) (dose equivalent to 181 g and 91 g LAS kg(-1) sludge, respectively). Significantly reduced reproduction was observed for E. crypticus (at 120 mg LAS kg(-1) soil+sludge corresponding to 72 g LAS kg(-1) sludge) compared to non-spiked sludge. The reproduction by E. crypticus was, however, comparable to the reproduction observed in the control soil without sludge. Compared to LAS directly spiked to soil, the reproductive output of organisms exposed to spiked sludge was either not significantly different (F. candida, E. crypticus) or significantly improved (A. caliginosa). More studies are needed in order to make firm conclusions on the potential effect of artificially contaminated sludge in soil systems.     

Dioxin screening in fish product by pattern recognition of biomarkers

Two alternative, cost- and time-effective dioxin screening methods relying on two categories of potential lipid biomarkers were investigated. A dioxin range varying from 1.1 to 47.1 pg PCDD/F TEQ-WHO/g lipid using 64 fish meal samples was used for model calibration. The methods were based on multivariate models using either (1) fatty acid composition monitored by GC-FID or (2) fluorescence landscape signals analysed using the PARAFAC model and in both cases predicting dioxin content as pgPCDD/F TEQ-WHO/g lipid. In both cases, Partial Least Squares (PLS) regression was performed for predicting the dioxin content of a sample. The GC-FID data analyses was based on automatic peak alignment and integration, enabling extraction of the area of 140 peaks from the gas chromatograms, as opposed to the 31 fatty acids usually considered for fish oil characterisation. In addition to classic PLS employing the whole dataset for calibration, a two-step local PLS modeling approach was performed based upon an initial selection of k number of calibration samples providing the best match to the prediction sample using a so-called k Nearest Neighbors (kNN) approach, then followed by PLS calibration on these kNN selected samples for dioxin prediction. Fluorescence spectroscopy offers a promising non-invasive and ultra-rapid technique, with less than two minutes analysis time. However, fluorescence spectroscopy using the pattern recognition "kNN-PLS" yielded a correlation of 0.76 (r2) and a high root mean square error of prediction of 11.4 pg PCDD/F TEQ-WHO/g lipid. The predictions were improved when the PLS calibration was performed on all the sample with a root mean square error of prediction of 7.0 pg PCDD/F TEQ-WHO/g lipid. Unfortunately, these results failed to demonstrate the potential of fluorophore monitoring as a screening method. In contrast, the overall best screening performance was obtained with the fatty acid profile, when the kNN-PLS combination employed for pattern recognition (kNN) all the areas of the 140 detected peaks and the PLS regression used the areas of 46 selected peaks. This "kNN-PLS" prediction with three latent variables and based upon the 12 nearest neighbors selected out of the 64 x 2 fatty acid profiles (duplicate analyses), yielded a correlation of 0.85 (r2) and a root mean square error of prediction of 2.1 pg PCDD/F TEQ-WHO/g lipid and resulted in a total analysis time of one and half hour per sample.     

POPs in the Lagoon of Venice: budgets and pathways

Dioxins and furans (PCDD/Fs), polychlorobiphenyls (PCBs) and hexachlorobenzene (HCB) in the ecosystem of the Lagoon of Venice were studied, in order to provide a general picture of conditions in the lagoon in terms of contamination by persistent organic pollutants (POPs). We present here novel data on atmospheric deposition, water, sediment and clam samples collected in the lagoon during the period January 2001-December 2004. Atmospheric deposition was sampled monthly at six sites located both close and far from large industrial and urban sources. Water samples were collected monthly from fifteen stations, and twenty-five samples of sediments and clams (Tapes philippinarum) were collected in four areas where clams are farmed and harvested inside the lagoon. All samples were analysed for PCDD/Fs, PCBs and HCB by HRGC/HRMS in the same laboratory. All samples examined (atmospheric deposition and water) substantially confirmed the spatial pattern reported in previously published data on sediments and atmospheric deposition: the zone surrounding the Porto Marghera petrochemical plant always had the highest levels of POPs (i.e., PCDD/Fs: atmosphere approximately 6 pg of 2,3,7,8-TCDD equivalents (I-TE) m(-2)d(-1); water 0.37 pg I-TEl(-1); sediment: 300 ng kg(-1); clam 2.8 pg I-TE g(-1)), and the minima were found at points on the margins of the lagoon (PCDD/Fs: atmosphere approximately 1 pg I-TEm(-2)d(-1); water 0.05 pg I-TEl(-1); sediment: approximately 5 ng kg(-1); clam approximately 0.2 pg I-TE g(-1)). Intermediate values were often encountered in the historical city centre of Venice and in the central part of the lagoon. To confirm this, new data on correlation between levels of PCDD/F in sediments and clams are reported, both for absolute values and for the PCDD/F "fingerprint". There is always a clear fingerprinting signature (PCDF/PCDD>1) for samples collected near Porto Marghera, and the opposite (PCDF/PCDD<1) in the rest of the lagoon.     

An experimental apparatus for testing biodiesels based on a CFR engine—setup and validation with different methyl ester blends

A cooperative fuel research (CFR) engine was modified and instrumented in order to control operating conditions and to measure engine parameters and in-cylinder pressure diagrams. Aiming at the comparison of different alternative fuels, an experimental procedure was defined, including cetane number (CN) evaluation and the definition of engine operating quantities in different working points, for fixed levels of compression ratio (CR) and injection advance. An investigation was made considering several blends of methyl-esters of rapeseed oil (RME) and of a mix of vegetable oils (VOME) with conventional diesel oil. The defined experimental procedure was applied to assess CN, engine brake thermal efficiency (bte) and exhaust emissions. Results show that the biodiesel content has a positive influence on soot emissions, with strong reduction, while thermal efficiency and NO_X emissions are negatively affected, which can be justified taking into account fuel properties and changes in combustion process. As observed outcomes are generally in line with those presented in literature, the facility proved to be a suitable tool for basic investigations on alternative fuels to be used in specific applications.     

Estuarine circulation in the Taranto Seas

The Taranto basin is a shallow water marine system in the South of Italy characterized by the presence of a lagoon environment together with a semi-enclosed bay connected to the Ionian Sea. This marine system experienced over the last few decades strong biochemical pollution and environmental degradation, and it is considered a hotspot study site for economic, ecological and scientific reasons. The aim of this study was to examine, on an annual temporal scale and with high spatial resolution, the main hydrodynamical processes and transport scales of the system by means of a 3D finite element numerical model application, adopting the most realistic forcing available. The model allowed us to assess the role played by baroclinic terms in the basin circulation, describing its estuarine nature. In particular, the main features of water circulation, salinity and temperature distribution, water renewal time and bottom stress were investigated. Our results allowed us to equate this system dynamic to that of a weakly stratified estuary, identifying the main driving sources of this mechanism. The vertical stratification over the whole year was proved to be stable, leading to a dual circulation flowing out on the surface, mainly through Porta Napoli channel, and inflowing on the bottom mainly through Navigabile channel. This process was responsible also for the renewal time faster on the bottom of the Mar Piccolo basin than the surface. Due to the great importance of the Taranto basin for what concerns sediment pollution, also the effect of currents in terms of bottom stress was investigated, leading to the conclusion that only in the inlets area the values of bottom stress can be high enough to cause erosion.     

Sediment pollution and dynamic in the Mar Piccolo of Taranto (southern Italy): insights from bottom sediment traps and surficial sediments

Major and trace element, PAH, and PCB concentrations were measured in surface sediments and particles from sediment traps collected in the First and Second Basin of the Mar Piccolo (Gulf of Taranto) in two periods (June–July and August–September, 2013). The aim of the study was to evaluate pollution degree, sediment transport and particle redistribution dynamic within the area. Results confirm the higher contamination of sediments from the First Basin observed by previous researches, particularly for Cu, Hg, Pb, total PAHs, and total PCBs. Advective transport from the First to the Second Basin appears to be the leading transfer mechanism of particles and adsorbed contaminants, as evidenced by measured fluxes and statistical analyses of contaminant concentrations in surficial sediments and particles from sediment traps. Long-range selective transports of PAHs and microbial anaerobic degradation processes for PCBs have been also observed. These results are limited to a restricted time window but are consistent with the presence of transport fluxes at the bottom of the water column. This mechanism deserves further investigation and monitoring activities, potentially being the main responsible of pollutant delivering to the less contaminated sectors of the Mar Piccolo.     

Long-term phenol, cresols and BTEX monitoring in urban air

This paper reports the results of a long-term monitoring of benzene, toluene, ethylbenzene, xylenes (BTEX), phenol and cresols in the air of Padua during a wide period of the year 2007 using two radial passive samplers (Radiello system) equipped with BTEX- and phenol-specific cartridges. Two sites were monitored, one in the industrial area and one close to the town centre. Relevant pollution episodes have been observed during both the winter and summer periods. Benzene, together with toluene, ethylbenzene and xylenes showed their maximum concentrations during the winter season, but the secondary pollutant phenol was higher than benzene for a large period of the year when the meteorological conditions blocked the pollutants in the lower layers of the atmosphere and solar radiation increased the benzene photo-oxidation process.     

Environmental and biological monitoring of benzene in traffic policemen, police drivers and rural outdoor male workers

To evaluate exposure to benzene in urban and rural areas, an investigation into personal exposure to benzene in traffic policemen, police drivers and rural (roadmen) male outdoor workers was carried out. Personal samples and data acquired using fixed monitoring stations located in different areas of the city were used to measure personal exposure to benzene in 62 non-smoker traffic policemen, 22 police drivers and 57 roadmen. Blood benzene, urinary trans-trans muconic acid (t,t-MA) and S-phenyl-mercapturic acid (S-PMA) were measured at the end of work shift in 62 non-smoker traffic policemen, 22 police drivers and 57 roadmen and 34 smoker traffic policemen, 21 police drivers and 53 roadmen. Exposure to benzene was similar among non-smoker traffic policemen and police drivers and higher among non-smoker urban workers compared to rural workers. Blood benzene, t,t-MA and S-PMA were similar among non-smoker traffic policemen and police drivers; blood benzene and t,t-MA were significantly higher in non-smoker urban workers compared to rural workers. Significant increases in t,t-MA were found in smokers vs. non-smokers. In non-smoker urban workers airborne benzene and blood benzene, and t,t-MA and S-PMA were significantly correlated. This study gives an evaluation of the exposure to benzene in an urban area, comparing people working in the street or in cars, to people working in a rural area. Benzene is a certain carcinogen for humans. The results we showed should lead to more in-depth studies about the effects on health of these categories of workers.