A multidisciplinary weight of evidence approach for classifying polluted sediments: Integrating sediment chemistry, bioavailability, biomarkers responses and bioassays

Evaluation of chemical bioavailability and onset of biological alterations is fundamental to assess the hazard of environmental pollutants, particularly when associated to sediments which need to be removed. In the present work, five sediment samples were collected from the Venice Lagoon and data from sediment chemistry were integrated with those of bioaccumulation of chemicals in European eel (Anguilla anguilla) exposed under laboratory conditions, responses of a wide battery of biomarkers, and standardized ecotoxicological bioassays. The overall results were elaborated within a recently developed, software-assisted weight of evidence (WOE) model which provides synthetic indices for each of considered line of evidence (LOE), before a general evaluation of sediment hazard. Levels of chemicals in sediments were not particularly elevated when compared to sediment quality guidelines of Venice Protocol. On the other hand, bioavailability was evident in some samples for Cd, Cu, Zn and, especially, polycyclic aromatic hydrocarbons. The ecotoxicological approach provided further evidence on the biological and potentially harmful effects due to released contaminants, and oxidative-mediated responses appeared of primary importance in modulating sublethal responses and the onset of cellular alterations. Biomarkers variations were sensitive, and more evident variations included significant changes of cytochrome P450 biotransformation pathway, antioxidant responses, onset of oxidative damages, lysosomal membrane stability and genotoxic effects. The results obtained from the battery of bioassays indicated that responses measured at organism level were in general accordance but less marked compared to the onset of sublethal changes measured through biomarkers. Overall this study revealed differences when comparing evaluations obtained from different LOEs, confirming the importance of considering synergistic effects between chemicals in complex mixtures. Compared to a qualitative pass-fail approach toward normative values, the proposed WOE model allowed a quantitative characterization of sediment hazard and a better discrimination of on the basis of various types of chemical and biological data.     

Investigation of the solvent extracts of humic organic matter (HOM) isolated from the Ravenna Lagoon to study environmental pollution and microbial communities

Solvent extracts of HOM isolated from highly polluted sediments from the Ravenna Lagoon were studied. Diagnostic indicators included polycyclic aromatic hydrocarbons (PAHs) and nonylphenols as hazardous organic pollutants to characterize anthropogenic pollution, as well as fatty acids (FA, analysed as methyl esters, FAME) to characterize microbial communities responsible for natural attenuation processes. The distribution of PAHs including cyclopentafused surrogates pointed to a significant pyrogenic origin, characteristic for methane combustion. The PAH distribution was characterized by high concentrations of highly carcinogenic analytes with molecular weights of 276Da (benzo[ghi]perylene prevailing) and 300Da (coronene prevailing). The PAH pattern as obtained by solvent extraction was very different from that obtained from pyrolysis/thermochemolysis of the HOM polymeric matrix. The FA pattern indicated strong bacterial input, with a significant contribution from methanotrophic bacteria as revealed by monounsaturated members with n:1omega8 and n:1omega5 double bonds in the alkyl chain. Terrestrial inputs as revealed by FAME analysis beyond C(20) with pronounced even-over-odd discrimination were of minor significance. This was confirmed by the pattern of nC(24)-nC(30) alcohols in strong even-over-odd prevalence occurring in relatively low concentrations. The hopane hydrocarbon distribution reflected a distinctive impact from industrial processes utilizing heavy fractions of petroleum as feedstock. Hopanols along with the 17beta(H),21beta(H)-bishomohopanoic acid pointed to hopane producers, including methanotrophic and sulfate-reducing bacteria. Nonylphenols, which could not be detected in the pyrograms of solvent-extracted HOM matrix, had a total concentration of about 70microg g(-1) referred to the HOM in the solvent extract. In addition to common phytosterols including beta-sitosterol, coprostanol could be detected in the solvent extracts pointing to human fecal matter contamination. Concentration of resin acids turned out to be very low, thus no harmful environmental effects are to be expected from these compounds.     

Combined application of non-discriminated conventional pyrolysis and tetramethylammonium hydroxide-induced thermochemolysis for the characterization of the molecular structure of humic acid isolated from polluted sediments from the Ravenna Lagoon

Humic acid (HA) isolated from highly polluted sediment from the Ravenna Lagoon (Italy) was subjected to pyrolysis/tetramethylammonium hydroxide (TMAH)-induced thermochemolysis to reveal the impact of industrial activities on humification. Special effort was made to distinguish between analytes originating from the polymeric humic organic matter network along with sequestered compounds (which cannot be released by solvent extraction), and the solvent-extractable lipid fraction sorbed onto the organic matrix. Exhaustive solvent extraction of the isolated HA proved mandatory to avoid biased results when identifying the origin of the pyrolyzates of untreated samples. Conventional pyrolysis at 750 degrees C of the "degreased" HA revealed a characteristic polycyclic aromatic hydrocarbon (PAH) pattern, which was significantly different than patterns obtained from the pyrolysis of natural humic acids. TMAH-induced thermochemolysis at 500 degrees C provided information on carboxylic acids covalently bound inside the HA network via ester bonds. Thermochemolysis of the "degreased" matrix at 750 degrees C, resulting in the cleavage of C-O and C-C bonds, revealed a significant PAH pattern very similar to that obtained by conventional pyrolysis. The uncommon PAH pattern points to the formation of bound residues as the humification/detoxification pathway. Recalcitrant hopane hydrocarbons showed very similar patterns for both the untreated and exhaustively solvent-extracted samples, which points to hopanes being linked inside the humic network via C-C bonds. The technique of non-discriminating flash pyrolysis used in this study, based on extremely rapid capacitive discharge heating in a Silcosteel capillary, proved to be an excellent method to obtain high-boiling pyrolyzates (PAHs beyond 252Da molecular weight, C(29)-C(31)-hopanes).     

Adaptations to semi-terrestrial life in embryos of East African mangrove crabs: a comparative approach

In this experimental study, we compared the embryonic respiration rate in air and water of six East African sesarmid species with intertidal, supratidal and arboreal habits, to highlight possible adaptations in embryonic metabolism to their different lifestyles. The embryos of all analysed crabs showed bimodal respiration, but we did not find a trend towards an enhanced embryonic oxygen uptake in air from the intertidal to the arboreal and supratidal species. However, the late-stage embryos of the most land-adapted species, Chiromantes spp., showed an enhanced metabolism when immersed in sea water that we interpreted as an adaptive recovery mechanism to cope with the storage of by-products due to marine-based metabolic pathways during long emersion periods. Thus, we showed that the embryos of land-adapted species, although still strongly water dependent, are well adapted to semi-terrestrial habitats and represent a minor limiting factor for females, which are not restricted in their emersion period by the oxygen requirements of their embryos.     

Study of the SRF-derived ashes melting behavior and the effects generated by the optimization of their composition on the furnaces energy efficiency in the incineration plants

As regards the incineration process of the urban solid waste, the composition correct management allows not only the valorization of precise civil and industrial groups of waste as alternative fuels but also a considerable increase of the furnace work temperature leading to a remarkable improvement of the related energy efficiency. In this sense, the study of the melting behavior of ashes deriving from several kinds of fuels that have to be processed to heat treatment is really important. This approach, indeed, ensures to know in depth the features defining the melting behavior of these analyzed samples, and as a consequence, gives us the necessary data in order to identify the best mixture of components to be incinerated as a function of the specific working temperatures of the power plant. Firstly, this study aims to find a way to establish the softening and melting temperatures of the ashes because they are those parameters that strongly influence the use of fuels. For this reason, in this work, the fusibility of waste-derived ashes with different composition has been investigated by means of the heating microscope. This instrument is fundamental to prove the strict dependence of the ashes fusion temperature on the heating rate that the samples experienced during the thermal cycle. In addition, in this work, another technological feature of the instrument has been used allowing to set an instantaneous heating directly on the sample in order to accurately reproduce the industrial conditions which characterize the incineration plants. The comparison between the final results shows that, in effect, the achievement of the best performances of the furnace is due to the a priori study of the melting behavior of the single available components.     

The value of rapid damage assessment for efficient earthquake response

Every year earthquakes cause substantial economic losses and loss of life in many parts of the world. Earth observations may provide valuable information on spatial damage distribution and through that increase the efficiency of rapid response actions, finally resulting in reduction of earthquake induced losses. However, a methodology for quantitative assessment of the potential value of information in such a context has not yet been developed. That knowledge would be of high importance for planning and development of Earth observation systems on both regional and international levels when aiming at sustainable development goals. In this paper we suggest a stochastic modeling approach to assess the value of information for earthquake rapid response. Our analysis is focused on a rather short time interval after an earthquake occurrence (order of several hours) when there is a maximum need for urgent help to the earthquake victims. We use rescue efficiency as a performance measure of earthquake response actions; this efficiency is described in terms of timely arrival of rescue teams at places, where their help is mostly needed. We quantify the benefit of using spatial damage distribution information in terms of cost reduction/rescue efficiency gains. We intentionally conduct our analysis at a methodological level and do not go deeper into case studies to keep general conclusions traceable. The modeling exercise we present in the paper is a first step towards a more detailed and integrated approach that could contribute to better systematic understanding of earthquake response actions and ultimately improve their efficiency.     

An abiotic typology and reference conditions for nutrients and chlorophyll-a in subtropical reservoirs (São Paulo State,Brazil)

Environmental Science and Pollution Research - The establishment of reference conditions and typology are two important steps in water resources management. The reference conditions enable the...     

Comparison of PM10 concentrations and metal content in three different sites of the Venice Lagoon: An analysis of possible aerosol sources

The Venice Lagoon is exposed to atmospheric pollutants from industrial activities, thermoelectric power plants, petrochemical plants, incinerator, domestic heating, ship traffic, glass factories and vehicular emissions on the mainland. In 2005, construction began on the mobile dams (MOSE), one dam for each channel connecting the lagoon to the Adriatic Sea as a barrier against high tide. These construction works could represent an additional source of pollutants. PM₁₀ samples were taken on random days between 2007 and 2010 at three different sites: Punta Sabbioni, Chioggia and Malamocco, located near the respective dam construction worksites. Chemical analyses of V, Cr, Fe, Co, Ni, Cu, Zn, As, Mo, Cd, Sb, Tl and Pb in PM₁₀ samples were performed by Inductively coupled plasma-quadrupole mass spectrometry (ICP-QMS) and results were used to identify the main aerosol sources. The correlation of measured data with meteorology, and source apportionment, failed to highlight a contribution specifically associated to the emissions of the MOSE construction works. The comparison of the measurements at the three sites showed a substantial homogeneity of metal concentrations in the area. Source apportionment with principal component analysis (PCA) and positive matrix factorization (PMF) showed that a four principal factors model could describe the sources of metals in PM₁₀. Three of them were assigned to specific sources in the area and one was characterised as a source of mixed origin (anthropogenic and crustal). A specific anthropogenic source of PM₁₀ rich in Ni and Cr, active at the Chioggia site, was also identified.     

Comparison of different probe molecules for the quantification of hydroxyl radicals in aqueous solution

We show that the transformation of benzene into phenol is a more selective probe for the hydroxyl radical than the transformation of nitrobenzene or the generation of 4-hydroxybenzoic acid from benzoic acid. The benzene to phenol system showed adequate performance as a probe upon irradiation of lake water samples and humic acids. We show that the use of nitrobenzene and benzoic acid as hydroxyl probes should be avoided because of poor selectivity. Moreover, all the tested probe molecules underwent important interference by irradiated antraquinone-2-sulphonate, and considerably overestimated the formation of the hydroxyl radicals.     

Uncontrolled methane emissions from a MSW landfill surface: Influence of landfill features and side slopes

Sanitary landfills for Municipal Solid Waste (MSW) disposal have been identified as one of the most important anthropogenic sources of methane (CH₄) emissions; in order to minimize its negative effects on the environment, landfill gas (LFG) recovery is a suitable tool to control CH₄ emissions from a landfill site; further, the measurement of CH₄ emissions can represent a good way to evaluate the effectiveness of LFG recovering systems. In general, LFG will escape through any faults in the landfill capping or in the LFG collection system. Indeed, some areas of the capping can be more permeable than others (e.g. portions of a side slope), especially when considering a temporarily capped zone (covered area that is not expected to receive any further waste for a period of at least 3 months, but for engineering reasons does not have a permanent cap yet). These areas, which are characterized by abnormal emissions, are usually defined as “features”: in particular, a feature is a small, discrete area or an installation where CH₄ emissions significantly differ from the surrounding zones. In the present study, the influence that specific features have on CH₄ emissions has been investigated, based on direct measurements carried out in different seasons by means of a flux chamber to the case study of Palermo (IT) landfill (Bellolampo). The results showed that the flux chamber method is reliable and easy to perform, and the contoured flux maps, obtained by processing the measured data were found to be a suitable tool for identifying areas with abnormal (high) emissions. Further, it was found that a relationship between methane emission rates and landfill side slope can be established. Concerning the influence of the temporary HDPE cover system on CH₄ recovery efficiency, it contributed to a significant decrease of the free surface area available for uncontrolled emissions; this aspect, coupled to the increase of the CH₄ volumes collected by the LFG recovery system, led to a significant increase of the recovery efficiency.