Impact of dredging in a shallow coastal lagoon: Microtox Basic Solid-Phase Test, trace metals and Corophium bioassay

The aim of this work was to measure survival of the amphipod Corophium insidiosum and luminescence inhibition in the marine bacterium Vibrio fisheri on surface sediment samples collected from a shallow coastal lagoon (Pialassa Baiona, northern Adriatic Italian coast) before execution of dredging operations to deepen the main inner channel of the lagoon and restore the water circulation. Trace metal (Cd, Cu, Cr, Hg, Ni, Pb) concentrations, grain size and organic carbon matter content as loss of ignition were also measured. Toxicity testing with V. fisheri was carried out according to the Microtox Basic Solid-Phase Test (BSPT) protocol. The preliminary outcomes of this work show that: (a) the investigated area can be categorised as moderately degraded; (b) there is no evident spatial pattern in sediment toxicity and trace metal concentrations; (c) Microtox responses are not biased by sediment characteristics such as silt, clay and organic matter content.     

Removal and degradation of aromatic compounds from a highly polluted site by coupling soil washing with photocatalysis

The possible application of two environmental remediation technologies - soil washing and photocatalysis - to remove and decompose various aromatic pollutants present in excavated soils of a contaminated industrial site has been investigated. Aqueous solutions containing the non-ionic surfactant Brij 35 were used to extract the contaminants from the soil samples. The photocatalytic treatment of the obtained washing wastes, performed in the presence of TiO(2) suspensions irradiated with simulated sunlight, showed a slow abatement of the toxic compounds due to the relevant concentrations of organics in the waste. A neat improvement of the process performances, obtained by operating in the presence of added potassium peroxydisulfate, suggests a feasible treatment route.     

CO2 capture and storage from a bioethanol plant: Carbon and energy footprint and economic assessment

Biomass energy and carbon capture and storage (BECCS) can lead to a net removal of atmospheric CO₂. This paper investigates environmental and economic performances of CCS retrofit applied to two mid-sized refineries producing ethanol from sugar beets. Located in the Region Centre France, each refinery has two major CO₂ sources: fermentation and cogeneration units. “carbon and energy footprint” (CEF) and “discounted cash flow” (DCF) analyses show that such a project could be a good opportunity for CCS early deployment. CCS retrofit on fermentation only with natural gas fired cogeneration improves CEF of ethanol production and consumption by 60% without increasing much the non renewable energy consumption. CCS retrofit on fermentation and natural gas fired cogeneration is even more appealing by decreasing of 115% CO₂ emissions, while increasing non renewable energy consumption by 40%. DCF shows that significant project rates of return can be achieved for such small sources if both a stringent carbon policy and direct subsidies corresponding to 25% of necessary investment are assumed. We also underlined that transport and storage cost dilution can be realistically achieved by clustering emissions from various plants located in the same area. On a single plant basis, increasing ethanol production can also produce strong economies of scale.     

Using lysosomal membrane stability of haemocytes in Ruditapes philippinarum as a biomarker of cellular stress to assess contamination by caffeine, ibuprofen, carbamazepine and novobiocin

Although pharmaceuticals have been detected in the environment only in the range from ng/L to g/L, it has been demonstrated that they can adversely affect the health status of aquatic organisms. Lysosomal membrane stability (LMS) has previously been applied as an indicator of cellular well-being to determine health status in bivalve mussels. The objective of this study is to evaluate LMS in Ruditapes philippinarum haemolymph using the neutral red retention assay (NRRA). Clams were exposed in laboratory conditions to caffeine (0.1, 5, 15, 50 μg/L), ibuprofen (0.1, 5, 10, 50 μg/L), carbamazepine and novobiocin (both at 0.1, 1, 10, 50 μg/L) for 35 days. Results show a dose-dependent effect of the pharmaceuticals. The neutral red retention time measured at the end of the bioassay was significantly reduced by 50% after exposure to environmental concentrations (p < 0.05) (caffeine = 15 μg/L; ibuprofen = 10 μg/L; carbamazepine = 1 μg/L and novobiocin = 1 μg/L), compared to controls. Clams exposed to these pharmaceuticals were considered to present a diminished health status (retention time < 45 min), significantly worse than controls (96 min) (p < 0.05). The predicted no environmental effect concentration (PNEC) results showed that these pharmaceuticals are very toxic at the environmental concentrations tested. Measurement of the alteration of LMS has been found to be a sensitive technique that enables evaluation of the health status of clams after exposure to pharmaceuticals under laboratory conditions, thus representing a robust Tier-1 screening biomarker.     

Continuous monitoring of photocatalytic treatments by flow injection. Degradation of dicamba in aqueous TiO2 dispersions.

The possible use of flow injection (FI) to monitor the photocatalytic mineralization of dicamba (3,6-dichloro-2-methoxybenzoic acid) present at the trace level in aqueous solutions containing TiO2 suspensions has been evaluated. Experiments were performed in a stirred photochemical reactor equipped with a simple FI manifold, integrating an online filtration unit able to perform the monitoring of the UV absorbance of the irradiated solution every 4 min. The light source used was a medium pressure mercury lamp (125 W). During the initial steps of the reaction the formation of UV absorbing intermediates, which completely disappear in less than 80 min, was evidenced. Additional HPLC, DOC and chloride ion measurements carried out on manually taken samples confirmed the complete mineralization of dicamba within about 90 min. The proposed on-line monitoring looks particularly suitable for the control of degradation treatments where primary degradation and mineralization steps take place after a comparable irradiation time.     

Bioaccumulation of cyclopenta[cd]pyrene and benzo[ghi]fluoranthene by mussels transplanted in a coastal lagoon

The bioaccumulation of two isomeric non-alternant non-priority polycyclic aromatic hydrocarbons (PAHs), namely cyclopenta[cd]pyrene and benzo[ghi]fluoranthene, was investigated in caged mussels (Mytilus galloprovincialis) exposed for 30 days in three sites of a coastal lagoon (Pialassa Baiona, Ravenna, Italy) contaminated by pyrogenic PAHs. The concentration of cyclopenta[cd]pyrene and benzo[ghi]fluoranthene increased from undetectable levels in reference mussels withdrawn from the Adriatic sea to 10-30 ng g(-1) dry weight in transplanted mussels. Other contaminants bioaccumulated by caged mussels included pyrene, fluoranthene and mercury. Whilst the isomer concentration ratio pyrene/fluoranthene in biota was comparable to that observed in sediments, the cyclopenta[cd]pyrene/benzo[ghi]fluoranthene ratio was much lower in mussels than in sediments. The lower sediment biota accumulation factor of cyclopenta[cd]pyrene with respect to that of benzo[ghi]fluoranthene was tentatively attributed to the greater biological activity of the former compound, which contains a reactive olefinic bond in the cyclopenta fused ring moiety. Given the higher mutagenic activity of cyclopenta[cd]pyrene with respect to other priority PAHs, its bioaccumulation from contaminated sediments may rise considerably the overall toxicity of PAH residues in exposed biota.     

Intermediate distributions and primary yields of phenolic products in nitrobenzene degradation by Fenton's reagent

Nitrobenzene thermal degradation was investigated using the Fenton reagent in different experimental conditions. Reaction products were analyzed by HPLC, GC-MS, LC-MS and IC. The products obtained at different nitrobenzene conversion degrees show that degradation mainly involves successive hydroxylation steps of the aromatic ring and its subsequent opening followed by oxidation of corresponding aliphatic compounds. Our results show as primary reaction products: 4-nitrophenol, 3-nitrophenol, 2-nitrophenol, phenol and 1,3-dinitrobenzene, indicating that both hydroxylation and nitration reactions are involved. The formation of phenolic products can be explained by postulating an initial step of HO() addition to nitrobenzene ring. The mechanisms of primary reaction pathways are discussed and a detailed kinetic analysis to obtain the true primary yields of phenolic products is proposed. The relative yields observed for nitrophenol isomers do not follow the expected orientation according to deactivating characteristics of the nitro group but significantly depend on Fe(+2), Fe(+3), H(2)O(2) and O(2) concentrations. The understanding of the effect of reaction conditions on the relative product distribution benefits the application of Fenton and Fenton-like systems to waste water treatment.     

Immunotoxicity of carbon black nanoparticles to blue mussel hemocytes

The potential for human and ecological toxicity associated with nanomaterials is a growing area of investigation. In mammalian cells, nanoparticles have been shown to induce inflammation and oxidative stress, and changes in cell signalling and gene expression. As the nanotechnology industries increase production, nanoscale products and by products will enter the aquatic environment, posing a possible threat to aquatic organisms. In particular, filter-feeding organisms may represent a unique target group for nanoparticle toxicology. In this work, the effects of commercial nanosized carbon black (NCB) on the immune cells, the hemocytes, of the bivalve mollusc Mytilus, and the possible mechanisms involved were investigated. The results demonstrate that NCB (1, 5, and 10 microg/ml), did not induce significant lysosomal membrane destabilization, as evaluated by the NR retention time assay. A concentration-dependent uptake of NCB by hemocytes was observed and it was associated by a rapid increase in extracellular lysozyme release, extracellular oxyradical production, and nitric oxide (NO) release. Moreover, at the highest concentration tested, NCB induced significant changes in mitochondrial parameters (decrease mitochondrial mass/number and membrane potential), as evaluated by flow cytometry. The effects of NCB were mediated by rapid activation of the stress-activated MAPKs (Mitogen Activated Protein Kinases) p38 and JNKs, that play a key role in immune and inflammatory responses. The results demonstrate that in mussel hemocytes like in mammalian cells NCB exposure can induce inflammatory processes, and indicate that bivalve immunocytes can represent a suitable model for investigating the effects and modes of action of nanoparticles in the cells of aquatic invertebrates.     

Photocatalytic degradation of bentazone in soil washing wastes containing alkylpolyoxyethylene surfactants

Three alkylpolyoxyethylene surfactants bearing the same hydrophobic chain and a different number of oxyethylene groups were investigated as suitable candidates for the soil washing treatment of contaminated soil samples containing bentazone. Comparable good recoveries of the pesticide were obtained working with these surfactants. The photocatalytic treatment of the collected washing wastes, performed in the presence of suspended TiO₂ particles under irradiation with simulated sunlight, leads to the effective degradation of bentazone residues after a time depending on the nature and concentration of the chosen amphiphile. Brij 35 was found to be the best surfactant candidate, giving the faster abatement of the pesticide in the collected wastes. The overall treatment time depends on the bentazone mineralization kinetics, markedly slow in the presence of surfactants. Useful information about the photocatalytic degradation route was obtained from the HPLC-MS analysis of transient intermediates formed in water.