Is Arenicola marina a suitable test organism to evaluate the bioaccumulation potential of Hg, PAHs and PCBs from dredged sediments?

This paper presents the results of investigations on the suitability of lugworms (Arenicola marina) to study the bioaccumulation potential of Hg, PCB and PAH compounds from dredged sediments upon laboratory exposure. The results of tissue concentrations for several sediments from Spanish ports showed that it is possible to identify increased levels of contaminants in lugworms just after 10 days of exposure although different bioaccumulation trends were shown amongst compounds and sediments. Total and organic Hg compounds were accumulated following a non-linear trend, with a sharp increase of tissue concentrations in lugworms exposed to levels of contamination associated to a significant increase in mortality. Interestingly organic Hg compounds accounted for an average of 40% of the total Hg in lugworms exposed to sediments presenting sublethal concentrations while, when exposed to sediments presenting lethal concentrations, organic Hg compounds only accounted for 4% of the total Hg accumulated in lugworms. While lugworms seem to readily accumulate Hg and PCB compounds, with some variability explained by the organic matter content in sediments or other factor for which it accounts for, the results for PAHs suggest a more complex process of bioaccumulation as no relationship was observed between the measured concentrations in sediments and in lugworms, not even after correcting the results for this factor. Besides, the differences in the calculated BSAFs for each compound and for each sediment supported the use of bioassays for evaluating the bioaccumulation potential of sediment-bound contaminants as part of the assessment framework required in pre-dredging investigations, as they still offer unique information about the bioavailability of sediment-bound contaminants.     

Influence of resorcinol chemical oxidation on the removal of resulting organic carbon by activated carbon adsorption

Activated carbon adsorption and chemical oxidation followed by activated carbon adsorption of resorcinol in water has been studied. Three chemical oxidants have been used: hypochlorite, permanganate and Fenton's reagent. The influence of concentrations of resorcinol and activated carbon on adsorption removal rates has been investigated. Both isotherm and adsorption kinetics have been studied. Results are fit well by Freundlich isotherms and adsorption rates of resorcinol were found to follow a pseudo-second-order kinetic model. However, pyrogallol, an intermediate of resorcinol oxidation with permanganate and Fenton's reagent, showed an unfavourable isotherm type. At the conditions investigated, chemical oxidation allows slight reductions of TOC and intermediates formed were found to inhibit the adsorption rate of TOC in the case of permanganate and Fenton's reagent oxidation, likely due to formation of some polymer pyrogallol product. The adsorption process was found to be controlled by pore internal diffusion, which justifies the poor affinity of oxidation intermediates toward activated carbon since molecules of larger size should diffuse rapidly for the adsorption to be effective.     

Combining TiO2-photocatalysis and wetland reactors for the efficient treatment of pesticides

In the present work the photocatalytic and biological degradation of two commercial mixtures of pesticides (Folimat and Ronstar) and two fungicides (pyrimethanil and triadimenol) has been studied. The evolution of some components of these commercial products (dicofol, tetradifon and oxadiazon) and that of the two fungicides has been monitored by means of HPLC, GC-MS, TOC and toxicity (Lemna minor toxicity test) measurements. The photocatalytic method was able to degrade dicofol, tetradifon, pyrimethanil, triadimenol and the components of Ronstar with the exception of oxadiazon. In addition to this, the photocatalytic method eliminated pyrimethanil toxicity and reduced that of triadimenol by a 90%, Ronstar by a 78% and Folimat by an 87%. Nevertheless, the wetland reactors alone could reduce the toxicity of only the former. Finally, the proper dosage of the water containing the pesticides to a photocatalytic reactor followed by a wetland reactor resulted to be the most successful strategy for the detoxification of the studied compounds and their mixtures.     

Evaluation of the Spanish hot dip galvanising sector as a source of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans

A survey to estimate the polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) emissions of Spanish hot dip galvanising sector was carried out during 2002. This investigation is the first presenting Spanish experimental data related to this industrial sector. Three different matrices: flue gas, ash and filter dust were tested to quantify the PCDD/Fs generated during the galvanising process. The organic source of PCDD/F formation could be from the insufficient degreasing o from inhibitors or additives used in the pickling steps such as quinoline, isoquinoline, 8-methylquinoline or polyether phosphoric acid. Low levels PCDD/Fs were achieved in air emissions when air control devices are used. On the contrary, filter dusts are highly contaminated; indicating that the absence of air control devices would increase the risk of fugitive emissions. Homologue profiles and Principal Component Analysis demonstrate there are differences in the formation mechanisms in the bath zone (ashes) compared to the stack location (filter dusts and air emissions), related to the de novo synthesis and reaction time. The annual PCDD/F emission to the atmosphere for this sector during 2002 has been estimated in 0.023g I-TEQ. The emission factor of plants with air control devices has been calculated at 0.030microg I-TEQ/ton of galvanised steel.     

Solar TiO2-assisted photocatalytic degradation of IGCC power station effluents using a Fresnel lens

The heterogeneous TiO2 assisted photocatalytic degradation of wastewater from a thermoelectric power station under concentrated solar light irradiation using a Fresnel lens has been studied. The efficiency of photocatalytic degradation was determined from the analysis of cyanide and formate removal. Firstly, the influence of the initial concentration of H2O2 and TiO2 on the degradation kinetics of cyanides and formates was studied based on a factorial experimental design. Experimental kinetic constants were fitted using neural networks. Results showed that the photocatalytic process was effective for cyanides destruction (mainly following a molecular mechanism), whereas most of formates (degraded mainly via a radical path) remained unaffected. Finally, to improve formates degradation, the effect of lowering pH on their degradation rate was evaluated after complete cyanide destruction. The photooxidation efficiency of formates reaches a maximum at pH around 5-6. Above pH 6, formate anion is subjected to electrostatic repulsion with the negative surface of TiO2. At pH<4.5, formate adsorption and photon absorption are reduced due to some catalyst agglomeration.     

Application of fluorescence in situ hybridization technique to detect simazine-degrading bacteria in soil samples

We propose a new approach to evaluate the natural attenuation capacity of soil by using fluorescence in situ hybridization (FISH). A specific oligonucleotide probe AtzB1 was designed based on the sequence data of the atzB gene involved in the hydrolytic deamination of s-triazines; this gene, located in a multiple copy plasmid was detected by the optimized FISH protocol. Two agricultural soils (Lodi and Henares) with a history of simazine treatments, and two natural soils (Soto and Monza), without previous exposure to simazine, were studied. AtzB1 probe-target cells were found only in the agricultural soils and, in a greater percentage, in the Lodi soil, compared to the Henares one. Moreover, the greatest percentage of AtzB1 probe-target cells in Lodi was accompanied by a greater mineralization rate, compared to the Henares soil. The FISH method used in this study was suitable for the detection of simazine-degrading bacteria and could be a useful indicator of the potential of soil bioremediation.     

Evaluation of Cu-PPHs as active catalysts for the SCR process to control NOx emissions from heavy duty diesel vehicles

Copper based catalysts supported on mesoporous materials, which were in turn based on a surfactant expanded zirconium phosphate for the formation of silica galleries in the interlayer space, were prepared by the impregnation method. They were then characterised and tested in the selective catalytic reduction of NO with ammonia as active catalysts for the control of the NOx emissions from heavy duty vehicles. Copper catalysts displayed a high catalytic performance, even in the presence of 14% (v/v) of H2O and 100 ppm of SO2. They also displayed improved catalytic behaviour when compared to a CuZSM5 catalyst.     

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.     

Trace organic chemicals contamination in ground water recharge

Population growth and unpredictable climate changes will pose high demands on water resources in the future. Even at present, surface water is certainly not enough to cope with the water requirement for agricultural, industrial, recreational and drinking purposes. In this context, the usage of ground water has become essential, therefore, their quality and quantity has to be carefully managed. Regarding quantity, artificial recharge can guarantee a sustainable level of ground water, whilst the strict quality control of the waters intended for recharge will minimize contamination of both the ground water and aquifer area. However, all water resources in the planet are threatened by multiple sources of contamination coming from the extended use of chemicals worldwide. In this respect, the environmental occurrence of organic micropollutants such as pesticides, pharmaceuticals, industrial chemicals and their metabolites has experienced fast growing interest. In this paper an overview of the priority and emerging organic micropollutants in the different source waters used for artificial aquifer recharge purposes and in the recovered water is presented. Besides, some considerations regarding fate and removal of such compounds are also addressed.