The troposphere is subject to continuous inputs, production and removal processes of ozone and its precursors from natural processes and human activities acting together within a very complex system. In order to assess the behaviour of background ozone in the Mediterranean area, a description of trends, seasonal and diurnal behaviours of free tropospheric ozone is provided. In the Mediterranean area and southern Europe the background tropospheric ozone concentration appears significantly affected by three main air mass transport processes: (i) transport of polluted air masses on regional and long-range scales, (ii) downward transport of stratospheric air masses, and (iii) transport of mineral dust from the Sahara desert. In this review of the literature of the last two decades, we present an overview of these phenomena, mainly monitored at high baseline mountain stations representative of background atmospheric conditions. How background ozone is influenced by vertical and horizontal transport processes in the southern Europe and the Mediterranean area.

Concentrations of the elements Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn were measured in the leaves and bark of Robinia pseudoacacia and the soil in which it grew, in the town of Oleśnica (SW Poland) and at a control site. We selected this town because emission from motor vehicles is practically the only source of air pollution, and it seemed interesting to evaluate its influence on soil and plants. The self-organizing feature map (SOFM) yielded distinct groups of soils and R. pseudoacacia leaves and bark, depending on traffic intensity. Only the map classifying bark samples identified an additional group of highly polluted sites along the main highway from Wrocław to Warszawa. The bark of R. pseudoacacia seems to be a better bioindicator of long-term cumulative traffic pollution in the investigated area, while leaves are good indicators of short-term seasonal accumulation trends. Once trained, SOFM could be used in the future to recognize types of pollution.

River sediment at a disused lead-zinc mine was analysed to provide an understanding of the chemical nature of the source term for contaminated sediment exported from the site. Changes in concentration and geochemical associations of Pb and Zn were measured using aqua regia digestion and the BCR sequential extraction procedure. Sediment in the immediate vicinity of the mine was highly contaminated with Pb (max. c. 11,000 mg kg⁻¹) and Zn (max. c. 30,000 mg kg⁻¹), but these values declined rapidly within 1 km of the mine due to dilution and hydraulic sorting. Lead fractionation changed from being predominantly in the reducible fraction to being in the acetic acid-extractable fraction, whereas Zn was predominantly in the residual fraction. This material is transported as fine sediment in the river system. Metal concentrations and fractionation have defined the source characteristics of Pb and Zn dispersed from a disused mine and transported by fluvial processes.

A series of European Marine Sites has been designated as Special Areas of Conservation (SAC) in England. The aim of this study was to develop a practical methodology to assess the condition of SACs by applying a suite of biomarkers. Biomarkers were applied to the blue mussel Mytilus edulis and the shore crab Carcinus maenas from the Fal and Helford SAC (Cornwall). Individual biomarkers provided useful diagnostic information on the activity of certain classes of contaminants and an integrated Biomarker Response Index (BRI) was used to achieve a more holistic understanding of the condition of the SAC. The BRI indicated that the general health of both organisms was impacted in the upper part of the SAC (Fal Estuary) which correlated well with known chemical hotspots and sources of contamination. The BRI allows a pragmatic way to prioritise SAC sites that may require further investigative studies. A suite of biomarkers was successfully used to create a Biomarker Response Index to assess the health of aquatic organisms from European Marine Sites.

Differences in the toxicological and metabolic pathway of inorganic arsenic compounds are largely unknown for aquatic species. In the present study the effects of short-time and acute exposure to AsIII and AsV were investigated in gills and liver of the common carp, Cyprinus carpio (Cyprinidae), measuring accumulation and chemical speciation of arsenic, and the activity of glutathione-S-transferase omega (GST Ω), the rate limiting enzyme in biotransformation of inorganic arsenic. Oxidative biomarkers included antioxidant defenses (total glutathione-S-transferases, glutathione reductase, glutathione, and glucose-6-phosphate dehydrogenase), total scavenging capacity toward peroxyl radicals, reactive oxygen species (ROS) measurement and lipid peroxidation products. A marked accumulation of arsenic was observed only in gills of carps exposed to 1000 ppb AsV. Also in gills, antioxidant responses were mostly modulated through a significant induction of glucose-6-phosphate dehydrogenase activity which probably contributed to reduce ROS formation; however this increase was not sufficient to prevent lipid peroxidation. No changes in metal content were measured in liver of exposed carps, characterized by lower activity of GST Ω compared to gills. On the other hand, glutathione metabolism was more sensitive in liver tissue, where a significant inhibition of glutathione reductase was concomitant with increased levels of glutathione and higher total antioxidant capacity toward peroxyl radicals, thus preventing lipid peroxidation and ROS production. The overall results of this study indicated that exposure of C. carpio to AsIII and AsV can induce different responses in gills and liver of this aquatic organism. Common carp (Cyprinus carpio) presented marked differences between gills and liver after arsenic exposure in terms of antioxidant responses and also in biotransformation.

The geochemical processes of mercury in Dongfeng (DF) and Wujiangdu (WJD) reservoirs, which were constructed in 1992 and 1979, respectively in Wujiang River, which is the upper branch of Yangtze River were investigated. One sampling site was chosen upriver of 1 km from the dam for each reservoir. Three sampling campaigns were conducted at these sampling sites in December 2003, April 2004 and July 2004, respectively. The distributions of different mercury species in the water column, sediment, and sediment pore water were studied. We found that the sediment is the net source of both inorganic and MeHg to the water column for both reservoirs. The MeHg diffusion fluxes in WJD reservoir at all sampling campaigns were significantly higher than those in DF reservoir. Our study demonstrated that the high primary productivity in the reservoir produced elevated organic matter content that would favor the methylmercury production in sediment. Surface sediment in the reservoirs is the active mercury methylating sites in the systems.

Diethylene glycol (DEG) is largely used during oil and gas exploitation by offshore platforms. The aim of this work was to investigate if this compound induces direct molecular/cellular effects in marine organisms, or indirectly modulate those of produced waters (PWs). Sea bass (Dicentrarchus labrax) were exposed to DEG dosed alone or in combination with PWs from an Adriatic platform. A wide array of analysed biomarkers included cytochrome P450-dependent enzymatic activity, bile metabolites, glutathione S-transferases, acetylcholinesterase, peroxisomal proliferation, antioxidant defences (catalase, glutathione reductase, glutathione peroxidases, glutathione), total oxyradical scavenging capacity, malondialdehyde and DNA integrity (single strand breaks and frequency of micronuclei). Results did not reveal marked effects of DEG, while PWs influenced the biotransformation system, the oxidative status and the onset of genotoxic damages. Co-exposures caused only limited differences of biomarker responses at some experimental conditions, overall suggesting a limited biological impact of DEG at levels normally deriving from offshore activities. A biological risk for marine organisms can be excluded for DEG concentrations as those normally associated to produced waters discharged in the Adriatic Sea.

Lab scale mulch biofilm barriers were constructed and tested to evaluate their performance for preventing the migration of aqueous and surfactant solubilized PAHs. The spatial distribution of viable PAH degrader populations and resultant biofilm formation were also monitored to evaluate the performance of the biobarrier and the prolonged surfactant effect on the PAH degrading microorganism consortia in the biobarrier. Sorption and biodegradation of PAHs resulted in stable operation of the system for dissolved phenanthrene and pyrene during 150 days of experimentation. The nonionic surfactant could increase the solubility of phenanthrene and pyrene significantly. However, the biobarrier itself couldn't totally prevent the migration of micellar solubilized phenanthrene and pyrene. The presence of surfactant and the resultant highly increased phenanthrene or pyrene concentration didn't appear to cause toxic effects on the attached biofilm in the biobarrier. However, the presence of surfactant did change the structural composition of the biofilm. Mulch biofilm barrier showed potential for surfactant enhanced bioremediation, and the presence of surfactant changed the structural composition of the biofilm.

The effects of monoterpenes on the degradation of 14C-2,4-dichlorophenol (DCP) were investigated in soils collected from areas surrounding monoterpene and non-monoterpene-emitting vegetation. Indigenous microorganisms degraded 14C-2,4-DCP to 14CO2, after 1 d contact time. Degradation was enhanced by prior exposure of the soils to 2,4-DCP for 32 d, increasing extents of mineralisation up to 60%. Monoterpene amendments further enhanced 2,4-DCP degradation, but only following pre-exposure to both 2,4-DCP and monoterpene, with total 2,4-DCP mineralisation extents of up to 71%. Degradation was greatest at the higher monoterpene concentrations (>=1 μg kg-1). Total mineralisation extents were similar between concentrations, but higher than the control and the 0.1 μg kg-1 amendment, indicating that increases in monoterpene concentration has a diminishing enhancing effect. We suggest that monoterpenes can stimulate the biodegradation of 2,4-DCP by indigenous soil microorganisms and that monoterpene amendment in soils is an effective strategy for removing organic contaminants. A amendment of soils with monoterpenes may induce organic contaminant degradation by indigenous soil microorganisms.