[1] The Mediterranean and Black Seas are unique marine environments subject to important anthropogenic pressures due to atmospheric and riverine inputs of organic pollutants. They include regions of different physical and trophic characteristics, which allow the studying of the controls on pollutant occurrence and fate under different conditions in terms of particles, plankton biomass, interactions with the atmosphere, biodegradation, and their dependence on the pollutant physical chemical properties. Polycyclic Aromatic Hydrocarbons (PAHs) have been measured in samples of seawater (dissolved and particulate phases) and plankton during two east-west sampling cruises in June 2006 and May 2007. The concentrations of dissolved PAHs were higher in the south-western Black Sea and Eastern Mediterranean than in the Western Mediterranean, reflecting different pollutant loads, trophic conditions and cycling. Particle and plankton phase PAH concentrations were higher when lower concentrations of suspended particles and biomass occurred, with apparent differences due to the PAH physical chemical properties. The surface PAH particle phase concentrations decreased when the total suspended particles (TSP) increased for the higher molecular weight (MW) compounds, consistent with controls due to particle settling depletion of water column compounds and dilution. Conversely, PAH concentrations in plankton decreased at higher biomass only for the low MW PAHs, suggesting that biodegradative processes in the water column are a major driver of their occurrence in the photic zone. The results presented here are the most extensive data set available for the Mediterranean Sea and provide clear evidence of the important physical and biological controls on PAH occurrence and cycling in oceanic regions.
The overall objective of this work is to provide the first evaluation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) occurrence and deposition to Mediterranean open seawater. sigma2,3,7,8-PCDD/F air (gas+aerosol) concentrations over the Mediterranean Sea ranged from 60 to 1040 fg m(-3). The highest value (1555 fg m(-3)) was measured in a reference sample taken in the SW Black Sea. No consistent trend regarding the diel cycle of PCDD/Fs was observed. PCDD/Fs transported to the open sea waters from continental areas and across the Atlantic as well as ship emissions may be significant sources to the open Mediterranean. Seawater concentrations in the Mediterranean ranged from 42 to 64 fg L(-1). The sigma2,3,7,8-PCDD/F dry deposition fluxes in the Marmara and Black Seas (210 kg year(-1)) are from 2 to 55 times higher than dry fluxes in the Mediterranean Sea (4-156 kg year(-1)). Analysis of estimated diffusive air-water fluxes and air/water fugacity ratios show that a net volatilization of some PCDD congeners is feasible. However, evidence of a net absorption flux for the rest of PCDD/F is found. When both atmospheric deposition processes are considered together the open Mediterranean Sea is a net sink of PCDD/F, due to the importance of dry deposition fluxes of aerosol-bound PCDDFs.
Macroinvertebrates are one of the key components of lake ecosystems and are required to be monitored alongside other biological groups to define ecological status according to European Union legislation. Macroinvertebrate communities are highly variable and complex and respond to a diverse series of environmental conditions. The purpose of this study was to examine the relative importance of environmental variables in explaining macroinvertebrate abundance. A total of 45 sub-alpine lakes were sampled for macroinvertebrates in the shallow sublittoral. Environmental variables were grouped into four types: (1) aquatic physical and chemical parameters, (2) littoral and riparian habitat, (3) lake morphometric parameters and (4) sediment chemical characteristics. Nonparametric multiplicative regression (NPMR) was used to model the abundance of individual macroinvertebrate taxa. Significant models were produced for nine out of the 24 taxa examined. Sediment characteristics were the group most frequently included in models and also the factors to which taxa abundance was the most sensitive. Aquatic physical and chemical variables were the next group most frequently included in models although chlorophyll a was not included in any of the models and total phosphorus in only one. This indicates that many taxa may not show a direct easily interpretable response to eutrophication pressure. Lake morphometric factors were included in several of the models although the sensitivity of macroinvertebrate abundance tended to be lower than for sediment and aquatic physical and chemical factors. Habitat factors were only included in three models although riparian vegetation was found to have a significant influence on the abundance of Ephemera danica indicating that ecotone integrity is likely to play a role in its ecology. Overall, the models tended to be specific for species with limited commonality across taxa. Models produced by NPMR indicate that the response of macroinvertebrates to environmental variables can be successfully described but further research is required focussing in more detail on the response of key taxa to relevant environmental parameters and anthropogenic pressures
Ambient concentrations, congener patterns and multi-media distribution of PCDD/Fs and PCBs were determined in air, water, sediment and mussels in a semi-enclosed marine ecosystem (Thau lagoon, France). Sigma2,3,7,8-PCDD/F and sigma7ICES PCB air concentrations (0.2-1.4 and 31-57 pg m(-3), respectively) were typical of rural areas. Concentrations in the water column were very low for PCDD/Fs (163-476 fg L(-1)) and low for PCBs (138-708 pg L(-1)). PCDD/F and PCB concentrations found in surface sediment (0.15-1.6 and 2.5-33 ng g(-1) d.w., respectively) and mussel (13-21 pg g(-1) d.w. and 10-39 ng g(-1) d.w., respectively) were medium levels. PCDD/F congener patterns observed in air, water particulate phase and sediments were similar suggesting direct coupling among these compartments and atmospheric inputs of PCDD/Fs into the lagoon. Conversely, for the same set of samples, similar patterns were not observed for PCBs in the mentioned compartments.
A new, mechanistically based, in vitro strategy involving Balb/c 3T3 clone A31-1-1 mouse embryo fibroblasts has been proposed for the determination of the carcinogenic potential of inorganic chemicals, in order to establish priority of metal compounds to be tested and, whenever possible, to compare the in vitro results with the corresponding in vivo data. As a first step in this research, this study reports on the cytotoxic effects of 58 metal compounds in the Balb/3T3 cell line. After harmonisation and standardisation of the Balb/3T3 protocol, cells were exposed for 72 hours to a fixed dose (100μM) of 58 individual compounds. The cytotoxicity induced by some metal compounds was found to be related to their chemical form (for example, Cr(NO3)3 and Na2CrO4), suggesting that the Balb/3T3 cell line is a valuable cellular model in relation to this aspect of metal speciation. The results of the systematic study on the metal-induced cytotoxic effects in the Balb/3T3 cell line could be arbitrarily classified into three groups according to the degree of cytotoxicity. Group I includes 26 species that induced no observable effect or only a slight cytotoxic effect; Group II includes 13 metal compounds that exhibited an obvious degree of cytotoxicity; and Group III includes 19 metal species that displayed a strong cytotoxic response. Metal compounds of Groups II and III are considered to be of the highest priority for setting of dose–effect relationships for a subsequent in vitro study on metal-induced concurrent cytotoxicity and morphological transformation in the Balb/3T3 cell line.
We hypothesised that increasing winter affluence and summer temperatures, anticipated in southern Europe with climate change, will deteriorate the ecological status of lakes, especially in those with shorter retention time. We tested these hypotheses analysing weekly phytoplankton and chemistry data collected over 2 years of contrasting weather from two adjacent stratified lakes in North Italy, differing from each other by trophic state and water retention time. Dissolved oxygen concentrations were higher in colder hypolimnia of both lakes in the second year following the cold winter, despite the second summer was warmer and the lakes more strongly stratified. Higher loading during the rainy winter and spring increased nutrient (N, P, Si) concentrations, and a phytoplankton based trophic state index, whilst the N/P ratio decreased in both lakes. The weakened Si limitation in the second year enabled an increase of diatom biovolumes in spring in both lakes. Chlorophyll a concentration increased in the oligo-mesotrophic lake, but dropped markedly in the eutrophic lake where the series of commonly occurring cyanobacteria blooms was interrupted. The projected increase of winter precipitation in southern Europe is likely to increase the nutrient loadings to lakes and contribute to their eutrophication. The impact is proportional to the runoff/in-lake concentration ratio of nutrients rather than to the retention time, and is more pronounced in lakes with lower trophy.
The results are reported of the second stage in a programme for a systematic in vitro study on the carcinogenic potential of metal compounds with Balb/3T3 clone A31-1-1 mouse fibroblasts. Nineteen metal compounds that exhibited a strong cytotoxic effect during a previous screening run with a 100µM fixed dose were tested with a 72-hour exposure over a wide range of concentrations (from 0.1µM to 1000µM), to produce dose-effect curves to permit extrapolation of the 50% inhibition concentration (IC50) values for each metal compound. This allows the establishment of a suitable range of doses for individual metal species, for use in the subsequent Balb/3T3 assay based on a two-stage concurrent cytotoxicity and morphological transformation protocol. Another 13 metal compounds were also tested, to determine whether the Balb/3T3 cell transformation assay really is a valuable in vitro model in relation to the problem of metal speciation. Of the metal compounds assayed, 26 showed a dose related cytotoxic response with calculated IC50 values ranging from 0.25µM (CH 3 HgCl) to 140µM [(C 5 H 5) 2 TiCl 2 ], whereas six metal compounds, namely (NH 4) 6 Mo 7 O 24 •4H 2 O, CH 3 AsO(OH) 2 , (CH 3) 2 AsNaO 2 ⋅3H 2 O, KBr, CrCl 3 •6H 2 O and (NH 4) 2 [TiO(C 2 O 4) 2 ]⋅H 2 O, displayed no observable cytotoxicity or low cytotoxicity at all the doses tested. The determination of IC50 values permits a ranking of the cytotoxicity responses of metal compounds with the highest cytotoxicities. Dose-effect curves and IC50 values of different chemical forms of individual metal compounds of As, Br, Cr, Hg, Ir, Pt, Te, Ti and V (cationic/anionic inorganic or organometallic species) showed clearly how the chemical nature of the metal strongly influences the toxic response. This confirms that the Balb/3T3 cell line is a valuable in vitro model with respect to the problem of metal speciation. This is a fundamental aspect to be considered when incorporating the results from in vitro cell transformation assays of the carcinogenic potential of metal compounds into regulatory testing schemes. In this context, the choice of test metal species for the development and validation of such assays cannot disregard the possibility that humans will be exposed to specific chemical forms of individual metal compounds (different oxidation states, and inorganic or organometallic natures) that can profoundly affect their toxicity.
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