Monitoring of pharmaceutically active compounds on the Guadalquivir River basin (Spain): occurrence and risk assessment

Guadalquivir River (South of Spain) is among the major freshwater sources of the European Atlantic basin. Until now scientific efforts have been focused on contamination by heavy metals and some priority pollutants in Guadalquivir River. However, the presence of "emerging contaminants", such as pharmaceutically active compounds, has not yet been studied. In this work the occurrence and risk assessment of sixteen pharmaceutically active compounds, belonging to different therapeutic groups, in Guadalquivir River during its course through Seville city are reported. Wastewater effluents from four wastewater treatment plants discharging into Guadalquivir River and river water samples were analyzed. All studied pharmaceutically active compounds, except sulfamethoxazole, trimethoprim, estrone and clofibric acid, were detected in effluent wastewaters at concentration levels up to 28.9 μg L(-1). Among the pharmaceutically active compounds found in effluent wastewater, seven were present in Guadalquivir River samples at concentration levels up to 0.75 μg L(-1), which indicated an important dilution from effluent discharge. Environmental risk assessment reveals that potential ecotoxicological risk cannot be expected on Guadalquivir River at measured concentration levels. Only, the lipid regulator gemfibrozil showed a medium risk for the environment. The risk for acute toxic effects in the environment with the current use of active pharmaceutical ingredients is unlikely. However, the results do not rule out the potential for chronic environmental effects.     

Anguilla anguilla L. Genotoxic responses after in situ exposure to freshwater wetland (Pateira de Fermentelos, Portugal)

Pateira de Fermentelos is a Cértima River enlargement, close to its river mouth (by the Agueda River), where the introduction of agricultural chemicals such as fertilisers and pesticides, domestic sewage, as well as heavy metals from electroplating industries, results in increased water pollution. The present research work concerns a 48 h in situ exposure of caged eels (Anguilla anguilla L.) at the Pateira de Fermentelos. Five exposure sites were selected, i.e., site A, site B, site C, site D and site E in order to study its water genotoxicity potential, measured in gill, blood, liver and kidney as DNA strand breaks. Eels were also exposed at a reference site by the Cértima River spring. Bottom water samples were collected for further physical-chemical analysis. Site A exposure, significantly decreased gill, blood and liver DNA integrity. Gill and liver DNA integrity was also significantly decreased at site B. At site C only blood DNA integrity was significantly decreased. The present field in situ study demonstrated that the three exposure sites close to the Pateira initial part, such as A, B and C are polluted by pro and/or genotoxic compounds. The genotoxic effects induced in A. anguilla L. suggest a different contamination of the exposure sites A, B and C, in genotoxic chemicals. Thus, according to its genotoxic potential the exposure sites A, B and C, may be ordered as follows site A>site B>site C. No genotoxic effects on A. anguilla L. were observed at site E as DNA strand breaks increase.     

234U and 230Th determination by FIA-ICP-MS and application to uranium-series disequilibrium in marine samples

A 234U and 230Th determination method based on an extraction chromatographic separation on a flow injection system coupled to a quadruple ICP-MS was developed. Two-milliliter UTEVA (Eichrom Co.) cartridges were applied as separation tool and 236U and 229Th as spikes. Loading and washing steps were carried out in 3 M HNO3 solution and 0.05 M ammonium oxalate applied to elute both uranium and thorium. The method was applied initially to the IAEA-327 soil reference sample and NIST SRM 4357 ocean sediment reference material, with the obtained 234U and 230Th concentrations in agreement with the reference levels. Samples from a deep-sea sediment core (2450 m water depth) were analyzed and based on 230Th/234U dating, a mean sedimentation rate of 3.3 cm ky(-1) was calculated. Samples from two sediment layers were also dated by 14C-AMS and the observed ages agree with the 230Th/234U results.     

The use of the shanny Lipophrys pholis for pollution monitoring: a new sentinel species for the northwestern European marine ecosystems

The contamination of aquatic ecosystems by organic contaminants such as polycyclic aromatic hydrocarbons (PAHs) is a matter of great concern. Mussels have been extensively used as sentinel species in a large number of monitoring programs. However, the use of bivalves as the sole species has some limitations, because they are not as responsive as fish to Aryl Hydrocarbon Receptor agonists. Hence, for many marine areas, there is the need to validate new sentinel fish species that can be used in the assessment of pollution by organic contaminants. The shanny Lipophrys pholis is an intertidal fish that combines many characteristics required in a sentinel species: is abundant and easy to catch, has a wide geographical distribution and restrict home range. After larvae recruitment to the intertidal rocky shores, they remain in the same area for the rest of the life-cycle, thus reflecting local pollutants exposure. In order to evaluate the species sensitivity to organic contaminants under field conditions, L. pholis were collected at six sites reflecting different degrees of anthropogenic contamination. The induction of two biomarkers extensively validated in the assessment of PAHs contamination ethoxyresorufin-O-deethylase activity (EROD) and Fluorescent Aromatic Compounds (FACs) was evaluated. In parallel, mussels were collected at the same locations and levels of 16 PAHs and selected heavy metals determined. Overall, the specimens collected in the urban areas showed a significant induction of EROD and FACs (up to a six-fold induction) if compared with the reference sites. Additionally, a positive correlation was observed between the biomarkers and PAHs levels in mussel tissues. Even though further validation is currently in progress, the available data indicate that L. pholis is responsive to organic contaminants such as PAHs, suggesting its future integration in monitoring programmes designed to evaluate the presence of these contaminants in European marine ecosystems.     

Anguilla anguilla L. plasma cortisol, lactate and glucose responses to abietic acid, dehydroabietic acid and retene

Anguilla anguilla L. were exposed to 0, 0.1, 0.3, 0.9 and 2.7 microM abietic (AA), dehydroabietic (DHAA) acids and retene (Re) during 8, 16, 24 and 72 h. The eels plasma cortisol, glucose and lactate were measured. A significant decrease in plasma cortisol was observed at 72 h exposure to 0.9 and 2.7 microM Re. DHAA (0.1 microM) significantly decreased plasma cortisol in eels after 8 and 24 h exposure. However, a significant plasma cortisol increase was found after 16 h, 2.7 microM AA exposure and after 24 h exposure to 0.1 microM and 2.7 microM AA. Furthermore, 72 h exposure to 0.9 microM AA also induced a plasma cortisol increase. A general rise in plasma glucose was detected after all exposure periods to Re. The plasma lactate also increased after 72 h exposure to 2.7 microM AA and after 8 h exposure to 0.1 microM DHAA.     

Biomagnification of naturally-produced methoxylated polybrominated diphenyl ethers (MeO-PBDEs) in harbour seals and harbour porpoises from the Southern North Sea

Harbour seals and harbour porpoises are top predator species from the North Sea, have long life spans and hence, are known to accumulate high levels of anthropogenic contaminants. To gain knowledge about the behaviour of naturally-produced compounds in these marine mammals, the biomagnification of naturally-produced methoxylated polybrominated diphenyl ethers (MeO-PBDEs) was assessed. The biomagnification of MeO-PBDEs (2′-MeO-BDE 68 and 6-MeO-BDE 47) was lower in harbour seals (all biomagnification factors (BMFs) < 1) compared to the same age–gender groups of the harbour porpoises (all BMFs > 1). This may indicate a better metabolic breakdown of MeO-PBDEs in harbour seals, as was previously suggested for polybrominated diphenyl ethers (PBDEs). In both predators, 6-MeO-BDE 47 had the highest concentrations (range: 45–483 ng/g lw and 2–38 ng/g lw for harbour porpoises and seals, respectively) compared to 2′-MeO-BDE 68 (range: 2–28 ng/g lw and 1–6 ng/g lw for harbour porpoises and seals, respectively). In general, the highest concentrations were found in juveniles, suggesting an increased biotransformation capacity with age or the influence of dilution by growth for both species. Here we show that naturally-produced brominated organic compounds can biomagnify and accumulate in North Sea top predators, although to a lesser extent than anthropogenic lipophilic contaminants, such as polychlorinated biphenyls (PCBs) or PBDEs.     

Daily ingestion of 232Th, 238U, 226Ra, 228Ra and 210Pb in vegetables by inhabitants of Rio de Janeiro City

The concentrations of the naturally occurring radionuclides 232Th, 238U, 210Pb, 226Ra and 238Ra were determined in the vegetables (leafy vegetables, fruit, root, bean and rice) and derived products (sugar, coffee, manioc flour, wheat flour, corn flour and pasta) consumed most by the adult inhabitants of Rio de Janeiro City. A total of 88 samples from 26 different vegetables and derived products were analyzed. The highest contribution to radionuclide intake arises from bean, wheat flour, manioc flour, carrot, rice, tomato and potato consumption. The estimated daily intakes due to the consumption of vegetables and derived products are 1.9 mBq of 232Th (0.47 microg), 2.0 mBq of 238U (0.17 microg), 19 mBq of 236Ra, 26 mBq of 210Pb and 47 mBq of 228Ra. The estimated annual effective dose due to the ingestion of vegetables and their derived products with the long-lived natural radionuclides is 14.5 microSv. Taking into account literature data for water and milk from Rio de Janeiro the dose value increases to 29 microSv, with vegetables and derived products responsible for 50% of the dose and water for 48%. 210Pb (62%) and 228Ra (24%) were found to be the main sources for internal irradiation.