Effect of organochlorine contaminants and individual biological traits on blubber retinoid concentrations in bottlenose dolphins (Tursiops truncatus)

Here we assessed retinoids as biomarkers of contaminant exposure by studying whether the sex, age, lipid content and organochlorine concentrations of bottlenose dolphins induced variation in retinoid status and its deposition in blubber. Blubber samples were collected from 47 individuals of known age and gender from Sarasota Bay in June 2000 and 2001. The sample included a representative cross-section of the resident dolphin community, with ages ranging from 2 to 50 years. Organochlorine levels showed the age- and sex-related variation commonly observed in other species, with concentrations increasing in youngsters of both sexes and in adult males, and decreasing in adult females after the onset of maturity. Blubber lipid content was low in the overall population and significantly decreased with age in adult males. Retinoid blubber concentrations were comparable to other odontocete species previously studied, and were strongly determined by lipid content. As a consequence of the latter, retinoid concentration was observed to decrease with age in adult males. This effect could not be statistically dissociated from the negative correlation observed between levels of organochlorines and retinoid blubber concentration. Consequently, we could not clarify whether high organochlorine loads in this population lowered retinoid concentrations or, conversely, whether depleted lipid reserves were indeed responsible for the high organochlorine concentrations and the low retinoid levels detected in blubber. With the current knowledge, both options should be considered and investigated, with initial focus on male dolphins.     

Particulate matter and black smoke concentration levels in central Athens, Greece

This study presents the statistical analysis of PM(10) and PM(2.5) concentrations (measured at a central site, in the Athens area), along with black smoke (BS) data, for a 2-year period. The biennial average concentrations of PM(10) and PM(2.5) were 75 and 40 microg m(-3). The respective average concentration of BS, as estimated by the OECD method, was 108 microg m(-3). Severe exceedances of the PM(10) air quality standards were recorded. The seasonal variation of PM(10) and BS was less pronounced than the variation of PM(2.5), which concentration was elevated by 14.2% during the cold period. Concentrations of all three pollutants were significantly lower during weekends; however, PM(2.5) and BS displayed a more uniform weekly distribution pattern. PM(10) particles were found to be almost equally comprised by PM(2.5) and PM(10-2.5) particles (PM(2.5)/PM(10) ratio=0.53+/-0.09 microg/m(3)). The average PM(10)/BS value was found lower than unity revealing the inappropriateness of the used reflectance conversion method, for the estimation of mass-equivalent BS concentrations, in the study area, where diesel-powered vehicles mainly control emissions of light-absorbing substances. Important reductions in concentrations were observed during days when drivers of diesel-powered taxies and transportation buses went on strike (reaching 40% for BS). Calm wind conditions were found to have an incremental effect on particle concentrations and were also associated with the appearance of persistent episodic events. Increased PM levels were also observed during southern-southwestern wind flows while significantly lower-than-average concentrations were measured during precipitation events. Separate regression analyses were performed for PM(10), PM(2.5) with BS and NO(x) as independent variables, in an attempt to estimate the relative contribution of specific source types (diesel-powered vehicles) to measured particle levels. The contribution of the diesel-exhaust component to PM(10) mass was estimated at 49.9%, while the corresponding contributions to PM(2.5) mass concentrations was 53.8%. These results may have important implications with the oncoming decision of national authorities to allow the purchase of diesel-powered private cars to the residents of the Greater Athens Area, which was forbidden up to this day.     

Determination of non-steroidal anti-inflammatory drug (NSAIDs) residues in water samples

Pharmacologically active substances used to treat human and animal illnesses can enter the aquatic environment via effluents from wastewater treatment plants or in the case of veterinary drugs directly through liquid manure discharge. Some of these substances enter the environment either as the parent compound or as active/inactive metabolites. Due to their pharmacological activity, their determination and understanding their behavior and fate in the environment are important. The scope of this paper was to develop an analytical procedure to determine common pharmaceutical residues in wastewaters. Pharmacologically active substances were chosen according to their wide spread application in Slovenia and Central Europe and are members of analgesics, e.g., non-steroidal anti-inflammatory drugs: ibuprofen, naproxen, ketoprofen and diclofenac. Selected compounds were isolated from synthetic water using a novel SPE sorbent Strata X. Due to the non-volatile nature of these compounds they were first silylised prior to gas chromatographic-mass spectrometric detection. The developed procedure was tested with synthetic wastewaters and their extraction efficiency (>84%) and method limits of detection (2-6 ng L(-1)) were determined. Our procedure has been adopted and optimised for "real" water samples and applied to eleven drinking and ten river water samples from Slovenia. The results showed no traces of NSAIDs in all potable water samples and low-range contamination (ng L(-1)) of Slovene rivers. These results show that NSAIDs contamination of Slovene waters is comparable with published results of water contamination in Central Europe.     

Atmospheric bulk deposition to the lagoon of Venice Part I. Fluxes of metals, nutrients and organic contaminants

First available data on atmospheric fall-out were provided by sampling monthly bulk depositions in four sites inside the Lagoon of Venice (550 km2). Sampling was carried out monthly during the period July 1998-July 1999, in one site near an industrial area (Porto Marghera; site D), another site in the city of Venice (site A), and the remaining two in the southern- and northernmost ends of the Lagoon (Valle Figheri, site C; Valle Dogà site B). The following determinations were carried out for each samples: pH, conductivity, grain-size, particulate load, and dissolved nutrients (N, P). Samples were then subdivided into soluble and insoluble fractions, and Al, Ca, Na, K, Mg, Si, Mn, Fe, Zn, Ni, Cr, Cu, Pb, Cd, As, Hg, Ti, V, S, P, Se and Sb were analysed on both fractions. Total organic micropollutants (PAH, PCB, HCB, DDT, PCDD/F) were measured. As regards particle size distribution, there was great variability among sampling sites. The percentage of the < or =2 microm grain-size fraction was higher in the southern and northern ends of the Lagoon. Small differences were found among sites for major elements, whereas higher variability was observed for inorganic and organic micropollutants, with standard deviations between 20% and 60% of the fluxes measured. Major differences in annual fluxes between the most polluted sites (mostly D and A) and background (site B) were seen for Cd (0.26 vs. 0.06 mg m(-2) year(-1)), Hg (41 vs. 15 microg m(-2) year(-1)), PCB ( approximately 2500 vs. approximately 500 ng m(-2) year(-1)) and HCB ( approximately 8000 vs. approximately 1000 ng m(-2) year(-1)). Comparisons with previous data, collected in the periods 1993-1994 and 1995-1997, were only available for a few trace metals. A definite decline in the annual Pb flux in the city of Venice was detected, from 18 to 13 mg m(-2) in 1996/1997 and 1995/1996 respectively, to approximately 5 mg m(-2) in the present study. Total annual deposition was calculated by means of two different methods, which gave very similar results: (i) the mean value of deposition in the four sites was multiplied by lagoon area (550 km2); (ii) the monthly rain isopleths were combined to normalize deposition values. The figures are: 15-34 kg of Hg and Sb, approximately 200 kg of As, approximately 100 kg of Cd and PAH, 0.7-1.3 tons of Cr, Ni and V, more than 2 tons of Cu and Pb, 17 of Zn, 55 of total P, approximately 200 of Al, and 3900 of DIN. Total fluxes of organics inside the lagoon were: PAH approximately 100 kg; HCB approximately 1 kg; DDT approximately 0.4 kg. PCB and PCDD/F fluxes were approximately 500 g and approximately 10 g, corresponding respectively to 0.1 and 0.4 g I-TE. The correlations between fluxes of inorganic micropollutants and grain-size were significant. Multivariate statistical analysis was applied to investigate more accurately relationships between the insoluble and dissolved fractions of inorganic micropollutants and grain-size fractions. In particular, significant correlations were highlighted between the dissolved fraction of As and the < or =1 mum particle size fraction. Relations between levels of SigmaPCDDF, SigmaPCDD, PCB and PAH congeners and grain-size revealed significant correlation coefficients for the remote sites (B, C), and none in the urban and industrial sites (A, D). In particular, significant correlations were highlighted between SigmaPCDDF, SigmaPCDD and particle size fraction < or =2 mum, and between benzo(a)pyrene and PCB 167 and particle size fraction 4-8 mum.     

Reconstruction of historical trends of PCDD/Fs and PCBs in the Venice Lagoon, Italy

Historical trends of PCDD/Fs and PCBs from the year 1900 have been reconstructed for the Venice Lagoon area by using a fugacity-based dynamic multimedia model. A novel approach to estimate the inputs to the system was applied. Emissions to the lagoon were estimated by studying dated sediment cores taken from salt marshes located in the lagoon area. These cores have recently proven to be a suitable tool to reconstruct the temporal trends of atmospheric deposition of POPs. According to the model, concentrations of PCBs and PCDD/Fs in air and water reflect the trends of their production and usage, peaking during the 1960s. The peaks in the sediment were delayed by 5-40 years depending on the congener. Predicted concentrations are in good agreement with experimental results. The most important input parameters, identified by a sensitivity analysis, are the degradation constants, K(ow), the Henry's law constant, vapour pressure, active sediment depth, sediment resuspension, and deposition rates, and water residence time in the lagoon.     

Seasonal variation of the radiocaesium transfer soil-to-Swiss chard (Beta vulgaris var. cicla L.) in allophanic soils from the Lake Region, Chile

The transfer factor (TF) of radiocaesium from soil-to-Swiss chard (Beta vulgaris var. cicla L.) was studied in two different characteristic allophanic soils (umbric andosol and dystric fluvisol) of the Lake Region, an important agricultural region situated in central-south Chile. To investigate especially the time dependence and the effect of K-fertilisation on the TF, field experiments were conducted. Plots of 7.6 m2 were labelled with 100 kBq 134Cs m(-2) at Santa Rosa Experiment Station close to the city of Valdivia characterised by a temperate climate and high precipitation rates. The variation in time of the radiocaesium TF soil-to-Swiss chard was observed during two consecutive years after soil contamination by sequential harvests and radiocaesium analyses of the plants. The TFs showed no significant ageing effect, but a pronounced seasonal decrease with effective half-lives of about 140 and 160 days for the umbric andosol without and with K-fertilisation, respectively, and of 50 and 60 days for the dystric fluvisol without and with K-fertilisation, respectively. The effect of K-fertilisation on the absolute values of the TF was determined by the ratio between the median TF values obtained for corresponding dates without and with use of K-fertiliser. A ratio of TF(without K)/TF(with K) = 1.8 for the umbric andosol and TF(without K)/TF(with K) = 2.9 for the dystric fluvisol was obtained, indicating a reduction of the TF by applying 90 kg K ha(-1). The maximal values of the TF to chard predicted by the equation characterising the seasonal decrease of the TF at the beginning of the harvest periods are 0.19 for the umbric andosol and 0.11 for the dystric fluvisol, both values for soil treated with common K-fertilisation.     

A new approach for calculating the relative risk level of pesticides

The following paper describes a new, easier to use approach to the calculation of relative risk levels of alternative pesticides. An insect, a plant disease, and a weed were selected for describing the application procedure of a new ranking method that is based on the intrinsic properties of pesticides rather than on the processes that occur both on land and in water after they are applied to soil. The approach is based on the Toxicity-Human health-Persistency (THP) Hazard Rating System, and a consumption factor is added to the method in order to calculate the environmental risk of pesticides. The available substitute pesticides are ranked in terms of their relative risk levels from lowest to highest in order of magnitude difference. Such a ranking method may be used as a practical quantitative tool to generate significant findings aiding in the selection of the most environmentally friendly substitute against a certain pest, especially in developing countries that still face the misuse and/or unconscious use of pesticides.     

Evaluation of the sensitivity of marine microalgal strains to the heavy metals, Cu, As, Sb, Pb and Cd

The sensitivity of nine marine microalgal species (consisting of five divisions and seven genera) to the five heavy metals, Cu(II), As(V), Sb(III), Pb(II) and Cd(II) was studied by using a fluorometric growth-inhibition assay with 96-well microplates. The algal strains studied were Cylindrotheca sp. and the LPP group that respectively characterize aggregating and filamentous types, and Chlorococcum littorale, Chlorococcum sp., Isochrysis galbana, Tetraselmis tetrathele, Heterocapsa sp., Synechococcus sp. and Prasinococcus sp. for types that occur as single cells. A good linear relationship was observed between the chlorophyll a concentration and intensity of chlorophyll fluorescence (485-nm excitation filter and 645-nm emission filter) when the chlorophyll a concentration was within the range of 0.10-5.0 microg ml(-1). A starting cell concentration of 0.10 or 0.25 microg Chl a ml(-1) was therefore selected. In accordance with OECD 201 standard procedures, the IC(50) value (concentration of a metal producing 50% growth inhibition relative to the control) was determined 72 h after adding a heavy metal by using the biomass integral. The microplate toxicity test used in this study is considered to be applicable to diverse algae, not only enumerating species but also hardly enumerating ones.     

Accumulation and release of 241Am by a macrophyte of the Yenisei River (Elodea canadensis)

The source of radioactive contamination of the Yenisei River floodplain, including contamination with transuranic elements, is the Mining-and-Chemical Combine of the Russian Ministry of Atomic Energy, which has for many years been producing weapons-grade plutonium. Transuranic elements have been detected not only in the soil and sediment of the river but also in the biomass of aquatic plants. This work is an investigation of accumulation and release of 241Am by a submerged macrophyte of the Yenisei River (Elodea canadensis) in laboratory experiments. In 2000-2003, laboratory experiments were carried out with biomass of E. canadensis Mich. and filtered river water. The samples were collected from the Yenisei River upstream of the discharge of the Combine's radioactive effluent. The experiments showed that 241Am is accumulated by Elodea biomass: the activity concentration of 241Am can reach 3280+/-240 Bq/g, with the concentration factor for 241Am 16 600+/-2200l/kg. Results of chemical fractionation have proved that in the course of 241Am accumulation by Elodea biomass, 241Am tightly bound to biomass increases from 11% to 27% of the total 241Am in the biomass. Release of 241Am from the decaying Elodea biomass has been evaluated experimentally. By the end of the experiment (lasting up to 127 days), the Elodea plants had lost up to 65% of their initial 241Am activity and the rate of 241Am release into the water environment reached 23 Bq/day.     

241Am, 137Cs, Sr and Pb uptake by tobacco as influenced by application of Fe chelators to soil

To determine the potential for phytoextraction of 241Am and other contaminants from soil, accumulation of 241Am, 137Cs, Sr, Fe, Al, Pb, and Mg by tobacco was determined for soil applications of two concentrations of ethylenediaminetetraacetic acid (EDTA), citric acid, and ascorbic acid. In tobacco receiving EDTA at 3.1 mmol/kg of soil, 241Am content of plants averaged 15 Bq/kg (ranging up to 26 Bq/kg) while Fe concentrations became constant at 4.5 mmol/kg. Soil treatment with 18.8 mmol/kg EDTA resulted in average 241Am concentrations of 29 Bq/kg (19 times higher than controls). Uptake of Pb was similar to 241Am. In these samples, Fe increased to a maximum of almost 18 mmol/kg and 241Am content increased linearly with both Fe and Al. Plants receiving ascorbic and citric acids took up smaller quantities of 241Am, Pb, and Fe, even though these reagents were able to elute about as much Fe from the soil as EDTA. Synchrotron microbeam X-ray fluorescence (SXRF) was used to determine radial distributions of elements in roots and stems with and without EDTA treatment. SXRF maps indicate differences in behavior between Fe and Pb that are consistent with the bulk plant observations and provide insight into changes in metal content of the roots in the presence of EDTA.