Determination of selected pharmaceuticals and caffeine in sewage and seawater from Tromsø/Norway with emphasis on ibuprofen and its metabolites

Selected pharmaceuticals, among them analgesics, ss-blockers and anti-depressants as well as caffeine, the anti-bacterial triclosan and the insect repellent N,N-diethyl-3-toluamide (DEET) were determined in different sewage samples (sewage treatment plants, hospital effluents) from Troms?/Norway and in seawater from Troms?-Sound, into which the sewage is discharged. While caffeine, triclosan, ibuprofen and its major metabolites hydroxy- and carboxy-ibuprofen were present in all sewage samples, additional pharmaceuticals were observed in sewage containing hospital effluents. Concentrations were in the range of 20-293 microg/l (caffeine), 0.2-2.4 microg/l (triclosan) and 0.1-20 microg/l (sum ibuprofen + metabolites). In seawater, only caffeine (7-87 ng/l), DEET (0.4-13 ng/l) and ibuprofen + metabolites (sum concentration < LOQ-7.7 ng/l) were detected. Ibuprofen and its metabolites hydroxy- and carboxy-ibuprofen were quantified individually by use of the respective reference compounds. Relative amounts of the three compounds were determined in different types of water showing characteristic patterns, with hydroxy-ibuprofen being the major component in sewage whereas carboxy-ibuprofen was dominant in seawater samples. The patterns which were compared to those observed in similar samples from Germany indicated different transformation behaviour under limnic and marine conditions.     

Fate of 14C-bisphenol A in soils

Bisphenol A (BPA; 2,2-(4,4(')-dihydroxydiphenyl)propane) is predominantly used as an intermediate in the production of polycarbonate plastics and epoxy resins. Traces of BPA released into the environment can reach the soil via application of sewage sludge from wastewater treatment systems that receive wastewaters containing BPA, or from leachate from uncontrolled landfills. The biodegradability of BPA has been previously investigated in several studies designed to simulate surface waters and biological wastewater treatment systems. However, there is little information available about the fate of BPA in soil. Therefore, laboratory soil degradation and batch adsorption studies were conducted with 14C-BPA and four soils according to international guidelines. The soils represented a broad range of physico-chemical properties. An important result of the degradation study was that, independent of the soil type, 14C-BPA was rapidly dissipated and not detectable in soil extracts following 3 days of incubation. Based on this result, a dissipation half-life of less than 3 days was estimated. The major route of dissipation of 14C-BPA in soil was the formation of bound residues that could not be recovered by exhaustive Soxhlet extraction. 14C-BPA was also shown to be transiently converted to up to five metabolites, but within 3 days, neither 14C-BPA nor 14C-metabolites were detectable in the soils. After 120 days incubation, significant amounts (up to 20% of the radioactivity applied) of the parent compound were recovered as 14CO(2). Soil adsorption experiments indicated that the distribution coefficients (K(oc)) were between 636 and 931, classifying BPA as having low mobility for all tested soils. From the results of this study, it was concluded that if BPA reaches the soil compartment, it is not expected to be stable, mobile, or bioavailable.     

Comparison of three extraction methods for 17beta-estradiol in sand, bentonite, and organic-rich silt loam

Extraction is an important procedure for samples that contain soil because other compounds in soil may affect analysis of estrogens. This study was conducted to evaluate three different extraction methods for 17beta-estradiol in soil. Sand, bentonite, and organic-rich silt loam were spiked with 1 mg kg(-1) of 17beta-estradiol as a model compound of estrogens. 17beta-estradiol and its metabolites, estrone and estriol, were extracted using (i) a modified Bligh and Dyer extraction, (ii) a pressurized fluid extraction, and (iii) a diethyl ether extraction, and measured by liquid chromatography tandem mass spectrometry. There were significant differences in the extraction efficiency for 17beta-estradiol among the extraction methods and the soils: the efficiencies ranged from 10% to 97%. Overall, the diethyl ether extraction method had the largest efficiency of 17beta-estradiol with 45% and 57% for bentonite and silt loam, respectively. Transformation of 17beta-estradiol to estrone and estriol in the different extraction methods was less than 3.6% during the extraction procedures. This study underlined the importance of sample preparation for estrogen analysis in soil samples.     

Ecotoxicological Characterisation and Classification of Existing Chemicals

GOAL, SCOPE AND BACKGROUND: In 1998, the International Council of Chemical Associations (ICCA) launched a global initiative to investigate more than 1,000 HPV chemicals (High Production Volume, > or = 1,000 t/a) within the refocused OECD HPV Chemicals Programme. Up to the OECD SIDS Initial Assessment Meeting in April 2004 (SIAM 18) 147 ICCA dossiers (ca. 230 CAS-No) have been assessed based on a harmonised data set. The environmental profile and an ecotoxicological characterisation of these chemicals are presented here. Data for acute aquatic toxicity were correlated among each other, as well as data for fish (LC50, LD50) and rodents (LD50). The data for acute aquatic toxicity are compared with other existing chemicals. METHODS: Data of the ICCA HPV chemicals from the OECD SIAM 11-18 are presented for: log Kow (as an indicator for bioaccumulation potential), biodegradation, acute aquatic toxicity and availability of long-term toxicity data. Correlation analysis was performed with log transformed data and a linear regression model was fitted to the data, if a significant correlation was found. Acute toxicity for fish and acute oral toxicity for rodents were correlated on a molar basis. Acute aquatic toxicity of the chemicals is compared with data from BUA reports 1-234 and a random EINECS sample (Knacker et al. 1995). RESULTS AND DISCUSSION: According to the dossier information, 71 of the 147 ICCA chemicals are not 'readily biodegradable', 21 have a log Kow > or = 3, and 44 are 'toxic' (LC/EC50 < or = 10 mg/L) or 'very toxic' (LC/EC50 < or = 1 mg/L) to aquatic organisms. For 77, only the base set (acute fish, Daphnia and algae) is available, for the rest at least one long-term test (fish or Daphnia) is available and three tests for a mere 14 others. Based on the data presented, the SIAM gives recommendations for Environment and Human Health. 22 chemicals have been identified as a 'candidate for further work' for Environment and 16 for Human Health. The highest correlation coefficient was obtained correlating fish and Daphnia (r2 = 0.79). LC50 (fish) is significantly correlated with LD50 (rodent), but data are widely scattered. The correlation is not improved after transforming LC50 (fish) to LD50 (fish), using BCF QSAR. Based on acute aquatic toxicity, 25.1% of the chemicals from the BUA reports 1-234 are classified as 'very toxic' (LC/EC50 < or = 1 mg/L). This proportion is 2.5-fold higher than the ICCA HPV chemicals and 1.4-fold higher than the random EINECS sample. CONCLUSIONS: Correlation coefficients for aquatic toxicity data are rather uniform (0.57-0.79) compared with literature data, but also the best correlation was observed between fish and Daphnia. Because the scatter around the regression lines is still considerable, simple predictions of ecotoxicity between species are not possible. Correlation of LC50 (fish) and LD50 (rodent) indicates that toxicity is different. Surprisingly, the correlation of fish and rodent toxicity is not improved by transforming LC50 values to internal LD50s. The selection of ICCA chemicals by market significance (production volume) leads to a classification of toxicity, which is more comparable to a random sample of EINECS chemicals than to German BUA chemicals. The latter were chosen for concern (for Environment or Human Health). RECOMMENDATIONS AND OUTLOOK: Of 147 dossiers assessed between SIAM 11-18, ca. 75% were sponsored by the three following countries: Germany (42), USA (37) and Japan (33). The current output is about 50 dossiers per year (70-100 CAS-No), but a trend for an increase of output is noticeable. Industry, national authorities, and OECD work on a further development to speed up the output. The number of chemicals with 'low priority for further work' and the work recommended for the 'candidates' (mainly exposure assessment) indicate that the data presented were adequate for an initial hazard assessment according to OECD requirements. From the ICCA HPV list (n = 880, state of 1999) 44% of the chemicals have data available to cover all SIDS endpoints for Environment and only 33% for Human Health (Allanou et al. 1999). This indicates the importance of the Initiative to provide information on existing chemicals. The authors agree with the expectation "...that the scientific information provided by this global initiative will be considered as an internationally accepted and harmonised basis for further steps of chemicals management." (ICCA 2002 b).     

Effects of nitrogen enrichment on coastal dune grassland: a mesocosm study

Mesocosms filled with dune sand were planted with graminoid (Calamagrostis epigejos, Carex arenaria) and herbaceous species (Carlina vulgaris, Galium verum). Strong effects of nitrogen addition on the vegetation were found within two to three years. The above-ground biomass of C. epigejos and C. arenaria increased at deposition rates between 10 and 80 kg N ha(-1) yr(-1). Both grasses were limited by N. In latter stages P limitation was suggested for C. arenaria. At high N-levels, C. epigejos dominated the vegetation within two years. C. vulgaris and G. verum declined drastically as a result of increased competition for light by the highly competitive grass C. epigejos. It is concluded that increased (ambient) N inputs are of major importance for the increased dominance of tall grasses in stable dune grasslands.     

STEP WISE,MULTIPLE OBJECTIVE CALIBRATION OF A HYDROLOGIC MODEL FOR A SNOWMELT DOMINATED BASIN1

ABSTRACT: The ability to apply a hydrologic model to large numbers of basins for forecasting purposes requires a quick and effective calibration strategy. This paper presents a step wise, multiple objective, automated procedure for hydrologic model calibration. This procedure includes the sequential calibration of a model's simulation of solar radiation (SR), potential evapotranspiration (PET), water balance, and daily runoff. The procedure uses the Shuffled Complex Evolution global search algorithm to calibrate the U.S. Geological Survey's Precipitation Runoff Modeling System in the Yampa River basin of Colorado. This process assures that intermediate states of the model (SR and PET on a monthly mean basis), as well as the water balance and components of the daily hydrograph are simulated consistently with measured values.     

DATA ANALYSIS OF WATER QUALITY TIME SERIES IN LAKE ERIE1

ABSTRACT: A comprehensive data analysis study is carried out for detecting trends and other statistical characteristics in water quality time series measured in Long Point Bay, Lake Erie. In order to glean an optimal amount of useful information from the available data, the exploratory and confirmatory data anslysis stages are adhered to. To test a range of hypotheses regarding the statistical properties of the time series, a wide variety of both parametric and nonparametric techniques are employed. A particularly useful nonparametric method for discovering trends is the seasonal Mann-Kendall test.     

Phenotypic analysis of fetal blood leucocytes: Potential for prenatal diagnosis of immunodeficiency disorders

Recent technological advances allow the detection and quantitation of subsets of leucocytes using monoclonal antibodies. We have taken advantage of this to study the ontogeny of fetal blood leucocytes, using very small blood samples obtained at fetoscopy. By 14 weeks gestation T cells represent 35 per cent or more of fetal leucocytes and the distribution of the helper/inducer and suppressor/cytotoxic subsets is similar to that of adults. B lymphocytes before 161/2 weeks are low (4–20 per cent), but rise to a mean of 28 per cent in 17–26 week fetuses. Granulocytic cells, many of which are phenotypically immature, represent 18–34 per cent of total leucocytes. The methodology employed is very reliable and offers the opportunity for the prenatal diagnosis of some immunodeficiency disorders, since using the same reagents we have diagnosed children with severe combined immunodeficiency shortly after birth.