The occurrence of micopollutants in the aquatic environment: a new challenge for water management.

The occurrence of micropollutants in the aquatic environment has become a crucial topic in the last two decades owing to the innovative development of analytical instrumentation such as LC tandem MS. Using these new techniques it became obvious that pesticides, pharmaceuticals, ingredients of personal care products, biocides, flame retardants, and perfluorinated compounds are entering rivers and streams via treated wastewater. Also contamination of bank filtrates, groundwater and in a few cases even drinking water was identified. Wastewater treatment plants are not designed to remove polar persistent organic pollutants occurring in the sub-mg/L range and hence many of these organic pollutants are passing WWTPs to a high extent. Waterworks with a potential pesticide contamination in their raw water are equipped with advanced techniques such ozonation, activated carbon or nanofiltration enabling the removal of a high variety of other organic compounds. However, waterworks without an expected pesticide contamination are frequently equipped with common treatment processes not enabling the removal of these kinds of organic pollutants. Therefore, comprehensive management activities for protection of aquatic environments and water resources must consider the removal of all micropollutants relevant to water quality and ecology, independent of their usage or origin.     

Antioxidative constituents of Rosmarinus officinalis and Salvia officinalis. II. Isolation of carnosic acid and formation of other phenolic diterpenes.

The phenolic diterpene carnosic acid appears to be the main substance for general oxidation leading to artifacts with gamma- or delta-lactone structure in extracts of Rosmarinus officinalis and Salvia officinalis. Until now it was only possible to prepare carnosic acid by hydrogenolysis of carnosol. A semipreparative HPLC method has been developed isolating carnosic acid among other phenolic diterpenes. The separated substances were identified by 13C-nuclear magnetic resonance (NMR), 1H-NMR, mass and IR spectroscopy. Conversion of carnosic acid and carnosol to other phenolic diterpenes was investigated by HPLC.     

Removal of micropollutants in municipal wastewater treatment plants by powder-activated carbon

Micropollutants (MP) are only partly removed from municipal wastewater by nutrient removal plants and are seen increasingly as a threat to aquatic ecosystems and to the safety of drinking water resources. The addition of powder activated carbon (PAC) is a promising technology to complement municipal nutrient removal plants in order to achieve a significant reduction of MPs and ecotoxicity in receiving waters. This paper presents the salient outcomes of pilot- and full-scale applications of PAC addition in different flow schemes for micropollutant removal in municipal wastewater treatment plants (WWTPs). The sorption efficiency of PAC is reduced with increasing dissolved organic carbon (DOC). Adequate treatment of secondary effluent with 5-10 g DOC m(-3) requires 10-20 g PAC m(-3) of effluent. Counter-current use of PAC by recycling waste PAC from post-treatment in a contact tank with an additional clarifier to the biology tank improved the overall MP removal by 10 to 50% compared with effluent PAC application alone. A dosage of 15 g PAC m(-3) to a full-scale flocculation sand filtration system and recycling the backwash water to the biology tank showed similar MP elimination. Due to an adequate mixing regime and the addition of adapted flocculants, a good retention of the fine fraction of the PAC in the deep-bed filter were observed (1-3 g TSS m(-3); TSS: total suspended solids). With double use of PAC, only half of the PAC was required to reach MP removal efficiencies similar to the direct single dosage of PAC to the biology tank. Overall, the application of PAC in WWTPs seems to be an adequate and feasible technology for efficient MP elimination (>80%) from wastewater comparable with post ozonation.     

Behavior of pharmaceuticals, cosmetics and hormones in a sewage treatment plant

Two cosmetic ingredients (galaxolide, tonalide), eight pharmaceuticals (carbamazepine, diazepam, diclofenac, ibuprofen, naproxen, roxithromycin, sulfamethoxazole and iopromide) and three hormones (estrone, 17beta-estradiol and 17alpha-ethinylestradiol) have been surveyed along the different units of a municipal Sewage Treatment Plant (STP) in Galicia, NW Spain. Among all the substances considered, significant concentrations in the influent were only found for the two musks (galaxolide and tonalide), two anti-inflammatories (ibuprofen and naproxen), two natural estrogens (estrone, 17beta-estradiol), one antibiotic (sulfamethoxazole) and the X-ray contrast medium (iopromide), where the other compounds studied were below the limit of quantification. In the primary treatment, only the fragrances (30-50%) and 17beta-estradiol (20%) were partially removed. On the other hand, the aerobic treatment (activated sludges) caused an important reduction in all compounds detected, between 35% and 75%, with the exception of iopromide, which remained in the aqueous phase. The overall removal efficiencies within the STP ranged between 70-90% for the fragrances, 40-65% for the anti-inflammatories, around 65% for 17beta-estradiol and 60% for sulfamethoxazole. However, the concentration of estrone increased along the treatment due to the partial oxidation of 17beta-estradiol in the aeration tank.     

Trace determination of fluoroquinolone antibacterial agents in urban wastewater by solid-phase extraction and liquid chromatography with fluorescence detection

Fluoroquinolones (FQs) are among the most important antibacterial agents (synthetic antibiotics) used in human and veterinary medicine. An analytical method based on reversed-phase liquid chromatography with fluorescence detection was developed and validated for the simultaneous determination of nine FQs and the quinolone pipemidic acid in urban wastewater. Aqueous samples were extracted using mixed-phase cation-exchange disk cartridges that were subsequently eluted by ammonia solution in methanol. Recoveries were above 80% at an overall precision of better than 10%. Instrumental quantification limits varied between 150 and 450 pg injected. The presented method was successfully applied to quantify FQs in effluents of urban wastewater treatment plants. The two most abundant human-use FQs, ciprofloxacin and norfloxacin, occurred in primary and tertiary waste-water effluents at concentrations between 249 and 405 ng/L and from 45 to 120 ng/L, respectively. The identity of FQs in urban wastewater was confirmed by recording full fluorescence spectra and liquid chromatography directly coupled to tandem mass spectrometry. These results indicate that conventional environmental risk assessment overestimates FQ concentrations in surface waters by 1 to 2 orders of magnitude.     

Determination ofp-cymene-2,3-diol, thymol, and carvacrol in different foodstuffs

p-Cymene-2,3-diol, carvacrol and thymol are components of thyme that exhibit antioxidant activities. The concentration of each substance was determined in different foodstuffs containing thyme extract. The stabilities ofp-cymene-2,3-diol, carvacrol and thymol were examined by heating lard containing thyme extract at temperatures from 80 °C to 160 °C.     

Determination of antibiotics in different water compartments via liquid chromatography-electrospray tandem mass spectrometry

The mechanisms by which BCG exerts its antitumour activity remain unclear. Attachment of BCG to the bladder via FN has been shown to be an important step in initiating its antitumorigenic activity. The mechanism(s) by which BCG operates requires LAK cells, BCG-activated killer cells, T lymphocytes (CD4) helper cells and CD8 suppressor/cytotoxic cells) and monocytes. The optimal route of administration is intravesical. The efficacy of a BCG vaccine depends on the viability, dose and strain. Differences in efficacy and side-effects have not been shown between different strains. Low-dose regimens successfully protect from recurrences, with fewer side-effects. The initial schedule of BCG is a course of six instillations in 6 weeks; when the patient fails this course, two possibilities arise. The first is maintenance therapy; response rates improve but there is more local and systemic toxicity. The second is a further 6-week course, and this seems most useful in those with a sustained response to the initial treatment. The clinical response to BCG therapy can be monitored using cytokine measurements or p53 determinations. Toxicity remains a major problem in BCG treatment and triple antituberculosis combination therapy should be given for 3 months in those with severe systemic side-effects. The use of prophylactic isoniazid is not recommend to decrease side-effects. The clinical results of BCG have been good, with success rates of 58-100%, with a minimal follow-up of one year in prophylaxis. BCG seems superior to intravesical therapy, but at the cost of inducing more adverse effects. BCG is not indicated for low- and intermediate-risk patients, in whom chemotherapy is the first choice. BCG can also be used to eliminate tumour after an incomplete TUR, or in patients who are unfit for surgery, with a 60-70% success rate. The primary and best treatment for CIS is intravesical BCG; encouraging results have been reported, with success rate of 42-83% after a minimal follow-up of one year. Although currently BCG seems to be the choice for high-risk superficial TCC, many questions remain unanswered, especially about the mechanism(s) of action, the optimal dose and clinical schedule.     

Untersuchungen über die transkristalline Spannungsrißkorrosion austenitischer Chrom-Nickel-Stähle in heißen Chloridlösungen

Investigations into the transcrystalline stress corrosion cracking of austenitic chrome-nickel steel in hot chloride solutions To obtain a further clarification of various details in respect of the transcrystalline stress corrosion cracking of austenitic Cr-Ni steels, tensile strength tests were carried out with X 5 CrNi 18 9 in hot, highly concentrated MgCl₂, solutions. Tests without extraneous currents showed that, depending on the test conditions, the relationship between stress and service life can be formally described by an exponential function. Down to stresses of 2 kg/mm², there was no discernible threshold below which stress corrosion cracking does not occur at all. By means of potentiostatic holding tests at different stresses, it was possible to plot a potential/tensile stress/service life diagram. The occurrence of stress corrosion cracking shows a distinct threshold on the side of negative potentials; on the side of positive potentials, however, the occurrence of stress corrosion cracking is increasingly accompanied by pit corrosion. Strain measurements carried out during the tests yielded, in a non-destructive way, a sufficiently exact criterion for the division of the total test period into incubation period and tearing period. The length of the incubation period depends on the tensile stress as well as on the specimen potential. As regards the tearing period it was found that the growth rate of the cracks is formally proportional to the stress at the bottom of the crack. The proportionality constant, in its turn, is a linear function of the test potential. By means of extrapolation, it is possible to deter-mine the minimum potential below which stress corrosion cracking can no longer occur. Electro-chemical measurements showed that, in the tested solutions, it is the hydrogen reduction which represents the vital catholic part-process. The tested material is in the state of passive stability; its rest potential in the non-stressed condition lies at the lower threshold of the pit corrosion range. Tensile stresses, or the deformations caused by them, have the effect of shifting the minimum potential for heterogeneous corrosion into the negative range.     

Environmental fate of pharmaceuticals in water/sediment systems

In recent years there has been growing interest on the occurrence and the fate of pharmaceuticals in the aquatic environment. Nevertheless, few data are available covering the fate of the pharmaceuticals in the water/sediment compartment. In this study, the environmental fate of 10 selected pharmaceuticals and pharmaceutical metabolites was investigated in water/sediment systems including both the analysis of water and sediment. The experiments covered the application of four 14C-labeled pharmaceuticals (diazepam, ibuprofen, iopromide, and paracetamol) for which radio-TLC analysis was used as well as six nonlabeled compounds (carbamazepine, clofibric acid, 10,11-dihydro-10,11-dihydroxycarbamazepine, 2-hydroxyibuprofen, ivermectin, and oxazepam), which were analyzed via LC-tandem MS. Ibuprofen, 2-hydroxyibuprofen, and paracetamol displayed a low persistence with DT50 values in the water/sediment system < or =20 d. The sediment played a key role in the elimination of paracetamol due to the rapid and extensive formation of bound residues. A moderate persistence was found for ivermectin and oxazepam with DT50 values of 15 and 54 d, respectively. Lopromide, for which no corresponding DT50 values could be calculated, also exhibited a moderate persistence and was transformed into at least four transformation products. For diazepam, carbamazepine, 10,11-dihydro-10,11-dihydroxycarbamazepine, and clofibric acid, system DT90 values of >365 d were found, which exhibit their high persistence in the water/sediment system. An elevated level of sorption onto the sediment was observed for ivermectin, diazepam, oxazepam, and carbamazepine. Respective Koc values calculated from the experimental data ranged from 1172 L x kg(-1) for ivermectin down to 83 L x kg(-1) for carbamazepine.