Selected widely prescribed pharmaceuticals: toxicity of the drugs and the products of their photochemical degradation to aquatic organisms.

Cholesterol-lowering drugs, antidiabetics, antiarrhythmics, antidepressants, and antibiotics belong to the most prescribed drugs worldwide. Because of the manufacture, excretion, and improper disposal of leftover drugs, the drugs enter waste waters and, subsequently, surface waters. They have been detected in surface waters all over the world, from concentrations of ng/l to concentrations several orders of magnitude higher. Since pharmaceuticals are designed to be both biologically and chemically stable, photochemical degradation by sun radiation represents a way of transformation in the natural environment. This review provides a survey of how selected drugs of the above-mentioned classes affect aquatic organisms of different trophic level. The emphasis is on the harmful effects of phototransformation products, an area of scientific investigation that has only attracted attention in the past few years, revealing the surprising fact that products of photochemical degradation might be even more toxic to aquatic organisms than the parent drugs.

Cigarette butts as a source of phenolic compounds for the environment.

Cigarette butts (CBs) are small residues with mixed composition. Produced in large amounts, their accumulation in the environment has become alarming. It is possible to classify more than 7000 chemical components generated either in the burning process or when distilled from the tobacco. The aim of this work was to describe the rate of release of phenolic compounds from CBs, to determine the content of these compounds in freshly smoked CBs and to monitor the release of phenols from CBs into fresh natural waters. The kinetics of release of selected phenolic compounds (hydroquinone, resorcinol, pyrocatechol, phenol, guaiacol, o-cresol, m-cresol, p-cresol) into water was monitored for 48 h. More than 90% of the content was extracted within 10 h for all analytes. The phenolic content was determined in the CBs of five different brands. The total content of phenols determined for each sample of freshly smoked CB was 215-861 µg/CB. For all CBs analysed, phenol, pyrocatechol and hydroquinone were the most abundant analytes, accounting for up to 75% of the content of all phenols determined. Phenol was the most abundant analyte (64.6-267.8 µg/CB) in all analysed samples. The content of pyrocatechol, the second most abundant analyte, was 45.6-221.2 µg/CB and the third most abundant analyte was hydroquinone (41.71-157.5 µg/CB). Monitoring the release of phenols from CBs into fresh natural waters (river, stream, pond) under steady and slight moving conditions showed that the kinetics of release is not influenced by the type of water. On the contrary, the process of decomposition of the released compounds is influenced by the type of water. The maximum concentrations of individual phenols in CBs extracts were comparable to those determined via laboratory extraction, thus indicating that within 72 h, most of the phenolic compounds are released from CBs into natural water. This research provides missing information on the phenolic content in CBs and the rate of release into water. It thus complements previously published information on CBs as a source of environmental contamination.

Photochemical degradation of triazine herbicides - comparison of homogeneous and heterogeneous photocatalysis.

Photochemical degradation of atrazine under different conditions was studied and compared, namely degradation via photocatalysis on TiO2, UV C photolysis, and homogeneous photocatalysis in the presence of added ferric ions. The reaction rate constants in heterogeneous photocatalytic reactions on TiO2 and of photolytic degradation by means of UV C light are similar, 0.018 min(-1) and 0.020 min(-1), respectively. The reaction rate constants in homogeneous photocatalytic reactions with Fe(III) added depend strongly on the Fe(III) concentration, 0.0017 min(-1) for 1.6 × 10(-6) mol l(-1) Fe(III) to 0.105 min(-1) for 3.3 × 10(-4) mol l(-1) Fe(III). In all types of reactions, dechlorination was observed; in homogeneous photocatalytic reactions and in UV C (250-300 nm) photolysis, dechlorination proceeds with a 1 : 1 stoichiometry to atrazine degradation, in photocatalytic reactions on TiO2, dechlorination measured as chloride ion release reaches only 1/5 of the substrate degradation. In photocatalytic reactions on TiO2, mineralisation of 40% carbon was observed.

Photodegradation of fluoroquinolones in aqueous solution under light conditions relevant to surface waters, toxicity assessment of photoproduct mixtures.

Photochemical degradation of fluoroquinolones ciprofloxacin, enrofloxacin and norfloxacin in aqueous solution under light conditions relevant to surface waters at neutral and alkaline pH was found to proceed readily with half-lives between 0.9 and 2.7 min. The products of photochemical degradation identified by HPLC-MS included defluorinated, hydroxylated, and decarboxylated structures as well as structures with opened cyclic structures. For all of the studied substances, the reaction pathways were influenced significantly by the pH of the reaction system, with more products formed at alkaline pH than at neutral pH: the ratios of products in neutral and alkaline pH were 16/26, 9/19, 15/23 for ciprofloxacin, enrofloxacin, and norfloxacin, respectively. The structures of photoproducts and pathways of photochemical degradation are proposed. The antibacterial activities of photoproduct mixtures tested on E. coli and S. epidermidis were significantly higher in comparison to parental antibiotics in the case of both ciprofloxacin and enrofloxacin with p-values less than 0.0001 in most cases. The effect of the photoproducts was shown to be dependent on the pH value of the original antibiotic solutions before photodegradation: for ciprofloxacin, antibacterial activity against E. coli was more notably pronounced with regard to neutral pH photoproducts, while a less significant, or in one case not significant, effect of pH was observed against S. epidermidis; for norfloxacin, antibacterial activity against both E. coli and S. epidermidis was especially high with regard to alkaline pH photoproducts.

Toxicity assessment of verapamil and its photodegradation products.

Pathways of photochemical degradation of a cardiovascular drug verapamil under conditions relevant to natural waters and the toxicity of the photoproducts to Daphnia magna were investigated. Photodegradation was shown to proceed via photocatalysed mechanism. Two main photodegradation pathways were recognised: the first leading to hydroxylation at the methylamino position followed by splitting of verapamil molecule into two fragments, and the second providing the main active metabolite of verapamil, norverapamil, and a series of norverapamil isomers, followed again by their splitting at the amino group position. Twenty-two products of photodegradation were identified. Toxicity assays in sublethal concentrations of the parental drug, of the photoproduct mixture, and of norverapamil revealed no direct negative response in Daphnia magna to verapamil. On the other hand, photochemical products significantly lowered the number of juveniles, number of clutches, and body size of Daphnia. The exposition of Daphnia to norverapamil showed the same but even more pronounced effects than its exposition to the mixture of photoproducts, which leads to the conclusion that norverapamil is mainly responsible for the toxicity of photoproduct mixture and represents a noteworthy threat to aquatic invertebrates.

Toxicity of atrazine and the products of its homogeneous photocatalytic degradation on the aquatic organisms Lemna minor and Daphnia magna.

Usage of atrazine, a widely used herbicide, is now banned in many countries. Although forbidden to use, significant concentration of this herbicide is still present in the environment. The study focused not only on the toxicity of atrazine itself but also on products of homogeneous photocatalytic degradation. Such degradation was very fast in given conditions (sufficient amount of Fe(III) in the reaction system)-more than 95% of the initial amount of atrazine was eliminated after 30 min of irradiation. The toxicity of atrazine and its photodegradation products were examined on the aquatic plant Lemna minor and microcrustacean Daphnia magna in both acute and chronic tests. While the growth inhibition assay of atrazine for Lemna minor revealed EC50 value of 128.4 µg dm-3, the herbicide did not affect Daphnia in the acute toxicity assay. A degradation product, desethyl-atrazine, has been demonstrated to have a pronounced negative effect on the plant growth. Both atrazine and desethyl-atrazine affect negatively the number of juveniles and number of clutches of Daphnia magna in the chronic toxicity assay. Photocatalytic degradation lowers the negative effect of atrazine in Daphnia magna while photodegradation products still negatively affect Lemna growth.

Degradation of Verapamil hydrochloride in water by gliding arc discharge.

This study investigated the influence of gliding arc plasma discharge on the degradation of Verapamil hydrochloride in water. The plasma discharge was characterized by means of optical emission spectroscopy. Spectra of various atomic and molecular species were observed. Aqueous solution of Verapamil hydrochloride was exposed to gliding arc discharge operated in continuous discharge at atmospheric pressure and room temperature. The identification of Verapamil, the degradation mechanisms of Verapamil and its transformation products were performed using liquid chromatography - mass spectrometry (HPLC-MS). Experimental results indicate that the atmospheric pressure gliding arc plasma treatment has noticeable effects on Verapamil with satisfactory degradation efficiency. Plausible mechanisms of the degradation were discussed.

Photochemical production of ionic and particulate aluminum and iron in lakes.

Photochemical liberation of allochthonous organically bound aluminum (Al) and iron (Fe) and in-lake hydroxide precipitation are important sources of these metals to lake sediments. Mass budgets of ionic Al and Fe (Ali, Fei), organically bound Al and Fe (Alo, Feo), and particulate Al and Fe (Alp, Fep) were measured for two western Czech Republic forest lakes (Plesne and Certovo) in the 2000-2003 hydrological years. The lakes were net sinks of Ali, Alo, and Feo and net sources of Alp and Fep. The average Alo and Feo inputs from terrestrial sources (66-110 and 12-17 mmol m(-2) yr(-1), respectively, on a lake area basis) were reduced 45% and 25% in the lakes. Mass budgets of dissolved organic carbon, particulate organic C, and Al species indicated that only a minor part of the observed in-lake retention of Alo could be explained by coagulation and sedimentation of organic matter, or from Ali hydrolysis and formation of Alp. Laboratory experiments with a short-time irradiation (approximately 300 nm, approximately 800 W m(-2)) of water from inlets to Plesne Lake showed the importance of photochemical processes in the liberation of Al and Fe from Alo and Feo. After 12 h of irradiation, Alo and Feo concentrations decreased 54 +/- 6% and 70 +/- 16%, respectively, compared to those of the dark controls. The photoliberated Alo and Feo increased the Ali and Fei concentrations reciprocally, on a 1:1 mass basis. The subsequent hydrolysis of Ali and Fe1 in lakes forms insoluble hydroxides, increasing the sediment concentrations of Al and Fe.