Neglected sources of pharmaceuticals in river water--footprints of a Reggae festival.

Wastewater treatment plants (WWTPs) are commonly considered as the main source of pharmaceuticals in surface waters. Here, however, we show that an open-air festival, attracting approximately 10,000 visitors per year at the shores of River Fyris upstream of Uppsala WWTP, can temporarily result in a higher pharmaceutical input into the river water than the WWTP. Studying the influence of Uppsala Reggae festival on the occurrence of ten commonly used acidic and basic pharmaceuticals upstream, in the effluent, and downstream of the Uppsala WWTP, we found that occasional heavy rainfalls during the festival in 2008 severely increased the mass flows of all pharmaceuticals at the WWTP upstream site. Also, strong increases in ammonium (210-fold), nitrate (21-fold), and total nitrogen (21-fold) mass flows were observed. The pharmaceutical mass flows at the upstream site were up to 3.4 times higher than those observed in the WWTP effluent. In contrast, in 2009, the festival was not accompanied with rainfalls and no major additional input of pharmaceuticals and nitrogen was observed. The findings of this study give new insights into risk assessments and are relevant for monitoring programmes.

Photochemical transformation of the thyroid hormone levothyroxine in aqueous solution.

PURPOSE: The direct aqueous photolysis of the thyroid hormone levothyroxine (T(4)) has been studied. METHODS AND RESULT: One of the major photoproducts, i.e., 4-[4-(2-amino-2-carboxy-ethyl)-2,6-diiodo-phenoxy]-penta-2,4-dienoic acid (P1), was isolated by liquid chromatography and structurally assigned by mass spectrometric (MS) and nuclear magnetic resonance spectroscopic methods. The identity of a second major product, i.e., 3,5-diiodo-L: -thyrosine (P3), was confirmed through access to a commercially available standard. Furthermore, the structures of three additional transformation products are proposed on the basis of data obtained by high-resolution MS analyses. UV absorption spectra were determined for T(4) and the two photoproducts P1 and P3. Disappearance quantum yields were calculated for T(4) (ϕ = 0.014 at pH 12) and P3 (ϕ = 0.024 at pH 12 and ϕ = 0.010 at pH 8.5), whereas the compound P1 was found to be stable under the studied conditions (T(1/2) = 600 min). CONCLUSION: The results indicate that solar UV light may have a significant impact on the fate of T(4) in the aquatic environment.

Analysis of thyroid hormones in raw and treated waste water.

An analytical method for the quantification of thyroid hormones (3,5,3',5'-tetraiodo-L-thyronine, 3,3',5-triiodo-L-thyronine, 3,3',5'-triiodothyronine, 3,5-diiodothyronine, 3,3'-diiodothyronine) in different water matrices has been developed. The method, consisting of solid phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS), was validated for tap and surface water as well as raw and treated waste water. The limits of quantifications (LOQs) were lowest in tap water, where they ranged from 1.1 to 13.3 ng L(-1), and highest in raw wastewater (10.5-84.9 ng L(-1)). Of the target analytes 3,5,3',5'-tetraiodo-L-thyronine (T(4)) could be quantified in the influent and effluent of a waste water treatment plant (WWTP) in Finland. The study showed that despite a relatively high removal rate during treatment (66%), part of the incoming T(4) will reach the aquatic environment and, due to the high endocrine activity of this compound, further studies are needed in order to assess its environmental fate and impact on natural ecosystems.

Seasonal variations in the occurrence and fate of basic and neutral pharmaceuticals in a Swedish river-lake system.

The seasonal variations in the occurrence of carbamazepine, atenolol, metoprolol, sotalol, and acebutolol were studied at seven sites along River Fyris from December 2007 to December 2008. Samples were collected from the effluent of a waste water treatment plant (WWTP), at one upstream site, and five downstream sites of the WWTP. During one occasion in May 2008, water samples were collected at different locations and depths in the recipient lake. All analytes except of acebutolol were present in both the river and the lake at quantifiable amounts at all sampling occasions. Carbamazepine was found in similar concentrations (about 90 ng L(-1)) at all sampling sites and all studied depths (0.5-40 m) in the lake, indicating high environmental persistence of this compound. A clear seasonal pattern was observed for the natural attenuation of the beta-blockers in the river, with the highest attenuation occurring in summer and the lowest in winter. The loss of beta-blockers on a distance of 1320 m reached up to 75% during summer time but was insignificant during winter. The seasonal variations in the loss followed the seasonal variations in water temperature and chlorophyll a mass flow suggesting that biotransformation and adsorption are the main processes responsible for the loss of the studied pharmaceuticals in River Fyris downstream the WWTP.

A photochemical study of diclofenac and its major transformation products.

The photolytic transformation of 2-(2-(2,6-dichlorophenylamino)phenyl)acetic acid (diclofenac) and its transformation products (TPs) (8-chloro-9H-carbazol-1-yl) acetic acid (Cz1), 2-(2-chloro-phenylamino)-benzaldehyde (Ald) and (1,4-dioxo-4,9-dihydro-1H-carbazol-8-yl) acetic acid (Cz4) in aqueous solutions have been studied. The previously unreported TP (Cz4) was isolated by LC and completely characterized by NMR and MS. UV-absorption spectra of diclofenac and three of its TPs were determined and used to calculate disappearance quantum yields. The dominating transformation pathway of diclofenac occurs via initial formation of Cz1 and proceeds to form mainly (Cz4) over 200 min of UV-irradiation. A second minor transformation pathway, which yields Ald as the sole product, was observed only under deaerated conditions.

Winter accumulation of acidic pharmaceuticals in a Swedish river.

PURPOSE: In this study, seasonal variations in the concentration profile of four analgesics and one lipid regulator were monitored on their way from a wastewater treatment plant (WWTP) effluent, along a river, and into a lake. METHODS: From December 2007 to December 2008, water samples were collected monthly (n=12) from an upstream point, the effluent, four downstream points of the WWTP, and at the point where the river merges with the lake, and the concentrations of ibuprofen, naproxen, bezafibrate, diclofenac, and ketoprofen were determined. The analytical methodology involved solid-phase extraction of the target compounds from water samples followed by liquid chromatography coupled with tandem mass spectrometry for compound separation and detection. RESULTS: The studied pharmaceuticals were found in the effluent at concentrations ranging from 31 to 1,852 ng l(-1) depending on the season. In the river and lake, the concentrations were much lower (6-400 ng l(-1)) mainly due to dilution but also to a season-dependent contribution from natural transformation processes. The mean mass flow of all analgesics was highest during winter while the highest mean mass flow of the lipid regulator bezafibrate was observed in spring. CONCLUSIONS: The WWTP is the main source of the target compounds in the aquatic environment. The observed winter accumulation signifies the importance of natural transformation processes, which can only be estimated based on mass flow data, on the fate of pharmaceuticals in the environment.