Comparative aquatic toxicity of propranolol and its photodegraded mixtures: algae and rotifer screening.

Transformation products of pharmaceuticals formed by human metabolism within sewage treatment plant or receiving waters are predicted, in most cases, to be less toxic than the parent compound to common aquatic species. However, there is little available data to demonstrate whether this is generally the case. In the present study, a framework was developed to guide testing of transformation products using phototransformation of the beta-blocker propranolol to test the hypothesis for this particular transformation route. Phototransformation is an important depletion mechanism of some pharmaceuticals in surface waters with fast reaction rate constants at environmentally relevant conditions. Samples of propranolol in deionized water (DIW) and river water (RW) were exposed to a solar simulator (lambda: 295-800 nm) and comparative toxicity of propranolol and its degraded mixtures measured using algal (Pseudokirchneriella subcapitata) and rotifer (Brachionus calyciflorus) screening tests. Results suggested a reduction of toxicity in photodegraded mixtures compared to the parent active pharmaceutical ingredient in all samples tested. Chemical analysis of effect test solutions supported the hypothesis that propranolol was transformed into compounds that appear to be less toxic to the organisms tested under the study conditions. Although the reactions were much faster in RW than in DIW, profiles of transformation products were similar in both matrices at two starting concentrations (1 and 10 mg/L). Results for propranolol implied that the reduction of toxicity using algal and rotifer screening tests was probably due to the production of more hydrophilic and more polar transformation products. Such results will provide useful insights into the environmental risk assessment of pharmaceuticals by taking into account their transformation products.

Photo-induced environmental depletion processes of beta-blockers in river waters.

In order to improve the understanding of the fate and behaviour of pharmaceuticals in the environment there is a need to investigate in-stream depletion mechanisms, e.g. phototransformation of active pharmaceutical ingredients (APIs) in natural surface waters. In this study, abiotic and biotic degradation of selected beta-blockers was measured simultaneously in non-sterilised and sterilised river waters and deionised water (DIW) under simulated sunlight (lambda: 295-800 nm) and dark conditions, and at environmentally relevant concentrations, i.e.

Kinetics and degradation products for direct photolysis of beta-blockers in water.

Related to improving persistence assessment of active pharmaceutical ingredients (APIs), direct aqueous photolysis of beta-blockers: propranolol (hydrochloride salt), atenolol, and metoprolol (succinate salt) were investigated by exposing the samples (0.0003-10 mg L(-1)) to a solar irradiator (filtered xenon lamp: 290-800 nm) at 20-26 degrees C. Results suggested that direct photolysis in optically dilute solutions followed pseudo first-order kinetics. The measured half-lives of propranolol, atenolol, and metoprolol were approximately 16, 350, and 630 h, respectively. These were 3-5 orders of magnitude slower than the estimated minimum half-lives. The measured half-lives were related to day light surface conditions by comparing the light intensity of the lamp and the sun at different latitudes and seasons. Major direct photolysis products were identified from propranolol that led to a proposed reaction pathway, involving ring oxidation, rearrangement, and deoxygenation. Electron paramagnetic resonance (EPR) spectroscopy results confirmed that at least one carbon-based radical intermediate was formed during the direct photolysis of propranolol in aqueous solutions. The overall results demonstrated that with fast direct photolysis half-lives, propranolol is unlikely to be persistent in natural waters. Further work is needed to investigate indirect photolysis of atenolol and metoprolol in surface waters in order to understand the overall persistence of these APIs in the environment.

Modeling the impact of direct phototransformation on predicted environmental concentrations (PECs) of propranolol hydrochloride in UK and US rivers.

There is currently uncertainty on the persistence of active pharmaceutical ingredients (APIs) and on their depletion mechanisms in natural surface waters such as rivers, and hence predictions of their fate are often poor. In this study, a beta-adrenergic receptor, propranolol hydrochloride, was selected as a model API to explore the relative significance of direct phototransformation as a potential removal process of hydrophilic APIs in rivers. Phototransformation kinetics of propranolol was measured under simulated solar irradiation in the laboratory, which were then converted to the kinetics applicable in UK and US rivers. The effects of light intensity, light penetration, river size and flow were examined. The extrapolated phototransformation half-lives were applied in the river catchment models of GREAT-ER and PhATE. Results demonstrated that direct phototransformation significantly reduced the predicted environmental concentrations of propranolol in the water phase. Predicted reductions of mean concentrations in the River Aire (UK) were 27% in summer and 3% in winter; and for the US rivers simulated, reductions were 28-68% in summer and 11-41% in winter. The highest reductions were predicted for long rivers with low turbidity and low flow conditions.

Using experimental and forest soils to investigate the uptake of polycyclic aromatic hydrocarbons (PAHs) along an urban-rural gradient.

Spatial and temporal variation in the atmospheric deposition of PAHs to soil was examined by deploying experimental soils for approximately 165 days and conducting a survey of forest soils at several sites along an urban-rural transect extending from downtown Toronto to approximately 80 km north of the city. PAH concentrations decreased with distance from the urban centre-by a factor of 2 and 60 for the experimental and forest soils respectively. The large gradient for the forest soils is generally consistent with air concentrations of PAHs measured using high volume and passive air samplers. The smaller gradient for the experimental soils was due to kinetic limitations of PAH accumulation and the relatively short deployment period of approximately 165 days. Mean effective deposition velocities (gas+particle) for the full range of PAHs for the experimental soils at the urban, suburban, and the rural sites were 2, 31 and 26 cm s(-1), respectively. These were incorporated into a dynamic model that was used to assess the long-term uptake of PAHs in forest soils. Model results indicate that lower molecular weight PAHs may achieve equilibrium and become involved in soil-air exchange whereas higher molecular weight PAHs are accumulated for much longer time periods.

Characterization of polar organic compounds in the organic film on indoor and outdoor glass windows.

Organic films on an impervious surface (window glass) were sampled at paired indoor-outdoor sites in July 2000 and characterized for their paraffinic and polar organic compositions along an urban-rural transect. Four classes of polar compounds (C11-C31 aliphatic monocarboxylic, C6-C14 dicarboxylic, nine aromatic polycarboxylic, and five terpenoid acids) constituted between 81 and 95% (w/w) of the total organic fraction analyzed comprising n-alkanes (C10-C36), 46 PAH, 97 PCBs, and 18 OC pesticides. Concentrations of the polar compounds plus their precursors, n-alkanes, ranged from 8 to 124 microg m(-20 and were dominated by monocarboxylic acids (67-89%, w/w). On outdoor windows, n-alkanes, aromatic acids, and terpenoid acids decreased in concentration along the urban-rural transect. The carbon preference index values and the interpretations of individual compounds indicate that the main sources of n-alkanes were plant waxes followed by petrogenic sources; monocarboxylic and dicarboxylic acids were from plant waxes and animal fats. Results of principal component analysis showed closer correspondence between outdoor and indoor signatures than among locations. In outdoor films, these compounds are suggested to play an important role in mediating chemical fate in urban areas by air-film exchange and facilitating "wash-off" due to their surfactant-like properties. In indoor films, these compounds provide a medium for the accumulation of more toxic compounds.

Accumulation of metals, trace elements and semi-volatile organic compounds on exterior window surfaces in Baltimore.

Organic films have been found to develop on window surfaces [Diamond et al., Environmental Science and Technology 34 (2000a) 2900]. The film contains organic compounds that are in dynamic equilibrium with the gas-phase in air, and organic and inorganic compounds and elements associated with deposited air particles. In this study, the exterior surfaces of windows were sampled in downtown and suburban Baltimore, Maryland. Higher concentrations of PCBs, PAH, metals and trace elements were found at downtown than a suburban site. PCBs in the films at downtown sites were dominated by penta and hexa homologue groups and PAH signatures resembled that of vehicle emissions. Twenty-six metals and trace elements were separated into two groups according to their enrichment factors (EF). Ag, Hg, Se, Sb and Zn had EF > 100, suggesting anthropogenic sources of these metals in the films; whereas Fe, Ca, Co, Cr and others had EF <10, suggesting a crustal origin. An unusual profile dominated by deca- and nona- PCBs and relatively higher concentrations of Ag, Hg and Zn may be attributable to emissions from a medical waste incinerator. Dry deposition fluxes of selected metals on windows were 1.4-94 times higher on windows with than without films, indicating that the film increases the dry deposition of particles and their associated chemicals. This implies that film development, which is associated with elevated VOC and SOC emissions to urban air, will increase film development that will, in turn, increase the accumulation of other atmospherically deposited constituents such as metals.