Environmental risk assessment and bioaccumulation of pharmaceuticals in a large urbanized estuary.

We screened for the presence of 66 different pharmaceutical residues in surface waters and in multiple invertebrate and fish species of the Tejo estuary to produce an environmental risk assessment of individual pharmaceuticals and their mixtures, as well as evaluate the bioaccumulation of pharmaceuticals in one of Europe's largest estuarine systems. Sixteen pharmaceutical residues, from seven therapeutic classes, were detected in estuarine waters, with environmental mixture concentrations ranging from 42 to 1762 ng/L. Environmental risk assessment via the determination of risk quotients, demonstrated high ecological risk for the antibiotic amoxicillin and angiotensin II receptor blockers irbesartan and losartan. Moderate risk was estimated for antidepressants, antiepileptics, anxiolytics and beta-blockers, but the risk quotient of the accumulated mixture of compounds was over 380-fold higher than the no risk threshold, driven by antibiotics and angiotensin II receptor blockers. In biota, higher risk therapeutic groups were found in higher concentrations, with nine pharmaceutical residues detected, including six antibiotics and two neuroactive compounds, and maximum tissue concentrations up to 250 µg/kg. Bioaccumulation was species- and compound-specific, with only two compounds found simultaneously in water and biota, likely a result of the complex dynamics and fate of pharmaceuticals in estuarine waters. Nonetheless, higher detection frequencies were observed in species living directly on or just above the substrate (i.e. benthic and demersal species), underpinning the importance of habitat use, as well the potential role of sediment and diet based routes for pharmaceutical uptake. Ultimately, results support urgent action on managing the impact of pharmaceuticals in coastal environments, striving for improved monitoring schemes tailored to the dynamic nature and ecological diversity of estuaries and coastal ecosystems.

Depressed, hypertense and sore: Long-term effects of fluoxetine, propranolol and diclofenac exposure in a top predator fish.

Pharmaceutical compounds are continuously released into the aquatic environment, resulting in their ubiquitous presence in many estuarine and coastal systems. As pharmaceuticals are designed to produce effects at very low concentrations and target specific evolutionary conserved pathways, there are growing concerns over their potential deleterious effects to the environment and specifically to aquatic organisms, namely in early life-stages. In this context, the long-term effects of exposure of juvenile meagre Argyrosomus regius to three different pharmaceuticals were investigated. Fish were exposed to environmental concentrations of one of three major used pharmaceuticals: the antidepressant fluoxetine (0.3 and 3 µg/L for 15 days), the anti-hypertensive propranolol and the non-steroidal anti-inflammatory agent diclofenac (0.3 and 15 µg/L for 30 days). Pharmaceuticals bioconcentration in fish muscle was examined, along with biomarkers in different tissues related with antioxidant and biotransformation responses (catalase, superoxide dismutase, ethoxyresorufin-O-deethylase and glutathione S-transferase), energetic metabolism (lactate dehydrogenase, isocitrate dehydrogenase and electron transport system activities), neurotransmission (acetylcholinesterase activity) and oxidative damage (DNA damage and lipid peroxidation levels). Overall, each pharmaceutical had different potential for bioconcentration in the muscle (FLX > PROP > DCF) and induced different biological responses: fluoxetine was the most toxic compound to juvenile meagre, affecting fish growth, triggering antioxidant defense responses, inhibiting detoxification mechanisms and increasing lipid peroxidation and DNA damage in the liver; propranolol exposure increased DNA damage and decreased aerobic metabolism in fish muscle; and diclofenac showed no potential to bioconcentrate, yet it affected fish metabolism by increasing cellular energy consumption in the muscle and consequently reducing fish net energy budget. The diverse response patterns evidence the need for future research focused on pharmaceuticals with different modes of action and their exposure effects on organismal physiological mechanisms and homeostatic status. Ultimately, the combination of sub-individual and individual responses is key for ecologically relevant assessments of pharmaceutical toxicity.

Fate and effects of two pesticide formulations in the invertebrate Folsomia candida using a natural agricultural soil.

Degradation rates of two widely used pesticides were assessed, and acute and chronic effects on a standard invertebrate species investigated. An herbicide (Montana®) and fungicide (Bravo500®) formulations were investigated and results were compared to the isolated active substances of each formulation (glyphosate and chlorothalonil, respectively). Tests were performed using the invertebrate Folsomia candida as test species and an agricultural natural soil. Degradation rate tests were determined under aerobic conditions at 20 ±â€¯2 °C, using an ecologically relevant concentration of 5 mg (a.i.) kg-1 of soil for both chemicals. Results demonstrated degradation half-lives (DT50) of 2.2 days for Montana® and 2.8 days when pure glyphosate was tested. Values of 1.1 and 2.9 days were registered for Bravo500® and its active substance chlorothalonil, respectively. There were no effects on survival for the tested concentrations of both forms of the herbicide (up to 17.3 mg kg-1). However, reproduction was affected, but only by the herbicide formulation, with an estimated EC50 value of 4.63 mg (a.i.) kg-1. Effects were most unlikely related to glyphosate. For chlorothalonil, both tested forms affected survival and reproduction. The estimated LC50 values were 117 mg (a.i.) kg-1 and 73.5 mg (a.i.) kg-1, and the EC50 41.3 mg (a.i.) kg-1 and 14.9 mg kg-1 for the formulation and the active ingredient, respectively. The effects of the active ingredient were significantly stronger, indicating the major influence of the active substance in the effects caused also by the formulation. Overall results demonstrate the importance of evaluating the effects of the formulated chemicals, as they are applied in the field, and not only their isolated active ingredients.