Impacts of compound properties and sediment characteristics on the sorption behaviour of pharmaceuticals in aquatic systems

Sorption is a key factor in determining the persistence, attenuation and bioavailability of sediment-associated contaminants. However, our understanding of the sorption behaviour of pharmaceuticals in sediments is poor. In this study, we investigated the sorption behaviour of a diverse set of pharmaceuticals in a range sediment types. Sorption affinity of pharmaceuticals for all sediments was found to increase in the order mefenamic acid <cimetidine <atenolol <amitriptyline <diltiazem. Comparison of the experimental observations with predictions from an existing model for estimating sorption revealed the model worked poorly for the study pharmaceuticals. Multiple linear regression analysis was therefore used to develop new models for estimating sorption of individual pharmaceuticals based on sediment properties. The analyses indicated that sorption is related to properties such as Log Dow of a compound in the sediment (lipophilicity corrected for the sediment pH), cation exchange capacity, clay%, organic carbon content and exchangeable Ca2+, although, with the exception of atenolol, robust relationships between sediment properties and sorption were not obtained. Overall, the results demonstrate how complex the processes are that drive the sorption of pharmaceuticals in sediments and highlight the need for generation of further experimental data and further model development work

Interactions Between Plastic, Microbial Biofilms and Gammarus pulex : An Initial Investigation

There is increasing evidence that microbial biofilms which form on the surface of marine plastics can increase plastics palatability, making it more attractive to organisms. The same information, however, does not exist for freshwater systems. This study observed the response of the freshwater amphipod Gammarus pulex when exposed to 3 cm-diameter discs of biofilm-covered plastic, both alone and when presented alongside its natural food. G. pulex did not fragment or consume the plastic materials, and the presence of colonised plastic in the immediate environment did not alter the amount of time organisms spent interacting with their natural food. This study provides baseline information for virgin and microbially colonised low-density polyethylene and polylactic acid film. Further studies, with other types of plastic possessing different physical properties and with different microbial biofilm compositions are now required to build further understanding of interactions between plastic, microbial biofilms, and freshwater shredding invertebrates

An in vitro method for determining the bioaccessibility of pharmaceuticals in wildlife

Wildlife can be exposed to human pharmaceuticals via prey that have accumulated the compounds from wastewater, surface water, sediment and soil. One factor affecting internal absorption of pharmaceuticals is bioaccessibility, the proportion of the compound that enters solution in the gastrointestinal tract. Currently, the bioaccessibility of most pharmaceuticals in prey remains unknown for most wildlife species. Here, we evaluate the potential of a two-compartment in vitro gastrointestinal tract model to compare the bioaccessibility of the antidepressant fluoxetine from invertebrate prey for birds and mammals. Samples of gizzard (or stomach) and intestinal phase digestive juices were obtained from the in vitro models along with the residual solid material. HPLC analysis revealed that the bioaccessibility of fluoxetine in the avian in vitro models (75.9% and 78.6%) was statistically significantly lower than in the mammalian models (88.2-89.6%) as a percentage of what was recovered; however there were no statistically or biologically significant inter-species difference in terms of the amount recovered per gram of 'food' inserted at the start of the simulation. Nevertheless, this in vitro model provides a useful method of comparing the bioaccessibility of pharmaceuticals in different prey for species with different gastrointestinal conditions. There may be merit for ecological risk assessments in further developing this in vitro approach to improve estimates of internal exposure for organics. This article is protected by copyright. All rights reserved

Evaluation and development of models for estimating the sorption behaviour of pharmaceuticals in soils

Sorption is one of the key process that affects the fate and mobility of pharmaceuticals in the soil environment. Several models have been developed for estimating the sorption of organic chemicals, including ionisable compounds, in soil. However, the applicability of these models to pharmaceuticals has not been extensively tested. In this study, we generated a high-quality dataset on the sorption of twenty-one pharmaceuticals in different soil types and used these data to evaluate existing models and to develop new improved models. Sorption coefficients (Kd) of the pharmaceuticals ranged from 0.2 to 1249.2 L/kg. Existing models were unable to adequately estimate the measured sorption data. Using the data, new models were developed, incorporating molecular and soil descriptors, that outperformed the published models when evaluated against external data sets. While there is a need for further evaluation of these new models against broader sorption datasets obtained at environmentally relevant concentrations, in the future they could be highly useful in supporting environmental risk assessment and prioritization efforts for pharmaceutical ingredients

Assessment of the Risks of Mixtures of Major Use Veterinary Antibiotics in European Surface Waters

Effects of single veterinary antibiotics on a range of aquatic organisms have been explored in many studies. In reality, surface waters will be exposed to mixtures of these substances. In this study, we present an approach for establishing risks of antibiotic mixtures to surface waters and illustrate this by assessing risks of mixtures of three major use antibiotics (trimethoprim, tylosin, and lincomycin) to algal and cyanobacterial species in European surface waters. Ecotoxicity tests were initially performed to assess the combined effects of the antibiotics to the cyanobacteria Anabaena flos-aquae. The results were used to evaluate two mixture prediction models: concentration addition (CA) and independent action (IA). The CA model performed best at predicting the toxicity of the mixture with the experimental 96 h EC50 for the antibiotic mixture being 0.248 μmol/L compared to the CA predicted EC50 of 0.21 μmol/L. The CA model was therefore used alongside predictions of exposure for different European scenarios and estimations of hazards obtained from species sensitivity distributions to estimate risks of mixtures of the three antibiotics. Risk quotients for the different scenarios ranged from 0.066 to 385 indicating that the combination of three substances could be causing adverse impacts on algal communities in European surface waters. This could have important implications for primary production and nutrient cycling. Tylosin contributed most to the risk followed by lincomycin and trimethoprim. While we have explored only three antibiotics, the combined experimental and modeling approach could readily be applied to the wider range of antibiotics that are in use

Are pharmaceutical residues in crops a threat to human health?

The application of biosolids, manure, and slurry onto agricultural soils and the growing use of treated wastewater in agriculture result in the introduction of human and veterinary pharmaceuticals to the environment. Once in the soil environment, pharmaceuticals may be taken up by crops, resulting in consequent human exposure to pharmaceutical residues. The potential side effects of pharmaceuticals administered in human medicine are widely documented; however, far less is known regarding the risks that arise from incidental dietary exposure. The aim of this study was to evaluate human exposure to pharmaceutical residues in crops and assess the associated risk to health for a range of pharmaceuticals frequently detected in soils. Estimated concentrations of carbamazepine, oxytetracycline, sulfamethoxazole, trimethoprim, and tetracycline in soil were used in conjunction with plant uptake and crop consumption data to estimate daily exposures to each compound. Exposure concentrations were compared to Acceptable Daily Intakes (ADIs) to determine the level of risk. Generally, exposure concentrations were lower than ADIs. The exceptions were carbamazepine, and trimethoprim and sulfamethoxazole under conservative, worst-case scenarios, where a potential risk to human health was predicted. Future research therefore needs to prioritize investigation into the health effects following exposure to these compounds from consumption of contaminated crops

FACTORS AFFECTING THE DISSIPATION OF PHARMACEUTICALS IN FRESHWATER SEDIMENTS

Degradation is one of the key processes governing the impact of pharmaceuticals in the aquatic environment. Most studies on the degradation of pharmaceuticals have focused on soil and sludge with fewer exploring persistence in aquatic sediments. Here we investigate the dissipation of six pharmaceuticals from different therapeutic classes in a range of sediment types. Dissipation of each pharmaceutical was found to follow first-order exponential decay. Half-lives in the sediments ranged from 9.5 d (atenolol) to 78.8 d (amitriptyline). Under sterile conditions, the persistence of pharmaceuticals was considerably longer. Stepwise multiple linear regression analysis was performed to explore the relationships between half-lives of the pharmaceuticals, sediment physicochemical properties and the sorption coefficients for the compounds. Sediment clay, silt and organic carbon content and microbial activity were the predominant factors related to the degradation rates of diltiazem, cimetidine and ranitidine. Regression analysis failed to highlight a key property which may be responsible for observed differences in the degradation of the other pharmaceuticals. The present study results suggest degradation rate of pharmaceuticals in sediments is determined by different factors and processes and does not exclusively depend on a single sediment parameter. This article is protected by copyright. All rights reserved

Fur : A non-invasive approach to monitor metal exposure in bats

This paper presents a novel assessment of the use of fur as a non-invasive proxy to biomonitor metal contamination in insectivorous bats. Concentrations of metals (cadmium, copper, lead and zinc) were measured using ICP-MS in tissues (kidneys, liver, stomach and stomach content, bones and fur) obtained from 193 Pipistrellus pipistrellus/pygmaeus bats. The bats were collected across a gradient of metal pollution in England and Wales. The utility of small samples of fur as an indicator of metal exposure from the environment was demonstrated with strong relationships obtained between the concentrations of non-essential metals in fur with concentrations in stomach content, kidneys, liver and bones. Stronger relationships were observed for non-essential metals than for essential metals. Fur analyses might therefore be a useful non-invasive proxy for understanding recent, as well as long term and chronic, metal exposure of live animals. The use of fur may provide valuable information on the level of endogenous metal exposure and contamination of bat populations and communities

Evaluation of a Novel Approach for Reducing Emissions of Pharmaceuticals to the Environment

Increased interest over the levels of pharmaceuticals detected in the environment has led to the need for new approaches to manage their emissions. Inappropriate disposal of unused and waste medicines and release from manufacturing plants are believed to be important pathways for pharmaceuticals entering the environment. In situ treatment technologies, which can be used on-site in pharmacies, hospitals, clinics, and at manufacturing plants, might provide a solution. In this study we explored the use of Pyropure, a microscale combined pyrolysis and gasification in situ treatment system for destroying pharmaceutical wastes. This involved selecting 17 pharmaceuticals, including 14 of the most thermally stable compounds currently in use and three of high environmental concern to determine the technology’s success in waste destruction. Treatment simulation studies were done on three different waste types and liquid, solid, and gaseous emissions from the process were analyzed for parent pharmaceutical and known active transformation products. Gaseous emissions were also analyzed for NOx, particulates, dioxins, furans, and metals. Results suggest that Pyropure is an effective treatment process for pharmaceutical wastes: over 99 % of each study pharmaceutical was destroyed by the system without known active transformation products being formed during the treatment process. Emissions of the other gaseous air pollutants were within acceptable levels. Future uptake of the system, or similar in situ treatment approaches, by clinics, pharmacists, and manufacturers could help to reduce the levels of pharmaceuticals in the environment and reduce the economic and environmental costs of current waste management practices

ARE EXPOSURE PREDICTIONS, USED FOR THE PRIORITISATION OF PHARMACEUTICALS IN THE ENVIRONMENT, FIT FOR PURPOSE?

Prioritisation methodologies are often used for identifying those pharmaceuticals that pose the greatest risk to the natural environment and to focus laboratory testing or environmental monitoring towards pharmaceuticals of greatest concern. Risk-based prioritisation approaches, employing models to derive exposure concentrations, are commonly used but the reliability of these models is unclear. The present study evaluated the accuracy of exposure models commonly used for pharmaceutical prioritisation. Targeted monitoring was conducted for 95 pharmaceuticals in the Rivers Foss and Ouse in the City of York, UK. Predicted environmental concentration (PEC) ranges were estimated based on localised prescription, hydrological data, reported metabolism and wastewater treatment plant (WwTP) removal rates, and were compared to measured environmental concentrations (MECs). For the River Foss, PECs, obtained using highest metabolism and lowest WwTP removal, were similar to MECs. In contrast, this trend was not observed for the River Ouse, possibly due to pharmaceutical inputs beyond our modelling. Pharmaceuticals were ranked by risk based on either MECs or PECs. With two exceptions (dextromethorphan and diphenhydramine), risk ranking based on both MECs and PECs produced similar results in the River Foss. Overall, these findings indicate that PECs may well be appropriate for prioritisation of pharmaceuticals in the environment when robust and local data on the system of interest are available and reflective of most source inputs to the system. This article is protected by copyright. All rights reserved