Investigation of pharmaceutical residues and polybrominated diphenyl ethers in selected river estuaries and canal in Eastern Cape Province, South Africa

The increasing global pollution by contaminants of emerging concern due to industrialization, development, and improper handling of industrial and domestic waste is alarming. Some of these emerging contaminants are endocrine disruptors and persistent organic pollutants. Two groups of compounds (pharmaceuticals and polybrominated diphenyl ethers (PBDEs)) were considered for this study. Pharmaceuticals are drugs which we take to cure and nourish human and animal bodies, ranging from antibiotics, stimulants, psychiatric, to hormonal recipes among others. They are potentially toxic and comprise chemicals or active ingredients capable of disrupting hormones. They have been related to human and aquatic organisms' ecological risks, such as feminization and masculinization of fish, cancer, and disruption of the immune system. In recent times, pharmaceuticals are being tested in the Rivers of South Africa. PBDEs are human influential chemicals usually incorporated into products such as flame retardants, which can travel over a long distance. They are hydrophobic, lipophilic, environmentally persistent, and easily absorbed by aquatic organisms. About 209 congeners exist, and BDE- 17, 47, 66, 100, 153, 154, and 183 are frequently detected in the environment. The higher brominated congeners can debrominate to more toxic and lower congeners. Though they have low acute toxicity, their effect of interfering with the thyroid gland is long-term. They pose a risk such as immunological, neurological, carcinogenicity, and reproductive disruption. Water and sediment samples considered for investigation were collected from five different sites (Buffalo River Estuary, Sundays River Estuary, Swartkops River Estuary, Nahoon River Estuary, and Markman Canal stormwater). These sites are located in the two major cities hosting the two major Ports (East London and Port Elizabeth) in the Eastern Cape Province of South Africa. Five sampling points were chosen for the collection of both water and sediment samples across three seasons that span from August to December in each of the mentioned sites. Nahoon River Estuary that was not sampled in winter seasons due to logistics and the global pandemic of year 2020; sediment sample was not collected at point NH5 for the spring season because of inaccessibility and topography of the sampling point. Ultrasonic extraction was utilized for sediment samples while SPE method with C-18 cartridges, was used to extract pharmaceuticals in water samples and for the purification of sediment extracts. A chromatographic column was employed for sediment purification. Analytes considered in this study were carbamazepine, caffeine, trimethoprim, sulfamethoxazole, and testosterone. Nahoon River Estuary and Markman canal were considered for investigation of water and sediments for PBDEs. The samples were processed for analysis immediately on arrival to the laboratory after being stored in an ice chest at 4 oC. Physicochemical properties of water samples were taken on site. The temperature ranges from 15.5-24.5 oC for Markman and 24.5- 26.6 oC. Nahoon River Estuary. There was a correlation among the congeners except for BDE-153, which do not correlate with BDE- 17, 47, and 183 in Markman. However, BDE- 153 correlated with BDE-66 in Markman. The Ʃ5PBDE for water and Ʃ6PBDE sediment for all seasons were BDL – 1357 ng/L and BDL – 408.14 ng/g, respectively. The PBDEs mean concentrations in Nahoon water samples ranges from BDL-247 ng/L (spring). The dominant congeners in Nahoon Estuary and Markman Canal samples were BDE- 17 and BDE – 66. The temperature and pH of Swartkops River Estuary range from 16.66 – 25.15 oC, and 8.1 – 10.4, respectively. The pH of the Estuary was higher than that of the Markman Canal. The concentrations of pharmaceuticals in water samples were below detection limit. However, carbamazepine gave the highest concentration in sediment samples (23.86 μg/kg). SLF was not detected in sediment samples. The range of temperature for Buffalo River Estuary was lower than the other sites (18.10 – 20.22 oC); however, the pH showed no difference. Human and ecotoxicological risks were estimated for Markman Canal, Nahoon, Swartkops, Buffalo and Sundays River estuaries. The concentrations obtained for the two classes of contaminants in this study showed that PBDEs in Markman Canal sediment could pose a potential risk to humans, while Nahoon River Estuary poses no risk from PBDEs. Furthermore, the concentrations of caffeine in surface water of Sundays Estuary indicates low ecotoxicological risk to aquatic organisms (fish). Also, carbamazepine and trimethoprim levels (BDL – 9.50 and 1.39-2.00 μg/kg, respectively) suggest a high risk to aquatic organisms (bacteria, invertebrate, algae) in sediment of Buffalo, Sundays, and Swartkops estuaries, as well as Markman Canal. The situation report shows that the estuaries and canal in East London and Port Elizabeth are polluted by organic pollutants such as pharmaceuticals and polybrominated diphenyl ethers. Measures has to be taken to monitor the pollution of these rivers that are of economic value to South Africa.Thesis (PhD) -- Faculty of Science and Agriculture, 202