ENVIRONMENTAL OCCURRENCE AND ECOTOXICOLOGICAL RISKS OF CONTAMINANTS OF EMERGING CONCERN IN THE RIVER ATHI BASIN, KENYA: ANALYTICAL AND KINETIC ADSORPTION STUDIES USING AGRICULTURAL WASTE BIOCHARS

Abstract

Globally, the environmental occurrence of Contaminants of Emerging Concern (CECs) including Active Pharmaceutical Ingredients (APIs), Personal Care Products (PCPs) and pesticides has raised ecological and human health concerns. However, as the developed world make efforts to establish regulatory measures to mitigate their effects, developing nations including Kenya are lagging, partly due to unavailability of adequate data. Remediation of CECs in water can be achieved via photodegradation, advanced oxidation process, bioremediation, chemical degradation and activated carbon utilization. Adsorption, a cheaper and convenient alternative using the available agricultural wastes products, as biosorbent materials have not been fully explored. The objectives of this study were to determine multi-class CECs load and concentrations, determine ecotoxicological risks towards algae, Daphnia magna and fish, and potential point-of-use technologies via adsorption using Rice Husk Biochar (RHB), Avocado Seed Biochar (ASB)and Banana Peel Biochar (BPB). Water samples were collected from 24 sites across the River Athi basin area, Kenya. Extraction of water samples was done using Solid-Phase Extraction (SPE) and the CECs were analyzed using Ultra-High-Performance Liquid Chromatography coupled to High Resolution Orbitrap Mass Spectrometry (UHPLC-HRMS). The equilibrium adsorption isotherm studies were conducted for 86 CECs using ASB, BPB and RHB and the data was correlated using the non-linear curves of Langmuir and Freundlich rate equations. RHB was used in the adsorption kinetic studies for 86 CECs and the kinetic data acquired were correlated with the non-linear curves of Pseudo-First Order (PFO), Pseudo Second Order (PSO), Elovich and the Weber-Morris intraparticle diffusion models. The fitting performance of each model onto the kinetic data was guaranteed using adjusted R2 and the chi square values. The results of this analysis indicated that 57 CECs comprising 31APIs (0.4 ng L-1 – 142 µg L-1), 6 PCPs (0.7 – 570 ng L-1) and 20 pesticides (0.3 ng L-1 – 8.3 µg L-1) were detected. The maximum loads varied from 217 g day-1 (APIs) to 46 g day-1 (PCPs). Individually, Carbamazepine, Nevirapine, Sulfamethoxazole and DEET were the most ubiquitous CECs, with detection frequencies (DF) higher than 80%. The highest concentrations were observed at river sites that are heavily impacted by informal settlements, highlighting the critical role of slums in pollution of urban rivers. At least 8 CECs including Acetamiprid, Alachlor, Atrazine, Diuron, Nevirapine and Paracetamol showed potential risk to algae, Daphnia magna and fish, as exemplified by Risk Quotients (RQ) up to 174. Similarly, potential risk of antibiotic resistant bacteria development is evident due to exposure to Metronidazole, Sulfamethoxazole and Trimethoprim (RQ up to 64). Comparison of removal efficiencies of the CECs using the ASB, BPB and RHB showed that ASB and RHB had impressive % Removal efficiencies (94.0% - 98% and 87% - 99%) respectively compared to BPB (87% -93%). The lower %RE (% Removal Efficiencies) at lower concentrations for all the selected biochars is attributed to formation of bulky water clusters which may not be accommodated in the micropores on the surfaces of the biochars. The adsorption mechanism may be attributed to π-π electron donor- acceptor interaction, pore filling, ionic interactions and hydrogen bonding between the CECs molecules and the surfaces of the biochars. The kinetic adsorption analysis revealed that the kinetic data acquired for virtually 80% of the compounds were best described by the Elovich kinetic model, indicating that chemisorption was more pronounced on a heterogenous adsorbent surface as to physisorption and the intra – particle diffusion mechanisms. The R2 values approached unity and low Chi-square values approached zero. The equilibrium isotherm data fitted well both with Langmuir and Freundlich models with R2 approaching unity in most instances. However, Freundlich model had higher rate constants as to Langmuir models, an indicator that adsorption process was best described with a multilayer structure than the monolayer. There is a need to sensitize communities in informal settlements on proper waste disposal methods and the government agencies should include CECs in their monitoring schedule. ASB and RHB should be considered in the development of point-of-u