• An investigation of anticoccidial veterinary drugs as emerging organic contaminants in groundwater

      Mooney, D.; Richards, Karl G.; Danaher, Martin; Grant, Jim; Gill, L.; Mellander, Per-Erik; Coxon, C.E.; Teagasc Walsh Scolarship Programme; Science Foundation Ireland; European Union; et al. (Elsevier BV, 2020-12)
      Intensification of the food production system to meet increased global demand for food has led to veterinary pharmaceuticals becoming a critical component in animal husbandry. Anticoccidials are a group of veterinary products used to control coccidiosis in food-producing animals, with primary prophylactic use in poultry production. Excretion in manure and subsequent land-spreading provides a potential pathway to groundwater. Information on the fate and occurrence of these compounds in groundwater is scant, therefore these substances are potential emerging organic contaminants of concern. A study was carried out to investigate the occurrence of anticoccidial compounds in groundwater throughout the Republic of Ireland. Twenty-six anticoccidials (6 ionophores and 20 synthetic anticoccidials) were analysed at 109 sites (63 boreholes and 46 springs) during November and December 2018. Sites were categorised and selected based on the following source and pathway factors: (a) the presence/absence of poultry activity (b) predominant aquifer category and (c) predominant groundwater vulnerability, within the zone of contribution (ZOC) for each site. Seven anticoccidials, including four ionophores (lasalocid, monensin, narasin and salinomycin) and three synthetic anticoccidials (amprolium, diclazuril and nicarbazin), were detected at 24% of sites at concentrations ranging from 1 to 386 ng L−1. Monensin and amprolium were the two most frequently detected compounds, detected at 15% and 7% of sites, respectively. Multivariate statistical analysis has shown that source factors are the most significant drivers of the occurrence of anticoccidials, with no definitive relationships between occurrence and pathway factors. The study found that the detection of anticoccidial compounds is 6.5 times more likely when poultry activity is present within the ZOC of a sampling point, compared to the absence of poultry activity. This work presents the first detections of these contaminants in Irish groundwater and it contributes to broadening our understanding of the environmental occurrence and fate of anticoccidial veterinary products.
    • A new sensitive method for the simultaneous chromatographic separation and tandem mass spectrometry detection of anticoccidials, including highly polar compounds, in environmental waters

      Mooney, D; Coxon, C; Richards, Karl G.; Gill, L.W.; Mellander, Per-Erik; Danaher, Martin; Science Foundation Ireland; European Union; Teagasc Walsh Fellowship Programme; Irish Centre for Research in Applied Geosciences (iCRAG); et al. (Elsevier, 2020-01-10)
      A sensitive and selective method was developed and validated for the determination of 26 anticoccidial compounds (six ionophores and twenty chemical coccidiostats) in surface and groundwater samples at parts-per-quadrillion (pg L−1) to parts-per-trillion (ng L−1) levels by ultra-high performance liquid chromatography with tandem mass spectrometry detection (UHPLC–MS/MS). A range of different analytical columns and mobile phase compositions were evaluated to enhance selectivity and retention of a number of highly polar and basic anticoccidials along with other non-polar coccidiostats. A combined separation, including these problematic polar compounds, was achieved on a phenyl-hexyl column, by binary gradient elution with water/acetonitrile using ammonium formate and formic acid as additives. The anticoccidial residues were extracted from raw, unfiltered, water samples (250 mL) using polymeric divinylbenzene solid phase extraction (SPE) cartridges, with subsequent elution (methanol:acetonitrile:ethyl acetate, 40:40:20, v/v) and concentration prior to determination. The method recovery (at a concentration representative of realistic expected environmental water concentrations based on literature review) ranged from 81% to 105%. The method was successfully validated for 26 anticoccidials, at four concentration levels, in accordance to Commission Decision 2002/657/EC and SANTE/11813/2017 guidelines. Trueness and precision, under within-laboratory reproducibility conditions, ranged from 88% to 111% and 0.9% to 10.3% respectively.