• Acrylamide formation in potato products

      Brunton, Nigel; Gormley, Ronan T.; Butler, Francis; Cummins, Enda; Danaher, Martin; O'Keeffe, Michael (Teagasc, 2006-08)
      Acrylamide, a substance classified as a potential carcinogen, occurs in heated starchy foods at concentrations many times in excess of levels permitted in drinking water. Early surveys indicated that levels of acrylamide in potato products such as French fries and potato crisps were the highest of the foodstuffs investigated. The present project addressed this issue by determining levels of acrylamide precursors (asparagine and reducing sugars) in raw potatoes and levels of acrylamide in (i) potato products from different storage regimes, (ii) spot-sampled potatoes purchased from a local supermarket, (iii) samples that received pre-treatments and were fried at different temperatures and (iv) French fries reheated in different ovens.A risk assessment of the estimated acrylamide intake from potato products for various cohorts of the Irish population was also conducted.
    • Benzimidazole carbamate residues in milk: Detection by Surface Plasmon Resonance-biosensor, using a modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method for extraction

      Keegan, Jemma; Whelan, Michelle; Danaher, Martin; Crooks, Steven; Sayers, Riona; Anastasio, Aniello; Elliott, C.; Brandon, David; Furey, A.; O'Kennedy, Richard (Elsevier, 2009-09-26)
      A surface plasmon resonance (SPR) biosensor screening assay was developed and validated to detect 11 benzimidazole carbamate (BZT) veterinary drug residues in milk. The polyclonal antibody used was raised in sheep against a methyl 5(6)-[(carboxypentyl)-thio]-2-benzimidazole carbamate protein conjugate. A sample preparation procedure was developed using a modified QuEChERS method. BZT residues were extracted from milk using liquid extraction/partition with a dispersive solid phase extraction clean-up step. The assay was validated in accordance with the performance criteria described in 2002/657/EC. The limit of detection of the assay was calculated from the analysis of 20 known negative milk samples to be 2.7 μg kg−1. The detection capability (CCβ) of the assay was determined to be 5 μg kg−1 for 11 benzimidazole residues and the mean recovery of analytes was in the range 81–116%. A comparison was made between the SPR-biosensor and UPLC–MS/MS analyses of milk samples (n = 26) taken from cows treated different benzimidazole products, demonstrating the SPR-biosensor assay to be fit for purpose.
    • Biofortification of Chicken Eggs with Vitamin K—Nutritional and Quality Improvements

      O’Sullivan, Siobhan M.; E. Ball, M. Elizabeth; McDonald, Emma; Hull, George L. J.; Danaher, Martin; Cashman, Kevin D.; Department of Agriculture, Food and the Marine; Science Foundation Ireland; 15F670; 16/RI/3710 (Multidisciplinary Digital Publishing Institute, 2020-11-06)
      National nutrition surveys have shown that over half of all adults in Ireland, the United Kingdom (UK), and the United States of America (USA) have low vitamin K intakes. Thus, dietary strategies to improve vitamin K intakes are needed, and vitamin K biofortification of food may be one food-based approach. The primary aim of our study was to establish whether increasing the vitamin K3 content of hen feed can increase the vitamin K content of eggs, and the secondary aims were to examine the effects on hen performance parameters, as well as egg and eggshell quality parameters. A 12 week hen feeding trial was conducted in which Hyline chickens were randomized into four treatment groups (n = 32/group) and fed diets containing vitamin K3 (as menadione nicotinamide bisulfite) at 3 (control), 12.9, 23.7, and 45.7 mg/kg feed. Vitamin K1, menaquinone (MK)-4, MK-7, and MK-9 were measured in raw whole eggs via a liquid chromatography tandem mass spectrometry method. MK-4 was the most abundant form of vitamin K (91–98%) found in all eggs. Increasing the vitamin K3 content of hen feed over the control level significantly (p < 0.001) enhanced the MK-4 content of eggs (mean range: 46–51 µg/100 g, representing ~42–56% of US Adequate Intake values). Vitamin K biofortification also led to significant (p < 0.05) increases in the yellowness of egg yolk and in eggshell weight and thickness, but no other changes in egg quality or hen performance parameters. In conclusion, high-quality vitamin K-biofortified eggs can be produced with at least double the total vitamin K content compared to that in commercially available eggs.
    • Current trends in sample preparation for growth promoter and veterinary drug residue analysis

      Kinsella, Brian; O'Mahony, John; Malone, Edward; Moloney, Mary; Cantwell, Helen; Furey, A.; Danaher, Martin; Department of Agriculture, Food and the Marine, Ireland; 06RDTAFRC479; 07FHRITAFRC5 (Elsevier, 09/09/2009)
      A comprehensive review is presented on the current trends in sample preparation for isolation of veterinary drugs and growth promotors from foods. The objective of the review is to firstly give an overview of the sample preparation techniques that are applied in field. The review will focus on new techniques and technologies, which improve efficiency and coverage of residues. The underlying theme to the paper is the developments that have been made in multi-residue methods and particularly multi-class methods for residues of licensed animal health products, which have been developed in the last couple of years. The role of multi-class methods is discussed and how they can be accommodated in future residue surveillance.
    • Deltamethrin Residues in Milk and Cheese of Lactating Goats (Capra hircus)

      Marrone, Raffaele; Ramkumar, Abilasha; Smaldone, Giorgio; Rufrano, Domenico; Chirollo, Claudia; Veneziano, Vincenzo; Danaher, Martin; Anastasio, Aniello; University of Naples Federico II (MDPI AG, 2019-01-31)
      The distribution of pyrethroid insecticide deltamethrin (DLM) in goat milk and cheese (caciotta) following pour-on administration at the sheep dosage (DLMS-10 mL/60 kg body weight) and double dosage (DLMD-20 mL/60 kg body weight) was studied. DLM concentrations were measured in milk collected from study animals (No.14) before treatment and at 2, 4, 8, 12, 16, 24, 30, 36, 48, 56, until 168 h (7 days) post treatment and in caciotta cheese at 12 and 24 h post treatment. At both dosages, the maximum level of DLM residues in goat milk and cheese was below the maximum residue limit (MRL) of 20 μg kg−1 established for bovine milk (EU No 37/2010) at all time points. However, in terms of public health, higher DLM residues in cheese show that further specific studies should be performed on double dosage efficacy and pharmacokinetic and pharmacodynamics properties of ectoparasites in lactating goats.
    • Detection of banned nitrofuran metabolites in animal plasma samples using UHPLC–MS/MS

      Radovnikovic, Anita; Moloney, Mary; Byrne, Patrick; Danaher, Martin (Elsevier, 2010-12-07)
      The use of nitrofurans as veterinary drugs in food-producing animals has been banned in the EU since the 1990s. Monitoring programs in the EU are based on the detection of protein-bound metabolites after slaughter. An UHPLC–MS/MS method was developed and validated for pre slaughter determination of four nitrofuran metabolites (AHD, AOZ, SEM, AMOZ) in animal plasma (bovine, ovine, equine and porcine). This method is proposed as an alternative method for on-farm surveillance. Plasma samples were derivatised with 2-nitrobenzaldehyde and subsequently extracted with organic solvent. Extracts were concentrated and then analysed by UHPLC–MS/MS. The method was validated according to Commission Decision 2002/657/EC. Inter-species recovery for AHD, AOZ, SEM and AMOZ was 72, 74, 57 and 71%, respectively. Decision limits (CC ) were calculated from within laboratory reproducibility experiments to be 0.070, 0.059, 0.071 and 0.054 gkg−1, respectively. In addition, the assay was applied to incurred plasma samples taken from pigs treated with furazolidone.
    • Detection of benzimidazole carbamates and amino metabolites in liver by surface plasmon resonance-biosensor

      Keegan, Jemma; O'Kennedy, Richard; Crooks, Steven; Elliott, C.; Brandon, David; Danaher, Martin; Department of Agriculture, Food and the Marine, Ireland; 05/R&D/TN/355 (Elsevier, 14/01/2011)
      Two surface plasmon resonance (SPR) biosensor screening assays were developed and validated to detect 11 benzimidazole carbamate (BZT) and four amino-benzimidazole veterinary drug residues in liver tissue. The assays used polyclonal antibodies, raised in sheep, to detect BZTs and amino-benzimidazoles. A modified Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) extraction method was developed to isolate benzimidazole carbamate residues. Liver samples were extracted using an acetonitrile extraction method. BZTs were purified by dispersive solid phase extraction (d-SPE) using C18 sorbent. Residues of amino-benzimidazoles were effectively cleaned-up using a simple cyclohexane defatting step. The assays were validated in accordance with the performance criteria described in 2002/657/EC. The BZT assay limit of detection was calculated to be 32 μg kg−1, the detection capability (CCβ) was determined to be 50 μg kg−1 and the mean recovery of analytes was in the range 77–132%. The amino-benzimidazole assay limit of detection was determined to be 41 μg kg−1, the CCβ was determined to be 75 μg kg−1 and analyte recovery was in the range 103–116%. Biosensor assay performance was tested by analysing liver tissue from animals treated with benzimidazole drugs and comparing the results with an ultra high performance liquid chromatography tandem mass spectrometry (UHPLC–MS/MS) confirmatory method. All non-compliant samples were identified using the biosensor assays.
    • Determination and Occurrence of Phenoxyacetic Acid Herbicides and Their Transformation Products in Groundwater Using Ultra High Performance Liquid Chromatography Coupled to Tandem Mass Spectrometry

      McManus, Sarah-Louise; Moloney, Mary; Richards, Karl G.; Coxon, Catherine E.; Danaher, Martin; Teagasc Walsh Fellowship Programme; Department of Agriculture, Food and the Marine, Ireland (MDPI AG., Basel, Switzerland, 10/12/2014)
      A sensitive method was developed and validated for ten phenoxyacetic acid herbicides, six of their main transformation products (TPs) and two benzonitrile TPs in groundwater. The parent compounds mecoprop, mecoprop-p, 2,4-D, dicamba, MCPA, triclopyr, fluroxypr, bromoxynil, bentazone, and 2,3,6-trichlorobenzoic acid (TBA) are included and a selection of their main TPs: phenoxyacetic acid (PAC), 2,4,5-trichloro-phenol (TCP), 4-chloro-2-methylphenol (4C2MP), 2,4-dichlorophenol (DCP), 3,5,6-trichloro-2-pyridinol (T2P), and 3,5-dibromo-4-hydroxybenzoic acid (BrAC), as well as the dichlobenil TPs 2,6-dichlorobenzamide (BAM) and 3,5-dichlorobenzoic acid (DBA) which have never before been determined in Irish groundwater. Water samples were analysed using an efficient ultra-high performance liquid chromatography (UHPLC) method in an 11.9 min separation time prior to detection by tandem mass spectrometry (MS/MS). The limit of detection (LOD) of the method ranged between 0.00008 and 0.0047 µg·L−1 for the 18 analytes. All compounds could be detected below the permitted limits of 0.1 µg·L−1 allowed in the European Union (EU) drinking water legislation [1]. The method was validated according to EU protocols laid out in SANCO/10232/2006 with recoveries ranging between 71% and 118% at the spiked concentration level of 0.06 µg·L−1. The method was successfully applied to 42 groundwater samples collected across several locations in Ireland in March 2012 to reveal that the TPs PAC and 4C2MP were detected just as often as their parent active ingredients (a.i.) in groundwater.
    • Determination of the presence of pathogens and anthelmintic drugs in raw milk and raw milk cheeses from small scale producers in Ireland

      Lourenco, Antonio; Fraga-Corral, Maria; De Colli, Lorenzo; Moloney, Mary; Danaher, Martin; Jordan, Kieran; Depart of Agriculture, Food and the Marine; 15/F/690 (Elsevier, 2020-04-03)
      This aim of this study was to assess the microbiological and anthelmintic drug residue risks associated with raw milk used for cheesemaking and raw milk cheese, over an 18-month period. Samples of raw milk, milk filters, curd and cheese from nine raw milk artisan cheese producers in the south of Ireland were tested. Numbers of presumptive Bacillus cereus group, Escherichia coli, Salmonella spp., Staphylococcus aureus and Listeria monocytogenes were determined. The determination of anthelmintic drug residues, including benzimidazoles, flukicides, macrocyclic lactone (avermectin and milbemycins), levamisole and morantel was also performed. Neither L. monocytogenes, nor Salmonella spp. were detected in any of the samples tested and no anthelmintic drug residues were detected. Only one of the samples did not conform with regulatory numbers for other bacteria. This survey has shown a good microbiological and residue quality (and low risk) of the raw milk cheese and raw milk used for raw milk cheese produced in Ireland. Moreover, it has shown the importance of frequent assessment of raw milk used for cheesemaking and for raw milk cheese, as it allows the identification of potential problems facilitating resolution of these issues before they cause any public health threat.
    • Determining the Prevalence and Seasonality of Fasciola hepatica in Pasture-based Dairy herds in Ireland using a Bulk Tank Milk ELISA

      Bloemhoff, Yris; Forbes, Andrew; Danaher, Martin; Good, Barbara; Morgan, Eric; Mulcahy, Grace; Sekiya, Mary; Sayers, Riona; Irish Dairy Levy Research Trust; Merial (Biomed Central, 09/07/2015)
      Background Fasciola hepatica is a helminth parasite of global importance in livestock, with major economic impact. However information on F. hepatica infections in Irish pasture-based dairy herds is limited. Therefore this study was conducted in order to determine the prevalence, seasonality and management factors associated with F. hepatica. A total of 319 Irish dairy herds were selected for this study. Bulk tank milk (BTM) samples were collected from 290 dairy farms on a quarter year basis, while from a further 29 dairy farms BTM samples were collected on a monthly basis to provide a more detailed pattern of F. hepatica exposure in Irish herds. BTM samples were analysed using a commercially available F. hepatica antibody detection ELISA. Furthermore, within-herd prevalence of F. hepatica was assessed in a subset of these 29 herds (n = 17); both individual serum samples and bulk tank milk samples were collected. Results A within-herd prevalence of ≤ 50 % was found for herds with negative bulk tank milk samples. The mean prevalence of the 290 study herds was 75.4 % (Range 52 %–75.1 %), with the highest prevalence being observed in November (75.1 %). The seasonal pattern of F. hepatica shows elevated antibodies as the grazing season progressed, reaching a peak in January. A significant association was found between F. hepatica and age at first calving. Conclusion This study demonstrates that F. hepatica is present in a large proportion of Irish dairy herds and provides a basis on which control practices, particularly in adult dairy cows, can be reviewed.
    • Development and validation of a quantitative confirmatory method for 30 β-lactam antibiotics in bovine muscle using liquid chromatography coupled to tandem mass spectrometry

      Di Rocco, Melissa; Moloney, Mary; O’Beirne, T.; Earley, S.; Berendsen, B.; Furey, A.; Danaher, Martin; Department of Agriculture, Food and the Marine; 13/F484 (Elsevier BV, 2017-06)
      A method was developed for the confirmatory and quantitative analysis of 30 β-lactam antibiotic residues in bovine muscle. The method includes 12 penicillins (amoxicillin, ampicillin, cloxacillin, dicloxacillin, mecillinam, methicillin, nafcillin, oxacillin, penicillin G, penicillin V, piperacillin, ticarcillin), 12 cephalosporins (cefacetrile, cefadroxil, cephalexin, cefalonium, cefazolin, cefoperazone, cefotaxime, cefquinome, cefuroxime, desacetyl cephapirin, desfuroylceftiofur cysteine disulfide, desfuroylceftiofur dimer), five carbapenems (biapenem, doripenem, ertapenem, imipenem, meropenem) and faropenem. Samples were extracted using a simple solvent extraction with acetonitrile:water (80:20, v/v) and C18 dispersive solid-phase extraction (d-SPE) clean-up, followed by ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC–MS/MS) detection. Chromatography was performed on a reversed phase CSH C18 column, using a binary gradient separation comprising of 0.01% formic acid and 0.2 mM ammonium acetate in water (mobile phase A) and 0.01% formic acid in acetonitrile (mobile phase B). The mass spectrometer was operated in the positive electrospray ionisation mode (ESI(+)). Validation was performed following the 2002/657/EC guidelines. Trueness ranged between 69% and 143% and precision ranged between 2.0% and 29.9% under within-laboratory reproducibility conditions. The developed method uses minimal sample preparation and 30 test samples can be analysed by a single analyst in a single day. To the best of our knowledge, this is the first method for carbapenems in foodstuff that does not require derivatisation.
    • Development and validation of a quantitative method for 15 antiviral drugs in poultry muscle using liquid chromatography coupled to tandem mass spectrometry

      Douillet, Clément; Moloney, Mary; Di Rocco, Melissa; Elliott, Christopher; Danaher, Martin; European Union; Chinese Ministry of Science and Technology; 727864 (Elsevier BV, 2022-02)
      The objective of this work was to develop a quantitative multi-residue method for analysing antiviral drug residues and their metabolites in poultry meat samples. Antiviral drugs are not licensed for the treatment of influenza in food producing animals. However, there have been some reports indicating their illegal use in poultry. In this study, a method was developed for the analysis of 15 antiviral drug residues in poultry muscle (chicken, duck, quail and turkey) using liquid chromatography coupled to tandem mass spectrometry. This included 13 drugs against influenza and associated metabolites, but also two drugs employed for the treatment of herpes (acyclovir and ganciclovir). The method required the development of a novel chromatographic separation using a hydrophilic interaction chromatographic (HILIC) BEH amide column, which was necessary to retain the highly polar compounds. The analytes were detected using a triple quadrupole mass spectrometer operating in positive electrospray ionization mode. A range of different sample preparation protocols suitable for polar compounds were evaluated. The most effective procedure was based on a simple acetonitrile-based protein precipitation step followed by a further dilution in a methanol/water solution. The confirmatory method was validated according to the EU 2021/808 guidelines on different species including chicken, duck, turkey and quail. The validation was performed using various calibration curves ranging from 0.1 µg kg−1to 200 µg kg−1, according to the analyte. Depending on the analyte sensitivity, decision limits achieved ranged from 0.12 µg kg−1 for arbidol to 34.7 µg kg−1 for ribavirin. Overall, the reproducibility precision values ranged from 2.8% to 22.7% and the recoveries from 84% to 127%. The method was applied to 120 commercial poultry samples from the Irish market, which were all found to be residue-free.
    • A dual validation approach to detect anthelmintic residues in bovine liver over an extended concentration range

      Kinsella, Brian; Whelan, Michelle; Cantwell, Helen; McCormack, Martin; Furey, A.; Lehotay, Stephen J.; Danaher, Martin; Department of Agriculture, Food and the Marine, Ireland; European Union; 06RDTAAFRC479; et al. (Elsevier, 21/08/2010)
      This paper describes a method for the detection and quantification of 38 residues of the most widely used anthelmintics (including 26 veterinary drugs belonging to the benzimidazole, macrocyclic lactone and flukicide classes) in bovine liver using two different protocols for MRL and non-MRL levels. A dual validation approach was adopted to reliably quantify anthelmintic residues over an extended concentration range (1–3000 gkg−1). Sample extraction and purification was carried out using a modified QuEChERS method. A concentration step was included when analysing in the low gkg−1 range. Rapid analysis was carried out by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC–MS/MS), which was capable of detecting residues to <2 gkg−1. The method has been single-laboratory validated according to the 2002/657/EC guidelines and met acceptability criteria in all but a few cases. The inclusion of 19 internal standards, including 14 isotopically labelled internal standards, improved accuracy, precision, decision limit (CC˛) and detection capability (CCˇ).
    • Identification of existing and emerging chemical residue contamination concerns in milk

      Danaher, Martin; Jordan, Kieran; Department of Agriculture, Food and the Marine, Ireland (Teagasc (Agriculture and Food Development Authority), Ireland, 2013)
      In order to maintain the quality of Irish milk and meet increasingly demanding specifications, it is necessary to focus on chemical residues in milk, in addition to other quality issues. The objective of the work was to assess the current status of chemical contaminant analysis and to identify technological and knowledge needs. This was achieved through a review of literature with respect to chemical contaminants. Quaternary ammonium compounds (QACs) have been identified as an area of concern for the dairy industry because of the recent reports of QAC residues in dairy products internationally. Analytical support to analyse QAC residues in milk and dairy products on an ongoing basis is required. Furthermore, the source of QAC residues along the milk production chain needs to be identified. Similarly, analytical support and research is needed in the area of phthalates, to support the development of intervention strategies to reduce contamination, if present. Cephalosporin antibiotics have been a concern for the dairy industry because of the lack of suitable chemical tests to measure these substances.
    • Improving the chromatographic selectivity of β-lactam residue analysis in milk using phenyl-column chemistry prior to detection by tandem mass spectrometry

      Di Rocco, Melissa; Moloney, Mary; Haren, Deirdre; Gutierrez, Montserrat; Earley, Seán; Berendsen, Bjorn; Furey, Ambrose; Danaher, Martin; Department of Agriculture, Food and the Marine; 13/F484 (Springer Science and Business Media LLC, 2020-05-23)
      Analyte isobaric interferences can limit the development of a comprehensive analytical method for the quantitative liquid chromatography-tandem mass spectrometry profiling of an important cohort of veterinary drugs. In this work, a selective chromatographic separation was developed for the analysis of 32 β-lactam antibiotic residues (12 penicillins, 14 cephalosporins, five carbapenems and faropenem) in milk samples. A range of analytical columns with different stationary phases and mobile phases were evaluated for retention and separation of the β-lactam compounds. Results showed that, among the columns tested, only phenyl-hexyl could adequately separate ampicillin from cephalexin and amoxicillin from cefadroxil, which had shown isobaric interferences on a number of stationary phases. Chromatography was performed using a water/acetonitrile binary gradient with formic acid and ammonium acetate. The β-lactam residues were extracted from the milk samples using a water:acetonitrile solution and purified by C18 dispersive solid-phase extraction (d-SPE) clean-up, followed by concentration under nitrogen and ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) determination. Analytes were monitored in positive electrospray ionisation mode (ESI(+)). Possible interfering matrix effects were overcome by using 13 internal standards. The method was fully validated according to 2002/657/EC guidelines, showing satisfactory performance characteristics. Under within-laboratory reproducibility conditions, trueness and precision ranged from 91 to 130% and from 1.4 to 38.6%, respectively. Decision limits (CCα) were in the range 2.1–133 μg kg−1. Limits of detection (LODs) and quantitation (LOQs) ranged between 0.0090 and 1.5 μg kg−1 and from 0.030 to 5.0 μg kg−1, respectively.
    • 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.
    • Protocols and strategies to study the migration of veterinary drug residues into milk and dairy products in licensed trials

      Power, C.; Sayers, Riona; O'Brien, Bernadette; Furey, A.; Danaher, Martin; Jordan, Kieran (Teagasc (Agriculture and Food Development Authority), Ireland, 2013)
      In the interest of animal welfare, and in order that the results from animal trials are considered valid for inclusion in the development of regulations, it is necessary that such trials are undertaken in accordance with the appropriate licensing arrangements. In January 2013, new licensing arrangements were introduced in the European Union. The aim of this paper is to outline the legislative strategy required for obtaining licences for animal trials and based on live animal trials with flukicides, establishes a blueprint for obtaining the appropriate licences and undertaking the experiments.
    • Protocols and strategies to study the migration of veterinary drug residues into milk and dairy products in licensed trials – Corrigendum

      Power, C.; Sayers, Riona; O'Brien, Bernadette; Furey, A.; Danaher, Martin; Jordan, Kieran (Teagasc (Agriculture and Food Development Authority), Ireland, 2014)
    • Residue analyses and exposure assessment of the Irish population to nitrofuran metabolites from different food commodities in 2009–2010

      Radovnikovic, Anita; Conroy, Emma-Rose; Gibney, Mike; O'Mahony, John; Danaher, Martin; Department of Agriculture, Food and the Marine, Ireland; Health Research Board; 07FHRIAFRC5 (Taylor & Francis, 16/09/2013)
      An exposure assessment to nitrofuran residues was performed for three human populations (adults, teenagers and children), based on residue analyses of foods of animal origin (liver, honey, eggs and aquaculture) covering the 2-year period 2009– 2010. The occurrence of nitrofuran metabolites in food on the Irish market was determined for the selected period using the data from Ireland’s National Food Residue Database (NFRD) and from results obtained from the analysis of retail samples (aquaculture and honey). Laboratory analyses of residues were performed by methods validated in accordance with Commission Decision 2002/657/EC regarding performance of the analytical method and interpretation of results. Semicarbazide (SEM) was the contaminant most frequently identified and its content ranged from 0.09 to 1.27 μg kg−1. SEM is currently used as a marker of nitrofuran abuse, but it may also occur from other sources. The presence of nitrofuran metabolite 3-amino-2-oxazolidinone (AOZ) was detected in two aquaculture samples (prawns) at 1.63 and 1.14 μg kg−1, but such a low number of positive cases did not present sufficient data for a full AOZ exposure assessment. Therefore, the evaluation of exposure was focused on SEM-containing food groups only. Exposure assessments were completed using a probabilistic approach that generated 10 iterations. The results of both the upper- and lower-bound exposure assessments demonstrate that SEM exposure for Irish adults, teenagers and children from selected food commodities are well below EFSA-estimated safe levels.