• 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, Chrtistopher; Brandon, David; Furey, Ambrose; 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.
    • 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, Ambrose; Danaher, Martin (Elsevier, 2009-09-09)
      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.
    • 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; Elliot, Christopher; Brandon, David; Danaher, Martin (Elsevier, 2011-01-14)
      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 (MDPI AG., Basel, Switzerland, 2014-12-10)
      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.
    • 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 (Biomed Central, 2015-07-09)
      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.
    • 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, Ambrose; Lehotay, Stephen J.; Danaher, Martin (Elsevier, 2010-08-21)
      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 (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.
    • Mycotoxin occurrence on baled and pit silages collected in Co. Meath

      McElhinney, C.; Danaher, Martin; Elliott, C.; O'Kiely, Padraig (Teagasc (Agriculture and Food Development Authority), Ireland, 2015-12-30)
      Recent studies of baled silages produced in Ireland have identified considerable filamentous fungal contamination. Many of these fungi are toxigenic, capable of producing secondary metabolites, namely mycotoxins. Mycotoxins are potentially detrimental to livestock health and some can pose a risk to consumers of animal products. Baled (n=20) and pit (n=18) silages from a sample of farms (n=38) in Co. Meath were examined to assess the occurrence of mycotoxins and ascertain whether sampling position within the pit silos (feed face vs. 3 m behind the feed face) has an effect on mycotoxin content or other chemical compositional variables. Of the 20 mycotoxins assayed, baled silages contained [mean of positive values (no. of values in mean)] mycotoxin concentrations (μg/kg dry matter) of beauvericin 36 (2), enniatin (enn.) A 9.3 (3), enn. A1 54 (8), enn. B 351 (9), enn. B1 136 (10), mycophenolic acid (MPA) 11,157 (8) and roquefortine C (Roq. C) 1037 (8) and pit silages contained beauvericin 25 (2) enn. A1 18 (2), enn. B 194 (9), enn. B1 57 (3), MPA 287 (6), Roq. C 3649 (6) and zearalenone 76 (1). There was no difference (P>0.05) observed in the mycotoxin concentrations between baled and pit silages, and 11 of the 20 mycotoxins assayed were below the limits of detection. The position of sampling had no effect on the mycotoxin concentration detected in pit silages. It is concluded that mycotoxin concentrations detected in these pit and baled silages in Co. Meath did not exceed EU regulation or guidance limits, and that similar chemical composition and mycotoxin concentration values occurred at the pit silage feed face and 3 m behind this feed face.
    • 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'Mahoney, John; Danaher, Martin (Taylor & Francis, 2013-09-16)
      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.
    • Review of studies on flukicide residues in cows’ milk and their transfer to dairy products

      Power, C.; Sayers, Riona; O'Brien, Bernadette; Furey, A.; Danaher, Martin; Kieran, Jordan (Teagasc (Agriculture and Food Development Authority), Ireland, 2013)
      Flukicides are widely used to treat infestations of liver fluke in dairy cattle. This could result in flukicide residues in milk if animals are improperly treated or if withdrawal periods are not properly observed. The purpose of this review is to summarise the results of studies on depletion of flukicides from milk and the transfer of flukicide residues to dairy products, if present in the milk. As the depletion of flukicide residues from milk of animals treated during lactation was relatively slow, the studies support the view that the dry period (when milk is not being used for human consumption) is the most suitable time for flukicide treatment. Migration of residues to product occurred at different rates, depending on the drug in question. Generally, concentration of flukicides occurred in cheese, butter and skim milk powder. Pasteurisation or heat treatment during spray drying had no impact in reducing residues.