The use of sterol profiles, supported with other faecal source tracking methods, to apportion septic tanks contamination in rural catchments.

Identifying the origin of faecal pollution in water is needed for effective water management decisions to protect both human health and aquatic ecosystems. Traditionally used indicators of faecal contamination, such as E. coli, only indicate pollution from warm-blooded animals and not the specific source of contamination; hence, more source specific tracers are required. The study has focussed on separating the two main sources of contaminants within rural catchments in Ireland, agriculture and on-site wastewater treatment systems (predominantly septic tanks). While human-specific effluent tracers may assist in identifying potential pathways from individual septic tanks to surface waters, it is difficult to quantify the cumulative impact of such systems at a catchment scale. This study has investigated faecal sterols as a method to quantify such an impact on four small catchments in areas of low subsoil permeability with high densities of septic tanks. The results demonstrate the usefulness of faecal sterols which provide a quantitative evaluation of the respective impact between agricultural pasture inputs and on-site effluent showing differences between the four catchments. The study also highlights the need to derive more specific local reference sterol profile databases for specific countries or regions, using local source material of animal faeces and effluent. Two intensive sampling campaigns on the four catchments then used faecal sterols in parallel to fluorescent whitening compounds (FWCs), caffeine, artificial sweeteners and selected pharmaceuticals to gain further insights and confirmation about contamination hotspots as well as providing comparison between the different parameters. The combination of sterols, FWCs, caffeine, acesulfame and cyclamate has proven suitable to provide an estimate of the extent of human contamination in these rural catchments and has yielded additional information about potential pollution pathways and proximity of contamination. Overall, this methodology can help to facilitate a targeted and effective water management in such catchments.

Modelling potential human exposure to the urease inhibitor NBPT through the environment-food pathway.

The urease inhibitor N-(n-butyl) thiophosphoric triamide (NBPT) has recently attracted a lot of attention attributing to its efficiency in reducing ammonia loss from urea fertiliser applied to temperate grassland soils. Ammonia gas lost to the environment causes soil acidification, eutrophication and contributes to global warming through increased greenhouse gas emissions and ozone layer depletion. The active chemical NBPT blocks the soil microbial enzyme (urease) and reduces ammonia emission. Furthermore, NBPT's use in agriculture might benefit farmers by reducing reliance on expensive nitrate fertiliser and aiding in a shift to more urea-based fertiliser (using NBPT co-applied with urea is more cost-effective). The present study was carried out to characterise the potential transfer of NBPT from grass to liquid milk and compute the associated human health risks. Using probabilistic risk assessment techniques, an exposure assessment model was developed to calculate the Estimated Daily Intake (EDI) of NBPT from milk, following co-application of NBPT with a urea N-fertiliser. Results show that the predicted mean concentration of NBPT in milk is 2.5 × 10-8 mg NBPT/kg milk, while the mean daily intake (EDI) of NBPT is 5 × 10-11 mg NBPT /kg BW/day). Back-calculations revealed that, under the studied conditions, for the EDI to exceed ADI of 3 × 10-2 mg NBPT/kg BW/ day, the NBPT application rate would need to exceed the NBPT fertiliser limit (0.09-0.2% by mass of urea nitrogen) set in the Commission Regulation (EC) No 1107/2008, and the bio-transfer factor would need to be over 100% (implausible). Sensitivity analysis revealed soil pH (SPH), phytoaccumulation factor (PF), NBPT permissible levels in fertiliser (NBPT%), pasture cover (P), and grazing rotation length (t) as critical factors influencing the EDI of NBPT. The present study concludes that NBPT presents negligible risk to human health under the conditions and assumptions studied.

Chlorate Levels in Dairy Products Produced and Consumed in Ireland.

In recent years, chlorate has become a residue of concern internationally, due to the risk that it poses to thyroid gland function. However, little is known about its occurrence in dairy products of Irish origin. To address this, a study was conducted in which samples of milk (n = 317), cream (n = 199), butter (n = 178), cheese (n = 144) and yoghurt (n = 440) were collected from grocery stores in the Republic of Ireland. Sampling was conducted across spring, summer, autumn and winter of 2021. Samples from multiple manufacturers of each respective dairy product were procured and analysed for chlorate using UPLC-MS/MS. Chlorate was detected in milk, cream, natural, blueberry, strawberry and raspberry yoghurts. Mean chlorate levels detected in these products were 0.0088, 0.0057, 0.055, 0.067, 0.077 and 0.095 mg kg-1, respectively. Chlorate was undetected in butter and cheese (<0.01 mg kg-1). All products sampled, except yoghurt, were found to be compliant with the EU limit for chlorate in milk (0.10 mg kg-1). Some manufacturers produced product with greater incidence and levels of chlorate. Chlorate levels from samples tested at different times of the year did not differ significantly, with the exception of strawberry and raspberry yoghurts which had higher chlorate levels in the winter period.

Isolation and identification of chlorate-reducing Hafnia sp. from milk.

Chlorate has become a concern in the food and beverage sector, related to chlorine sanitizers in industrial food production and water treatment. It is of particular concern to regulatory bodies due to the negative health effects of chlorate exposure. This study investigated the fate of chlorate in raw milk and isolated bacterial strains of interest responsible for chlorate breakdown. Unpasteurized milk was demonstrated to have a chlorate-reducing capacity, breaking down enriched chlorate to undetectable levels in 11 days. Further enrichment and isolation using conditions specific to chlorate-reducing bacteria successfully isolated three distinct strains of Hafnia paralvei. Chlorate-reducing bacteria were observed to grow in a chlorate-enriched medium with lactate as an electron donor. All isolated strains were demonstrated to reduce chlorate in liquid medium; however, the exact mechanism of chlorate degradation was not definitively identified in this study.

Measurement of grass uptake of the urease inhibitor NBPT and of the nitrification inhibitor dicyandiamide co-applied with granular urea.

Grass uptake and phytoaccumulation factors of N-(n-butyl) thiophosphoric triamide (NBPT) and dicyandiamide (DCD) were quantified. Following the application of urea fertilizer treated with the inhibitors in Irish grassland, grass samples were collected at 5, 10, 15, 20, and 30 day time intervals following five application cycles. Uptake of NBPT by grass was below the limit of quantitation of the analytical method (0.010 mg NBPT kg-1). Dicyandiamide concentrations in grass ranged from 0.004 to 28 mg kg-1 with the highest concentrations measured on days 5 and 10. A reducing trend in concentration was found after day 15. The DCD phytoaccumulation factor was ranged from 0.004% to 1.1% showing that DCD can be taken up by grass at low levels when co-applied with granular urea. In contrast, NBPT was not detected indicating that grass uptake is unlikely when co-applied with granular urea fertilizer. The contrasting results are likely due to very different longevity of DCD and NBPT along with the much lower rate of NBPT, which is used compared with DCD.

Verification of Bound Aminoguanidine as the Marker Residue for the Banned Antibiotic, Nitrovin, in Pig Tissues.

Nitrovin (NTV) belongs to a class of antibiotics called nitrofurans, which are classified as nonallowed pharmacologically active substances that do not have a maximum residue limit listed in EU legislation. The objectives of this study were to confirm aminoguanidine (AGN) as a suitable marker residue to monitor NTV abuse and to investigate its persistence in porcine tissues. In this work, pigs were fed with NTV-medicated feed (50 mg/kg), and tissues (kidney, muscle, and liver) and plasma were collected on different withdrawal days. All samples were analyzed for bound AGN, total AGN, and the parent drug NTV itself. The highest concentrations of AGN residues were found in the liver, while the lowest were in muscle. Parent NTV was only detected in the kidney at low levels on day 0 of withdrawal. The findings are in support of using AGN as the marker residue for monitoring the illegal use of NTV in animal-derived products.

Development and validation of a quantitative method for 15 antiviral drugs in poultry muscle using liquid chromatography coupled to tandem mass spectrometry.

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.

Development and validation of a rapid LC-MS/MS method for the confirmatory analysis of the bound residues of eight nitrofuran drugs in meat using microwave reaction.

A rapid analytical method was developed and validated for the analysis of eight bound nitrofurans in animal tissue, shortening laboratory turnaround times from 4 to 2 days. The majority of methodologies for nitrofuran analysis focus on the detection of only four drugs (nitrofurantoin, furazolidone, furaltadone and nitrofurazone), and is time-consuming given the 16-h overnight derivatisation step and a double liquid-liquid extraction. In this study, the narrow scope of analysis was addressed by including further four important nitrofuran drugs (nifursol, nitrofuroxazide, nifuraldezone and nitrovin). Full chromatographic separation was achieved for the metabolites of all eight nitrofurans, using phenyl-hexyl column chemistry and a rigorous optimisation of the mobile phase additives and gradient profile. The conventional, lengthy sample preparation was substantially shortened by replacing the traditional overnight water bath derivatisation with a rapid 2-h microwave-assisted reaction, followed by a modified-QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) extraction. This confirmatory method was fully validated in accordance with the new 2021/808/EC legislation, and was shown to perform satisfactorily when applied to incurred tissues. The decision limit (CCα) for the eight analytes ranged between 0.013 and 0.200 µg kg-1, showing abundant sensitivity given that the current RPA for nitrofurans is 0.5 µg kg-1. This innovative method can play a major role in the surveillance of the illegal use of nitrofuran drugs.

Current knowledge on urease and nitrification inhibitors technology and their safety.

OBJECTIVE: Urea is one of the most widely used commercial fertilisers worldwide due to its high N density and cost effectiveness. However, it can be lost in the form of gaseous ammonia and other greenhouse gas (GHG) emissions which can potentially lead to environmental pollution. Farmers are compelled to apply more urea to account for those losses, thereby increasing their expenditure on fertilization. The objective of this paper is to present a literature review on current knowledge regarding inhibitor technologies such as urease inhibitor; n-(N-butyl) thiophosphoric triamide (NBPT), and nitrification inhibitor; dicyandiamide (DCD). METHODS: A thorough review of all the scientific literature was carried out and a proposed risk assessment framework developed. RESULTS: The study showed that the urease inhibitor NBPT significantly reduced NH3 loss from urea. However, concerns about NBPT safety to human health had been raised when the nitrification inhibitor DCD appeared as a residue in milk. This article presents a risk assessment framework for evaluating human exposure to chemicals like NBPT or DCD, following the consumption of foods of animal origin (e.g. milk) from cows grazing on inhibitor-treated pasture. CONCLUSION: The EU's target of a 40% reduction of greenhouse gas emissions by 2030 can be aided by using NBPT as part of an overall suite of solutions. A comprehensive risk assessment is advised for effective evaluation of potential risks from exposure to these inhibitors.

Agronomic Factors Influencing the Scale of Fusarium Mycotoxin Contamination of Oats.

Seven agronomic factors (crop season, farming system, harvest date, moisture, county, oat variety, and previous crop) were recorded for 202 oat crops grown across Ireland, and samples were analysed by LC-MS/MS for four major Fusarium mycotoxins: deoxynivalenol (DON), zearalenone (ZEN), T-2 toxin and HT-2 toxin. Type A trichothecenes were present in 62% of crops, with 7.4% exceeding European regulatory limits. DON (6.4%) and ZEN (9.9%) occurrences were relatively infrequent, though one and three samples were measured over their set limits, respectively. Overall, the type of farming system and the previous crop were the main factors identified as significantly influencing mycotoxin prevalence or concentration. Particularly, the adherence to an organic farming system and growing oats after a previous crop of grass were found to decrease contamination by type A trichothecenes. These are important findings and may provide valuable insights for many other types of cereal crops as Europe moves towards a much greater organic-based food system.

Development of One-Step Non-Solvent Extraction and Sensitive UHPLC-MS/MS Method for Assessment of N-(n-Butyl) Thiophosphoric Triamide (NBPT) and N-(n-Butyl) Phosphoric Triamide (NBPTo) in Milk.

N-(n-butyl) thiophosphoric triamide (NBPT) is a urease inhibitor utilised in urea-based fertilizers. In Ireland, fertilizer treated with NBPT is applied to pasture to mitigate both ammonia and nitrous oxide emissions, but concerns arise as to the potential for residues in milk products. A quick ultrafiltration extraction and ultra-high performance liquid chromatography coupled with mass spectrometry triple quadrupole (UHPLC-MS/MS) quantitation method was developed and validated in this study. The method was applied in the analysis of samples collected from a field study investigating potential transfer of NBPT residues into milk. NBPT and NBPTo residues, were extracted from fortified milk samples and analysed on a UHPLC-MS/MS with recoveries ranging from 74 to 114%. Validation of the UHPLC-MS/MS method at low (0.0020 mg kg-1) and high (0.0250 mg kg-1) concentration levels in line with SANTE/12682/2019 showed overall trueness in the range of 99 to 104% and precision between 1 and 10%, RSD for both compounds. The limit of quantitation (LOQ) was 0.0020 mg kg-1 and other tested parameters (linearity, sensitivity, specificity, matrix effect, robustness, etc.) satisfied acceptance criteria. Stability assessment using spiked samples revealed the compounds were stable in raw and pasteurised milk for 4 weeks at -80 °C storage temperature. Maintaining samples at pH 8.5-9.0 further improved stability. Analysis of 516 milk samples from the field study found that NBPT and NBPTo concentrations were below the LOQ of 0.0020 mg kg-1, thus suggesting very low risk of residues occurring in the milk. The method developed is quick, robust, and sensitive. The method is deemed fit-for-purpose for the simultaneous determination of NBPT and NBPTo in milk.

Natural Co-Occurrence of Multiple Mycotoxins in Unprocessed Oats Grown in Ireland with Various Production Systems.

The natural co-occurrence of 42 mycotoxins was investigated in unprocessed oat grains grown in Ireland. The sample set included a total of 208 oat crops harvested during 2015-2016 and produced using conventional, organic, or gluten free farming systems. A range of different toxins was identified, including the major type A (neosolaniol, HT-2 and T-2 toxins, T-2 triol, and T-2-glucoside, co-occurring in 21 samples) and B trichothecenes (deoxynivalenol, nivalenol, and deoxynivalenol-3-glucoside), enniatins (B1, B, and A1, co-occurring in 12 samples), as well as beauvericin, alternariol, mycophenolic acid, and sterigmatocystin. The influences of sowing season, year, and production system were investigated, eventually indicating that the latter factor may have a higher impact than others on the production of certain mycotoxins in oats. The most frequently quantified compounds were HT-2 (51%) and T-2 (41%) toxins, with gluten free oats containing significantly lower concentrations of HT-2 compared to conventionally produced oats. Although the prevalence and concentrations of mycotoxin found in oat samples in this study should be substantially reduced by processing. However, as mycotoxin occurrence is clearly influenced by multiple factors, controlled field trials should be carried out to define optimal agronomic practices and mitigate mycotoxin production. Furthermore, this work highlights the need for regularly testing cereal-based foods with multi-residue analytical methods with wider specificities than the traditionally screened and regulated toxins, to generate knowledge on the occurrence of several mycotoxins that are, to date, rarely investigated.

An assessment of contamination fingerprinting techniques for determining the impact of domestic wastewater treatment systems on private well supplies.

Private wells in Ireland and elsewhere have been shown to be prone to microbial contamination with the main suspected sources being practices associated with agriculture and domestic wastewater treatment systems (DWWTS). While the microbial quality of private well water is commonly assessed using faecal indicator bacteria, such as Escherichia coli, such organisms are not usually source-specific, and hence cannot definitively conclude the exact origin of the contamination. This research assessed a range of different chemical contamination fingerprinting techniques (ionic ratios, artificial sweeteners, caffeine, fluorescent whitening compounds, faecal sterol profiles and pharmaceuticals) as to their use to apportion contamination of private wells between human wastewater and animal husbandry wastes in rural areas of Ireland. A one-off sampling and analysis campaign of 212 private wells found that 15% were contaminated with E. coli. More extensive monitoring of 24 selected wells found 58% to be contaminated with E. coli on at least one occasion over a 14-month period. The application of fingerprinting techniques to these monitored wells found that the use of chloride/bromide and potassium/sodium ratios is a useful low-cost fingerprinting technique capable of identifying impacts from human wastewater and organic agricultural contamination, respectively. The artificial sweetener acesulfame was detected on several occasions in a number of monitored wells, indicating its conservative nature and potential use as a fingerprinting technique for human wastewater. However, neither fluorescent whitening compounds nor caffeine were detected in any wells, and faecal sterol profiles proved inconclusive, suggesting limited suitability for the conditions investigated.

Biofortification of Chicken Eggs with Vitamin K-Nutritional and Quality Improvements.

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.

Determination of 42 mycotoxins in oats using a mechanically assisted QuEChERS sample preparation and UHPLC-MS/MS detection.

A method was developed and validated for the simultaneous determination of 42 mycotoxins in oats. The method includes all the mycotoxins listed under Commission Regulation 1881/2006 and Commission Recommendation 165/2013, the emerging mycotoxins (beauvericin, alternariol, alternariol-methyl-ether and enniatins), and two masked metabolites, namely deoxynivalenol-3-glucoside and T-2-glucoside. The method also focuses on a wide range of analytes of toxicological interest. The sample preparation involved extraction with an aqueous acetic acid solution and acetonitrile, followed by QuEChERS with mechanically assisted vibrational shaking. No further clean-up steps were employed, and analysis was performed using ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). Trueness ranged between 78% and 158%, while precision ranged from 1.7% to 49.9% under within-laboratory reproducibility conditions. Beside the high degree of accuracy and sample throughput provided, the method can be applied to a large number of compounds currently not regulated, thus generating knowledge and for risk assessment purposes.

Improving the chromatographic selectivity of ß-lactam residue analysis in milk using phenyl-column chemistry prior to detection by tandem mass spectrometry.

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 ß-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 ß-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 ß-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.

Vibrational extraction QuEChERS for analysis of antiparasitic agents in fish by liquid chromatography coupled with tandem mass spectrometry.

A method was developed for the analysis of 22 antiparasitic residues belonging to the benzoylurea, organophosphate, pyrimidinamine, pyrethrin and pyrethroid classes in salmon by liquid chromatography coupled with tandem mass spectrometry. Samples were extracted with acetonitrile-water as the extraction solvent with use of a vibrational shaking apparatus with a ceramic homogenizer. After extraction, the acetonitrile extracts were cleaned up by incubation at low temperature (-20 °C, 1 h) to remove fat, followed by dispersive solid-phase extraction using Z-Sep+ and primary-secondary amine as sorbents. Validation was performed following the 2002/657/EC and SANTE/11813/2017 guidelines. The trueness of the method ranged from 87% to 121% and precision ranged from 4.1% to 23.7%, with the exception of cyphenothrin, dicyclanil and azamethiphos. The method developed is particularly advantageous because the use of a vibrational shaker allows unattended extraction of samples and eliminates a laborious tissue disruption step, which increases sample throughput in the laboratory. The sample preparation and chromatographic separations can be performed in 5 and 4 h, respectively, for 36 samples. Graphical abstract.

Development and Optimisation of a Multiresidue Method for the Determination of 40 Anthelmintic Compounds in Environmental Water Samples by Solid Phase Extraction (SPE) with LC-MS/MS Detection.

A comprehensive multiresidue method was developed and validated for the determination of 40 anthelmintic compounds, including 13 transformation products, in surface and groundwater samples at sub nanogram per litre (ng L-1) levels. Anthelmintic residues were extracted from unfiltered water samples using polymeric divinylbenzene solid phase extraction (SPE) cartridges, and eluted with methanol: acetone (50:50, v/v). Purified extracts were concentrated, filtered and injected for UHPLC-MS/MS determination. The method recovery (at a concentration representative of realistic expected environmental water levels based on literature review) ranged from 83-113%. The method was validated, at three 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 88-114% and 1.1-19.4%, respectively. The applicability of the method was assessed in a pilot study whereby 72 different surface and groundwater samples were collected and analysed for the determination of these 40 compounds for the first time in Ireland. This is the most comprehensive method available for the investigation of the occurrence of both anthelmintic parent compounds and their transformation products in raw, unfiltered environmental waters.

Deltamethrin Residues in Milk and Cheese of Lactating Goats (Capra hircus).

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.

A review of methodology for the analysis of pyrethrin and pyrethroid residues in food of animal origin.

Pyrethrin and pyrethroid pesticides are commonly used in crop protection and animal health, to control pests. As a result, they can potentially transfer into food if good agricultural practice is not followed or even due to accidental contamination. The analysis of these compounds has been widely reported in crops and the environment. However, the analysis of pyrethrin and pyrethroids has not been reported frequently in foods of animal origin, particularly animal tissues. The focus of this review is to report on pyrethrin and pyrethroid analysis including key aspects such as chemistry, choice of target matrix, sample preparation, chemical analysis, legislation and method validation. This review shows that most methodologies for the analysis of these compounds are based on gas chromatography with the trend in recent years to move towards GC-MS or GC-MS/MS based platforms. This review shows that these compounds can also be satisfactorily analysed by LC-MS/MS, which can be advantageous because of shorter chromatographic run times. A wide range of sample preparation procedures have been applied in analytical methods and more complex protocols are required for GC applications, whereas more crudely prepared extracts can be analysed by LC-MS/MS. This review demonstrates that pyrethrin and pyrethroid residues should be included as analytes in multi-class analytical methods for pesticides and veterinary drug residues in animal derived foods.