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.

A Review of In Situ Methods-Solid Phase Adsorption Toxin Tracking (SPATT) and Polar Organic Chemical Integrative Sampler (POCIS) for the Collection and Concentration of Marine Biotoxins and Pharmaceuticals in Environmental Waters.

Solid Phase Adsorption Toxin Tracking (SPATT) and Polar Organic Chemical Integrative Sampler (POCIS) are in situ methods that have been applied to pre-concentrate a range of marine toxins, pesticides and pharmaceutical compounds that occur at low levels in marine and environmental waters. Recent research has identified the widespread distribution of biotoxins and pharmaceuticals in environmental waters (marine, brackish and freshwater) highlighting the need for the development of effective techniques to generate accurate quantitative water system profiles. In this manuscript, we reviewed in situ methods known as Solid Phase Adsorption Toxin Tracking (SPATT) and Polar Organic Chemical Integrative Sampler (POCIS) for the collection and concentration of marine biotoxins, freshwater cyanotoxins and pharmaceuticals in environmental waters since the 1980s to present. Twelve different adsorption substrates in SPATT and 18 different sorbents in POCIS were reviewed for their ability to absorb a range of lipophilic and hydrophilic marine biotoxins, pharmaceuticals, pesticides, antibiotics and microcystins in marine water, freshwater and wastewater. This review suggests the gaps in reported studies, outlines future research possibilities and guides researchers who wish to work on water contaminates using Solid Phase Adsorption Toxin Tracking (SPATT) and Polar Organic Chemical Integrative Sampler (POCIS) technologies.

Novel metallomic profiling and non-carcinogenic risk assessment of botanical ingredients for use in herbal, phytopharmaceutical and dietary products using HR-ICP-SFMS.

Knowledge of element concentrations in botanical extracts is relevant to assure consumer protection given the increased interest in plant-based ingredients. This study demonstrates successful multi-element investigations in order to address the lack of comprehensive profiling data for botanical extracts, while reporting for the first time the metallomic profile(s) of arnica, bush vetch, sweet cicely, yellow rattle, bogbean, rock-tea and tufted catchfly. Key element compositions were quantified using a validated HR-ICP-SFMS method (µg kg-1) and were found highly variable between the different plants: Lithium (18-3964); Beryllium (3-121); Molybdenum (75-4505); Cadmium (5-325); Tin (6-165); Barium (747-4646); Platinum (2-33); Mercury (5-30); Thallium (3-91); Lead (12-4248); Bismuth (2-30); Titanium (131-5827); Vanadium (15-1758); Chromium (100-4534); Cobalt (21-652); Nickel (230-6060) and Copper (1910-6340). Compendial permissible limits were not exceeded. Overall, no evidence of a health risk to consumers could be determined from consumption of the investigated plants at reasonable intake rates. Mathematical risk modelling (EDI, CDI, HQ, HI) estimated levels above safe oral thresholds only for Cd (16%) and Pb (8%) from higher intakes of the respective plant-derived material. Following high consumption of certain plants, 42% of the samples were categorised as potentially unsafe due to cumulative exposure to Cu, Cd, Hg and Pb. PCA suggested a potential influence of post-harvest processing on Cr, Ti and V levels in commercially-acquired plant material compared to wild-collected and farm-grown plants. Moreover, a strong correlation was observed between Pb-Bi, Be-V, Bi-Sn, and Tl-Mo occurrence. This study may support future research by providing both robust methodology and accompanying reference profile(s) suitable for the quality evaluation of essential elements and/or metal contaminants in botanical ingredients.

From Monographs to Chromatograms: The Antimicrobial Potential of Inula helenium L. (Elecampane) Naturalised in Ireland.

With antimicrobial resistance rising globally, the exploration of alternative sources of candidate molecules is critical to safeguard effective chemotherapeutics worldwide. Plant natural products are accessible, structurally diverse compounds with antimicrobial potential. The pharmacological applications of plants in medicine can be guided by the attestation of traditional use, as demonstrated in this study. In Irish ethnomedical literature, Inula helenium L. (elecampane) is often indicated for respiratory and dermal ailments. This is the first assessment of antimicrobial sesquiterpene lactones from the roots of elecampane, naturalised in Ireland. Traditional hydro-ethanolic extracts were prepared from multi-origin elecampane roots. A novel clean-up strategy facilitated the bioactivity-guided fractionation of a subset of anti-staphylococcal fractions (the compositions of which were investigated using HPLC-DAD, supported by 1H NMR). The natural products attributing to the antimicrobial activity, observed in vitro, were identified as alantolactone (1), isoalantolactone (2), igalan (3), and an unseparated mixture of dugesialactone (4) and alloalantolactone (5), as major compounds. The findings suggest that the geographical origin of the plant does not influence the anti-bacterial potency nor the chemical composition of traditional elecampane root. Considering the prevalence of staphylococci-associated infections and associated broad spectrum resistance in Irish hospitals, currently, further research is warranted into the usage of the identified compounds as potential candidates in the control of staphylococcal carriage and infection.

Development, Validation and Application of an ICP-SFMS Method for the Determination of Metals in Protein Powder Samples, Sourced in Ireland, with Risk Assessment for Irish Consumers.

A method has been developed, optimised and validated to analyse protein powder supplements on an inductively coupled plasma-sector field mass spectrometer (ICP-SFMS), with reference to ICH Guideline Q2 Validation of Analytical Procedures: Text and Methodology. This method was used in the assessment of twenty-one (n = 21) elements (Al, Au, Ba, Be, Bi, Cd, Co, Cr, Cu, Fe, Hg, Li, Mg, Mn, Mo, Pb, Pt, Sn, Ti, Tl, V) to evaluate the safety of thirty-six (n = 36) protein powder samples that were commercially available in the Irish marketplace in 2016/2017. Using the determined concentrations of elements in samples (µg·kg-1), a human health risk assessment was carried out to evaluate the potential carcinogenic and other risks to consumers of these products. While the concentrations of potentially toxic elements were found to be at acceptable levels, the results suggest that excessive and prolonged use of some of these products may place consumers at a slightly elevated risk for developing cancer or other negative health impacts throughout their lifetimes. Thus, the excessive use of these products is to be cautioned, and consumers are encouraged to follow manufacturer serving recommendations.

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.

Development and Validation of a Novel Free Fatty Acid Butyl Ester Gas Chromatography Method for the Determination of Free Fatty Acids in Dairy Products.

Accurate quantification of free fatty acids in dairy products is important for both product quality control and legislative purposes. In this study, a novel fatty acid butyl ester method was developed, where extracted free fatty acids are converted to butyl esters prior to gas chromatography with flame ionization detection. The method was comprehensively validated to establish linearity (20-700 mg/L; R2 > 0.9964), limits of detection (5-8 mg/L), limits of quantification (15-20 mg/L), accuracy (1.6-5.4% relative error), interday precision (4.4-5.3% relative standard deviation), and intraday precision (0.9-5.6% relative standard deviation) for each individual free fatty acid. A total of 17 dairy samples were analyzed, covering diverse sample matrices, fat content, and degrees of lipolysis. The method was compared to direct on-column injection and fatty acid methyl ester methods and overcomes limitations associated with these methods, such as either column-phase absorption or deterioration, accurate quantification of short-chain free fatty acids, and underestimation of polyunsaturated free fatty acid.

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.

Overview of the potent cyanobacterial neurotoxin ß-methylamino-L-alanine (BMAA) and its analytical determination.

Blue-green algae are responsible for the production of different types of toxins which can be neurotoxic, hepatotoxic, cytotoxic and dermatotoxic and that can affect both aquatic and terrestrial life. Since its discovery the neurotoxin ß-methylamino-L-alanine (BMAA) has been a cause for concern, being associated with the neurodegenerative disease amyotrophic lateral sclerosis/Parkinsonism-dementia complex (ALS/PDC). The initial focus was on Guam where it was observed that a high number of people were affected by the ALS/PDC complex. Subsequently, researchers were surprised to find levels of BMAA in post mortem brains from Canadian patients who also suffered from ALS/PDC. Recent research demonstrates that BMAA has been found at different levels in the aquatic food web in the brackish waters of the Baltic Sea. There is emerging evidence to suggest that sand-borne algae from Qatar can also contain BMAA. Furthermore, there is now concern because BMAA has been found not only in warmer regions of the world but also in temperate regions like Europe. The aim of this review is to focus on the methods of extraction and analysis of the neurotoxic non-protein amino acid BMAA. We also consider the neurotoxicity, aetiology, and diverse sources and routes of exposure to BMAA. In recent years, different methods have been developed for the analysis of BMAA. Some of these use HPLC-FD, UPLC-UV, UPLC-MS and LC-MS/MS using samples that have been derivatised or underivatised. To date the LC-MS/MS approach is the most widely used analytical technique as it is the most selective and sensitive method for BMAA determination.

High-resolution mass spectrometry analysis of tetrodotoxin (TTX) and its analogues in puffer fish and shellfish.

Tetrodotoxin (TTX) is an emerging toxin in the European marine environment. It has various known structural analogues. It acts as a sodium channel blocker; the ability of each analogue to bind to the sodium channel varies with the particular structure of each analogue. Thus, each analogue will vary in its toxic potential. TTX analogues co-occur in food samples at variable concentrations. An LC-MS method was developed for the identification and quantitation of several analogues of TTX using an LTQ-Orbitrap XL mass spectrometer. The LTQ-Orbitrap XL mass spectrometer facilitates high mass accuracy measurement up to 100,000 full width at half maximum (FWHM). Using high resolution at 100,000 FWHM allows for the identification of TTX and its analogues in various matrices, including puffer fish and molluscan shellfish samples (Δ ppm = 0.28-3.38). The confirmation of characteristic fragment ions of TTX and its analogues was achieved by determining their elemental formulae via high mass accuracy. A quantitative method was then developed and optimised using these characteristic fragment ions. The limit of quantitation (LOQ) of the method was 0.136 µg g(-1) (S/N = 10) and the limit of detection (LOD) was 0.041 µg g(-1) (S/N = 3) spiking TTX standard into TTX-free mackerel fish extracts. The method was applied to naturally contaminated puffer fish and molluscan shellfish samples to confirm the presence of TTX and its analogues.

LC-MS/MS method for the determination of tetrodotoxin (TTX) on a triple quadruple mass spectrometer.

Tetrodotoxin (TTX), often referred to as the 'puffer fish' poison, is a marine toxin and it has been identified as the agent responsible for many food poisoning incidents around the world. It is a neurotoxin that blocks voltage-gated sodium channels, resulting in respiratory paralysis and even death in severe cases. It is known to occur in many different species of fish and other organisms. The toxin is mainly found in the Southeast Asia region. Worryingly, TTX is starting to appear in European waters. It is suspected that this is a consequence of Lessepsian migration, also known as the Erythrean invasion. Therefore, straightforward and reliable extraction and analytical methods are now urgently required to monitor seafood of European origin for TTX. This paper provides a versatile, dependable and robust method for the analysis of TTX in puffer fish and trumpet shellfish using LC-MS/MS. A three-stage approach was implemented involving: (1) the screening of samples using fast multiple reaction monitoring (MRM) mass spectral analysis to identify quickly positive samples on a triple quadrupole mass spectrometer (QqQMS/MS), the API 3000; (2) a Fourier-transform (FT)-MS full-scan analysis of positive samples to collect qualitative data; and (3) a method with a longer chromatography run to identify and quantitate the positive samples using the QqQMS. The quantitative LC-QqQMS method delivered excellent linearity for solvent-based standards (0.01-7.5 µg ml-1; R2 ≥ 0.9968) as well as for matrix-matched standards (0.05-37.50 µg g-1; R2 ≥ 0.9869). Good inter-day repeatability was achieved for all the relevant analytes with %RSD values (n = 9) ranging from 1.11% to 4.97% over a concentration range of 0.01-7.5 µg ml-1. A sample clean-up procedure for the puffer fish and trumpet shellfish was developed to ensure acceptable and reproducible recoveries to enable accurate and precise determination of TTX in a myriad of tissues types. Blank mackerel matrix was used for the TTX standard spiking studies in order to calculate the recoveries of the toxin during the extraction procedure. The recovery was 61.17% ± 5.42% for the extraction protocol. MS/MS studies were performed on a linear-trap quadruple-Orbitrap mass spectrometer (LTQ-Orbitrap) to obtain high-mass-accuracy data of the target analytes and their characteristic fragment ions in the puffer fish and trumpet shellfish samples. This facilitated identification of TTX and its associated analogues. These high-mass-accuracy studies facilitated the development of a rapid MRM-based quantitative method for TTX determination on the LC-QqQMS.

Antifungal sourdough lactic acid bacteria as biopreservation tool in quinoa and rice bread.

The use of sourdough fermented with specific strains of antifungal lactic acid bacteria can reduce chemical preservatives in bakery products. The main objective of this study was to investigate the production of antifungal carboxylic acids after sourdough fermentation of quinoa and rice flour using the antifungal strains Lactobacillus reuteri R29 and Lactobacillus brevis R2Δ as bioprotective cultures and the non-antifungal L. brevis L1105 as a negative control strain. The impact of the fermentation substrate was evaluated in terms of metabolic activity, acidification pattern and quantity of antifungal carboxylic acids. These in situ produced compounds (n=20) were extracted from the sourdough using a QuEChERS method and detected by a new UHPLC-MS/MS chromatography. Furthermore, the sourdough was applied in situ using durability tests against environmental moulds to investigate the biopreservative potential to prolong the shelf life of bread. Organic acid production and TTA values were lowest in rice sourdough. The sourdough fermentation of the different flour substrates generated a complex and significantly different profile of carboxylic acids. Extracted quinoa sourdough detected the greatest number of carboxylic acids (n=11) at a much higher concentration than what was detected from rice sourdough (n=9). Comparing the lactic acid bacteria strains, L. reuteri R29 fermented sourdoughs contained generally higher concentrations of acetic and lactic acid but also the carboxylic acids. Among them, 3-phenyllactic acid and 2-hydroxyisocaproic acid were present at a significant concentration. This was correlated with the superior protein content of quinoa flour and its high protease activity. With the addition of L. reuteri R29 inoculated sourdough, the shelf life was extended by 2 days for quinoa (+100%) and rice bread (+67%) when compared to the non-acidified controls. The L. brevis R2Δ fermented sourdough bread reached a shelf life of 4 days for quinoa (+100%) and rice (+33%). However, the shelf life was similar to the chemically acidified control indicating that the preservation effect of the carboxylic acids seems to have a minor contribution effect on the antifungal activity in gluten-free breads.

Clinical applications of HPLC-ICP-MS element speciation: A review.

Arsenic (As), Selenium (Se) and Mercury (Hg) are three trace elements that have been the subject of much analytical discussion and investigation over the last three decades. While Selenium (Se) is among the list of essential trace elements necessary for the regulation of metabolic processes and overall health, As and Hg are not, and have been the centre of various cases surrounding the contamination of food, water and the environment. The focus of this review is to explore the area of chemical speciation, particularly as it relates to the measurement of these elements in various clinical matrices by HPLC-ICP-MS. This review will highlight the importance of accurately identifying the various chemical species of each of these elements, especially when considering their respective toxicological impacts on human health.

Comparison and validation of 2 analytical methods for the determination of free fatty acids in dairy products by gas chromatography with flame ionization detection.

Accurate quantification of free fatty acids (FFA) in dairy products is important for quality control, nutritional, antimicrobial, authenticity, legislative, and flavor purposes. In this study, the performance of 2 widely used gas chromatographic flame ionization detection methods for determination of FFA in dairy products differing in lipid content and degree of lipolysis were evaluated. We used a direct on-column approach where the isolated FFA extract was injected directly and a derivatization approach where the FFA were esterified in the injector to methyl esters using tetramethylammonium hydroxide as a catalyst. A comprehensive validation was undertaken to establish method linearity, limits of detection, limits of quantification, accuracy, and precision. Linear calibrations of 3 to 700mg/L (R(2)>0.999) and 20 to 700mg/L (R(2)>0.997), and limits of detection and limits of quantification of 0.7 and 3mg/L and 5 and 20mg/L were obtained for the direct injection on-column and the derivatization method, respectively. Intraday precision of 1.5 to 7.2% was obtained for both methods. The direct injection on-column method had the lower levels of limits of detection and quantification, because FFA are directly injected onto the GC as opposed to the split injection used in the derivatization method. However, the direct injection on-column method experienced accumulative column phase deterioration and irreversible FFA absorption because of the acidic nature of the injection extract, which adversely affected method robustness and the quantification of some longer chain FFA. The derivatization method experienced issues with quantification of butyric acid at low concentrations because of coelution with the injection solvent peak, loss of polyunsaturated FFA due to degradation by tetramethylammonium hydroxide, and the periodic emergence of by-product peaks of the tetramethylammonium hydroxide reaction that interfered with the quantification of some short-chain FFA. The derivatization method is more robust, and because the derivatization step can be automated, it is more suitable for routine analysis of FFA in dairy products. However, considerable scope exists to develop an alternative gas chromatography with flame ionization detection method to quantify FFA in dairy products without any limitations that is robust and accurate.

Trace metal determination as it relates to metallosis of orthopaedic implants: Evolution and current status.

In utilising metal surfaces that are in constant contact with each other, metal-on-metal (MoM) surgical implants present a unique challenge, in the sense that their necessity is accompanied by the potential risk of wear particle generation, metal ion release and subsequent patient toxicity. This is especially true of orthopaedic devices that are faulty and subject to failure, where the metal surfaces undergo atypical degradation and release even more unwanted byproducts, as was highlighted by the recent recall of orthopaedic surgical implants. The aim of this review is to examine the area of metallosis arising from the wear of MoM articulations in orthopaedic devices, including how the surgical procedures and detection methods have advanced to meet growing performance and analytical needs, respectively.

Antifungal activities of three different Lactobacillus species and their production of antifungal carboxylic acids in wheat sourdough.

This study was undertaken to assess the antifungal performance of three different Lactobacillus species.Experiments were conducted in vitro and in situ to extend the shelf life of wheat bread. Standard sourdough analyses were performed characterising acidity and carbohydrate levels. Overall, the strains showed good inhibition in vitro against the indicator mould Fusarium culmorum TMW4.2043. Sourdough bread fermented with Lactobacillus amylovorus DSM19280 performed best in the in situ shelf life experiment. An average shelf life extension of six more mould-free days was reached when compared to the non-acidified control bread. A range of antifungal-active acids like 3-phenyllactic acid, 4-hydroxyphenyllactic acid and 2-hydroxyisocaproic acid in quantities between 0.1 and 360 mg/kg were present in the freeze-dried sourdoughs. Their concentration differed greatly amongst the species.However, a higher concentration of these compounds could not completely justify the growth inhibition of environmental moulds. In particular, although Lb. reuteri R29 produced the highest total concentration of these active compounds in the sourdough, its addition to bread did not result in a longest shelf life. Nevertheless, when the artificial compounds were spiked into a chemically acidified dough, it succeeded in a longer shelf life (+25 %) than achieved only by acidifying the dough. This provides evidence of their contribution to the antifungal activity and their synergy in concentration levels far below their single minimal inhibition concentrations under acidic conditions.

Assessment of emerging biotoxins (pinnatoxin G and spirolides) at Europe's first marine reserve: Lough Hyne.

Active and passive sampling methods were employed over a four-month period, at a site off the South-West coast of Ireland, to characterise the occurrence of cyclic imines in the water column. The marine toxins 13-desmethyl-SPXC, 20-methyl SPXG toxins and pinnatoxin G were detected using active sampling from Diaion HP-20 resin. Seven water depths were sampled to determine stratification of the toxins in the water column using Solid Phase Adsorption and Toxin Tracking (SPATT). Both 13-desmethyl-SPXC and pinnatoxin G were detected using two different resin types; Diaion HP-20 and Amberlite XAD761. HP-20 proved more effective at accumulating the toxins, with a higher percentage of positive samples and a higher ratio of toxin adsorbed relative to XAD761. No temporal variation in toxin-quantities was detected, indicating that there was no change in density of causative algal species in the water column. Pinnatoxin G was detected more frequently from surface to 30 m depth, with a similar pattern observed for 13-desmethyl-SPXC occurrence using XAD761. No difference in the occurrence of 13-desmethyl-SPXC was observed between depths using HP-20 resin. This is the first reported incidence of pinnatoxin G in Irish waters and highlights cyclic imines as emerging toxins in European waters.

Application of Lactobacillus amylovorus DSM19280 in gluten-free sourdough bread to improve the microbial shelf life.

The present study investigated the antifungal activity of Lactobacillus amylovorus DSM19280 as a starter culture for gluten-free quinoa sourdough bread under pilot-plant conditions to extend the microbial shelf life. Challenge tests against environmental moulds were conducted and a negative control with non-antifungal strain, L. amylovorus DSM20531(T), as well as a chemically acidified and a non-acidified control were included. Organic acid production, antifungal metabolites, carbohydrates changes during fermentation and bread quality were compared to wheat counterparts. The application of quinoa sourdough fermented with the antifungal L. amylovorus DSM19280 extended the mould free shelf life by 4 days compared to the non-acidified control. No significant difference in lactic acid production was found between the lactobacilli strains. HPLC-UV/DAD was used to quantify antifungal compounds. The concentration of 4-hydroxyphenyllactic acid, phloretic acid, 3-phenyllactic acid and hydroferulic acid were significantly higher (P < 0.01) in the quinoa sourdough fermented with the antifungal L. amylovorus DSM19280 when compared to the non-antifungal strain, thus indicating their contribution to the antifungal activity. Evaluation of bread characteristics such as specific volume or crumb hardness, revealed that the addition of L. amylovorus fermented sourdough also improved bread quality. In conclusion, the combination of quinoa flour fermented with the antifungal L. amylovorus DSM19280 serves a great potential biopreservative ingredient to produce gluten-free breads with an improved nutritional value, better bread quality and higher safety due to an extended shelf life, and therefore meeting consumer needs for good quality and preservatives-free food products.

Determination of the persistence of dimetridazole, metronidazole and ronidazole residues in black tiger shrimp (Penaeus monodon) tissue and their stability during cooking.

The depletion of three banned nitroimidazole drugs - dimetridazole (DMZ), metronidazole (MNZ) and ronidazole (RNZ) - was investigated in black tiger shrimp (Penaeus monodon) following in-water medication. The highest concentrations of residues were measured immediately after the 24-h immersion (d0). At this time, MNZ and MNZ-OH residues were measured in shrimp tissue samples at concentrations ranging from 361 to 4189 and from 0.28 to 6.6 µg kg(-1), respectively. DMZ and its metabolites HMMNI ranged in concentration between 31,509 and 37,780 and between 15.0 and 31.9 µg kg(-1), respectively. RNZ and HMMNI concentrations ranged from 14,530 to 24,206 and from 25.0 to 55 µg kg(-1), respectively. MNZ, DMZ and RNZ were the more persistent marker residues and can be detected for at least 8 days post-treatment. MNZ-OH was only detectable on d0 following treatment with MNZ. HMMNI residues were only detectable up to d1 (0.97-3.2 µg kg(-1)) or d2 (1.2-4.5 µg kg(-1)) following DMZ and RNZ treatment, respectively. The parent drugs MNZ, DMZ and RNZ were still measureable on d8 at 0.12-1.0, 40.5-55 and 8.8-18.7 µg kg(-1), respectively. The study also investigated the stability of nitroimidazole residues under various cooking procedures (frying, grilling, boiling, and boiling followed by microwaving). The experiments were carried out in shrimp muscle tissue containing both high and low concentrations of these residues. Different cooking procedures showed the impact on nitroimidazole residue concentration in shrimp tissue. Residue concentration depleted significantly, but partially, by boiling and/or microwaving, but the compounds were largely resistant to conventional grilling or frying. Cooking cannot therefore be considered as a safeguard against harmful nitroimidazole residues in shrimp.