Content and Bioaccessibility of Minerals and Proteins in Fish-Bone Containing Side-Streams from Seafood Industries.

With the aim to upcycle fish side-streams, enzymatic hydrolysis is often applied to produce protein hydrolysates with bioactive properties or just as a protein source for food and feed. However, the production of hydrolysates generates a side-stream. For underutilized fish and fish backbone this side-stream will contain fish bones and make it rich in minerals. The aim of this study was to assess the relative bioaccessibility (using the standardized in vitro model INFOGEST 2.0) of minerals in a dietary supplement compared to bone powder generated after enzymatic hydrolysis of three different fish side-streams: undersized whole hake, cod and salmon backbones consisting of insoluble protein and bones. Differences in the bioaccessibility of protein between the powders were also investigated. The enzyme hydrolysis was carried out using different enzymes and hydrolysis conditions for the different fish side-streams. The content and bioaccessibility of protein and the minerals phosphorus (P), calcium (Ca), potassium (K) and magnesium (Mg) were measured to evaluate the potential of the powder as an ingredient in, e.g., dietary supplements. The bone powders contained bioaccessible proteins and minerals. Thus, new side-streams generated from enzymatic hydrolysis can have possible applications in the food sector due to bioaccessible proteins and minerals.

Influence of the processing on composition, protein structure and techno-functional properties of mealworm protein concentrates produced by isoelectric precipitation and ultrafiltration/diafiltration.

Edible insects represent a great alternative protein source but food neophobia remains the main barrier to consumption. However, the incorporation of insects as protein-rich ingredients, such as protein concentrates, could increase acceptance. In this study, two methods, isoelectric precipitation and ultrafiltration-diafiltration, were applied to produce mealworm protein concentrates, which were compared in terms of composition, protein structure and techno-functional properties. The results showed that the protein content of the isoelectric precipitation concentrate was higher than ultrafiltration-diafiltration (80 versus 72%) but ash (1.91 versus 3.82%) and soluble sugar (1.43 versus 8.22%) contents were lower. Moreover, the protein structure was affected by the processing method, where the ultrafiltration-diafiltration concentrate exhibited a higher surface hydrophobicity (493.5 versus 106.78 a.u) and a lower denaturation temperature (161.32 versus 181.44 °C). Finally, the ultrafiltration-diafiltration concentrate exhibited higher solubility (87 versus 41%) and emulsifying properties at pH 7 compared to the concentrate obtained by isoelectric precipitation.

Influence of acidification and re-neutralization on mineral equilibria and physicochemical properties of model cheese feed.

Cheese feed is used as spray-dryer feed in cheese powder production, where there is growing consumer demand to eliminate calcium-chelating salts (ES). To develop ES-free feed production processes, it is essential to investigate the relationship between pH, structural changes, and mineral solubilization. This study investigated the influence of acidification and pH re-neutralization on calcium equilibria and stability of ES-free model cheese feeds. The goal was to increase protein availability by solubilizing colloidal calcium phosphate (CCP) and to assess whether CCP solubilization is reversible upon re-neutralization. The extent of acidification (to pH 4.2 or pH 4.7) significantly affected the irreversibility of calcium solubilization upon re-neutralization. Moreover, re-neutralization treatment seemed to induce changes in protein-fat interactions. Feed viscosity was mainly influenced by the final pH, rather than the re-neutralization history. These results offer new insights into the complex interplay of pH, structural modifications, mineral solubilization, and stability in cheese feed production.

Recovery of Nutrients from Cod Processing Waters.

Liquid side-streams from food industries can be processed and used in food applications and contribute to reduce the environmental footprint of industries. The goal of this study was to evaluate the effectiveness and applicability of protein and phosphorus separation processes, namely microfiltration, ultrafiltration and flocculation, using protein-rich process waters with low (LS) and high (HS) salt content from the processing of salted cod (Gadus morhua). The application of different flocculants (chitosan lactate and Levasil RD442) were evaluated at different concentrations and maturation periods (0, 1 or 3 h). The results showed that different flocculation treatments resulted in different recoveries of the nutrients from LS and HS. Proteins in LS could be most efficiently recovered by using Levasil RD442 0.25% and no maturation period (51.4%), while phosphorus was most efficiently recovered when using Levasil RD442 1.23% and a maturation period of 1 h (34.7%). For HS, most of its protein was recovered using Levasil RD442 1.23% and a maturation period of 1 h (51.8%), while phosphorus was recovered the most using Levasil 1.23% and no maturation period (47.1%). The salt contents allowed interactions through intermolecular forces with Levasil RD442. The ultrafiltration method was effective on HS since it recovered higher percentages of nutrients in the retentate phase (57% of the protein and 46% of the phosphorus) compared to LS.

Development of Photonic Multi-Sensing Systems Based on Molecular Gates Biorecognition and Plasmonic Sensors: The PHOTONGATE Project.

This paper presents the concept of a novel adaptable sensing solution currently being developed under the EU Commission-founded PHOTONGATE project. This concept will allow for the quantification of multiple analytes of the same or different nature (chemicals, metals, bacteria, etc.) in a single test with levels of sensitivity and selectivity at/or over those offered by current solutions. PHOTONGATE relies on two core technologies: a biochemical technology (molecular gates), which will confer the specificity and, therefore, the capability to be adaptable to the analyte of interest, and which, combined with porous substrates, will increase the sensitivity, and a photonic technology based on localized surface plasmonic resonance (LSPR) structures that serve as transducers for light interaction. Both technologies are in the micron range, facilitating the integration of multiple sensors within a small area (mm2). The concept will be developed for its application in health diagnosis and food safety sectors. It is thought of as an easy-to-use modular concept, which will consist of the sensing module, mainly of a microfluidics cartridge that will house the photonic sensor, and a platform for fluidic handling, optical interrogation, and signal processing. The platform will include a new optical concept, which is fully European Union Made, avoiding optical fibers and expensive optical components.

Effect of Moderate Electric Fields on the Physical and Chemical Characteristics of Cheese Emulsions.

Cheese powder is a multifunctional ingredient that is produced by spray drying a hot cheese emulsion called cheese feed. Feed stability is achieved by manipulating calcium equilibrium using emulsifying salts. However, the increased demand for 'green' products created a need for alternative production methods. Therefore, this study investigated the impact of ohmic heating (OH) on Cheddar cheese, mineral balance, and the resulting cheese feed characteristics compared with a conventional method. A full factorial design was implemented to determine the optimal OH parameters for calcium solubilization. Electric field exposure and temperature had a positive correlation with mineral solubilization, where temperature had the greatest impact. Structural differences in pre-treated cheeses (TC) were analyzed using thermorheological and microscopic techniques. Obtained feeds were analyzed for particle size, stability, and viscosity. OH-treatment caused a weaker cheese structure, indicating the potential removal of calcium phosphate complexes. Lower component retention of OH_TC was attributed to the electroporation effect of OH treatment. Microscopic images revealed structural changes, with OH_TC displaying a more porous structure. Depending on the pre-treatment method, component recovery, viscosity, particle size distribution, and colloidal stability of the obtained feeds showed differences. Our findings show the potential of OH in mineral solubilization; however, further improvements are needed for industrial application.

Arsenic speciation in low-trophic marine food chain - An arsenic exposure study on microalgae (Diacronema lutheri) and blue mussels (Mytilus edulis L.).

Microalgae and blue mussels are known to accumulate undesirable substances from the environment, including arsenic (As). Microalgae can biotransform inorganic As (iAs) to organoarsenic species, which can be transferred to blue mussels. Knowledge on As uptake, biotransformation, and trophic transfer is important with regards to feed and food safety since As species have varying toxicities. In the current work, experiments were conducted in two parts: (1) exposure of the microalgae Diacronema lutheri to 5 and 10 µg/L As(V) in seawater for 4 days, and (2) dietary As exposure where blue mussels (Mytilus edulis L.) were fed with D. lutheri exposed to 5 and 10 µg/L As(V), or by aquatic exposure to 5 µg/L As(V) in seawater, for a total of 25 days. The results showed that D. lutheri can take up As from seawater and transform it to methylated As species and arsenosugars (AsSug). However, exposure to 10 µg/L As(V) resulted in accumulation of iAs in D. lutheri and lower production of methylated As species, which may suggest that detoxification mechanisms were overwhelmed. Blue mussels exposed to As via the diet and seawater showed no accumulation of As. Use of linear mixed models revealed that the blue mussels were gradually losing As instead, which may be due to As concentration differences in the mussels' natural environment and the experimental setup. Both D. lutheri and blue mussels contained notable proportions of simple methylated As species and AsSug. Arsenobetaine (AB) was not detected in D. lutheri but present in minor fraction in mussels. The findings suggest that low-trophic marine organisms mainly contain methylated As species and AsSug. The use of low-trophic marine organisms as feed ingredients requires further studies since AsSug are regarded as potentially toxic, which may introduce new risks to feed and food safety.

Gelatin from Saithe (Pollachius virens) Skin: Biochemical Characterization and Oxidative Stability in O/W Emulsions.

This study performed the extraction of gelatin from saithe (Pollachius virens) skin and compared it to commercial marine gelatin. As a first stage, we investigated the physicochemical and biochemical properties of the gelatin. SDS-PAGE analysis revealed the presence of α-chains, ß-chains, and other high-molecular-weight aggregates. DSC thermograms showed typical gelatin behavior, while the FTIR spectra were mainly situated in the amide band region (amide A, amide B, amide I, amide II, and amide III). In the second stage, we produced O/W emulsions and analyzed their physical and oxidative stability over 9 days. Oil droplets stabilized with the gelatins obtained from saithe fish skin had a size of ~500 nm and a ζ-potential ~+25 mV, which is comparable to oil droplets stabilized with commercial gelatin products. Moreover, the oxidative stability of the emulsions stabilized with gelatin from saithe fish skin showed promising results in terms of preventing the formation of some volatile compounds towards the end of the storage period compared to when using the commercial gelatins. This study indicates the potential application of fish skin gelatin in the fields of food and cosmetics, as well as suggesting that further investigations of their techno-functional properties.

Arsenic species in mesopelagic organisms and their fate during aquafeed processing.

A responsible harvest of mesopelagic species as aquafeed ingredients has the potential to address the United Nations Sustainable Development Goal 14, which calls for sustainable use of marine resources. Prior to utilization, the levels of undesirable substances need to be examined, and earlier studies on mesopelagic species have reported on total arsenic (As) content. However, the total As content does not give a complete basis for risk assessment since As can occur in different chemical species with varying toxicity. In this work, As speciation was conducted in single-species samples of the five most abundant mesopelagic organisms in Norwegian fjords. In addition, As species were studied in mesopelagic mixed biomass and in the resulting oil and meal feed ingredients after lab-scale feed processing. Water-soluble As species were determined based on ion-exchange high-performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). This was supplemented by extracting arsenolipids (AsLipids) and determining total As in this fraction. The non-toxic arsenobetaine (AB) was the dominant form in mesopelagic crustaceans and fish species, accounting for approximately 70% and 50% of total As, respectively. Other water-soluble species were present in minor fractions, including carcinogenic inorganic As, which, in most samples, was below limit of quantification. The fish species had a higher proportion of AsLipids, approximately 35% of total As, compared to crustaceans which contained 20% on average. The feed processing simulation revealed generally low levels of water-soluble As species besides AB, but considerable fractions of potentially toxic AsLipids were found in the biomass, and transferred to the mesopelagic meal and oil. This study is the first to report occurrence data of at least 12 As species in mesopelagic organisms, thereby providing valuable information for future risk assessments on the feasibility of harnessing mesopelagic biomass as feed ingredients.

Validation and Demonstration of an Atmosphere-Temperature-pH-Controlled Stirred Batch Reactor System for Determination of (Nano)Material Solubility and Dissolution Kinetics in Physiological Simulant Lung Fluids.

In this study, we present a dissolution test system that allows for the testing of dissolution of nano- and micrometer size materials under highly controlled atmospheric composition (O2 and CO2), temperature, and pH. The system enables dissolution testing in physiological simulant fluids (here low-calcium Gamble's solution and phagolysosomal simulant fluid) and derivation of the temporal dissolution rates and reactivity of test materials. The system was validated considering the initial dissolution rates and dissolution profiles using eight different materials (γ-Al2O3, TiO2 (NM-104 coated with Al2O3 and glycerin), ZnO (NM-110 and NM-113, uncoated; and NM-111 coated with triethoxycaprylsilane), SiO2 (NM-200-synthetic amorphous silica), CeO2 (NM-212), and bentonite (NM-600) showing high intra-laboratory repeatability and robustness across repeated testing (I, II, and III) in triplicate (replicate 1, 2, and 3) in low-calcium Gamble's solution. A two-way repeated-measures ANOVA was used to determine the intra-laboratory repeatability in low-calcium Gamble's solution, where Al2O3 (p = 0.5277), ZnO (NM-110, p = 0.6578), ZnO (NM-111, p = 0.0627), and ZnO (NM-113, p = 0.4210) showed statistical identical repeatability across repeated testing (I, II, and III). The dissolution of the materials was also tested in phagolysosomal simulant fluid to demonstrate the applicability of the ATempH SBR system in other physiological fluids. We further show the uncertainty levels at which dissolution can be determined using the ATempH SBR system.

Influence of Pre-Dispersion Media on the Batch Reactor Dissolution Behavior of Al2O3 Coated TiO2 (NM-104) and Two ZnO (NM-110 and NM-111) Nanomaterials in Biologically Relevant Test Media.

Dissolution plays an important role on pulmonary toxicity of nanomaterials (NMs). The influence of contextual parameters on the results from dissolution testing needs to be identified to improve the generation of relevant and comparable data. This study investigated how pre-dispersions made in water, low-calcium Gamble's solution, phagolysosomal simulant fluid (PSF), and 0.05% bovine serum albumin (BSA) affected the dissolution of the Al2O3 coating on poorly soluble TiO2 also coated with glycerine (NM-104) and rapidly dissolving uncoated (NM-110) and triethoxycaprylsilane-coated ZnO (NM-111) NMs. Dissolution tests were undertaken and controlled in a stirred batch reactor using low-calcium Gamble's solution and phagolysosomal simulant fluid a surrogate for the lung-lining and macrophage phagolysosomal fluid, respectively. Pre-dispersion in 0.05% BSA-water showed a significant delay or decrease in the dissolution of Al2O3 after testing in both low-calcium Gamble's solution and PSF. Furthermore, use of the 0.05% BSA pre-dispersion medium influenced the dissolution of ZnO (NM-110) in PSF and ZnO (NM-111) in low-calcium Gamble's solution and PSF. We hypothesize that BSA forms a protective coating on the particles, which delays or lowers the short-term dissolution of the materials used in this study. Consequently, the type of pre-dispersion medium can affect the results in short-term dissolution testing.

Biochemical Characterization and Storage Stability of Process Waters from Industrial Shrimp Production.

Shrimp boiling water (SBW) and shrimp peeling water (SPW), generated during shrimp processing, were characterized in terms of crude composition, volatile compounds, as well as nutritional and potentially toxic elements over a 13 month sampling period. The storage stability of both waters was also evaluated. Results showed that SBW contained on median 14.8 g/L protein and 2.2 g/L total fatty acids with up to 50% comprising eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA). Astaxanthin esters, which dominated the total astaxanthin, were 2.8 mg/L on median. SPW, on the other hand, contained on median 1.0 g/L of protein, 0.21 g/L of total fatty acids, and 1.2 mg/L astaxanthin esters. For both side-streams, essential amino acids were up to 50% of total amino acids. For SBW and SPW, the most abundant nutritional elements were Na, K, P, Ca, Cu, and Zn. The contents of all potentially toxic elements were below the detection limits, except for As. SBW was more stable at 4 °C compared to SPW as shown, e.g., by thiobarbituric acid reactive substances and relative changes in total volatile basic nitrogen. The extensive compositional mapping of SBW/SPW provides crucial knowledge necessary in the exploitation and value-adding of such side-streams into food or feed products.

Assessing Mineral Availability in Fish Feeds using Complementary Methods Demonstrated with the Example of Zinc in Atlantic Salmon.

Assessing the availability of dietary micro-minerals is a major challenge in mineral nutrition of fish species. The present article aims to describe a systematic approach combining different methodologies to assess the availability of zinc (Zn) in Atlantic salmon (Salmo salar). Considering that several Zn chemical species can be present in an Atlantic salmon feed, it was hypothesised that Zn availability is influenced by the Zn chemical species present in the feed. Thus, in this study, the first protocol is about how to extract the different Zn chemical species from the feed and to analyze them by a size exclusion chromatography-inductively coupled plasma mass spectroscopy (SEC-ICP-MS) method. Subsequently, an in vitro method was developed to evaluate the solubility of dietary Zn in Atlantic salmon feeds. The third protocol describes the method to study the impact of changing Zn chemical species composition on the uptake of Zn in a fish intestinal epithelial model using a rainbow trout gut cell line (RTgutGC). Together, the findings from the in vitro methods were compared with an in vivo study examining the apparent availability of inorganic and organic sources of Zn supplemented to Atlantic salmon feeds. The results showed that several Zn chemical species can be found in feeds and the efficiency of an organic Zn source depends very much on the amino acid ligand used to chelate Zn. The findings of the in vitro methods had less correlation with that outcome of the in vivo study. Nevertheless, in vitro protocols described in this article provided crucial information regarding Zn availability and its assessment in fish feeds.

Ultra-trace speciation analysis of Cr(III) and Cr(VI) in rice using species-specific isotope dilution and HPLC-ICP-MS.

The study aims to clarify the current controversy related to conflicting reports on whether presence of Cr(VI) in rice is possible or not. For this purpose, a method was employed for the single run speciation analysis of Cr(III) and Cr(VI) in rice samples using species-specific isotope dilution (SS-ID) and high performance liquid chromatography coupled to inductively coupled mass-spectrometry (HPLC-ICP-MS) and selective single run species complexation/derivatisation. The quantification limits (LOQs) were 0.014 µg kg-1 for Cr(III) and 0.047 µg kg-1 for Cr(VI), while the detection limits (LODs) were 0.004 and 0.014 µg kg-1 for Cr(III) and Cr(VI), respectively. A total of 10 rice samples of different origin and colour (depending on the type of industrial processing) were analysed in this study. The content of Cr(VI) was below the limit of quantification in all of the rice samples analysed, while the Cr(III) levels ranged between 0.59 (whole grain rice) up to 104 µg kg-1 (brown rice). All samples were also analysed for their total Cr (Crtotal) content by ICP-MS solely and the results were in all cases comparable with the Cr(III) levels determined in the same samples. To assess the stability of Cr(III) and Cr(VI) in rice, one sample was spiked with Cr(III) and Cr(VI) (individually) at different levels (5.0, 10, 15 and 20 µg kg-1), held for 2 h, and then analysed by SS-ID HPLC-ICP-MS. The results showed a complete reduction of Cr(VI) to Cr(III), while Cr(III) remained stable at all spiking levels. These findings support the general statement from the European Food Safety Authority related to the complete absence of Cr(VI) in foods and confirms that Cr in rice is found solely as Cr(III) species.

Physico-chemical and colloidal properties of protein extracted from black soldier fly (Hermetia illucens) larvae.

The black soldier fly larvae (BSFL), Hermetia illucens (Linnaeus), has been largely utilized for animal feed. Due to its interesting composition, BSFL has great potential to be further implemented in the human diet. Herein we compared the flour and protein extract composition based on their moisture, ash, amino acids, mineral, and protein content. To have wide knowledge on protein profile and behavior, SDS-page electrophoresis, Fourier-transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) were used to give information about protein structure and thermal stability, respectively. The flour and protein extract contained respectively 37.3% and 61.1% of protein. DSC graph reported a glass transition temperature around 30 °C, recognizable by a shift in the curve, and an endothermic peak for solid melting at around 200 °C. FTIR analysis showed the main amide bands (A, B, I, II, III) for the flour and protein extract. The foam properties of BSFL protein extract were explored under different temperatures treatment, and the best foam stability was reached at 85 °C with 15 min of treatment. The data highlight the promising techno-functional properties of BSFL protein extract, and that the nutritional composition might be suitable for further use of BSFL as food fortification system.

Dietary exposure to potentially toxic elements through sushi consumption in Catalonia, Spain.

Although sushi is considered as a healthy food, it can also be a route of exposure to chemical contaminants such as potentially toxic trace elements. In this study, we analysed the concentration of Cd, I, Ni, Pb and total Hg, as well as iAs and MeHg in sushi samples. Iodine levels were higher in samples containing seaweed, while iAs concentrations were greater in rice-containing sushi. In turn, total Hg and MeHg were significantly higher in sushi samples with tuna. Health risks of sushi consumption were assessed for three population groups: children, adolescents and adults. Considering an average intake of 8 sushi pieces for adults and adolescents, and 3 sushi pieces for children, the estimated exposure to MeHg by adolescents exceeded the tolerable daily intake set by EFSA, while MeHg intake by children and adults was below, but close to that threshold. A relatively high daily exposure of Ni and Pb was also found, especially for adolescents. Since this study focused only on the consumption of sushi, the contribution of other food groups to the overall dietary exposure should not be disregarded. It might lead to an exposure to MeHg and other trace elements above the health-based guideline values.

Speciation analysis of organoarsenic species in marine samples: method optimization using fractional factorial design and method validation.

Organoarsenic species in marine matrices have been studied for many years but knowledge gaps still exist. Most literature focuses on monitoring of arsenic (As) species using previously published methods based on anion- and cation-exchange high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS). These studies are often limited to few As species and/or only specific method performance characteristics are described. Most marine certified reference materials (CRMs) are only certified for arsenobetaine (AB) and dimethylarsinate (DMA), making it difficult to evaluate the accuracy of analytical methods for other organoarsenic species. To address these gaps, the main objective of this work was to develop and validate a method for speciation analysis of a broad range of organoarsenic species in marine matrices. Optimum extraction conditions were identified through a 27-3 fractional factorial design using blue mussel as test sample. The effects of sample weight, type and volume of extraction solution, addition of H2O2 to the extraction solution, extraction time and temperature, and use of ultrasonication were investigated. The highest As recoveries were obtained by using 0.2 g as sample weight, 5 mL of aqueous methanol (MeOH:H2O, 50% v/v) as extractant, extraction carried out at 90 °C for 30 min, and without ultrasonication. Anion- and cation-exchange HPLC-ICP-MS settings were subsequently optimized. The method detected a total of 33 known and unknown As species within a run time of 23 and 20 min for cation-exchange and anion-exchange, respectively. A single-laboratory validation was conducted using several marine CRMs: BCR 627 (tuna fish tissue), ERM-CE278k (mussel tissue), DORM-4 (fish protein), DOLT-5 (dogfish liver), SQID-1 (cuttlefish), TORT-3 (lobster hepatopancreas), and CRM 7405-b (hijiki seaweed). Method performance characteristics were evaluated based on selectivity, limits of detection and quantification, linearity, trueness, precision, and measurement uncertainty. This work proposes an extraction procedure which allowed satisfactory quantification of As species with low solvent and energy consumption, supporting "Green Chemistry" principles. The study also presents a new set of As speciation data, including methylated arsenic species and arsenosugars, in recently issued marine CRMs, which will be valuable for future speciation studies on As. This work is the first to report a total of 33 different As species in marine CRMs.

Characterisation and chemometric evaluation of 17 elements in ten seaweed species from Greenland.

Several Greenland seaweed species have potential as foods or food ingredients, both for local consumption and export. However, knowledge regarding their content of beneficial and deleterious elements on a species specific and geographical basis is lacking. This study investigated the content of 17 elements (As, Ca, Cd, Cr, Cu, Fe, Hg, I, K, Mg, Mn, Na, Ni, P, Pb, Se and Zn) in 77 samples of ten species (Agarum clathratum, Alaria esculenta, Ascophyllum nodosum, Fucus distichus, Fucus vesiculosus, Hedophyllum nigripes, Laminaria solidungula, Palmaria palmata, Saccharina latissima and Saccharina longicruris). Element profiles differed between species but showed similar patterns within the same family. For five species, different thallus parts were investigated separately, and showed different element profiles. A geographic origin comparison of Fucus species indicated regional differences. The seaweeds investigated were especially good sources of macrominerals (K > Na > Ca > Mg) and trace minerals, such as Fe. Iodine contents were high, especially in macroalgae of the family Laminariaceae. None of the samples exceeded the EU maximum levels for Cd, Hg or Pb, but some exceeded the stricter French regulations, especially for Cd and I. In conclusion, these ten species are promising food items.

Chromium speciation analysis in raw and cooked milk and meat samples by species-specific isotope dilution and HPLC-ICP-MS.

This study aimed at the assessment of the impact of various culinary processes on the fate of chromium (Cr) species (Cr(III) and Cr(VI)) in infant formula milk, semi-skimmed milk and bovine meat samples. The cooking procedures were boiling at 70°C/100°C (milk samples) and frying without and with oil (95°C and 120°C) (bovine meat). The levels of Cr(III) and Cr(VI) in raw and cooked samples were determined by high-performance liquid chromatography (HPLC) coupled to inductively coupled plasma mass spectrometry (ICP-MS) using double spike species-specific-isotope dilution (SS-ID). The species were extracted by sequential complexation of Cr(III) with ethylenediaminetetraacetic acid and of Cr(VI) with 1,5-diphenylcarbazide in the same analytical run by heating at 70°C for 50 min. Anion exchange chromatography using a Dionex IonPac™ AG7 column and a mobile phase consisting of 10 mM HNO3, 2.5% MeOH and 30 mM EDTA at pH 2 was employed for species separation. The quantification limits were 0.013 and 0.049 µg kg-1 for Cr(III) and Cr(VI), respectively. ANOVA test used to compare the mean Cr species concentrations showed no significant differences between raw and cooked samples. The results obtained in the present study show that oxidation of Cr(III) to Cr(VI) does not occur during thermal cooking of milk and bovine meat samples. A selection of 10 samples of each type were analysed in terms of total Cr (Crtotal) as well as speciation (Cr(III) and Cr(VI)). Cr(VI) was not quantified in any of these samples, whereas Cr(III) levels ranged from 0.22 (infant formula milk) up to 80 µg kg-1 (chorizo sausage). Additionally, Cr(III) and Crtotal levels were comparable hence demonstrating that in the samples analysed in this study, Cr is found exclusively as Cr(III) species.

Iodine determination in animal feed by inductively coupled plasma mass spectrometry - results of a collaborative study.

A collaborative study was conducted in order to fully validate the performance characteristics and to evaluate the suitability of a method for determination of iodine in animal feed. The method consists of an alkaline extraction in tetramethylammonium hydroxide (TMAH) solution followed by the determination of iodine by inductively coupled plasma-mass spectrometry (ICP-MS). The method was validated for different types of feed and feed materials with a broad concentration range of 0.65-622 mg I/kg. Good agreement was found between the overall mean mass fraction values from the collaborative trial (13.8 ± 1.3 mg I/kg and 0.657 ± 0.228 mg I/kg) and the values previously determined in proficiency tests for two of the test materials (12.65 ± 2.47 mg I/kg and 0.72 ± 0.22 mg I/kg) indicating satisfactory accuracy of the method. Reproducibility standard deviations were between 7.85% and 34.65% and the HorRat values were under the acceptable limit of 2 so the between-laboratory precision was considered acceptable. Based on the statistical evaluation of the results it was concluded that the method is suitable for its intended purpose; it has been accepted as European Standard EN17050:2017 by the European Committee for Standardisation (CEN).