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While the demand for Spirulina dietary supplements continues to grow, product inspection in terms of authenticity and safety remains limited. This study used the stable isotope ratios of light elements (C, N, S, H, and O) and the elemental composition to characterize Spirulina dietary supplements available on the Slovenian market. Forty-six samples were labelled as originating from the EU (1), non-EU (6), Hawaii (2), Italy (2), Japan (1), Portugal (2), Taiwan (3), India (4), and China (16), and nine products were without a declared origin. Stable isotope ratio median values were -23.9‱ (-26.0 to -21.8‱) for δ13C, 4.80‱ (1.30-8.02‱) for δ15N, 11.0‱ (6.79-12.7‱) for δ34S, -173‱ (- 190 to -158‱) for δ2H, and 17.2‱ (15.8-18.8‱) for δ18O. Multivariate statistical analyses achieved a reliable differentiation of Hawaiian, Italian, and Portuguese (100%) samples and a good separation of Chinese samples, while the separation of Indian and Taiwanese samples was less successful, but still notable. The study showed that differences in isotopic and elemental composition are indicative of sample origins, cultivation and processing methods, and environmental conditions such that, when combined, they provide a promising tool for determining the authenticity of Spirulina products.
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The ISO/IEC 17025 standard requires that all significant contributions have to be propagated to the measurement uncertainty, including also sampling uncertainties. We evaluated soil sampling uncertainties for gamma-ray spectrometry by using in-house and split-sample methods. By in-house method, the sampling uncertainty was determined by comparing standard deviations of measurement results and average analytical uncertainty. With split-sample method, it was calculated using between-sample and between-analysis variances. If analytical uncertainty is reliably determined, the in-house method is recommended because fewer measurements are needed.
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The microalgae Spirulina may be a popular dietary supplement rich in essential nutrients and vitamins, but oversight of the supplement industry, in general, remains limited, and increasing incidents of adulteration, misbranding, and undeclared ingredients together with misleading claims create potential risks. In response, this study characterized the elemental, amino acid and fatty acid content of commercially available Spirulina supplements in Slovenia using EDXRF, ICP-MS and GC-MS and compared the results with their nutritional declaration. The gathered data confirm that Spirulina supplements are a good source of calcium (0.15 to 29.5% of RDA), phosphorous (3.36-26.7% of RDA), potassium (0.5 to 7.69% of RDA) and selenium (0.01 to 38.6% of RDA) when consumed within recommended amounts. However, although iron contents were relatively high (7.64 to 316% of RDA), the actual bioavailability of iron was much lower since it was mainly present as the ferric cation. This study also confirms that pure Spirulina supplements are a good source of essential and non-essential amino acids, and ω-6 but not ω-3 polyunsaturated fatty acids. The presence of additives resulted in significant variation in nutrient content and, in some instances, lower product quality. Moreover, a high proportion (86.7%) of inappropriate declarations regarding the elemental content was observed. Overall, the study conclusions underline the need for a stricter control system for Spirulina-based supplements.
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We appreciate Dr Horacek's interest in our paper and his feedback [...].
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The present study investigated the effects of cultivation practices on grain (oats) yield and yield components, such as straw yield, harvest index, thousand kernel weight, and plant lodging. In addition, multi-element composition and isotopic signature (δ13C, δ15N) of the oat grains were studied. The spring oat cultivar 'Noni' was grown in a long-term field experiment during 2015-2020, using three management practices: control without organic amendment, incorporation of manure every third year and incorporation of crop residues/cover crop in the rotation. Synthetic nitrogen (N) (0, 55, 110 and 165 kg/ha) was applied during oat development in each system. Multi-element analysis of mature grains from two consecutive years (2016 and 2017) was performed using EDXRF spectroscopy, while stable isotope ratios of carbon (C) and nitrogen (N) were obtained using an elemental analyzer coupled to an isotope ratio mass spectrometer (EA/IRMS). The results show how cultivation practices affect yield components and isotopic and elemental signatures. Increasing the N rate improved both the oat grain and straw yields and increased susceptibility to lodging. The results show how the elemental content (Si, Ca, Zn, Fe, Ti, Br and Rb) in the oat grains were influenced by intensification, and a noticeable decrease in elemental content at higher N rates was the result of a dilution effect of increased dry matter production. The mean δ15N values in oat grains ranged from 2.5‱ to 6.4‱ and decreased with increasing N rate, while δ13C values ranged from -29.9‱ to -28.9‱. Based on the δ15N values, it was possible to detect the addition of synthetic N above an N rate of 55 kg/ha, although it was impossible to differentiate between different management practices using stable isotopes.
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The current study involves two analytical research techniques, inductively coupled plasma-mass spectrometry (ICP-MS) and energy dispersive X-ray fluorescence (EDXRF) spectroscopy, used to determine the elemental composition of different legumes usually produced and consumed in Slovenia. Results indicate that data obtained using these methods are in agreement with certified reference materials. In total, nineteen elements were determined from twenty legume samples. An intercomparison between four macro- (P, S, K, Ca) and three microelements (Fe, Zn, Mo) measured using ICP-MS and EDXRF methods showed a strong correlation. The EDXRF was found to be a cheaper, simpler and more environmentally friendly method for determination of elements P, S, Cl, K, Ca, Fe, Zn, Mo, Sr, Rb, Ti and Br in legumes, while for the identification and determination of Na, Mg, V, Cr, Mn, Co and Cu content ICP-MS was the method of choice due to its excellent sensitivity and accuracy. Using principal component analysis (PCA), the samples of the studied legumes were classified into four groups according to their elemental composition.
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Fabaceae/química , Espectrometria de Massas/métodos , Espectrometria por Raios X/métodos , Fabaceae/metabolismo , Magnésio/análise , Análise de Componente Principal , Eslovênia , Sódio/análise , Vanádio/análiseRESUMO
This work presents the first use of Sr isotope ratios for determining the provenance of bovine milk from different regions of Slovenia. The analytical protocol for the determination of 87Sr/86Sr isotope ratio was optimised and applied to authentic milk samples. Considerable variability of 87Sr/86Sr ratios found in Slovenian milk reflects the substantial heterogeneity of the geological background of its origin. The results, although promising, cannot discount possible inter-annual or annual variation of the Sr isotopic composition of milk. The 87Sr/86Sr ratios of groundwater and surface waters are in good correlation with milk, indicating that the Sr isotopic fingerprint in milk is reflective of cow drinking water. The 87Sr/86Sr ratio has the potential to distinguish between different milk production areas as long as these areas are characterised by geo-lithology. Discriminant analysis (DA) incorporating the elemental composition and stable isotopes of light elements showed that 87Sr/86Sr ratio together with δ13Ccas and δ15Ncas values have the main discrimination power to distinguish the Quaternary group (group 6) from the others. Group 1 (Cretaceous: Carbonate Rocks and Flysch) is associated with Br content, 1/Sr and δ18Ow values. The overall prediction ability was found to be 63.5%. Pairwise comparisons using OPLS-DA confirmed that diet and geologic parameters are important for the separation.
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A field trial of white cabbage (Brassica oleracea var. Capitata L.) was carried out under the humid temperate climate conditions in Central Slovenia to investigate the effects of calcium ammonium nitrate (0, 180 and 240 kg N ha-1) and gypsum (0 and 40 kg S ha-1) fertilisation on yield, yield quality (nitrate, glucosinolate levels and glucosinolate profile) and nitrogen use efficiency. The highest marketable yield, dry matter yield and nitrogen uptake were obtained at the highest nitrogen fertilisation rate when in combination with sulphur. For this treatment, the nitrogen surplus in the soil after harvesting was lower than for the same nitrogen fertilisation without sulphur application. For the combination N240S40, the sulphur addition significantly increased nitrogen use efficiency, which resulted in reduced nitrate content in the cabbage heads. The chemical forms of glucosinolates showed that 80-85% were aliphatic glucosinolates with the remainder as the indole group. For the aliphatic glucosinolates, significant interactions between nitrogen and sulphur fertilisations were reflected in increased levels of progoitrin and glucoiberin when sulphur was applied at the lower nitrogen fertilisation rates. For the indole group, the levels of glucobrassicin and the indole group itself decreased at higher nitrogen fertilisation rates, independent of sulphur fertilisation.
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Utilization of magnetic nanoparticle-mediated conversion of electromagnetic energy into heat is gaining attention in catalysis as a source of heat needed for a substrate's chemical reaction (electrification of chemical conversions). We demonstrate that rapid and selective heating of magnetic nanoparticles opens a way to the rapid synthesis of a nanocatalyst. Magnetic heating caused rapid reduction of Ru3+ cations in the vicinity of the support material and enabled preparation of a Ru nanoparticle-bearing nanocatalyst. Comparative synthesis conducted under conventional heating revealed significantly faster Ru3+ reduction under magnetic heating. The faster kinetic was ascribed to the higher surface temperature of the support material caused by rapid magnetic heating. The nanocatalyst was rigorously tested in the hydrotreatment of furfural. The activity, selectivity and stability for furfural hydrogenation to furfuryl alcohol, a valuable biobased monomer, remained high even after four magnetic recycles.
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This work examines the use of stable isotopes and elemental composition for determining geographical origin and authenticity of cow milk from four geographical regions of Slovenian. Samples (277) were collected during summer and winter (2012-2014). It was possible to discriminate milk samples according to the year, season and production region using discriminant analysis (DA). The overall temporal prediction variability was 84.6% and 56.4% for regional differences. It was also possible to discriminate milk from three geographic regions, although Alpine samples overlap with Dinaric and Pannonian ones. Prediction ability was the highest for the Pannonian (82.1%) and lowest (26.9%) for the Alpine region. Pairwise comparison using OPLS-DA also displaying good regional predictability (≥0.77) with δ13Ccas values and Br content carrying the most variance. A model based on DD-SIMCA was also developed and applied to the control of Slovenian milk. The results revealed the mislabeling of three Slovenian milk products.
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Isótopos/análise , Leite/química , Animais , Isótopos de Carbono/análise , Bovinos , Análise Discriminante , Feminino , Geografia , Isótopos de Nitrogênio/análise , Estações do Ano , EslováquiaRESUMO
Organic crop production has become a highly attractive way of production over the world and thus the need for robust analytical techniques for their authentication. The main aim of this study is to identify appropriate biomarkers to discriminate between organic and conventionally grown chicory. Chicory is an appreciated leafy vegetable among producers and consumers, especially due to its undemanding cultivation and content of bioactive substances. Six different fertility management practices (control, two organic, two mineral, and a combination of organic and mineral fertilizers) were used to produce five chicory cultivars in a glasshouse pot experiment. Analysis of bioactive compounds, nitrogen assimilation, multi-elemental profiling and stable isotope ratio determination of carbon (C), nitrogen (N) and sulphur (S) were performed to differentiate between organic and conventional production. In this study, nitrogen isotopes are found to be an excellent way of identifying organically produced chicory of a different variety with the highest δ15N values. Conversely, the same samples had the lowest δ34S values indicating that also stable isotopes of S could be used as a marker for the authentication of organic production.
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Cichorium intybus/química , Cichorium intybus/crescimento & desenvolvimento , Agricultura , Isótopos de Carbono/análise , Análise Discriminante , Alimentos Orgânicos/análise , Isótopos de Nitrogênio/análise , Agricultura Orgânica , Folhas de Planta/química , Folhas de Planta/crescimento & desenvolvimento , Isótopos de Enxofre/análise , Verduras/química , Verduras/crescimento & desenvolvimentoRESUMO
Dietary supplements based on algae, known for their nutritional value and bioactive properties, are popular products among consumers today. While commercial algal products are regarded safe by numerous studies, information about the production and origin of such products is scarce. In addition, dietary supplements are not as strictly regulated as food and medicinal drugs. We characterized different algal products (kelps: Laminariales, Spirulina spp., Chlorella spp., and Aphanizomenon flos-aquae), obtained on Slovenian market, based on their elemental composition (X-ray fluorescence, inductively coupled plasma-mass spectrometry), antioxidative potential [DPPH (2,2-diphenyl-1-picrylhydrazyl) assay, total phenolic content], and stable isotope values [carbon (C), nitrogen (N), and sulfur (S); elemental analyzer isotope ratio mass spectrometry (EA-IRMS) method]. Antioxidative potential is consistent among products of the same type, with A. flos-aquae samples having 4.4 times higher antioxidative potential compared to Chlorella spp. and 2.7 times higher compared to Spirulina spp. Levels of toxic trace elements (arsenic, cadmium, mercury, and lead) are below the maximum allowed values and as such do not pose risk to consumers' health. Samples of Spirulina spp. have relatively high δ15N (7.4 ± 4.4) values, which indicate use of organic nitrogen sources in certain samples. Likewise, different elemental composition and isotopic ratios of stable elements (C, N, and S) for the samples with Spirulina spp. or Chlorella spp. are the consequence of using different nutrient sources and algae-growing techniques. Statistical analysis (principal component analysis) has confirmed that all tested A. flos-aquae samples originate from the same source, supposedly Klamath Lake (Oregon, USA). Hawaiian Spirulina pacifica can also be differentiated from all the other samples because of its characteristically high metal content (iron, manganese, zinc, cobalt, nickel, vanadium). Chlorella spp. and Spirulina spp. require further analyses with larger number of samples, as differentiation is not possible based on results of this study.
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Jujube (Ziziphus jujuba Mill.) has favourable horticultural properties including adaptation to arid conditions, abiotic and biotic stresses, as well as positive impact on human health. The present study describes the characterization of genetic diversity of the germplasm of jujube from the Istrian peninsula, the determination of important chemical compounds, antioxidative properties in relation to antibacterial and antifungal activities of jujube fruit extracts, and the determination of nutritional properties of jujube fruit. The results of the genetic analysis showed that most of the samples from the Istrian peninsula belong to two recently introduced varieties, 'Li' and 'Lang', and the most widespread local variety 'Navadna zizola'. The local variety has smaller fruit than the 'Li' and 'Lang' varieties, with thick and fleshy mesocarp. Chemical analysis indicated that fruits of the local variety contained a valuable source of dietary fibre ((9.7±0.6) g/100 g) and were rich in minerals such as (in g/100 g dry mass): potassium (829±51), calcium (177±11) and phosphorus (129±19). Aqueous extracts showed slight antibacterial activity, while ethanol extracts had higher mass fractions of phenolic compounds (expressed as gallic acid equivalents (GAE), 5.8-8.7 mg/g) than the aqueous extracts, but did not show antimicrobial activity. Compounds other than phenolic compounds in jujube fruit may be more biologically active. Based on the results of these analyses, the local Istrian jujube variety is a promising candidate for cultivation potential.
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Fish from the Sava River are consumed daily by the local people: therefore, concern has been raised about the health implications of eating contaminated fish. In the present study, potentially toxic elements (PTE), such as Zn, Cu, Cr, Ni, Cd, Pb, As, Hg, and methylmercury (MeHg), were determined in ichthyofauna that are commonly consumed. PTE were determined in the fish muscle tissue. Fish were sampled at 12 locations from the source of the Sava River to its confluence with the Danube River during two sampling campaigns, namely; in 2014 under high water conditions and in 2015 under normal water conditions. Due to the different water regimes, different fish species were collected for chemical analysis. We observed that the concentrations of elements analysed in the fish muscle tissue were generally very low, except for those of Hg. Moreover, more than 90% of Hg present in the fish was in its most toxic form, namely MeHg. Especially in fish from the 2015 sampling campaign, Hg and MeHg concentrations increased with fish size, trophic level, and in the downstream direction. In addition, for Pb and As, and to some extent for Cd and Cr, spatial differences were detected in both years. The highest concentrations of PTE were detected in fish from sites with intensive industrial and agricultural activities. The consumption of fish in general does not pose a health risk for the PTE studied, except for Hg/MeHg at selected contaminated sites.
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Monitoramento Ambiental , Substâncias Perigosas/metabolismo , Músculos/metabolismo , Poluentes Químicos da Água/metabolismo , Animais , Peixes , Cadeia Alimentar , Contaminação de Alimentos/estatística & dados numéricos , Substâncias Perigosas/análise , Mercúrio/análise , Compostos de Metilmercúrio/análise , Músculos/química , Medição de Risco , Rios , Poluentes Químicos da Água/análiseRESUMO
For brewers, it is important to know the geographic origins of the hop plants (Humulus lupulus L.) used in their brewing processes since the contents and compositions of the bitter resins and essential oils in them depend on the environmental conditions during their growth. In this study, the multi-elemental profiles of hop plants from each of the world's main growing regions were determined by non-destructive energy dispersive X-ray fluorescence spectrometry (EDXRF). Understanding the multi-element profiles of the plants could be a useful tool in determining the geographic origins of produced hop plants.
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Humulus/química , Óleos Voláteis/química , Resinas Vegetais/química , Austrália , Análise Discriminante , Humulus/metabolismo , Nova Zelândia , Óleos Voláteis/análise , Análise de Componente Principal , Resinas Vegetais/análise , África do Sul , Espectrometria por Raios X , Estados UnidosRESUMO
This article presents yearly mean concentrations of cosmogenic radionuclides 7Be and 22Na occurring in dry and wet depositions (fallout) and aerosols. Time dependencies negatively correlated with the yearly mean number of sunspots. Activity concentrations of 7Be and 22Na in aerosols in the surface air had a correlation of near-unity. 7Be in aerosols exhibited a smoother time dependence than 22Na, implying that the production of 22Na is more sensitive to the solar activity than the production of 7Be. The effect of the measured doses on the general population through internal and external exposure to radiation from cosmogenic radionuclides was small.
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Poluentes Radioativos do Ar/análise , Berílio/análise , Doses de Radiação , Monitoramento de Radiação/métodos , Radioisótopos/análise , Radioisótopos de Sódio/análise , Atividade Solar , EslovêniaRESUMO
Plants of the genus Fagopyrum contain high levels of crystalline calcium oxalate (CaOx) deposits, or druses, that can affect the leaf optical properties. As selenium has been shown to modify the uptake and accumulation of metabolically important elements such as calcium, we hypothesised that the numbers of druses can be altered by selenium treatment, and this would affect the leaf optical properties. Tartary buckwheat (Fagopyrum tataricum Gaertn.) was grown outdoors in an experimental field. At the beginning of flowering, plants were foliarly sprayed with sodium selenate solution at 10â¯mgâ¯seleniumâ¯L-1 or only with water. Plant morphological, biochemical, physiological and optical properties were examined, along with leaf elemental composition and content. Se spraying did not affect leaf biochemical and functional properties. However, it increased leaf thickness and the contents of Se in the leaves, and decreased the density of calcium oxalate druses in the leaves. Except Se content, Se spraying did not affect contents of other elements in leaves, including total calcium per dry mass of leaf tissue. Redundancy analysis showed that of all parameters tested, only the calcium oxalate druses parameters were significant in explaining the variability of the leaf reflectance and transmittance spectra. The density of CaOx druses positively correlated with the reflectance in the blue, green, yellow and UV-B regions of the spectrum, while the area of CaOx druses per mm2 of leaf transection area positively correlated with the transmittance in the green and yellow regions of the spectrum.
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Oxalato de Cálcio/química , Oxalato de Cálcio/farmacologia , Fagopyrum/efeitos dos fármacos , Folhas de Planta/efeitos dos fármacos , Selênio/farmacologia , Clorofila/química , Clorofila A , Fagopyrum/química , Fagopyrum/efeitos da radiação , Folhas de Planta/química , Folhas de Planta/efeitos da radiação , Selênio/química , Espectrometria por Raios X , Raios UltravioletaRESUMO
This study characterises the genetic variability of local pomegranate (Punica granatum L.) germplasm from the Slovenian and Croatian areas of Istria. The bioactive components and antioxidant and antimicrobial properties of ethanol and water extracts of different parts of pomegranate fruit were also determined, along with their preliminary nutritional characterisation. Twenty-six different genotypes identified with microsatellite analysis indicate the great diversity of pomegranate in Istria. The pomegranate fruit ethanol extracts represent rich sources of phenolic compounds (mean value of the mass fraction in exocarp and mesocarp expressed as gallic acid is 23 and 16 mg/g, respectively). The ethanol extracts of pomegranate exocarp and mesocarp showed the greatest antimicrobial activity against Candida albicans, Candida parapsilosis, Rhodotorula mucilaginosa, Exophiala dermatitidis and Staphylococcus aureus, and the same water extracts against S. aureus and Escherichia coli. To the best of our knowledge, this study represents the first report of the characterisation of pomegranate genetic resources from Istria at different levels, including the molecular, chemical, antimicrobial and nutritional properties.
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A new fast decomposition procedure for solid samples was developed. In this study, we investigated decomposition of samples by lithium borates fusion in combination with salicylic acid. The method described shortens the time required for the sample to be digested and loaded to a resin to up to 2 h, and it was especially suitable for alpha spectrometry measurements in emergency situations. Additionally, the method results in high radiochemical recoveries and when compared to other digestion methods (classical digestion utilizing mineral acids, microwave digestion, and lithium borates fusion in combination with polyethylene glycol (PEG)) gives comparable activity concentration values. The method used was applied to various reference materials with inorganic and organic matrices as well as widely varying amounts of uranium radioisotopes content. The results obtained were compared with reference and literature values and show that the proposed method can be successfully implemented on various types of samples.
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Boratos/química , Compostos de Lítio/química , Ácido Salicílico/química , Animais , Bivalves/química , Bivalves/metabolismo , Micro-Ondas , Polietilenoglicóis/química , Radiometria , Alga Marinha/química , Alga Marinha/metabolismo , Solo/química , Espectrometria por Raios X , Urânio/químicaRESUMO
Celtis australis is a deciduous tree commonly known as Mediterranean hackberry or the European nettle tree. The fruit of hackberry are seldom used for nutritional purposes. The nutritional and physicochemical properties of ripe hackberry fruit from Istria (Marasi village near Vrsar, Croatia) were determined, including water, total fiber, protein, vitamin, mineral, and phenolic contents. This analysis demonstrates that the hackberry fruit is a valuable source of dietary fiber, protein, and vitamins, and of pigments such as lutein, ß-carotene, zeaxanthin, and tocopherols. The seasonal differences associated with the different growth stages for the element composition, total phenolic content, and phenolic profile were also determined for hackberry mesocarp and leaves. Water and ethanol extracts were prepared from mesocarp and leaves harvested at different growth stages and their phenolic profiles and antioxidant and antimicrobial activities were investigated. This study demonstrates that water and ethanol extracts of hackberry fruit and leaves collected at different growth stages contain epicatechin, gallic acid, vanillic acid, 3,4-dihydroxybenzaldehyde, delphinidin-3,5-di-O-glucoside, cyanidin-3,5-di-O-glucoside, and pelargonidin-3,5-di-O-glucoside. They also show some antimicrobial and antifungal activities. Further studies are needed to identify and define the active ingredients of these hackberry leaf ethanol extracts.