Contaminant uptake in wastewater irrigated tomatoes.

As population growth and climate change add to the problem of water scarcity in many regions, the argument for using treated wastewater for irrigation is becoming increasingly compelling, which makes understanding the risks associated with the uptake of harmful chemicals by crops crucial. In this study, the uptake of 14 chemicals of emerging concern (CECs) and 27 potentially toxic elements (PTEs) was studied in tomatoes grown in soil-less (hydroponically) and soil (lysimeters) media irrigated with potable and treated wastewater using LC-MS/MS and ICP-MS. Bisphenol S, 2,4 bisphenol F, and naproxen were detected in fruits irrigated with spiked potable water and wastewater under both conditions, with BPS having the highest concentration (0.034-0.134 µg kg-1 f. w.). The levels of all three compounds were statistically more significant in tomatoes grown hydroponically (

Reply to Horacek, M.; Cannavan, A. Comment on "Sinkovic et al. Isotope Fingerprints of Common and Tartary Buckwheat Grains and Milling Fractions: A Preliminary Study. Foods 2022, 11, 1414".

We thank Dr. Horacek and Dr. Cannavan for their interest [...].

Isotope Fingerprints of Common and Tartary Buckwheat Grains and Milling Fractions: A Preliminary Study.

The grains and milling fractions of common buckwheat (Fagopyrum esculentum Moench) and Tartary buckwheat (Fagopyrum tataricum (L.) Gaertn.) are widely used for both industrial and small-scale food and non-food products. This paper represents a preliminary study of the isotopic signature (δ13C, δ15N, and δ34S) to differentiate between buckwheat species (common vs. Tartary), organic and conventional cultivation farming, and different buckwheat fractions (light flour, semolina, and hulls) obtained by a traditional cereal stone-mill. Stable isotope ratios were analyzed using an elemental analyzer coupled to an isotope ratio mass spectrometer (EA/IRMS). The results indicated that δ13C, δ15N, and δ34S values could be used to verify the origin and production practices of buckwheat and even its products.

Geographical identification of strawberries based on stable isotope ratio and multi-elemental analysis coupled with multivariate statistical analysis: A Slovenian case study.

The geographical classification and authentication of strawberries were attempted using discriminant and class-modelling methods applied to stable isotopes of light elements and elemental composition. The work involved creating a database of 92 authentic Slovenian strawberry samples and 32 imported samples. All samples were harvested between 2018 and 2020. A good geographical classification of Slovenian and non-Slovenian strawberries was obtained despite different production years using discriminant approaches. However, for verifying compliance with a given specification (geographical indications), a class-modelling approach was used to build an unbiased verification model. Class models generated by data-driven soft independent modelling of class analogy (DD-SIMCA) had high sensitivity (96% to 97%) and good specificity (81% to 91%) on a yearly basis, while a more generalised model combining total yearly data gave a lower specificity (63%). Of the 33 commercially available samples (test samples) with declared Slovenian origin, 39% were from outside of Slovenia.

Differences in the Levels of the Selected Phytoestrogens and Stable Isotopes in Organic vs. Conventional Hops and Beer.

Xanthohumol (XN), isoxanthohumol (IX) and 8-prenylnaringenin (8-PN) are important prenylflavonoids present in hops with potential beneficial properties. In this study, we examined differences in the content of XN, IX and 8-PN in hops and beer produced under organic and conventional production regimes. A An ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) method for analysing XN, IX and 8-PN in hops and beer was developed and validated, with LOQ ranging from 0.5 to 10 ng/mL. Finally, we examined 15N/14N and 12C/13C isotope ratios in the hops and beer using isotope ratio mass spectrometry (IRMS). The results show no statistically significant difference in the content of the selected prenylflavonoids between organic and conventionally produced hops and beer-in the whole sample group, as well as between the matched pairs. Stable isotope analysis indicated that only δ15N values are statistically higher in organically produced hops and beer. However, the differentiation according to the type of production could not be made solely based on the δ15N signature, but it could be used to provide supporting evidence.

Milk Authentication: Stable Isotope Composition of Hydrogen and Oxygen in Milks and Their Constituents.

This paper summarises the isotopic characteristics, i.e., oxygen and hydrogen isotopes, of Slovenian milk and its major constituents: water, casein, and lactose. In parallel, the stable oxygen isotope ratios of cow, sheep, and goat's milk were compared. Oxygen stable isotope ratios in milk water show seasonal variability and are also 18O enriched in relation to animal drinking water. The δ18Owater values were higher in sheep and goat's milk when compared to cow milk, reflecting the isotopic composition of drinking water source and the effect of differences in the animal's thermoregulatory physiologies. The relationship between δ18Omilk and δ18Olactose is an indication that even at lower amounts (>7%) of added water to milk can be determined. This procedure once validated on an international scale could become a reference method for the determination of milk adulteration with water.

Food Matrix Reference Materials for Hydrogen, Carbon, Nitrogen, Oxygen, and Sulfur Stable Isotope-Ratio Measurements: Collagens, Flours, Honeys, and Vegetable Oils.

An international project developed, quality-tested, and measured isotope-delta values of 10 new food matrix reference materials (RMs) for hydrogen, carbon, nitrogen, oxygen, and sulfur stable isotope-ratio measurements to support food authenticity testing and food provenance verification. These new RMs, USGS82 to USGS91, will enable users to normalize measurements of samples to isotope-delta scales. The RMs include (i) two honeys from Canada and tropical Vietnam, (ii) two flours from C3 (rice) and C4 (millet) plants, (iii) four vegetable oils from C3 (olive, peanut) and C4 (corn) plants, and (iv) two collagen powders from marine fish and terrestrial mammal origins. An errors-in-variables regression model included the uncertainty associated with the measured and assigned values of the RMs, and it was applied centrally to normalize results and obtain consensus values and measurement uncertainties. Utilization of these new RMs should facilitate mutual compatibility of stable isotope data if accepted normalization procedures are applied and documented.

Fatty Acid and Stable Carbon Isotope Composition of Slovenian Milk: Year, Season, and Regional Variability.

This study examined the percentage and stable isotope ratios of fatty acids in milk to study seasonal, year, and regional variability. A total of 231 raw cow milk samples were analyzed. Samples were taken twice per year in 2012, 2013, and 2014, in winter and summer, covering four distinct geographical regions in Slovenia: Mediterranean, Alpine, Dinaric, and Pannonian. A discriminant analysis model based on fatty acid composition was effective in discriminating milk according to the year/season of production (86.9%), while geographical origin discrimination was less successful (64.1%). The stable isotope composition of fatty acids also proved to be a better biomarker of metabolic transformation processes in ruminants than discriminating against the origin of milk. Further, it was observed that milk from Alpine and Mediterranean regions was healthier due to its higher percentage of ω-3 polyunsaturated fatty acid and conjugated linoleic acid.

Geographical verification of Slovenian milk using stable isotope ratio, multi-element and multivariate modelling approaches.

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.

Can We Discover Truffle's True Identity?

This study used elemental and stable isotope composition to characterize Slovenian truffles and used multi-variate statistical analysis to classify truffles according to species and geographical origin. Despite the fact that the Slovenian truffles shared some similar characteristics with the samples originating from other countries, differences in the element concentrations suggest that respective truffle species may respond selectively to nutrients from a certain soil type under environmental and soil conditions. Cross-validation resulted in a 77% correct classification rate for determining the geographical origin and a 74% correct classification rate to discriminate between species. The critical parameters for geographical origin discriminations were Sr, Ba, V, Pb, Ni, Cr, Ba/Ca and Sr/Ca ratios, while from stable isotopes δ18O and δ13C values are the most important. The key variables that distinguish T.magnatum from other species are the levels of V and Zn and δ15N values. Tuber aestivum can be separated based on the levels of Ni, Cr, Mn, Mg, As, and Cu. This preliminary study indicates the possibility to differentiate truffles according to their variety and geographical origin and suggests widening the scope to include stable strontium isotopes.

Dietary habits of Slovenian inland and coastal primiparous women and fatty acid composition of their human milk samples.

The quantity and composition of fatty acids (FAs) in milk can influence an infant's growth and development through maternal diet. Therefore, associations between maternal diet and FA composition in 74 mature human milk samples were investigated. This study aimed to obtain FA patterns in mature milk arising from different dietary habits in two geographically different areas in Slovenia: Koper (KP), a coastal area, and Pomurje (MS), an inland area. The results revealed statistically significant differences in the dietary intake of game, freshwater fish, and fresh and frozen seafood between the study areas. Among the mean percentages of 35 individual FAs in milk, 19 were higher in KP and 16 were higher in MS. In KP, despite the higher intake of fresh seafood, the levels of saturated and monounsaturated FAs were higher and the levels of PUFAs, ω-3, and ω-6 were lower compared to those in MS. The ω-6:ω-3 ratio did not differ significantly between the study areas. This finding was not expected and indicates a discrepancy between the measured and self-reported data - the latter lack reliable data on dietary supplements. Therefore, determination of FA profile is important as a promising biomarker of dietary intake in environmental health studies.

Selected elements and fatty acid composition in human milk as indicators of seafood dietary habits.

The maternal diet and living environment can affect levels of chemical elements and fatty acid (FA) composition and their stable isotopes (δ13CFA) in human milk. Information obtained from questionnaires is frequently imprecise, thus limiting proper associations between external and internal exposures as well as health effects. In this study, we focused on seafood as a source of potentially toxic and essential elements and nutritional FAs. Concentrations of selected elements in human milk (As, Cd, Cu, Mn, Pb, Se and Zn) were determined using inductively coupled plasma mass spectrometry (ICP-MS) and Hg using cold vapour atomic-absorption spectrometry (CV-AAS). The identification and quantification of FAs in maternal milk were performed by an in-situ trans-esterification method (FAMEs), and the characterization of FAMEs was performed by gas chromatography with a flame ionisation detector (GC-FID). δ13CFA was determined by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). Seventy-four lactating Slovenian women from the coastal area of Koper (KP), with more frequent consumption of seafood, and the inland area of Pomurje (MS), with less frequent seafood consumption, were included in this study. Along with basic statistical analyses, data mining approaches (classification and clustering) were applied to investigate whether FA composition and δ13CFA could improve the information regarding dietary sources of potentially toxic elements. As and Hg levels in milk were found to be statistically higher in populations from KP than in those from MS, and 71% of individual FAs and 30% of individual δ13CFA values in milk differed statistically between the studied areas. In 19 cases, the levels of FAs in milk were higher in KP than in MS; these FAs include C20:5ω3 and C22:6ω3/C24:1ω9, which are typically contained in fish. In 16 cases, the mean percentage of FAs was higher in MS than in KP; these FAs include the PUFAs C18:2ω6, C18:3ω3, and C20:4ω6 which are important for human and infant growth. The difference in δ13C levels of C10:0, C12:0, C14:0, C16:1, C16:0, C18:1ω9c, C22:6ω3, and δ13C 18:0-16:0 in the study groups was statistically significant. In all seven cases where δ13C of FA significantly differed between KP and MS, δ13C was higher in KP, indicating a higher proportion of a marine-based diet. The data mining approaches confirmed that the percentage of selected FAs (iC17:0, C4:0, C18:2ω6t, aC17:0, CLA, and C22:4ω6) and δ13CFA of C18:1ω9c in human milk could be used to distinguish between high and low frequency of fresh seafood consumption.

Lessons learned from inter-laboratory studies of carbon isotope analysis of honey.

Forensic application of carbon isotope ratio measurements of honey and honey protein to investigate the degree of adulteration with high fructose corn syrup or other C4 plant sugars is well established. These measurements must use methods that exhibit suitable performance criteria, particularly with regard to measurement uncertainty and traceability - low levels of adulteration can only be detected by methods that result in suitably small measurement uncertainties such that differences of 1‰ or less can be reliably detected. Inter-laboratory exercises are invaluable to assess the state-of-the art of measurement capabilities of laboratories necessary to achieve such performance criteria. National and designated metrology institutes from a number of countries recently participated in an inter-laboratory assessment (CCQM-K140) of stable carbon isotope ratio determination of bulk honey. The same sample material was distributed to a number of forensic isotope analysis laboratories that could not participate directly in the metrological comparison. The results from these studies have demonstrated that the majority of participants provided isotope delta values with acceptable performance metrics; that all participants ensured traceability of their results; and that where measurement uncertainties were reported; these were fit-for-purpose. A number of the forensic laboratories only reported precision rather than full estimates of measurement uncertainty and this was the major cause of the few instances of questionable performance metrics. Reporting of standard deviations in place of measurement uncertainties is common practice outside metrology institutes and the implications for interpretations of small differences in isotopic compositions are discussed. The results have also highlighted a number of considerations that are useful for organisers of similar inter-laboratory studies in the future.

ISO-FOOD ontology: A formal representation of the knowledge within the domain of isotopes for food science.

To link and harmonize different knowledge repositories with respect to isotopic data, we propose an ISO-FOOD ontology as a domain ontology for describing isotopic data within Food Science. The ISO-FOOD ontology consists of metadata and provenance data that needs to be stored together with data elements in order to describe isotopic measurements with all necessary information required for future analysis. The new domain has been linked with existing ontologies, such as Units of Measurements Ontology, Food, Nutrient and the Bibliographic Ontology. To show how such an ontology can be used in practise, it was populated with 20 isotopic measurements of Slovenian food samples. Describing data in this way offers a powerful technique for organizing and sharing stable isotope data across Food Science.

Authentication of key aroma compounds in apple using stable isotope approach.

Gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) for the analysis of key volatile compounds sampled using headspace solid phase microextraction (HS-SPME) is an appropriate tool for authenticity assessment of apple aromas. The current research characterises 18 laboratory produced and 15 commercial apple recovery aroma samples, establishes a database of δ13C values of 16 aroma compounds with respect to their origin (synthetic and natural), and assesses the authenticity of commercially available aroma compounds. Analysis of so-called natural aroma products, revealed δ13C values that were within the expected authentic range although the data did reveal possible falsifications. The sensitivity of the method was evaluated through simple isotope mass balance calculation. Falsification identification is possible for most aromatic substances when the amount of added synthetic compound is in tens of percent.