A framework for tracing timber following the Ukraine invasion.

Scientific testing including stable isotope ratio analysis (SIRA) and trace element analysis (TEA) is critical for establishing plant origin, tackling deforestation and enforcing economic sanctions. Yet methods combining SIRA and TEA into robust models for origin verification and determination are lacking. Here we report a (1) large Eastern European timber reference database (Betula, Fagus, Pinus, Quercus) tailored to sanctioned products following the Ukraine invasion; (2) statistical test to verify samples against a claimed origin; (3) probabilistic model of SIRA, TEA and genus distribution data, using Gaussian processes, to determine timber harvest location. Our verification method rejects 40-60% of simulated false claims, depending on the spatial scale of the claim, and maintains a low probability of rejecting correct origin claims. Our determination method predicts harvest location within 180 to 230 km of true location. Our results showcase the power of combining data types with probabilistic modelling to identify and scrutinize timber harvest location claims.

Poaching and illegal trade of Danube sturgeons.

A market study on sturgeon products in the Lower Danube countries (Bulgaria, Romania, Serbia and Ukraine) resulted in a total of 149 samples of caviar and meat, which we subjected to genetic-isotope analyses. The samples comprised 31 samples (21%) of illegal wild-caught origin, 17 samples (11.4%) sold in violation of CITES and EU regulations, and 47 cases (32%) of consumer deception. Although poaching and illegal wildlife trade are often considered a problem in developing countries, these findings bear evidence that a high ratio of poached sturgeon products originates from EU and accession candidate states. Therefore, caviar and sturgeon trade urgently needs improvement to ensure that sturgeon populations will have a future.

Constraining parameter uncertainty for predicting oxygen and hydrogen isotope values in fruit.

Understanding δ18O and δ2H values of agricultural products like fruit is of particular scientific interest in plant physiology, ecology, and forensic studies. Applications of mechanistic stable isotope models to predict δ18O and δ2H values of water and organic compounds in fruit, however, are hindered by a lack of empirical parameterizations and validations. We addressed this lack of data by experimentally evaluating model parameter values required to model δ18O and δ2H values of water and organic compounds in berries and leaves from strawberry and raspberry plants grown at different relative humidities. Our study revealed substantial differences between leaf and berry isotope values, consistent across the different relative humidity treatments. We demonstrated that existing isotope models can reproduce water and organic δ18O and δ2H values for leaves and berries. Yet, these simulations require organ-specific model parameterization to accurately predict δ18O and δ2H values of leaf and berry tissue and water pools. We quantified these organ-specific model parameters for both species and relative humidity conditions. Depending on the required model accuracy, species- and environment-specific model parameters may be justified. The parameter values determined in this study thus facilitate applications of stable isotope models where understanding δ18O and δ2H values of fruit is of scientific interest.

Using plant physiological stable oxygen isotope models to counter food fraud.

Fraudulent food products, especially regarding false claims of geographic origin, impose economic damages of $30-$40 billion per year. Stable isotope methods, using oxygen isotopes (δ18O) in particular, are the leading forensic tools for identifying these crimes. Plant physiological stable oxygen isotope models simulate how precipitation δ18O values and climatic variables shape the δ18O values of water and organic compounds in plants. These models have the potential to simplify, speed up, and improve conventional stable isotope applications and produce temporally resolved, accurate, and precise region-of-origin assignments for agricultural food products. However, the validation of these models and thus the best choice of model parameters and input variables have limited the application of the models for the origin identification of food. In our study we test model predictions against a unique 11-year European strawberry δ18O reference dataset to evaluate how choices of input variable sources and model parameterization impact the prediction skill of the model. Our results show that modifying leaf-based model parameters specifically for fruit and with product-independent, but growth time specific environmental input data, plant physiological isotope models offer a new and dynamic method that can accurately predict the geographic origin of a plant product and can advance the field of stable isotope analysis to counter food fraud.

Assessment of multiple stable isotopes for tracking regional and organic authenticity of plant products in Hesse, Germany.

As demand for regional and organically produced foodstuff has increased in Europe, the need has arisen to verify the products' origin and production method. For food authenticity tracking (production method and origin), we examined 286 samples of wheat (Triticum aestivum), potatoes (Solanum tuberosum), and apples (Malus domestica) from different regions in Germany for their stable isotope compositions of oxygen, hydrogen, carbon, nitrogen and sulphur. Single-variate authentication methods were used. Suitable isotope tracers to determine wheat's regional origin were δ18O and δ34S. δ13C helped to distinguish between organic and conventional wheat samples. For the separation of the production regions of potatoes, several isotope tracers were suitable (e.g. δ18O, δ2H, δ15N, δ13C and δ34S isotopes in potato protein), but only protein δ15N was suitable to differentiate between organic and conventional potato samples. For the apple samples, 2H and 18O isotopes helped to identify production regions, but no significant statistical differences could be found between organically and conventionally farmed apples. For food authenticity tracking, our study showed the need to take the various isotopes into account. There is an urgent need for a broad reference database if isotope measurements are to become a main tool for determining product's origin.

Decreasing δ13C and δ15N values in four coastal species at different trophic levels indicate a fundamental food-web shift in the southern North and Baltic Seas between 1988 and 2016.

Marine ecosystems are exposed to increasing human pressures and climatic change worldwide. It has therefore become essential to describe ecosystem statuses with respect to multinational protection schemes, often necessitating long-term monitoring programmes. Changes in the food-web structure, which can be monitored via stable isotope measurements, represent an important descriptor of the status of marine ecosystems. We investigated long-term changes (29 years) in isotopic values (δ13C and δ15N) in four indicative organisms at different trophic levels in the southern North and Baltic Seas: bladderwrack (Fucus vesiculosus), blue mussel (Mytilus ssp.), eelpout (Zoarces viviparus), and herring gull (Larus argentatus). Time series analyses using generalised additive models revealed largely consistent declines in δ13C and δ15N throughout all trophic levels of the coastal food web at all study sites, indicating a clear change in these coastal regions from 1988 to 2016. There were no clear long-term patterns in egg biometrics for herring gulls, except for a consistent increase in eggshell thickness. The declines in stable isotope values were in line with the results of previous long-term studies of single higher-trophic-level species, which suggested that the noted changes were mainly caused by altered foraging patterns of the studied species. The current results demonstrate that declines in δ13C and δ15N have occurred throughout the whole food web, not just in particular species. We discuss the possible reasons for the decrease in stable isotope values, including decreasing eutrophication and an increase in terrestrial carbon sources.

Intrinsic isotopic 13C labelling of polyphenols.

The intrinsic isotopic labelling of plants with (13)CO2 is an effective method to generate highly labelled compounds using photosynthesis and avoiding labour-intensive complex organic syntheses. In this study, the intrinsic isotopic labelling of polyphenols in parsley, spinach and peppermint is shown for the first time. The plants were grown in an atmosphere where (12)CO2 was replaced by (13)CO2, in order to generate highly labelled compounds. The total content of (13)C as well as the individual polyphenols were analysed by Isotopic Ratio-MS and HPLC-Iontrap-MS(n). After 34 days of plant growth under (13)CO2, degree of labelling was found to be higher than 90 atom% (13)C for most polyphenols, predominantly consisting of highly and fully labelled isotopomers; the total plant material contained more than 88 atom% (13)C. Such highly labelled compounds can be used in future studies to dissect both metabolism and bioavailability of polyphenols in humans.

Isotopic fingerprinting for the authenticity control of crop protection active compounds using the representative insecticide Fipronil.

Isotopic fingerprinting was evaluated for its potential to generate characteristic fingerprints of crop protection products in an extensive survey, using the insecticide Fipronil. One hundred and twenty batches of Fipronil from the BASF production site in France were analyzed for the isotope ratios of δ(13)C, δ(15)N, and δ(34)S. Samples spanned a production time of four years and were analyzed by elemental analysis, coupled to isotope ratio mass spectrometry (EA/IRMS). A number of Fipronil samples from other sources were analyzed in the same manner and were compared to the samples from BASF by means of multivariate data analysis. The isotopic fingerprint was sufficiently specific to differentiate between Fipronil from BASF production and Fipronil from other producers. This suggests that isotopic fingerprinting is suitable for the authenticity control of active compounds in crop protection products. It is anticipated that this technique will deliver great benefit in the defense against counterfeits and illegal parallel imports.