Jurian Hoogewerff

Fingerprints for Main Varieties of Argentinean Wines: Terroir Differentiation by Inorganic, Organic, and Stable Isotopic Analyses Coupled to Chemometrics

Our main goal was to investigate if robust chemical fingerprints could be developed for three Argentinean red wines based on organic, inorganic, and isotopic patterns, in relation to the regional soil composition. Soils and wines from three regions (Mendoza, San Juan, and Córdoba) and three varieties (Cabernet Sauvignon, Malbec, and Syrah) were collected. The phenolic profile was determined by HPLC-MS/MS and multielemental composition by ICP-MS; (87)Sr/(86)Sr and δ(13)C were determined by TIMS and IRMS, respectively. Chemometrics allowed robust differentiation between regions, wine varieties, and the same variety from different regions. Among phenolic compounds, resveratrol concentration was the most useful marker for wine differentiation, whereas Mg, K/Rb, Ca/Sr, and (87)Sr/(86)Sr were the main inorganic and isotopic parameters selected. Generalized Procrustes analysis (GPA) using two studied matrices (wine and soil) shows consensus between them and clear differences between studied areas. Finally, we applied a canonical correlation analysis, demonstrating significant correlation (r = 0.99; p < 0.001) between soil and wine composition. To our knowledge this is the first report combining independent variables, constructing a fingerprint including elemental composition, isotopic, and polyphenol patterns to differentiate wines, matching part of this fingerprint with the soil provenance.

Isotopic and Elemental Data for Tracing the Origin of European Olive Oils

H, C, and O stable isotope ratios and the elemental profile of 267 olive oils and 314 surface waters collected from 8 European sites are presented and discussed. The aim of the study was to investigate if olive oils produced in areas with different climatic and geological characteristics could be discriminated on the basis of isotopic and elemental data. The stable isotope ratios of H, C, and O of olive oils and the ratios of H and O of the relevant surface waters correlated to the climatic (mainly temperature) and geographical (mainly latitude and distance from the coast) characteristics of the provenance sites. It was possible to characterize the geological origin of the olive oils by using the content of 14 elements (Mg, K, Ca, V, Mn, Zn, Rb, Sr, Cs, La, Ce, Sm, Eu, U). By combining the 3 isotopic ratios with the 14 elements and applying a multivariate discriminant analysis, a good discrimination between olive oils from 8 European sites was achieved, with 95% of the samples correctly classified into the production site.

Sodium and bone health: impact of moderately high and low salt intakes on calcium metabolism in postmenopausal women.

High salt intake is a well‐recognized risk factor for osteoporosis because it induces calciuria, but the effects of salt on calcium metabolism and the potential impact on bone health in postmenopausal women have not been fully characterized. This study investigated adaptive mechanisms in response to changes in salt and calcium intake in postmenopausal women. Eleven women completed a randomized cross‐over trial consisting of four successive 5‐wk periods of controlled dietary intervention, each separated by a minimum 4‐wk washout. Moderately low and high calcium (518 versus 1284 mg) and salt (3.9 versus 11.2 g) diets, reflecting lower and upper intakes in postmenopausal women consuming a Western‐style diet, were provided. Stable isotope labeling techniques were used to measure calcium absorption and excretion, compartmental modeling was undertaken to estimate bone calcium balance, and biomarkers of bone formation and resorption were measured in blood and urine. Moderately high salt intake (11.2 g/d) elicited a significant increase in urinary calcium excretion (p = 0.0008) and significantly affected bone calcium balance with the high calcium diet (p = 0.024). Efficiency of calcium absorption was higher after a period of moderately low calcium intake (p < 0.05) but was unaffected by salt intake. Salt was responsible for a significant change in bone calcium balance, from positive to negative, when consumed as part of a high calcium diet, but with a low calcium intake, the bone calcium balance was negative on both high and low salt diets.

Development and evaluation of a standard method for the quantitative determination of elements in float glass samples by LA-ICP-MS.

Forensic analysis of glass samples was performed in different laboratories within the NITE-CRIME (Natural Isotopes and Trace Elements in Criminalistics and Environmental Forensics) European Network, using a variety of Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) systems. The main objective of the interlaboratory tests was to cross-validate the different combinations of laser ablation systems with different ICP-MS instruments. A first study using widely available samples, such as the NIST SRM 610 and NIST SRM 612 reference glasses, led to deviations in the determined concentrations for trace elements amongst the laboratories up to 60%. Extensive discussion among the laboratories and the production of new glass reference standards (FGS 1 and FGS 2) established an improved analytical protocol, which was tested on a well-characterized float glass sample (FG 10-1 from the BKA Wiesbaden collection). Subsequently, interlaboratory tests produced improved results for nearly all elements with a deviation of < 10%, demonstrating that LA-ICP-MS can deliver absolute quantitative measurements on major, minor and trace elements in float glass samples for forensic and other purposes.

Application of laser ablation (LA-ICP-SF-MS) for the elemental analysis of bone and teeth samples for discrimination purposes

Human bone and teeth fragments can be useful evidence when found in crime scenes and/or mass burials sites. The elemental and isotopic composition of these samples can provide information about environmental exposure events and could also be used to distinguish different individuals. The development and application of robust analytical methods for the quantification of trace elements in these biological matrices may lead to a better understanding of the potential utility of these measurements in forensic analyses. In this paper, we demonstrate the possibility of conducting quantitative analysis of trace metals found in bone remains and suggest a strategy to discriminate between individuals, based on this information. A LA-ICP-SF-MS method using non-matrix matched standard calibration was developed and optimized with bone standard reference materials (SRMs) and subsequently applied to the analysis of real samples. The developed method requires micrograms amount of sample (vs. milligrams required for solution-based analysis) while also reducing the analysis time and resulting in good accuracy (typically <10% bias) and precision (<15% RSD). Additionally, laser ablation allowed using spatial resolution analysis to assess the biogenic elemental composition in buried bone samples. Elemental analysis of bone samples from 12 different individuals provided better discrimination between the individuals when the femur and humerus bones were considered separately (42.7% correct classification with all bones vs. 75.2% and 63.1% for femur bones and humerus bones, respectively). Separation of individuals was achieved by elemental composition of whole teeth samples from 14 individuals, except one case where not all the teeth from the same individual were associated together. Separation of individuals was improved when using elemental composition of the enamel and dentine+cementum layers separately in a set of samples from 7 individuals. These are promising results for the use of elemental analysis by laser ablation ICP-MS for discrimination purposes.

A chemical and mineralogical reconstruction of Zn-smelter emissions in the Kempen region (Belgium), based on organic pool sediment cores.

The atmospheric pollution history of a former Belgian Zn-smelter complex is preserved in organic sediments of a nearby peat bog pool. The stratigraphy of trace metals, Pb-isotope ratios and mineralogy indicate extreme heavy metal pollution in recent sediments. In the pollutant trend, extremes coincide with maxima in 20th century metal production, minima during major war conflicts and the final shutdown of the smelter. Peak pollution concentrations measure up to 4.7 wt.% Zn, 1.1 wt.% Pb and 0.1 wt.% Cd, which correspond to calculated atmospheric deposition rates of 9.0, 1.6 and 0.16 g m(-2) yr(-1), respectively. 206Pb/207Pb isotope ratios show higher values in the polluted interval (1.135-1.162) relative to local geogenic values deeper down-core (1.194-1.215). Within the polluted interval, three significantly different 208Pb/206Pb plateaus are recognized and suggested to indicate changes in the origins of processed ores. Microprobe analyses on sediment thin sections show extensive in situ FeS2 and ZnS precipitation, which suggests that anoxic processes are responsible for the immobilization of the atmospheric metal inputs. The occurrence of oxidized smelter dusts in an independent surface soil sample indicates a rapid diagenetic transformation of metal oxides into sulfides. Morphology and chemical characteristics allow the distinction between smelter related and diagenetic mineral deposits, and give evidence for dust from open-air ore repositories, as well as smelter operation without dust filters.

Global dust teleconnections: aerosol iron solubility and stable isotope composition

Environmental context. Iron is an essential component of many enzyme systems of marine plants (phytoplankton), but in large areas of the global ocean iron is in such short supply as to hinder phytoplankton growth. This is of major environmental interest because phytoplankton growth can remove carbon from the atmosphere. This contribution seeks to improve the understanding of how dust transported through, and processed within, the atmosphere helps to supply usable iron to the plants of the remote ocean. Abstract. Soil dust mobilised from arid regions is transported through and processed within the atmosphere before deposition to marine and terrestrial ecosystems remote from the source regions. This process represents a significant source of iron to the oceans, which creates feedback loops throughout the Earth’s system. The very limited solubility of iron from dust makes the determination of this solubility, how it varies and how this may influence ocean biogeochemistry of considerable importance. In this short communication we summarise a series of recent studies of mechanisms that control solubility and then consider how these results influence the inputs of iron to the oceans and their isotopic signature.

Isoscapes to address large-scale Earth science challenges

Sugar cane cropping for biofuel production reduces water discharge from a northern Indian basin and threatens downstream communities. Regulators want to partition blame between climate change—induced declines in mountain snowpack and excessive evaporation from poorly managed fields. In the same basin, a tiger is found shot. Is it the nuisance animal that has been tormenting local communities, or is it a different animal poached from the upland forests?

Elemental and isotopic fingerprint of Argentinean wheat. Matching soil, water, and crop composition to differentiate provenance.

The aim of this study was to investigate if elemental and isotopic signatures of Argentinean wheat can be used to develop a reliable fingerprint to assess its geographical provenance. For this pilot study we used wheat cultivated at three different regions (Buenos Aires, Córdoba, and Entre Ríos), together with matching soil and water. Elemental composition was determined by ICP-MS. δ(13)C and δ(15)N were measured by isotopic ratio mass spectrometry, while (87)Sr/(86)Sr ratio was determined using thermal ionization mass spectrometry. Wheat samples from three sampling sites were differentiated by the combination of 11 key variables (K/Rb, Ca/Sr, Ba, (87)Sr/(86)Sr, Co, Mo, Zn, Mn, Eu, δ(13)C, and Na), demonstrating differences among the three studied regions. The application of generalized Procrustes analysis showed 99.2% consensus between cultivation soil, irrigation water, and wheat samples, in addition to clear differences between studied areas. Furthermore, canonical correlation analysis showed significant correlation between the elemental and isotopic profiles of wheat and those corresponding to both soil and water (r(2) = 0.97, p < 0.001 and r(2) = 0.96, p < 0.001, respectively). To our knowledge, this is the first report demonstrating the correspondence between soil, water, and wheat samples using different statistical methods, showing that wheat elemental and isotopic compositions are mainly related to soil and irrigation water characteristics of the site of growth.

Sr isotope measurements in beef: analytical challenge and first results

AbstractThe strontium isotope ratio (87Sr/86Sr) in beef, derived from 206 European cattle, has been measured. These cattle were located in 12 different European regions within France, Germany, Greece, Ireland, Italy, Spain and the UK. As animal protein is known to be a difficult material on which to conduct Sr isotope analysis, several investigations were undertaken to develop and improve the sample preparation procedure. For example, Sr isotope analysis was performed directly on freeze-dried meat and defatted dry mass from the same samples. It was found that enormous differences—sometimes exceeding the measurement uncertainty—could occur between the fractions and also within one sample even if treated in the same manner. These variations cannot be definitely allocated to one cause but are most likely due to inhomogeneities caused by physiological and biochemical processes in the animals as post mortem contamination during analytical processing could be excluded. For further Sr isotope measurements in meat, careful data handling is recommended, and for the authentic beef samples within this project, it was decided to use only freeze-dried material. It can be demonstrated, however, that Sr isotope measurements in beef proteins are a valuable tool for authentication of geographic origin. Although partly overlapping, some of the European sampling sites could be discriminated even by only using 87Sr/86Sr. FigureBox plot diagram displaying 87Sr/86Sr in authentic beef samples ordered by Trace sampling sites