Isotope Ratio Analysis Research Articles

Analysis of Mineral Composition and Isotope Ratio as Part of Chemical Profiles of Apples for Their Authentication

One of the consequences of the globalisation of food markets is the effort enabling the control of food security and its origin. This might be traced by using different chemical composition analyses. However, for Central Europe, there is a lack of knowledge about the original reference values as well as their heterogeneity among the lands and countries. This study focused on characterizing the mineral profiles of apple tree fruits and comparing these profiles among different districts in Central Europe. The fruits of the apple cultivars ‘Gala’ and ‘Golden Delicious’ originated in the Czech Republic and Poland. The mineral and isotopic content of the apple fruit flesh was analysed using ICP-MS. The data were processed using the ANOVA test and compositely analysed using the PCA and LDA models. The results show relatively high variation in element distribution, particularly 87Sr/86Sr, Mn, Zn, Cu, Ca, P, and B, ranging between 20.6 and67.9% for both cultivars on average. However, their high variability within particular districts complicates the resolution of the LDA model. The reasons are linked to the geomorphological and pedological heterogeneity of the analysed districts as well as the particular sensitivity of the set of chosen primers to agronomic practices and tree performance. For this region, only partial separation among districts could be obtained by P, Ca, and Cu content, as well as the isotopic ratio of 10B/11B. However, the resolution of the geographical discrimination needs to be improved by an enhanced set of primers, the use of more precise analytical techniques for the Sr isotopic ratio, or by multiple chemical analyses. Furthermore, the heterogeneity of the analysed districts could be tackled by more detailed analyses at the level of micro-regions.

Enhanced ICP-MS detection of 24 elemental impurities in complex, high matrix mineral, medicinal lanthanum carbonates according to ICH Q2 (R2).

Validation of the specificity of ICP-MS methods by ICH Q2 (R2) through spiking experiments cannot characterize the multi-atomic interference of complex high matrix samples, possibly affecting the accuracy of the method and reliability of results. In this study, we highlight this issue by investigating the elemental impurities in lanthanum carbonate raw materials and use isotope ratio analysis to overcome this limitation and establishing an accurate ICP-MS method for 24 elemental impurities (listed in ICH Q3D). An Agilent 7900 ICP-MS was used with an automatic sampler for sample determination in the He mode. The isotope ratio of elemental impurities in the spiked samples was analyzed to characterize polyatomic interference and select the exclusive mass number of elemental impurities. While the recovery rate of most elemental impurities met the requirements, that of selenium (default measurement mass number 78Se) exceeded the standard in the matric sample. The isotope ratio of Se (78Se/82Se) was much higher than the theoretical value, indicating that the response intensity of m/z 78 was formed by the combination of 78Se and other mass-to-charge ratios, such as LaOH2+ formed by the large amount of La in the matrix. Therefore, 82 was chosen as the mass number for Se. The validation results indicate that the method has strong specificity, high accuracy, and is simple and facile. This study provides technical support for the control of elemental impurities in lanthanum carbonates and isotope ratios can be used as a supplementary means of spiked recovery rates.

A biogeochemical approach to examining sub-adult diet and the weaning process at Neolithic Tepecik-Çiftlik, Türkiye

Tepecik-Çiftlik, a Neolithic settlement located in the Cappadocia region of Central Anatolia, within the boundaries of Niğde province in modern Türkiye is crucial for helping us to better understand social behaviour and human mobility in the Neolithic, as well as relations between different groups. To investigate dietary habits, subsistence practices, and intra-societal variations stable carbon and nitrogen isotope ratio analysis has been conducted on the Neolithic human and faunal population. Further to this, 21 sub-adults were also sampled for stable carbon and nitrogen isotope ratio analysis to examine sub-adult diet, complementary feeding, and the cessation of breastfeeding as part of the weaning process. This isotopic investigation into the weaning process is complemented by a previously conducted study using Sr/Ca ratios from bone apatite of the same population. The δ13C values of the sampled sub-adults range from −19.8 ‰ to −19.0 ‰ and the δ15N values range from 8.0 ‰ to 15.2 ‰. The isotopic data suggest a very early onset of complementary feeding (ca. 0.2 years of age) and a brief breastfeeding period, relative to other prehistoric populations. The cessation of breastfeeding and this very brief weaning process was likely completed by ca. 1–1.5 years old. This early commencement of complementary feeding was most probably a deliberate social and cultural choice, supported by the presence of bowls and feeding spoons in the graves of very young babies and infants. However, this cultural choice may also have affected the mortality profile of the Neolithic population.

Exploring circulation dynamics in Han Dynasty China: insights from isotopic analysis of lead glazed pottery

This study investigates lead provenance and circulation patterns in Han Dynasty (202BC-220AD) China through the analysis of lead glazed pottery. Four objects were studied using a combination of typological study, elemental chemistry and lead isotope ratio analysis. The results for each object were compared with databases of ‘lead mining districts’ (lead deposits) and ‘lead usage districts’ (lead-containing artifacts unearthed in different spatial and temporal ranges) to assess the lead sources used for each sample and offers a spatial-temporal range of the use of these lead resources. Three distinct groups of lead and their possible circulating spatial-temporal scales are identified across six samples in this study. A possible change in lead supply networks between the Western Han Dynasty (202BC-9AD) and the Eastern Han Dynasty (25AD-220AD) is proposed. This study also highlights the probable changes in the movement of lead resources from the Western Han Dynasty to the Tang Dynasty (618AD-690AD), suggesting improvements in long-distance transport capabilities, and the development of economic divisions and exchange connections in ancient Chinese society. Our findings contribute to a deeper understanding of the economic and political dynamics during the Han Dynasty and emphasize the significance of lead isotope analysis of glazed pottery in exploring resource movement.

Tracing potentially toxic elements in button mushroom cultivation and environmental implications: Insights via stable lead (Pb) isotope analysis

Elevated levels of potentially toxic elements (PTEs) have been frequently detected in substrates used for cultivating edible mushrooms. However, the distribution and accumulation pathways of PTEs within mushrooms and their cultivation substrates remain inadequately understood. This study specifically aims to clarify these aspects of button mushrooms (Agaricus bisporus). A systematic analysis was conducted on the distribution of PTEs (As, Cd, Cr, Cu, Ni, Pb, and Zn) and stable Pb isotope fingerprints across various components of the button mushroom cultivation systems, including the cultivation substrates (a mixture of wheat straw, chicken manure, soil, and additives), fruiting bodies (MR), and spent mushroom substrate (SMS). The methodology involved inductively coupled plasma mass‒spectrometry for PTE quantification and Pb isotope ratio analysis for source identification. The results demonstrated that wheat straw and additives were the main contributors to the endogenous accumulation of PTEs in MR, accounting for 35.0% and 33.2% of Pb accumulation, respectively. Furthermore, MR, wheat straw, and soil together contributed to more than 67% of the Pb loads in SMS. The study also revealed that the occurrence of PTEs in these substrates is predominantly driven by exogenous sources, particularly the significant contribution from anthropogenic activities. Overall, these findings provide valuable biogeochemical insights into the accumulation pathways and patterns of PTEs in button mushroom cultivation systems, with potential applications for cleaner food management and environmentally sustainable practices.

Online Isotope Analysis of Sulfur in Proteins via Capillary Electrophoresis Coupled With Multicollector ICP-MS (CE/MC-ICP-MS): A Proof of Concept Study.

Isotope ratio analysis of sulfur in biological samples using inductively coupled plasma-mass spectrometry (ICP-MS) has gained significant interest for applications in quantitative proteomics. Advancements like coupling separation techniques with multicollector ICP-MS (MC-ICP-MS) enhance the throughput of species-specific sulfur isotope ratio measurements, fostering new avenues for studying sulfur metabolism in complex biological matrices. This proof-of-concept study investigates the feasibility of online CE/MC-ICP-MS for directly analyzing sulfur isotope ratios in proteins (albumin). Leveraging our previous work on the applicability of CE/ICP-MS for quantifying sulfur-containing biological molecules, we explore its potential for sulfur isotope analysis. Our results demonstrate that direct analysis of sulfur isotopes in albumin protein using online capillary electrophoresis MC-ICP-MS (CE/MC-ICP-MS) eliminates the need for laborious pretreatment steps, while yielding isotope ratios comparable to the reference values. Although initial precision can be improved through further system optimization and protein injection techniques, this approach paves the way for future analysis of mixtures of various biological compounds in, for example, clinical diagnosis studies.

Egg authentication under seasonal variation using stable isotope analysis combined with machine learning classification

In the European Union (EU) eggs from laying hens are sold in different husbandry systems: enriched cage, barn, free-range and organic. An analytical distinction between the husbandry systems is of interest for the food control authorities, as fraudsters can make high profits by mislabelling the husbandry system of the eggs. In this study, a total of 180 hen's egg samples labelled to originate from barn, free-range and organic hens were taken from food retailers in Germany at monthly intervals over a period of 15 months. The eggs were analysed using stable isotope ratio analysis (IRMS) in order to identify potential influences of different husbandry methods. The analysis on a monthly basis showed that the feeding of the laying hens varied over the year, which makes it difficult to make a clear classification according to the type of husbandry. Temporary events such as the officially ordered poultry quarantine due to the avian influenza, had minor influence on the differentiation of the husbandry types. Various statistical models including linear discriminant analysis (LDA), random forest (RF) and multinomial logistic regression (Multinomial) based on a multi-element approach (δ13C, δ15N, δ34S) were used to classify the eggs according to the three types of husbandry. On average, the models achieved a correct classification of approximately 70%. The reduction of the prediction model to two classes (organic vs. conventional eggs) led to a correct classification of almost 80% across all samples. Additionally, significant differences in the mean values of the sulphur isotopes of the organic eggs showed a regional differentiation between Bavaria (southern Germany) and Schleswig-Holstein (northern Germany).

Tracking mercury sources in the Wabigoon River: Use of stable mercury isotopes in bioindicator organisms

Mercury concentrations remain elevated in sediments and biota of the Wabigoon River downstream from Dryden, Ontario, the home of a former chlor-alkali plant. Understanding the current extent and severity of mercury contamination downstream of this industrial legacy site is of great importance in managing the mercury contamination within the traditional territory of Asubpeeschoseewagong Anishinabek (Grassy Narrows First Nation), located downstream of Dryden. The objective of this study was to use mercury stable isotope ratio analysis to distinguish between legacy mercury from the former chlor-alkali plant and mercury from geogenic sources. Mercury concentrations in surface sediments and biota downstream of the historical source of mercury discharge are elevated relative to the chosen reference location, Wabigoon Lake (WL). Mean sediment mercury levels were as high as 3.27 μg/g at the hydroelectric dam location compared to 0.05–0.10 μg/g at Wabigoon Lake sediments. Isotope ratios in aquatic biota and sediments collected from within the system were distinct from Wabigoon Lake, indicating that anthropogenic mercury contamination is distinguishable from geogenic mercury. Average δ202Hg values of −2.46 ± 0.41 observed in sediments of WL were consistently more negative compared to downstream values, which varied from −1.34 to 0.30 ‰. Young-of-the-year Yellow Perch and Hexagenia were found to have significantly more positive δ202Hg values downstream from Wabigoon Lake.

CHEMOMETRIC EVIDENCE FOR SR AND RB ISOTOPES DUE TO THE SPECIFIC SOIL CHEMISTRY IN DIFFERENT GEOGRAPHICAL REGIONS

Strontium and rubidium are the commonly used metals for isotope-ratio analysis. Moreover, this geochemical marker varies between different rock types and formations. The 87Sr/86Sr ratio has been shown to vary widely in surface rocks, so any Sr released into soils, rivers, and groundwater has an isotopic signature that reflects its source. Sr and Rb isotopes have also been used to trace agricultural products, which have incorporated Sr, along with Ca, from soils incorporating the Sr-isotope ratios of the underlying rocks. The specific conditions in the soil represent characteristic conditions of the environment which is reflected in a certain way in the plants. Despite uncertainty about the organic compounds in a sample, the content of selected elements (trace and rare earth elements, REEs) reflects the growing conditions in the environment. For that instance, in the present research, we will give focus on the inorganic compounds’ identifications, due to the more stable response to the lithogenic nature of the soil-plant interaction. For the present study, the target isotopes were 88Sr, 87Sr, 86Sr, and 85Rb. The isotope analysis was conducted with the application of ICP-MS, following the protocol provided in the EPA METHOD 6020. In the validation process, no significant interference occurred that could affect the sensitivity of the measurement of the selected isotopes. Data analysis has been applied to the comparative issues between Sr and Rb content in soil from North Macedonia and selected regions in China. Moreover, the same chemometric model was applied for data analysis for selected plant species for both regions. Data analyses has improved the significant differences within the element contents and ratios as well between both geographical regions.

Detection of adulteration in Iranian grape molasses added glucose/fructose/sugar beet syrups with 13C/12C isotope ratio analysis method.

Grape molasses (GM), produced from grapes, is a traditional Iranian food and is widely consumed in Iran. However, GM adulteration is among the most widespread illegitimate procedures involving contamination of food with foreign materials, such as adding sugar-water solution, date syrup, sugar beet syrup, and grape sauce. This study used stable carbon 13C/12C isotope ratio analysis method to detect adulteration of GM samples with glucose syrups (GS), fructose syrups (FS), and beet sugar syrups (BS) at the ratio of 0%, 10%, 30%, and 50% (by weight). Physicochemical properties of GM including °Brix, conductivity, specific gravity, pH, moisture content, ash content, hydroxymethyl furfural, sugar content, and rheological properties of samples were investigated. The δ13C isotope ratio of the GM was determined as -26.61%, that of the GS as -13.23%, that of the FS as -13.42%, and that of the BS as -16.58%. The δ13C isotope ratio increased by the addition of adulterant syrups to GM. The addition of each adulterant syrup had a different effect on the physicochemical parameters; however, the °Brix and specific gravity had a positive correlation with the δ13C isotope ratio results. The magnitudes of G' and G" increase with an increase in frequency representing the viscoelastic behavior of samples. The obtained results of this study suggest the use of δ13C isotope ratio method as a fast and accurate method to investigate the adulteration of grape molasses.

Precise Determination of Cd Isotope Ratios at 3-10 ng Level by Thermal Ionization Mass Spectrometry Using a Molybdenum Silicide Emitter.

Thermal ionization mass spectrometry (TIMS) combined with the double spike technique has excellent analytical precision for Cd isotopic ratio analysis. However, because of the low ionization efficiency of Cd by TIMS, it is still not possible to obtain high precision Cd isotope ratios for small sample size (<100 ng) due to the lack of a highly sensitive emitter for Cd. A new loading method using molybdenum silicide (MoSi2) emitter has been developed for Cd isotope ratio measurements. This emitter produces a significant enhancement in the ionization efficiency of Cd and thus significantly reduces the required sample size to the 3-10 ng level. Analyses of δ114/110Cd for the NIST SRM 3108 using 108Cd-116Cd double spike method show excellent reproducibility (2 SD) that reaches ±0.032‰, ±0.042‰, and ±0.051‰ for 10, 5, and 3 ng of Cd, respectively. This method was further verified with a suite of geological reference materials. Replicate digestions and analyses (n = 8, 2 SD) of δ114/110Cd for NIST SRM 2711a, NOD A-1, and GBW08401 demonstrated good external reproducibility with results of 0.596 ± 0.024‰ for NIST SRM 2711a, 0.150 ± 0.036‰ for NOD A-1, and -0.665 ± 0.084‰ for GBW08401. These data clearly indicate that MoSi2 is an excellent alternative for traditional silica gel to Cd isotopic measurements, especially for samples with a low content of Cd.

Pretreatment method for oxygen stable isotope ratio analysis of the sugar-rich fraction in fruit juice via isotope ratio mass spectrometry.

The oxygen stable isotope ratio (δ18O) of the sugar-rich fraction of fruit juice is important as a tracer of the geographical origin of raw material. This study sought to minimize the inter-day variation of δ18O attributable to the influence of water to accurately monitor geographical origin labeling. Two drying devices (freeze dryer and vacuum oven) were compared. Then, two humidity levels (normal and low humidity) at which the samples were placed after drying were compared. The low-humidity environment was constructed using a glove bag and pure argon gas. δ18O was measured using thermal conversion elemental analyzer/isotope ratio mass spectrometry. Improvements were made to the measurement method based on aforementioned analyses results, and the performance of the initial and improved methods was compared. δ18O of juice dried in a vacuum oven was 3.30‰ lower than that of juice dried in a freeze dryer. Moreover, δ18O of juice samples exposed to normal humidity was 3.74‰ lower than that of samples exposed to low humidity. The combined inter-day and intra-day standard deviation was reduced from 1.20‰ in the initial method to 0.42‰ in the improved method. This study describes a pretreatment method for δ18O measurement in the sugar-rich fraction of fruit juice with less inter-day variation, and it will be useful for monitoring geographical origin labeling.

Feeding habits of splendid alfonsino Beryx splendens in the vicinity of Kuroshio, the south of Japan

AbstractGut contents and nitrogen isotope ratio (δ15N) analyses were conducted on splendid alfonsino Beryx splendens collected in the vicinity of Kuroshio from May 2015 to November 2016 (n = 708) to identify their feeding habits in the Western North Pacific. Micronektonic fish, shrimp, and squid were the dominant prey species, with the Decapoda Acanthephyra quadrispinosa, Prehensilosergia prehensilis, Cephalopoda Enoploteuthis chunii, Chiroteuthis calyx, Teleostei Sigmops gracilis, and Gonostoma elongatum. These micronektons are common in the Kuroshio Current; thus, B. splendens is a possible opportunistic feeder. Gut content weight (GCW), occurrence (%O) of fish and squid, and δ15N were significantly increased with the fork length (FL) of B. splendens. Only the %O of shrimp does not show a significant relationship with the FL of B. splendens. These indicated the ontogenetic shift of dominant prey from shrimp to fish. Fattened specimens could also prey on a greater number of fish. The seasonality of GCW and %O values was high in spring and autumn and low in summer and winter. This seasonality indicated that the feeding habits of B. splendens are controlled by primary productivity in the surface layer and/or by maturity. When the Kuroshio flowed in the north of Hachijojima Island, the GCW was significantly increased, and some organisms, including C. calyx, G. elongatum, and S. gracilis, were preyed on more. While the offshore area of the Kuroshio has low productivity, B. splendens can actively prey in this area, indicating that it is an important feeding ground for this species.

Bioarchaeological Perspectives on Late Antiquity in Dalmatia: Paleogenetic, Dietary, and Population Studies of the Hvar—Radošević burial site

Late Antiquity Dalmatia was a time and place of political unrest in the Roman Empire that influenced the lives of those in that region. The Late Antique burial site of Hvar – Radošević, spanning the 3rd to 5th centuries CE, is located on the Croatian Dalmatian island of Hvar. Given the time frame and location on a busy marine trade route, the study of this burial site offers us a glimpse into the lives of the Late Antique population living on this island. It comprises 33 individuals, with 17 buried within a confined grave tomb and the remaining individuals buried in separate locations in the tomb's proximity. The study aims to provide a new perspective on the lives of people on the island during those times by studying ancestry, population structure, possible differences within the buried population, dietary habits, and general health. The genetic analysis of the ancestral origins of the individuals buried at Hvar – Radošević revealed a diverse population reflective of the era's genetic variability. The identification of genetic outliers suggests a range of ancestries from distinct regions of the Roman Empire, possibly linked to trade routes associated with the Late Antique port in ancient Hvar. Stable isotope ratio analysis (δ13C and δ15N) indicated a diet mainly consisting of C3 plants, with minimal consumption of marine foods. High childhood mortality rates, physiological stress markers, and dental diseases suggest a low quality of life in the population. Assessment of kinship and dietary patterns revealed no discernible distinctions between individuals buried within the tomb and those buried outside, indicative of an absence of differential burial practices based on social status and familial ties among this specific buried population.

Melting of Totten Glacier, East Antarctica since the Last Glacial Maximum Revealed by Beryllium Isotope Ratios of Marine Sediment

The Totten Glacier of East Antarctica drains a basin containing about 3.5 m of sea-level rise equivalent ice. While Totten Glacier is generally considered somewhat more stable than the rapidly retreating sectors of the West Antarctic Ice Sheet, such as the Amundsen Sea Embayment and Getz Ice Shelf, our understanding of its intricate dynamics and interaction with the Southern Ocean since the Last Glacial Maximum remains incomplete. Situated in a precarious position grounded below sea level, Totten Glacier represents a critical yet enigmatic component of East Antarctic ice dynamics. Its susceptibility to marine ice sheet instability raises concerns, as positive feedback from grounding line retreat could trigger irreversible ice discharge or even complete collapse. A meticulous reconstruction of the retreat history of the Totten Glacier is imperative to comprehensively grasp the glacier's response to present and future climate changes.Here, we present a beryllium isotope ratio analysis of marine sediment from the continental slope proximal to Totten Glacier, the first such record from this location, supplemented by grain size data from the same sediment core. The results, when evaluated together with nearby proxy records, reveal that the initial deglaciation of the Totten Glacier sector of the East Antarctic Ice Sheet began at ca. 21 ka BP. The rapid deglaciation from ca. 7 ka BP that followed is determined to be caused by the intrusion of modified Circumpolar Deep Water, leading to melting at the grounding zone of the Totten Glacier and causing instability of the glacier system. The southward shift and intensification of Antarctic easterlies may be one of the causes of this intrusion. These results contribute to the body of knowledge regarding the dynamical response of marine-terminating glaciers to climate variability during the last deglaciation.

A multi-analytical approach for the identification of pollutant sources on black crust samples: Stable isotope ratio of carbon, sulphur, and oxygen

This study is focused on the identification of pollutant sources on black crust (BC) samples from the Monumental Cemetery of Milan (Italy), through a multi-analytical approach based on the determination of stable isotope ratios of carbon, sulphur, and oxygen. Six black crust samples, mainly developed on marble sculptures over a time span of 100–150 years, were analysed.For the first time, δ13C was measured for BC samples: δ13C values of the pulverized samples (from −1.2 to +1.3 ‰) are very close to the values obtained from the carbonate matrix, whereas after the removal of the matrix through acidification, δ13C values of BC samples from Milan range from −27.2 to −22.1 ‰, with no significant variation between samples with different ratios of organic carbon to elemental carbon. In sum, the δ13C values obtained for all BC samples fall within the range of anthropogenic emissions such as vehicle traffic, coal combustion and industrial emissions.δ34S and δ18O values of sulphate from BC samples range from −6.3 to +7.0 ‰ and from +7.6 to +10.5 ‰, respectively. Coupling the analysis of the oxygen isotope ratio with that of sulphur enables a more precise identification of the origin of sulphates: the observed isotopic composition falls in the range typical for anthropogenic emission of sulphur dioxide.Overall, in this study, C, S and O isotopes were combined for the first time to assess pollutant sources on black crust samples: this multi-stable isotope approach allowed to show that the BC formation on monuments from the Monumental Cemetery of Milan mostly results from anthropogenic emissions from fossil fuels combustion by road vehicles and factories, as well as domestic heating.

Investigation of fraud in the production of butter: a forensic case study of criminal association

Butter is among the most popular and commercially valuable dairy products. Its high commercial value makes it a major target for adulteration, which aims to reduce production costs by using lower-quality fats and oils from other sources. The annual global market is around USD 30 billion (2023), expected to reach USD 36 billion in 2028, which also justifies the enormous interest in adulteration. In this work, a confirmed case of butter adulteration was studied by Nuclear Magnetic Resonance (NMR) and Stable Carbon Isotopic Ratio Analysis (SCIRA) techniques, employed to detect the inclusion in butter production of vegetable oils, such as soybean and palm oils. A total of 21 samples seized by the Brazilian Federal Police were analysed by NMR and SCIR, and compared to original butter obtained from commercial sources. The composition of all the seized samples was a mixture of butter (dairy fat of animal origin) with fat of vegetable origin (soybean and palm oil) and did not contain milk as a major component. While NMR was an unequivocal choice to discriminate the chemical composition of food samples, identifying the short-chain saturated fatty acids present in milk fat, including the butyryl alkyl chain, SCIRA was able to discriminate the origin of fat present in the butter samples as C3 sources, such as palm vegetable oils.

Lithium isotope ratio analysis of geological samples using atomic absorption spectrometry with improved spectral resolution

This study introduces an improved spectrometric method with enhanced precision to determine isotope ratios in geological samples without chromatographic separation. Firstly, the improvement is achieved by increasing the spectral resolution of the spectrometer applied in well-known high-resolution continuum source atomic absorption spectrometry (HR-CS-AAS). The resulting resolving power and linear dispersion of the upgraded setup, which is denoted in the following as HR+CS-AAS, is well adapted to the line widths of the Li isotope components we investigated. Secondly, our proposed method combines optical absorption spectrometry with machine learning data analysis using an extreme gradient boosting algorithm (XGBoost). This method was applied to analyze certified geological reference materials with δLSVEC(7Li/6Li) (hereafter δ7Li) values ranging from −0.5 ‰ to 4.5 ‰. With a pixel related optical resolving power of λ/∆λ ≈ 780 000, we obtain precisions in δ7Li measurements from 1.0 ‰ to 2.5 ‰. The method is validated by comparing the results with multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), confirming its metrological compatibility. This work presents a fast, robust, and reliable method for δ7Li measurement in geological samples.

Colony‐forming and single‐cell picocyanobacteria nitrogen acquisition strategies and carbon fixation in the brackish Baltic Sea

AbstractPicocyanobacteria are widespread and globally significant primary producers. In brackish waters, picocyanobacterial populations are composed of diverse species with both single‐cell and colony‐forming lifestyles. Compared to their marine counterparts, brackish picocyanobacteria are less well characterized and the focus of research has been weighted toward single‐cell picocyanobacteria. Here, we investigate the uptake dynamics of single and colony‐forming picocyanobacteria using incubations with dual carbon‐13 and inorganic (ammonium and nitrate) or organic (urea and amino acids) nitrogen‐15 sources during August and September 2020 in the central Baltic Sea. Phytoplankton community and group‐specific uptake rates were obtained using an elemental analyzer isotope ratio mass spectrometer (EA‐IRMS) and nano secondary‐ion mass spectrometry (NanoSIMS). Picocyanobacteria contributed greater than one third of the ammonium, urea, amino acids, and inorganic carbon community uptake/fixation in September but &lt; 10% in August when phytoplankton biomass was higher. Overall, single‐cell ammonium and urea uptake rates were significantly higher for single‐celled compared to colonial picocyanobacteria. In a 6‐yr offshore central Baltic Sea time series (2015–2020), summer abundances of colonial picocyanobacteria reached up to 105 cells mL−1 and represented &gt; 5% of the average phytoplankton biomass, suggesting that they are periodically important for the ecosystem. Colonial strain identification was not distinguishable using 16S rRNA gene amplicon data, highlighting a need for refined tools for identification of colonial forms. This study shows the significance of single‐celled brackish picocyanobacteria to nutrient cycling and the importance of considering uptake and lifestyle strategies when assessing the role of picocyanobacteria in aquatic ecosystems.

Sensitive and isotopic interference-free analysis of Sb using hydride generation-microwave plasma torch-mass spectrometry under ambient condition

A sensitive and isotopic interference-free analysis method for Sb was developed based on hydride generation-microwave plasma torch-mass spectrometry (HG-MPT-MS). Compared to the conventional ICP-MS, MPT coupled to an ion trap mass spectrometer enabled much “softer” ionization of Sb under ambient condition, which provided multi-detection modes and various ion forms, such as Sb+, SbO+, SbO2−, SbO++H2O and so on. These ion formations can be easily regulated by tuning capillary voltage and tube lens voltage, which facilitated elimination of isotopic interference during analysis, for instance the interference of 123Te on 123Sb could be effectively excluded by optimizing parameters of capillary voltage and tube lens voltage. The potential application of HG-MPT-MS for Sb isotope ratio analysis was also demonstrated, which could be determined in different forms, e.g., 123Sb/121Sb or 123Sb16O/121Sb16O. The value of 123Sb/121Sb was determined to be 0.75110 ± 0.00038 (2σ, n > 50). In addition, the detection limit, linearity and spike recovery were also studied. Overall, HG-MPT-MS performed equally well on detection limit (0.05 μg/L) with ICP-MS or HG-AFS. The linearity (R2 = 0.998) was checked in the concentration range of 10–500 μg/L. Spike recovery were evaluated with two soil samples, and the obtained spike recovery ranged 90–100 %. In general, HG-MPT-MS was expected to be a versatile tool for study the biochemical or geochemical behaviors of Sb and other hydride forming elements under ambient condition in a much simpler and more efficient way.