Carbon Isotope Ratios Research Articles

Differentiating Pond-Intensive, Paddy-Ecologically, and Free-Range Cultured Crayfish (Procambarus clarkii) Using Stable Isotope and Multi-Element Analysis Coupled with Chemometrics.

The farming pattern of crayfish significantly impacts their quality, safety, and nutrition. Typically, green and ecologically friendly products command higher economic value and market competitiveness. Consequently, intensive farming methods are frequently employed in an attempt to replace these environmentally friendly products, leading to potential instances of commercial fraud. In this study, stable isotope and multi-element analysis were utilized in conjunction with multivariate modeling to differentiate between pond-intensive, paddy-ecologically, and free-range cultured crayfish. The four stable isotope ratios of carbon, nitrogen, hydrogen, and oxygen (δ13C, δ15N, δ2H, δ18O) and 20 elements from 88 crayfish samples and their feeds were determined for variance analysis and correlation analysis. To identify and differentiate three different farming pattern crayfish, unsupervised methods such as hierarchical cluster analysis (HCA) and principal component analysis (PCA) were used, as well as supervised multivariate modeling, specifically partial least squares discriminant analysis (PLS-DA). The HCA and PCA exhibited limited effectiveness in classifying the farming pattern of crayfish, whereas the PLS-DA demonstrated a more robust performance with a predictive accuracy of 90.8%. Additionally, variables such as δ13C, δ15N, δ2H, Mn, and Co exhibited relatively higher contributions in the PLS-DA model, with a variable influence on projection (VIP) greater than 1. This study is the first attempt to use stable isotope and multi-element analysis to distinguish crayfish under three farming patterns. It holds promising potential as an effective strategy for crayfish authentication.

Fate of soil organic carbon in estuarine mangroves: Evidences from stable isotopes and lignin biomarkers

Coastal wetlands are increasingly recognized for their role in climate change mitigation, particularly through the sequestration of soil organic carbon (SOC). Despite widespread acknowledgement of their importance, the variation in organic carbon (OC) sources among different estuarine mangrove wetlands, and how these sources interact with environmental factors, is not fully elucidated. This research focuses on the role of estuarine mangrove wetlands in climate change mitigation through SOC sequestration. It explores the distribution, sources, and decomposition of SOC in a wetland with four mangrove communities along a tidal gradient. These include a tidal flat, a Sonneratia apetala forest, a mixed S. apetala and Kandelia obovata forest, and a K. obovata forest. The study employs biogenic element analysis (C, N, lignin phenols) and natural stable carbon isotope ratios (δ13C and δ15N) to assess SOC. Key findings show a decrease in SOC and total nitrogen (TN) from the upstream K. obovata forest to the downstream tidal flat. A stable isotope mixing model reveals a diminishing mangrove-derived OC contribution in topsoil (0–40 cm), estimated at 62 % in the K. obovata forest, 45 % in the central region, and 24 % in tidal flats. Soil profiles suggest microbial decomposition as the main isotope fractionation mechanism, with lignin analysis indicating woody angiosperms as the primary OC source. These findings enhance understanding of OC origins and decomposition in coastal wetlands and inform “blue carbon” management, highlighting the terrestrial-estuary continuum's significance.

Seasonal trends in Subantarctic plankton δ13C and δ15N are driven by phytoplankton dynamics and nutrient preference

AbstractThe carbon and nitrogen isotope ratios (δ13C and δ15N) of marine plankton record biogeochemical processes at the base of the food web. In the Southern Ocean, such data, predominantly from summer, have been used to infer surface CO2 concentrations and the potential for biological carbon export. However, variability in plankton δ13C and δ15N remains poorly understood, with the lack of seasonal measurements from the Southern Ocean emerging as a particular limitation. Here, we investigate the δ13C and δ15N of suspended particulate matter (SPM) and zooplankton collected from the Subantarctic Ocean in winter, summer, and autumn. The low summertime δ13CSPM and δ15NSPM can be explained by strong diatom reliance on nitrate supplied during winter mixing. A subsequent increase in δ13CSPM and decrease in δ15NSPM by autumn is consistent with iron limitation in mid‐ to late‐summer favoring diatom succession by nano‐phytoplankton that consume mainly recycled ammonium. By winter, bacterial decomposition of biomass outpaces new biomass production, decreasing δ13CSPM and raising δ15NSPM. The δ13C and δ15N of contemporaneously sampled zooplankton generally reflect the variability in δ13CSPM and δ15NSPM, with one autumn mismatch suggesting that in situ SPM is not always the dominant zooplankton food source. Our study shows how nutrient dynamics and phytoplankton community composition shape the seasonality of the Subantarctic's isotopic baselines, emphasizing a key role for iron availability. This work has implications for isotope‐based food web studies, highlighting the need to consider seasonal variability in δ13CSPM and δ15NSPM, as well as the different turnover times of phytoplankton (i.e., SPM) vs. zooplankton biomass.

Stable carbon isotope evolution of formaldehyde on early Mars

Organic matter in the Martian sediments may provide a key to understanding the prebiotic chemistry and habitability of early Mars. The Curiosity rover has measured highly variable and 13C-depleted carbon isotopic values in early Martian organic matter whose origin is uncertain. One hypothesis suggests the deposition of simple organic molecules generated from 13C-depleted CO derived from CO2 photochemical reduction in the atmosphere. Here, we present a coupled photochemistry-climate evolution model incorporating carbon isotope fractionation processes induced by CO2 photolysis, carbon escape, and volcanic outgassing in an early Martian atmosphere of 0.5–2 bar, composed mainly of CO2, CO, and H2 to track the evolution of the carbon isotopic composition of C-bearing species. The calculated carbon isotopic ratio in formaldehyde (H2CO) can be highly depleted in 13C due to CO2-photolysis-induced fractionation and is variable with changes in atmospheric CO/CO2 ratio, surface pressure, albedo, and H2 outgassing rate. Conversely, CO2 becomes enriched in 13C, as estimated from the carbonates preserved in ALH84001 meteorite. Complex organic matter formed by the polymerization of such H2CO could explain the strong depletion in 13C observed in the Martian organic matter. Mixing with other sources of organic matter would account for its unique variable carbon isotopic values.

Improving the Determination of Carbon Isotope Ratios of Endogenous Steroids Found in Human Serum.

The determination of serum concentrations of testosterone (T) and 4-androstenedione (A4) was implemented into the steroidal module of the Athlete Biological Passport in 2023. Monitoring T, A4, and the ratio of T/A4 in a longitudinal manner enables the detection of the misuse of low-dose T administrations especially in female athletes, whereas urinary markers of the steroid profile may not be influenced significantly. In contrast to the urinary steroid profile, knowledge on confounding factors regarding serum concentrations of T and A4 is yet comparably scarce, and corroborating exogenous sources of the target analytes by isotope ratio mass spectrometry (IRMS) is desirable. In a recent study, it was demonstrated that carbon isotope ratios (CIRs) of serum steroids can be determined if analyte concentrations permit. The therein-employed method utilized 2D-GC/IRMS, and only a limited number of potential endogenous reference compounds were available. The here-presented approach uses complementary analyte purification strategies, addressing previous limitations. A high-performance liquid chromatography cleanup was developed and fully validated for serum steroids in order to enable all doping control laboratories to potentially implement this method alongside existing protocols for urinary steroids. Besides the already-investigated endogenous steroids cholesterol, dehydroepiandrosterone sulfate, androsterone sulfate, and epiandrosterone sulfate, two additional steroids were included in the test menu, namely, pregnenolone sulfate and 5-androstene-3β,17β-diol sulfate. Serum steroid concentrations down to 25 ng/mL were found to allow robust CIR determinations, and a reference population encompassing 124 male and female athlete samples was investigated to enable the calculation of population-based thresholds for all relevant steroid combinations.

Differences in reservoir quality within distributary channel belts at the braided river delta front in the Xinchang area of Western Sichuan’s 2nd member of the Xujiahe Formation: genesis and implications

AbstractThe tight sandstone reservoris are important exploration and production target in the Xujiahe Formation in Xinchang area of Western Sichuan. Due to the various lithofacies and diagenetic alteration in distributary channel belt sandstones, the reservoirs exhibit strong heterogeneity. The strong heterogeneity makes the identification of petrologically superior sandbodies a great challenge. In order to better understand reservoir quality, this study constructs a model between diagenetic alterations and reservoir quality within distributary channel belts. 73 plug samples were taken from 17 wells located in the channel belt. An integration of thin sections, X-ray diffraction, carbon and oxygen isotope ratios, cathodoluminescence, and micro-CT were analysed for the genesis and distribution of reservoir quality. The results show that subaqueous distributary channels are formed under various hydrodynamics, resulting in different lithofacies. The thicknesses of channels can be divided into less than 2 m, 2–6 m, and more than 6 m. The diagenetic alteration in lithofacies were identified. Coarse-grained sandstones with low content of rock fragments are relatively weakly compacted with less calcite and chlorite cementation. Fine-grained sandstones with high content of rock fragments are strongly compacted with calcite cementation during early diagenesis. The dissolution pores are related to the soluble mineral content and the distribution of mudstones. The subaqueous distributary channels formed in high-energy, moderate-energy, and low-energy hydrodynamic settings have experienced different diagenetic intensities. Additionally, fractures can effectively improve the reservoir properties. The distribution of good quality reservoirs is controlled by the combined influence of diagenetic heterogeneity and fractures. This would help to promote better understanding of reservoir quality within the subaqueous distributary channel belts in braided-river delta front.

The effects of fingerprinting agents on the stable isotope ratios of polyethylene films

Traditional forensic chemical comparisons of polymeric materials are often affected by fingerprinting agents that enhance and visualise finger-marks. This can inhibit detailed analysis used to provide an association or discrimination between two samples. In this study, we have demonstrated that the method for polymer comparisons using isotope ratio mass spectrometry analysis is not affected by fingerprinting matter on the surface in contrast to other forensic instrumental tests. A selection of resealable bags was analysed for carbon and hydrogen isotope ratio values of bags that had been subject to various fingerprinting agents and compared to values of untreated bags. The results showed no significant difference between samples that had been fingerprinted from those that were untreated.

Stable carbon isotope ratios of pristine carbohydrates preserved within nannofossil calcite

The geochemical characterization of phytoplankton-derived organic compounds found in marine sediments has been widely used to reconstruct atmospheric pCO2 throughout the Cenozoic. This is possible owing to a well-established relationship between the carbon isotope ratios of phytoplankton biomass and CO2 concentration in the ambient seawater. An ideal molecular target for such proxy reconstructions would be degradation resistant on geologic timescales and unambiguously associated with known, experimentally tractable, organisms, so that species-specific models can be developed, calibrated, and applied to appropriate material. However, existing organic matter targets do not meet these criteria, primarily owing to ambiguity in the source species of recalcitrant compounds in deep time. Here we explore the potential of a novel organic carbon target for isotopic analysis: acidic polysaccharides extracted from the calcite plates (coccoliths) that are produced by all calcifying haptophytes. Carbohydrates are usually rapidly remineralized in sediments, but coccolith-associated polysaccharides (CAPs) are mechanically protected from diagenesis within the coccolith calcite lattice. Coccoliths can be taxonomically separated by size and identified, often to species level, prior to CAP extraction, providing a species-specific record. Coccolith morphology and composition are important additional sources of information, which are then unambiguously associated with the extracted CAPs. We found that carbon isotope ratios of CAPs changed in response to the environmental changes associated with a glacial cycle, which we attribute to temperature-driven changes in average growth rate. Once the underlying biosynthetic processes and the associated isotope effects are better understood, this archive of pristine organic matter has the potential to provide insight into phytoplankton growth rates and atmospheric pCO2 far beyond the Cenozoic, to when the first coccolithophores inhabited the surface ocean over 200 million years ago.

Two-Dimensional Liquid Chromatography Purified GC/C/IRMS Doping Control Method: Analysis of Endogenous and Exogenous Sources in Urine Samples from Asian Subjects Administered a Low Dose of AICAR

AICAR (5-amino-4-imidazolecarboxyamide ribonucleoside), as a metabolic modulator, is classified in the S4 category by the World Anti-Doping Agency (WADA). Carbon Isotope Ratio Mass Spectrometry (CIR) is the mainstream method for distinguishing the endogenous and exogenous sources of AICAR in urine due to the significant individual difference in the concentration. The purpose of this study is to establish a gas chromatography combustion Isotope Ratio Mass Spectrometry (GC/C/IRMS) method for AICAR based on efficient two-dimensional liquid chromatography (2D-HPLC) separation. MethodIn this study, an automated 2D-HPLC separation technique was used to separate and purify AICAR and endogenous reference substances in urine samples. Then, AICAR was derivatized with 3-TMS as the main derivative product, while the endogenous reference compounds remained in their original form. Subsequently, the developed GC/C/IRMS method was utilized for the detection of the target and reference substances. Followed, we evaluated the applicability of this method using urine samples from two Asian males administered a low dose of AICAR (3 grams). ResultsThe advantages of this study include: 1) reduced sample pretreatment time: the established 2D-HPLC separation method can separate the target and endogenous reference substances in one step; 2) low interference: the isotope chromatograms have low background interference, and the separation of endogenous reference substances is purer; 3) more accurate result calculations: this method only requires derivatization and result correction for AICAR, with the endogenous reference substances measured in their original form, reducing biases from corrections of multiple substances. The detection method performed well, with a concentriton limit of 2500 ng/mL, meeting the needs of routine detection concentrations. The CIR results from volunteer samples indicated that samples collected within 16 hours post-administration exceeded the threshold set in the literature. ConclusionThis study successfully established a 2D-HPLC-GC/IRMS method that integrates CIR as the most stable indicator for distinguishing the internal and external sources of AICAR. After administering a low dose of AICAR to the Asian population, exogenous drug characteristics were manifested within 16 hours. This observation, when compared to the 40-hour detection window cited in the literature, suggests that the length of the detection window is positively correlated with the dosage of the test drug.

A long-term study of stable isotope ratios of fingernail keratin and amino acids in a mother-infant dyad.

To evaluate the potential of compound-specific isotope analysis of amino acids (CSIA-AA) for investigating infant feeding practices, we conducted a long-term study that compared infant and maternal amino acid (AA) nitrogen isotope ratios. Fingernail samples were collected from a single mother-infant dyad over 19 months postpartum. Carbon and nitrogen stable isotope ratios were measured in the bulk keratin of the fingernail samples. Selected samples were then hydrolyzed and derivatized for compound-specific nitrogen isotope analysis of keratin AAs. As in previous studies, infant bulk keratin nitrogen isotope values increased during exclusive breastfeeding and fell with the introduction of complementary foods and eventual cessation of breastfeeding. Infant trophic AAs had elevated nitrogen isotope values relative to the mother, while the source AAs were similar between the mother and infant. Proline and threonine appeared to track the presence of human milk in the infant's diet as the isotopic composition of these AAs remained offset from maternal isotope values until the cessation of breastfeeding. Although CSIA-AA is costly and labor intensive, it appears to hold potential for estimating the duration of breastfeeding, even after the introduction of complementary foods. Through the analysis of a full suite of AAs, it may also yield insights into infant physiology and AA synthesis.

Millennial-aged organic matter preservation in anoxic and sulfidic mangrove soils: Insights from isotopic and molecular analyses

Mangrove forests are known as coastal carbon sinks, but the long-term (millennium-scale) preservation processes of organic matter (OM) in their soils and the role of sulphur in these processes are still not fully understood. These processes are crucial for better estimating the impact of sea-level variations on the carbon dynamics in mangrove forests, which are particularly sensitive to sea-level changes due to their direct hydrological interactions with coastal waters. This study focuses on a soil layer enriched in mangrove-derived OM that accumulated during a stable sea-level period of the Holocene in New Caledonia (South Pacific). Radiocarbon dating situates this enriched layer at approximately 4000 cal BP. The aim of this study is to characterize the enriched OM layer using bulk (Rock-Eval), isotopic (δ13C and δ15N), and molecular (lignin and neutral carbohydrates) analyses. This OM has undergone diagenetic processes such as dehydrogenation, and the loss of components such as the main neutral carbohydrates: glucose, xylose, and galactose. However, some Rock-Eval parameters, the total lignin content, and carbon and nitrogen isotopic ratios are characteristic of well-preserved OM, suggesting differential decomposition/preservation processes. In addition, SEM observations highlighted the presence of pyrite associated to preserved root material. Along with high Sorg/TOC ratio, these results suggest potential processes of OM sulfurization preserving it from decomposition. Prolonged sea-level stability in addition to anoxic and sulfidic soil conditions enhanced OM accumulation and long-term sequestration in mangrove soils.

Essential amino acid carbon isotope ratios as indicators of marine macrophyte response to environmental variation

Essential amino acid carbon isotope ratios as indicators of marine macrophyte response to environmental variation

The helium and carbon isotopic signature of Ocean island basalts: Insights from Fogo volcano (Cape Verde archipelago)

Fluid inclusions (FI) entrapped in phenocrysts carried by Ocean Island Basalts (OIB) contain key information on volatiles’ abundance and origin in their mantle sources. Here, we add new piece of knowledge to our understanding of volatile geochemistry in global OIB magmas, by presenting new noble gas (He-Ne-Ar) and carbon (C) isotope results for olivine- and clinopyroxene-hosted FI from enclaves, lavas, tephra and volcanic gas samples from Fogo, the only frequently active volcano at the Cape Verde archipelago (eastern Atlantic Ocean). FI, together with crater fumaroles, constrain the Fogo 3He/4He signature at 7.14–8.44 Rc/Ra (where RC is the air-corrected 3He/4He isotope ratio, and Ra is the same ratio in air), which is within the typical MORB (Mid-Ocean Ridge Basalt) mantle. The carbon isotopic ratio (δ13C vs. Pee Dee Belemnite) of CO2 in FI and fumaroles range from -6.04 to -4.41 ‰. We identify systematic variations of δ13C and He/Ar* with FI entrapment pressure (estimated from a combination of host mineral barometry and FI microthermometry), from which we develop a model for volatile degassing in the mantle-to-crustal magma storage system. The model predicts a crustal-like signature for carbon (δ13C of -0.4 ± 1.0 ‰) in primary melts formed by mantle melting at ∼2200 MPa (∼77 km) and a source He/Ar* ratio of 0.90–0.24, which are indicative of variably depleted mantle metasomatized by carbon enriched melts/fluids from a crustal component. We also use our results to characterise regional (in the Cape Verde and Canary archipelagos) and global trends in C and He isotope composition from OIB. From a comparison with the few other OIB localities for which δ13C are available, we propose that a carbon enriched crustal component could be recurrent at a global scale in OIB magmatism, although often masked by isotope fractionation during magmatic degassing. We additionally find that, at regional scale, He isotopes in OIB scale inversely correlate with the degree of partial melting of the mantle beneath individual islands’ (inferred from the La/Yb ratio of erupted basalts). More widely, our results corroborate previously established global relationships between OIB He isotopic signature, plume buoyancy flux and overlying plate velocity. In this interpretation, the MORB-like 3He/4He (8 ± 1 Ra) at Fogo reflects a combination of (i) low to medium magma productivity, (ii) relatively low plume buoyancy flux (∼1.1 Mg/s), and (iii) slow average velocity (∼3 cm/yr) of the overlying plate.

Sourcing and long-range transport of particulate organic matter in river bedload: Río Bermejo, Argentina

Abstract. Fluvial transport of organic carbon from the terrestrial biosphere to the oceans is an important term in the global carbon cycle. Traditionally, the long-term burial flux of fluvial particulate organic carbon (POC) is estimated using river suspended sediment flux; however, organic carbon can also travel in river bedload as coarse particulate organic matter (POMBed). Estimates of fluvial POC export to the ocean are highly uncertain because few studies document POMbed sources, flux, and evolution during long-range fluvial transport from uplands to ocean basins. This knowledge gap limits our ability to determine the global terrestrial organic carbon burial flux. In this study we investigate the flux, sources, and transformations of POMBed during fluvial transport over a ∼1300 km long reach of the Río Bermejo, Argentina, which has no tributary inputs. To constrain sourcing of POMBed, we analyzed the composition and stable hydrogen and carbon isotope ratios (δ2H, δ13C) of plant wax biomarkers from POMBed at six locations along the Río Bermejo and compared this to samples of suspended sediment, soil, leaf litter, and floating organic debris (POMfloat) from both the lowland and headwater river system. Across all samples, we found no discernible differences in n-alkane average chain length or nC29 δ13C, indicting a common origin for all sampled POMBed. Leaf litter and POMfloat nC29 δ2H values decrease with elevation, making it a useful proxy for POMBed source elevation. Biomarker δ2H values suggest that POMBed is a mix of distally derived headwater and locally recruited floodplain sources at all sampling locations. These results indicate that POMBed can be preserved during transport through lowland rivers for hundreds of kilometers. However, the POMBed flux decreases with increasing transport distance, suggesting mechanical comminution of these coarse organic particles and progressive transfer into the suspended load. Our provisional estimates suggest that the carbon flux from POMBed comprises less than 1 % of the suspended load POC flux in the Río Bermejo. While this represents a small portion of the river POC flux, this coarse, high-density material likely has a higher probability of deposition and burial in sedimentary basins, potentially allowing it to be more effective in long-term CO2 drawdown relative to fine suspended particles. Because the rate and ratio of POMBed transport versus comminution likely vary across tectonic and climatic settings, additional research is needed to determine the importance of POMBed in the global carbon cycle.

Isotope-based inferences of the trophic niche of short-finned pilot whales in the Webbnesia

Knowledge of predator-prey interactions is key in ecological studies and understanding ecosystem function, yet this is still poorly explored in the deep-sea environment. Carbon (δ13C: 13C/12C) and nitrogen (δ15N: 15N/14N) stable isotope ratios of a deep-diving species, the short-finned pilot whale (Globicephala macrorhynchus), were used to explore knowledge gaps on its ecological niche and foraging habitats in the Webbnesia marine ecoregion (Tenerife Island, n = 27 animals vs. Madeira, n = 31; 500 km apart) where animals display distinct levels of site fidelity. Specifically, we tested whether intraspecific isotopic variation results from differences between geographic areas (due to possible foraging plasticity between regions), sexes, and/or years (2015–2020) using Generalized Linear Models. In general, significant differences (p < 0.05) were found in the stable isotope profiles of pilot whales between the two archipelagos, which were also reflected in their isotopic niche. The higher mean and wider range of δ15N values in Tenerife suggest that pilot whales consume prey of higher trophic levels and more diverse than Madeira. The higher mean and wider range of δ13C values in Madeira suggest that in that island, pilot whales rely on prey from more diverse habitats. There was significant variation between some years, but not between sexes. Finally, we discuss pilot whales' foraging strategies worldwide and infer the reliance on benthic or benthopelagic food sources in the Webbnesia.

A pilot study on the isotopic characterization of feeding habits of Diptera in a tropical rain forest

Flies (Diptera) are among the most diverse groups of insects and are known to utilize various food resources, including plants, detritus, microbial tissues, and fresh and dead animal tissues. However, their feeding habits in the field remain poorly understood. We conducted a pilot study to apply stable nitrogen (N) and carbon (C) isotope techniques to examine the feeding habits of flies in a tropical rain forest in Sarawak, Malaysia. The fly samples comprised 13 families and >18 species. The results showed significant differences in nitrogen and carbon isotope ratios (δ15N and δ13C) among families and species within a family. The observed pattern is largely consistent with their known feeding habits; flies that use carcasses and carrion as diets (e.g., Sarcophagidae and Calliphoridae) have significantly higher δ15N values than those likely utilizing plant-based diets (e.g., Cecidomyiidae). There were significant differences in δ15N values among the six species of Calliphoridae, which is consistent with insect succession on carcasses. The differences in δ15N may be explained by the use of carrion at different stages of decomposition, because microbial decomposition can lead to the 15N enrichment. Tachinid flies had relatively low δ13C values, reflecting the use of lepidopterans as a host. This pilot study shows that the δ15N and δ13C values of flies provide insights into the diversity of feeding habits of fly communities, which could also serve as an indicator of resource availability in an entire ecosystem.

Drone CO2 measurements during the Tajogaite volcanic eruption

Abstract. We report in-plume carbon dioxide (CO2) concentrations and carbon isotope ratios during the 2021 eruption of Tajogaite volcano, island of La Palma, Spain. CO2 measurements inform our understanding of volcanic contributions to the global climate carbon cycle and the role of CO2 in eruptions. Traditional ground-based methods of CO2 collection are difficult and dangerous, and as a result only about 5 % of volcanoes have been directly surveyed. We demonstrate that unpiloted aerial system (UAS) surveys allow for fast and relatively safe measurements. Using CO2 concentration profiles we estimate the total flux during several measurements in November 2021 to be 1.76±0.20×103 to 2.23±0.26×104 t d−1. Carbon isotope ratios of plume CO2 indicate a deep magmatic source, consistent with the intensity of the eruption. Our work demonstrates the feasibility of UASs for CO2 surveys during active volcanic eruptions, particularly for deriving rapid emission estimates.

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.

From swamp to sea: Quantifying terrestrial dissolved organic carbon in a tropical shelf sea using hydrogen isotope ratios

Dissolved organic carbon (DOC) is a key component of coastal biogeochemical cycles, but its composition and reactivity depend on the relative contribution of autochthonous aquatic versus allochthonous terrigenous DOC (tDOC). In complex coastal waters, tDOC is commonly quantified using the bulk DOC stable carbon isotope ratio (δ13CDOC). However, several limitations can hamper the use of δ13CDOC in marine ecosystems, such as (1) the narrow and often overlapping separation of the autochthonous and allochthonous endmembers, and (2) mineralization of tDOC to dissolved inorganic carbon creates a reservoir effect such that autochthonous DOC can acquire a terrigenous-like δ13CDOC. The stable isotope ratio of non-exchangeable hydrogen in the DOC (δ2Hn) has emerged as a new tool that can potentially overcome these limitations: (1) δ2Hn has a large separation between aquatic and terrigenous endmembers (>50‰) and (2) it is not subject to reservoir effects caused by tDOC mineralization. Here, we evaluate the potential of δ2Hn obtained from solid phase-extracted dissolved organic matter (SPE-DOM), by comparing it to δ13CDOC and chromophoric DOM (CDOM) optical properties. We collected samples at a site in Southeast Asia’s Sunda Shelf that experiences substantial seasonal variation in tDOC input, driven primarily by the monsoon-induced physical advection of peatland-derived tDOC. Over a 1-year monthly time series, the terrigenous fraction of DOC (fterr) determined using δ2Hn of SPE-DOM and δ13CDOC of bulk DOC was well correlated (r2 = 0.42), and there was no significant difference in fterr between the two isotope systems. In fact, δ2Hn displayed slightly stronger correlations with salinity and CDOM optical properties compared to δ13CDOC. Our results indicate that δ2Hn of SPE-DOM is effective for quantifying tDOC across coastal gradients, potentially offering greater sensitivity than δ13CDOC, and is a viable alternative in settings where δ13CDOC is inadequate.

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.