Multiple Stable Isotope Research Articles

Application of multiple stable isotopes to aid identification of the origin of regional and organic animal products in Hesse, Germany

ABSTRACT There is an increasing global demand for regional and organic produce. However, the growth of these markets depends on consumers’ trust. Thus, novel methods must be developed to aid the verification of the origin of produce. We built on our previous study to identify the geographical origin and production method of animal-derived food products. Thirty-samples of eggs, 99 of milk, 34 of beef, and 62 of pork were collected from different regions in central Germany and analysed for their stable isotopic composition. The analysis followed a single-variate authentification approach using five isotope signatures, δ 18O, δ 2H, δ 13C, δ 15N, and δ 34S. The best-performing indicators for verification of the geographical origin were δ 15N and δ 34S for beef; δ 18O, δ 2H, and δ 13C for milk, and δ 2H and δ 13C for pork. These tracers indicated statistically significant differences among regions with the exception of pork; the results recorded for eggs were inconclusive. It was possible to distinguish between production methods by means of δ 15N and δ 34S (beef); all five tracers (eggs), and δ 13C, δ 15N, and δ 34S (milk). This study demonstrated how the analysis of stable isotopes can be employed to determine the geographic region of origin and production method of animal-derived products in Germany.

Stable Isotope Provenance of Unidentified Deceased Migrants-A Pilot Study.

In the global migration crisis, one of the challenges in the effort to identify deceased migrants is establishing their region of origin, which facilitates the search for ante mortem data to be compared with the post mortem information. This pilot study explores the potential of using stable isotope analysis to distinguish between individuals coming from West Africa and the Horn of Africa. Six individuals (four of known origin and two of unknown origin) were sampled. δ13CVPDB(keratin), δ15NVPDB(keratin) and δ18OVSMOW(keratin) of hair were analysed using Elemental Analyzers coupled with Isotope Ratio Mass Spectrometry (IRMS). δ18OVSMOW(carbonate) and δ13CVPDB(carbonate) of bone were analysed using GasBench II with IRMS, while 87Sr/86Sr composition was determined in bone and dental enamel using laser ablation multi-collector inductively coupled plasma mass spectrometry. The stable isotope compositions of the individual from the Horn of Africa differed from the other individuals. The differences found between 87Sr/86Sr of enamel and bone and between δ18O and δ13C in bone and hair reflect changes in sources of food and water in accordance with regionally typical migration journeys. The analysis of multiple stable isotopes delivered promising results, allowing us to narrow down the region of origin of deceased migrants and corroborate the information about the migration journey.

Multiple stable isotopes (C, N & S) provide evidence for fin whale (Balaenoptera physalus) trophic ecology and movements in the Humboldt Current System of northern Chile

Reflecting the intense coastal upwelling and high primary productivity characteristic of the Humboldt Current System (HCS), the northern coast of Chile supports a diverse and productive community of marine consumers, including worldwide important pelagic fisheries resources. Although marine mammals are relatively understudied in the region, recent studies have demonstrated that fin whale (Balaenoptera physalus) is the most frequently encountered whale species, and forages in these waters year-round. However, a current lack of information limits our understanding of whether fin whales actively feed and/or remain resident in these waters or whether whales are observed feeding as they migrate along this part of the Pacific. Here, we use stable isotope ratios of carbon, nitrogen and sulphur of fin whale skin samples collected in early summer 2020 (n = 18) and in late winter 2021 (n = 22) to examine evidence of temporal isotopic shifts that could provide information on potential migratory movements and to estimate likely consumption patterns of putative prey (i.e. zooplankton, krill, pelagic fishes and Pleuroncodes sp.). We also analysed prey items in fin whale faecal plumes (n = 8) collected during the study period. Stable isotope data showed significant differences in the isotopic values of fin whales from summer and winter. On average, summer individuals were depleted in 15N and 34S relative to those sampled during winter. Whales sampled in summer showed greater isotopic variance than winter individuals, with several showing values that were atypical for consumers from the HCS. During winter, fin whales showed far less inter-individual variation in stable isotope values, and all individuals had values indicative of prey consumption in the region. Analysis of both stable isotopes and faeces indicated that fin whales sighted off the Mejillones Peninsula fed primarily on krill (SIA median contribution = 32%; IRI = 65%) and, to a lesser extent, zooplankton (SIA zooplankton = 29%; IRI copepod = 33%). These are the first isotopic-based data regarding the trophic ecology of fin whales in the north of Chile. They provide evidence that fin whales are seasonally resident in the area, including individuals with values that likely originated outside the study area. The information presented here serves as a baseline for future work. It highlights that many aspects of the ecology of fin whales in the Humboldt Current and wider SE Pacific still need to be clarified.

Combination of multiple stable isotope and elemental analyses in urban trees reveals air pollution and climate change effects in Central Mongolia

The Ulaanbaatar area in Mongolia has become one of the most polluted regions worldwide due to the rapid increase in urbanization, industrial activity and traffic. However, we critically lack knowledge on the impacts of air pollution on surrounding forest ecosystems that may be further amplified by the ongoing climate change. Here, we apply a novel combination of multiple stable isotope analyses (nitrogen: δ15N, carbon: δ13C, oxygen: δ18O, hydrogen: δ2H) in foliar and tree-ring samples from different tree species, including deciduous, broadleaf species (poplar and birch), a deciduous conifer (larch) and needle evergreen species (spruce and Scots pine). This was complemented by trace element analysis, to study the influence of air pollution and climate on urban, suburban and more remote forests in and around Ulaanbaatar. We found indications of pollution effects in urban and suburban sites in foliar material, particularly in δ15N, with unusually high values of > 10‰, that could be related to tree uptake of NOx. Results were similar for all species, but with a smaller effect for Scots pine. The tree-ring δ15N values were found to be clearly enriched in recent years compared to 50 years ago at the urban sites, consistent with a pollution signal. Leaves and needles at suburban and urban sites had accumulated higher concentrations of various trace elements including Al, B, Ba, Ca, Cr, Cu, Fe, Mg, Na, S and Zn compared to the more distant sites, confirmed by Principal Component Analysis. Our data on δ13C, δ18O and δ2H enabled us to infer possible physiological effects induced by air pollution. Consistently increasing tree-ring δ13C values over recent decades for all investigated species indicated increasing plant stress, like hampered stomatal conductance and photosynthesis, but this was found for all sites, suggesting climate change rather than air pollution effects. In summary, we show that our multi-isotope and -element approach provides new insights into the threats to forests in urban areas, where the occurrence of more frequent droughts acts together with air pollution.

Late Pleistocene Neanderthal exploitation of stable and mosaic ecosystems in northern Iberia shown by multi-isotope evidence

AbstractDuring the last glacial period, rapidly changing environments posed substantial challenges to Neanderthal populations in Europe. Southern continental regions, such as Iberia, have been proposed as important climatic “buffer” zones during glacial phases. Contextualising the climatic and ecological conditions Neanderthals faced is relevant to interpreting their resilience. However, records of the environments and ecosystems they exploited across Iberia exhibit temporal and spatial gaps in coverage. Here we provide new evidence for palaeotemperatures, vegetation structure, and prey herbivore ecology during the late Pleistocene (MIS 5–3) in northern Spain, by applying multiple stable isotope tracers (δ18O, δ13C, δ15N, δ34S) to herbivore skeletal remains associated with Neanderthal occupations at Axlor Cave, Bizkaia. The results show little change over time and indicate stable climatic conditions and ecosystems across different occupations. Large within-layer isotopic variability in nitrogen and sulphur suggests the presence of a mosaic environment and a variety of isotopic ecotones that were exploited by Neanderthals and their prey. We implement a combination of carbonate and phosphate δ18O measurements to estimate palaeotemperatures using a cost-effective workflow. We show that the targeted use of phosphate δ18O measurements to anchor summer peak and winter trough areas enables high-precision seasonal palaeoclimatic reconstructions.

Multiple isotopes reveal the driving forces of nitrogen cycling from freshwater to brackish water

Rivers play a crucial role in global nitrogen (N) cycling, but revealing the driving mechanism of N cycling remains challenging because of the complex natural background gradients. The Qiantang River Basin provides an opportunity to elucidate the driving mechanism due to the complex climatic and hydrological conditions. In this study, the multiple stable isotopes suggested that the conservative mixing of two end members was insufficient to explain the complex behavior of N in both seasons. In-soil processes were the primary N cycling processes that controlled riverine N loading during the wet season, whereas in-stream N biological transformation processes (nitrification and assimilation) were more prevalent during the dry season. The results of MixSIAR revealed that soil sources (soil N and N fertilizer) contributed the most to NO3− during the wet season, accounting for 64.3 %, followed by manure and sewage (31.6 %) and atmospheric precipitation (4.1 %). During the dry season, manure and sewage were the predominant contributors to NO3− (52.1 %), followed by soil N (26.6 %), N fertilizer (18.8 %), and atmospheric precipitation (2.5 %). The relationships between d-excess and δ15N-NH4+ or δ15N-NO3− suggested that both climatic and hydrological conditions would be the driving forces regulating the N transportation and transformation in this basin, leading to the high spatiotemporal heterogeneity in N loading and isotopic compositions. In the wet season, precipitation patterns served as the primary driving forces regulating in-soil biological processes and soil leaching. While the hydrological conditions, especially water residence time, were the crucial factors controlling in-stream biological processes during the dry season. This study elucidates N sources, biotransformation processes, and their driving forces from freshwater to brackish water, which has applications for understanding the N fate from terrene to ocean.

Nitrogen accumulation and attenuation in the Ganges-Brahmaputra-Meghna river system: An evaluation with multiple stable isotopes and microbiota

We examined dissolved inorganic nitrogen (DIN) accumulation and attenuation in the lower stream and estuary of the Ganges-Brahmaputra-Meghna River system. In the lower stream of Ganges, Meghna and Brahmaputra rivers, nitrate (NO3−) was the dominant component in the DIN pool apart from the site near an industrial center. Concentrations of NO3− displayed minor differences between surface and bottom water, accounting for >90 % of the riverine DIN pool. Sources of NO3− were likely to be municipal wastewater and fertilizer based on signals of 15N-NO3− and 18O-NO3−. In the Meghna River, ammonium concentration in river water increased due to sewage discharge from local industrial centers. In the estuary, likely due to the high-abundance nitrifiers, nitrification rates overwhelmed removal rates and led to NO3− accumulation. Towards coastal ocean, DIN concentrations decreased due to seawater dilution and biological assimilation, indicating a tight linkage between the riverine input and ecological stability in the receiving water.

Nitrogen sources and conversion processes in shallow groundwater around a plain lake (Northwest China): Evidenced by multiple isotopes and water chemistry

The groundwater quality is severely impacted by Nitrate (NO3−-N) pollution worldwide. Effective lake quality management depends on understanding the origin and fate of nitrogen (N) in the groundwater around lakes. This study combined data for multiple stable isotopes (δ2H–H2O and δ18O–H2O, δ15N–NO3 and δ18O–NO3) and hydrochemistry with the hydrodynamic monitoring profile and a Bayesian isotope mixing (MixSIAR) model to clarify the sources and transformation of N within shallow groundwater around Shahu Lake in the arid area plain of Northwest China. In May 2022, multiple water samples were collected from aquifers (n = 33), drainage water (n = 1), channel water (n = 1), and lake water (n = 7). The results showed that 57% of groundwater samples had high NO3−-N concentrations exceeding the World Health Organisation threshold for drinking water (10 mg/L). The high variation in δ15N–NO3 (from −9.21‰ to +27.57‰) and δ18O–NO3 (from −8.32‰ to +19.04‰) revealed multiple N sources and conversion processes. According to nitrate isotopes and the MixSIAR model, N fertilizer, soil organic N and manure, and sewage are the main sources of nitrogen in groundwater and lake water, which account for 40.61%, 35.86%, and 21.55% of groundwater NO3−-N, respectively, and 35.07%, 34.43%, and 27.49% of lake water NO3−-N. Hydrodynamic monitoring combined with water isotopes showed that upper groundwater (5–10 m) within 1.22 km of the adjacent lake shore strongly interacted with the lake. In groundwater, nitrification predominated, while local denitrification remained a possibility. In conclusion, this research offers a comprehensive approach to determining the sources and conversion of N in contaminated groundwater.

Combined use of carbon, nitrogen and sulfur stable isotopes reveal trophic structure and connections in deep-sea mesopelagic and demersal fish communities from the Southeastern Pacific Ocean

The trophic structure of deep-sea fish communities has been poorly studied in the Southeastern Pacific Ocean. Here, using the analysis of multiple (CNS) stable isotopes, we provide a first approach to characterize the structure of a marine food web including mesopelagic (9 species) and demersal (13 species) fishes. At a species level, Dissostichus eleginoides were the most 13C-depleted and the grenadier Coryphaenoides ariommus the most 13C-enriched species. The most 15N-depleted species was the lanternfish Diogenichthys laternatus and macrourid fishes Trachyrincus villagai and C. ariommus the most 15N-enriched. δ34S values showed less variation, but ranged considerably, varying between 10.5 and 17.7‰: C. ariommus was the most 34S-depleted species and D. eleginoides the most 34S-enriched. At a whole study level, individual δ13C and δ15N values were positively correlated. Relationships between δ13C and δ34S, and δ15N and δ34S were both negative. When analyses were conducted separately for demersal and mesopelagic fishes, δ13C showed a positive correlation with δ15N. There was a negative relationship between δ13C and δ34S in demersal fish but no apparent relationship between δ15N and δ34S. In mesopelagic fishes, there was no statistical support for relationships between δ13C and δ34S or δ15N and δ34S. Mean log-transformed total length (TL) and mean δ15N were related in mesopelagic fishes, but there was no apparent relationship between TL and δ13C or δ34S values. In the case of demersal fishes there was no relationship between TL and either δ15N, δ13C or δ34S. Using cluster analysis, species were classified into 4 distinct trophic groups (G1 - G4) that display different trophic strategies according to the literature. Groups G1 and G2 included zooplanktivorous, micronektonivorous and gelatinovorous fishes associated with pelagic habitats. Groups G3 and G4 include micronektonivorous, piscivorous and generalist fishes foraging in benthic habitats. The demersal fish Dissostichus eleginoides was classified as a member of G1, suggesting that its diet in northern Chile is likely dominated by pelagic prey. In addition, Macrourus holotrachys (G3) showed very marked individual variability in δ15N values indicating considerable intraspecific variation in diet and foraging behavior. Given that this species had isotope values that extended across values typical of benthic and pelagic habitats, it suggests that some individuals may perform vertical migrations. Our results also highlighted that some demersal species (M. holotrachys and Coryphaenoides ariommus) had δ34S values that indicate the assimilation of some chemosynthetic-derived sulfur.Our results provide isotopic information on deep-water species in this region and show likely coupling between the demersal and mesopelagic assemblages. This information improves our understanding of deep-sea ecosystem functioning and provides key information for fisheries management and conservation initiatives.

Identifying nitrate sources and transformations in an agricultural watershed in Northeast China: Insights from multiple isotopes

Accurate identification of riverine nitrate sources is required for preventing and controlling nitrogen contamination in agricultural watersheds. The water chemistry and multiple stable isotopes (δ15N–NO3, δ18O–NO3, δ2H–H2O, and δ18O–H2O) of the river water and groundwater in an agricultural watershed in China's northeast black soil region were analyzed to better understand the sources and transformations of riverine nitrogen. Results showed that nitrate is an important pollutant that affects water quality in this watershed. Affected by factors such as seasonal rainfall changes and spatial differences in land use, the nitrate concentrations in the river water showed obvious temporal and spatial variations. The riverine nitrate concentration was higher in the wet season than in the dry season, and higher downstream than upstream. The water chemistry and dual nitrate isotopes revealed that riverine nitrate came primarily from manure and sewage (M&S). Results from the SIAR model showed that it accounted for more than 40% of riverine nitrate in the dry season. The proportional contribution of M&S decreased during the wet season due to the increased contribution of chemical fertilizers and soil nitrogen induced by large amounts of rainfall. The δ2H–H2O and δ18O–H2O signatures implied that interactions occurred between the river water and groundwater. Considering the large accumulation of nitrates in the groundwater, restoring groundwater nitrate levels is essential for controlling riverine nitrate pollution. As a systematic study on the sources, migration, and transformations of nitrate/nitrogen in agricultural watersheds in black soil regions, this research can provide a scientific support for nitrate pollution management in the Xinlicheng Reservoir watershed and provide a reference for other watersheds in black soil regions in the world with similar conditions.

Precipitation frequency controls nitrogenous aerosol in a tropical coastal city and its implications for plant carbon sequestration

The concentration of nitrogenous aerosols is influenced by air mass transition, local meteorological conditions, local emissions, and the wet removal effect driven by precipitation. Deposited nitrogenous aerosols influence nitrogen availability in the canopy, affecting the amount of plant carbon sequestration. However, the factors controlling nitrogenous aerosol concentrations and their implications for plant carbon sequestration remain unclear. In this study, multiple stable nitrogen isotopes in atmospheric aerosols (δ15N-TN, δ15N–NO3–, and δ15N–NH4+) and rainwater (rainwater δ15N–NO3– and rainwater δ15N–NH4+) in one-year observations were analyzed to explore the main factors controlling nitrogenous aerosol concentrations. The results showed that NO3− and NH4+ were the major components of TN, and their concentrations in seasonal patterns were sensitive to frequent rainfall rather than local emissions or external contributions. The concentrations of nitrogenous aerosols were negatively correlated with precipitation frequency, indicating that increased precipitation frequency induced low concentrations of nitrogenous aerosols. Moreover, the positive matrix factorization (PMF) analysis showed that coarse mode NO3− was generated in the wet season but not in the dry season, reflecting the removal of precipitation. With the increased precipitation frequency from May to July, 42.4% of aerosol NO3− was scavenged into rainwater, indicated by the variations in the δ15N values of nitrogenous aerosols and rainwater. This result prompted us to calculate the loss of 12.1 ± 3.9 Gg carbon/yr plant carbon sequestration. Our study suggests that nitrogenous aerosols are captured by the high precipitation frequency in tropical areas, decreasing nitrogen availability in the canopy, which might decrease plant carbon sequestration.

Determination of 170,172Yb(α,n)173,175Hf reaction cross sections in a stacked-target experiment

Background: For understanding the synthesis of elements in the universe, precise knowledge of reaction rates and cross sections is paramount. This is especially true for the $p$ process because its study requires large network calculations including thousands of nuclei and nuclear reactions with little room for simplification. Therefore, robust theoretical methods for predicting cross sections are needed which are usually based on Hauser-Feshbach calculations. These calculations use physics input in the form of $\ensuremath{\gamma}$-ray strength functions, nuclear level densities, and particle $+$ nucleus optical-model potentials. These have to be constrained using experimental results.Purpose: To constrain the $\ensuremath{\alpha}$ optical-model potential $\ensuremath{\alpha}$-induced reactions are well suited. The ytterbium isotopic chain not only offers multiple stable isotopes on which cross sections can be measured and insights into the evolution of the $\ensuremath{\alpha}$ optical-model potential with the neutron-to-proton ratio can be gained but also includes the $p$ nucleus $^{168}\mathrm{Yb}$. Its abundance is significantly impacted by the $^{164,166}\mathrm{Yb}(\ensuremath{\alpha},\ensuremath{\gamma})$ reactions and is, therefore, also affected by the constraints resulting from the experiment presented in this paper.Method: To study the $^{170,172}\mathrm{Yb}(\ensuremath{\alpha},n)^{173,175}\mathrm{Hf}$ reaction cross sections the activation method was used. During irradiation the targets were arranged in stacks of four to reduce the required irradiation time. Aluminum degrader foils served as backings. The average interaction energy inside each ytterbium layer was determined via geant4 simulations. A third layer, consisting of manganese, was used to verify the simulations by comparing the measured $^{55}\mathrm{Mn}(\ensuremath{\alpha},(2)n)^{57,58}\mathrm{Co}$ reaction cross sections to previous results. For irradiation the 10 MV FN tandem accelerator located at the University of Cologne was used and the activation measurement was performed utilizing the Cologne Clover Counting setup consisting of two clover-type high-purity germanium detectors in a face-to-face geometry.Results: For the $^{170}\mathrm{Yb}(\ensuremath{\alpha},n)$ reaction seven cross sections at center-of-mass energies between 12.7 and 16.5 MeV were measured. For the $^{172}\mathrm{Yb}(\ensuremath{\alpha},n)$ reaction six cross sections for center-of-mass energies of 13.1 to 16.5 MeV could be determined with an additional upper limit at ${E}_{\mathrm{c}.\mathrm{m}.}=12.3$ MeV.Conclusion: Comparisons to theoretical models show that state-of-the-art $\ensuremath{\alpha}$-optical model potentials reproduce the measured cross sections very well. The ratios of $(\ensuremath{\alpha},n)$ reaction cross sections in the ytterbium isotopic chain can be accurately reproduced as well.

Using a Multi-isotope Approach and Isotope Mixing Models to Trace and Quantify Phosphorus Sources in the Tuojiang River, Southwest China.

Identifying phosphorus (P) sources is critical for solving eutrophication and controlling P in aquatic environments. Phosphate oxygen isotopes (δ18Op) have been used to trace P sources. However, the application of this method has been greatly restricted due to δ18OP values from the potential source having wide and overlapping ranges. In this research, P sources were traced by combining δ18Op with multiple stable isotopes of nitrogen (δ15N), hydrogen (δD), and dissolved inorganic carbon (δ13C). Then, a Bayesian-based Stable Isotope Analysis in R (SIAR) model and IsoSource model were used to estimate the proportional contributions of the potential sources in the Tuojiang River. δ18Op was not in equilibrium with ambient water, and statistically significant differences in the δ18Op values were found between the potential sources, indicating that δ18Op can be used to trace the P sources. δ15N, δD, and δ13C could assist δ18Op in identifying the main sources of P. The SIAR and IsoSource models suggested that industrial and domestic sewage was the largest contributor, followed by phosphate rock and phosphogypsum and agricultural sewage. The uncertainty of the calculation results of the SIAR model was lower than that of the IsoSource model. These findings provide new insights into tracing P sources using multiple stable isotopes in watersheds.

Foraging under extreme events: Contrasting adaptations by benthic macrofauna to drastic biogeochemical disturbance

Abstract Hydrothermal vent systems are important biodiversity hotspots that host a vast array of unique species and provide information on life's evolutionary adaptations to extreme environments. However, these habitats are threatened by both human exploitation and extreme natural events, both of which can rapidly disrupt the delicate balance of the food webs found in these systems. This is particularly true for shallow vent endemic animals due to their limited dietary niche and specialized adaptations to specific biogeochemical conditions. In this study, we used the shallow hydrothermal vents of Kueishantao off the coast of Taiwan as a natural laboratory to examine the response of a benthic food web to a M5.8 earthquake and a C5 typhoon that led to a two‐year “near shutdown” of the vents. These perturbations drastically altered the local biogeochemical cycle and the dietary availability of chemosynthetic versus photosynthetic food resources. Our analysis of multiple stable isotopes, including those of sulphur, carbon, and nitrogen (δ34S, δ13C, and δ15N), from different benthic macrofauna reveals that endemic and non‐endemic consumers exhibited different responses to sudden disruption in habitat and biogeochemical cycling. The endemic vent crab, Xenograpsus testudinatus, continued to partially rely on chemosynthetic sulphur bacteria despite photosynthetic sources being the most dominant food source after the disruption. We posit that X. testudinatus has an obligate nutritional dependence on chemoautotrophic sources because the decrease in chemoautotrophic production was accompanied by a dramatic decrease in the abundance of X. testudinatus. The population decline rate was ~19 individuals per m2 per year before the perturbation, but the decline rate increased to 40 individuals per m2 per year after the perturbation. In contrast, the non‐endemic gastropods exhibited much greater dietary plasticity that tracked the overall abundance of photo‐ and chemo‐synthetic dietary sources. The catastrophic events in shallow hydrothermal vent ecosystem presented a novel opportunity to examine dietary adaptations among endemic and non‐endemic benthic macrofauna in response to altered biogeochemical cycling. Our findings highlight the vulnerability of benthic specialists to the growing environmental pressures exerted by human activities worldwide. Read the free Plain Language Summary for this article on the Journal blog.

Geochemistry, stable isotopes and statistic tools to estimate threshold and source of nitrate in groundwater (Sardinia, Italy)

In the European Union, nitrate vulnerable zone (NVZ) should be designed for the mitigation of nitrate (NO3−) contamination caused by agricultural practices. Before establishing new NVZ, the sources of NO3− must be recognized. A geochemical and multiple stable isotopes approach (hydrogen, oxygen, nitrogen, sulfur and boron) and statistical tools were applied to define the geochemical characteristics of groundwater (60 samples), calculate the local NO3− threshold and assess potential sources of NO3− contamination in two study areas (hereafter Northern and Southern), located in a Mediterranean environment (Sardinia, Italy). Results of the integrated approach applied to two case study, permits to highlight the strengths of integrating geochemical and statistical methods to provide nitrate source identification as a reference by decision makers to remediate and mitigate nitrate contamination in groundwater.Hydrogeochemical features in the two study areas were similar: near neutral to slightly alkaline pH, electrical conductivity in the range of 0.3 to 3.9 mS/cm, and chemical composition ranging from Ca-HCO3− at low salinity to Na-Cl− at high salinity. Concentrations of NO3− in groundwater were in the range of 1 to 165 mg/L, whereas the nitrogen reduced species were negligible, except few samples having NH4+ up to 2 mg/L. Threshold values in the studied groundwater samples were between 4.3 and 6.6 mg/L NO3−, which was in agreement with previous estimates in Sardinian groundwater.Values of δ34S and δ18OSO4 of SO42− in groundwater samples indicated different sources of SO42−. Sulfur isotopic features attributed to marine SO42− were consistent with groundwater circulation in marine-derived sediments. Other source of SO42− were recognize due to the oxidation of sulfide minerals, to fertilizers, manure, sewage fields, and SO42− derived from a mix of different sources.Values of δ15N and δ18ONO3 of NO3− in groundwater samples indicated different biogeochemical processes and NO3− sources. Nitrification and volatilization processes might have occurred at very few sites, and denitrification was likely to occur at specific sites. Mixing among various NO3− sources in different proportions might account for the observed NO3− concentrations and the nitrogen isotopic compositions. The SIAR modeling results showed a prevalent NO3− source from sewage/manure. The δ11B signatures in groundwater indicated the manure to be the predominant NO3− source, whereas NO3− from sewage was recognized at few sites. Geographic areas showing either a predominant process or a defined NO3− source where not recognize in the studied groundwater. Results indicate widespread contamination of NO3− in the cultivated plain of both areas. Point sources of contamination, due to agricultural practices and/or inadequate management of livestock and urban wastes, were likely to occur at specific sites.

Shifts in the sources and fates of nitrate in shallow groundwater caused by agricultural intensification intensity: Revealed by hydrochemistry, stable isotopic composition and source contribution

Groundwater nitrogen (N) pollution in intensive agricultural regions is increasing globally, and understanding the effects of increasing agricultural intensity on the sources and fates of N is critical for the effective control of groundwater pollution. Using multiple stable isotopes (δ15N-NO3—, δ18O-NO3—, δ18O-H2O, δD-H2O), hydrochemistry and the Bayesian stable isotope mixing model, the sources and fates of N were expounded, and their contributions were quantified in shallow groundwater (SG, n = 325) from an intensive agricultural region, a facility agricultural region and a cropland fallow region. We found that NO3— accounted for 60% of total N, and 52% of SG samples exceeded the WHO NO3— drinking water threshold (10 mg N L−1). Each N form concentrations and NO3— exceeding the standard rate in the intensive and facility agricultural regions were significantly higher than those in the cropland fallow region. Soil N, N fertilizer and manure and sewage were the dominant NO3— contributors in the SG of intensive agricultural regions, contributing to 66%, 21% and 10% of NO3—, respectively. The highest contributions of manure and sewage occurred in the cropland fallow region (46%), followed by the soil N (33%) and N fertilizer (13%), while the N sources in the SG from the facility agricultural region were dominated by manure and sewage (35%), soil N (31%) and N fertilizer (25%). Denitrification was the primary N biogeochemical cycle process in SG from the intensive and facility agricultural regions, whereas nitrification mainly occurred in the cropland fallow region. These results indicated that the shifts in the sources and fates of N in SG were controlled by agricultural intensification intensity, and soil N and manure and sewage, rather than N fertilizer, may become the most dominant N sources in SG in intensive agricultural regions. The N contamination control in SG should pay attention to improving septic tanks and sewage pipelines, the scientific and reasonable stacking of manure, and reducing the soil N pool in intensive agricultural regions.

Identification of nitrate sources in tap water sources across South Korea using multiple stable isotopes: Implications for land use and water management

Stable nitrate isotopes (δ15N-NO3 and δ18O-NO3) in conjunction with stable water isotopes (δ18O-H2O and δD-H2O) were used to identify nitrogen (N) sources and N-biogeochemical transformation in tap water sources sampled from 11 water purification plants across South Korea. The raw water sources are taken from rivers within the water supply basins, which indicates the quality of tap water is highly dependent on surrounding the land use type. We estimated the proportional contribution of the various N sources (AD: atmospheric deposition; SN: soil nitrogen; CF: chemical fertilizer; M&S: manure/sewage) using Bayesian Mixing Model. As a result, the contribution of N sources exhibited large seasonal and spatial differences, which were related to the type of land use in the water supply basins. Commonly, the M&S and SN were the dominant N source during the dry and wet seasons in almost regions, respectively. However, in the regions with high N loading ratios from urban and industrial sources, the M&S was the dominant N source during both the wet and dry seasons. In addition, the regions were characterized by high NO3− concentrations due to the decreased dilution effect of precipitation during the dry seasons. In contrast, the SN was the dominant N source in the regions with high N loading ratios from agricultural areas during both the wet and dry seasons. The NO3−-N concentration during the wet season was significantly higher than those during the dry season in these regions due to the input of non-point sources with high concentrations. Meanwhile, denitrification and nitrification were observed in the watersheds. It is important to understand the isotope fractionation due to N-biogeochemical transformation for considering the potential misinterpretations of the origin and fate NO3−. Collectively, our findings provide a basis on N source control strategies to ensure tap water quality in complex land use areas.

Tracking anthropogenic nitrogen-compound sources of surface and groundwater in southwestern Nile Delta: hydrochemical, environmental isotopes, and modeling approach

This research aims to assign the specific and potential sources that control migration and transformation mechanisms of ammonium/nitrate contaminants of surface and groundwater systems in the southwestern Nile Delta, Egypt. To achieve that, an integration of hydrogeochemistry, multiple environmental stable isotopes (δ2H-H2O, δ18O-H2O, δ15N-NH4, and δ15N-NO3) coupled with three-dimensional nitrogen transport numerical model (MODFLOW-MT3D) was done. A set of representative water samples (20 canals and drainage water) and 14 groundwater samples were collected and analyzed for physical, chemical, and stable isotope analysis. NH4+ and NO3− concentrations in surface water samples varied from 0.29 to 124 mg/l and 0.52 to 39.67 mg/l, respectively. For groundwater samples, NH4+ and NO3− concentrations varied from 0.21 to 1.75 mg/l and 0.33 to 32.8 mg/l, respectively. Total risk quotient (THQ) level of nitrate (oral and dermal effects) from drinking water exceeds unity for all water samples indicating a potential noncancer risk for the southwestern Nile Delta residents. The potential sources of nitrogen compound pollution are water from sewage treatment plants used for irrigation, sludge and animal manure, septic tanks, soil nitrogen, and artificial fertilizers according to results of δ15N values. Results of ammonium/nitrate modeling in shallow groundwater aquifers are compared with observed concentrations and are found to be in good agreement. Some recommendations are given to decrease nitrogen loads in the study area through suggested a need for adoption of N-fertilizer management practices and treatment of sewage water before to application in agricultural activities.

Internal Quality Control of Residual Pesticides Analysis Using Multiple Stable Isotope Labeled Compounds

Internal quality control (IQC) is essential to ensure the reliability of the results of chemical analysis. In this study, we propose a novel method of IQC for multiresidue analysis of pesticides. A total of seven stable isotope labeled compounds (SILC) were added to analytical samples and were used to monitor and evaluate the quality of analytical results. In contrast to conventional IQC method in which only a limited number of control materials were analyzed to ensure the reliability of the results for an entire batch, the developed method can monitor the analytical quality of all the samples in the batch. It was shown that the developed method could achieve better performance than that of conventional method. Therefore, the developed method is considered to be promising for practical applications.(Received January 27, 2022; Accepted July 4, 2022).

Composition of organic matter in soils from tidal marshes around the Chesapeake Bay, USA, as revealed by lipid biomarkers and stable carbon and nitrogen isotopes

The ability of tidal marshes to maintain their elevation despite rising sea levels depends on the accumulation of organic matter (OM) from estuarine particulate matter and in situ marsh plant production. Although previous studies have examined carbon in marshes, few have used the source composition of OM in marsh soils to provide insight into the processes controlling the delivery, transformation, and fate of carbon within marshes. This study used multiple geochemical tools (i.e., n-alkanes, fatty acids (FA), sterols, and stable carbon and nitrogen isotopes) to characterize the sources of OM in surface (0–10 cm) and subsurface (30–40 cm) soils collected along transects from the marsh edge to the low marsh/high marsh transition in tidal marshes around the Chesapeake Bay. Four study sites were selected for their different physical settings and soil types, allowing us to characterize the dominant OM sources in the soils and identify factors that contributed to differences in marsh OM composition. Contributions of OM from estuarine (i.e., short-chain FA, brassicasterol, cholesterol), marsh plant (i.e., long-chain FA, mid- and long-chain n-alkanes, sitosterol, taraxerol), and microbial (i.e., branched fatty acids, ergosterol) sources were identified in all soils. Results from a stable isotope mixing model allowed us to quantify the relative contributions of these OM sources to the marsh soils and indicated that soil OM was comprised of 29.0 ± 9.0% estuarine POM, 22.7 ± 5.5% riverine POM, 22.1 ± 11.3% C3 marsh plant OM, and 37.9 ± 13.8% C4 marsh plant OM. Relative contributions from these sources varied depending on location in the marsh with estuarine OM contributing a greater fraction of OM near the marsh edge and to surface soils while marsh plants contributed larger amounts of OM to soils in the marsh interior and in the sub-surface. Our results suggest that long-term carbon sequestration in marsh soils in controlled by the marsh plant community, and that changes to a marsh's physical setting or plant community in response to changing climate or human activity could alter the sequestration of carbon in marshes.