Dual Isotope Approach Research Articles

New insights into the mechanisms of plant isotope fractionation from combined analysis of intramolecular 13C and deuterium abundances in Pinus nigra tree-ring glucose.

Understanding isotope fractionation mechanisms is fundamental for analyses of plant ecophysiology and paleoclimate based on tree-ring isotope data. To gain new insights into isotope fractionation, we analysed intramolecular 13C discrimination in tree-ring glucose (Δi', i = C-1 to C-6) and metabolic deuterium fractionation at H1 and H2 (εmet) combinedly. This dual-isotope approach was used for isotope-signal deconvolution. We found evidence for metabolic processes affecting Δ1' and Δ3', which respond to air vapour pressure deficit (VPD), and processes affecting Δ1', Δ2', and εmet, which respond to precipitation but not VPD. These relationships exhibit change points dividing a period of homeostasis (1961-1980) from a period of metabolic adjustment (1983-1995). Homeostasis may result from sufficient groundwater availability. Additionally, we found Δ5' and Δ6' relationships with radiation and temperature, which are temporally stable and consistent with previously proposed isotope fractionation mechanisms. Based on the multitude of climate covariables, intramolecular carbon isotope analysis has a remarkable potential for climate reconstruction. While isotope fractionation beyond leaves is currently considered to be constant, we propose significant parts of the carbon and hydrogen isotope variation in tree-ring glucose originate in stems (precipitation-dependent signals). Asbasis for follow-up studies, we propose mechanisms introducing Δ1', Δ2', Δ3', and εmet variability.

Characterizing the impact of reservoir storage and discharge on nitrogen dynamics in an upstream wetland using a δ15N and δ18O dual-isotope approach

The identification of nitrate sources in reservoir water is important for watershed-scale surface pollution management. Significant fluctuations in river water levels arising from reservoir storage and discharge influence nitrate sources and transport processes. The Sanmenxia Reservoir, in the middle reaches of the Yellow River in China, undergoes significant water level changes (290–316 m), altering the composition of the nitrogen sources. This study employed a δ15N and δ18O dual-isotope method and MixSIAR modeling to quantify the contributions of nitrate sources. This reveals the impact of reservoir water impoundment and discharge on nitrogen dynamics in the upstream region of the wetland and the model sensitivity for each nitrate source. The results showed that the average concentrations of nitrate‑nitrogen (NO- 3-N) were elevated during the impoundment period compared to the discharge period. Nitrogen sources exhibited varying proportions in surface water, groundwater, and soil water during both the impoundment and discharge periods. The predominant sources include manure and sewage (MS), with a maximum proportion of 57.4 % in surface water. Soil nitrogen (SN) accounted for 25.8 % of groundwater nitrogen and 32.1 % of soil water nitrogen during the impoundment period, whereas, during the discharge period, soil nitrogen made up 41.4 % of surface water nitrogen, manure and sewage contributed 44.8 % of groundwater nitrogen, and manure and sewage dominated with 56.7 % of soil water nitrogen. Sensitivity analysis of the MixSIAR model revealed that the isotopic composition of the manure and sewage primary source most significantly influenced the apportionment results of the riverine nitrate source. Reservoir discharge facilitates the dissimilatory nitrate reduction to ammonium (DNRA). The migration of NO- 3 from surface water to soil water and groundwater occurred from the impoundment period to the discharge period.

The comprehensive evaluation of nitrate origin and transformation pathways in the oxic alluvial aquifer in Serbia.

Accurate pollution source identification is essential for establishing adequate water management strategies, particularly in groundwater with slow flow and prolonged recharge process allowing long-term pollution retention. An integrated study based on hydrogeochemical, dual isotopic (δ15NNO3 and δ18ONO3), and microbiological approaches (DN, IRB, and SRB BART tests) along with the statistical data processing was conducted to determine nitrate origin and fate in oxic alluvial groundwater source Ključ in Serbia. The findings from a comprehensive investigation, encompassing 20 groundwater sampling locations during the period 2010-2019, delineated three distinct zones - the hinterland (anthropogenic impact area-untreated sewage inflow), the middle zone (area of mixed influence from fertilizer application, accompanied by a mitigated anthropogenic impact), and the zone of riparian denitrification. Significant linear relationship between anthropogenic impact parameters (Na, Cl, B, NO3-, NH4+, and electrical conductivity) along with the isotopic signatures (δ15N-NO3- ranking from + 10.01 to + 11.18‰ and δ18O-NO3- ranking from + 1.15 to + 6.24‰) and grouped sampling objects by cluster analysis indicated that hinterland is burdened by the nitrates originating from anthropogenic impact. The cross-section of groundwater flow data, concurrent increase of NH4+, and pH levels, along with the highest values of δ15N-NO3- (+ 12.90‰) and δ18O-NO3- (+ 9.70‰), indicated area of fertilizers (urea) impact. BART test results, pH increase, and low oxygen concentration, along with the groundwater flow data in riparian zone, indicated the unfolding of denitrification process. Presented research emphasizes the importance, necessities, and advantages of simultaneous and complementary use of hydrogeochemical, microbiological, and isotopic data.

Dual C–Cl isotope fractionation offers potential to assess biodegradation of 1,2-dichloropropane and 1,2,3-trichloropropane by Dehalogenimonas cultures

1,2-dichloropropane (1,2-DCP) and 1,2,3-trichloropropane (1,2,3-TCP) are hazardous chemicals frequently detected in groundwater near agricultural zones due to their historical use in chlorinated fumigant formulations. In this study, we show that the organohalide-respiring bacterium Dehalogenimonas alkenigignens strain BRE15 M can grow during the dihaloelimination of 1,2-DCP and 1,2,3-TCP to propene and allyl chloride, respectively. Our work also provides the first application of dual isotope approach to investigate the anaerobic reductive dechlorination of 1,2-DCP and 1,2,3-TCP. Stable carbon and chlorine isotope fractionation values for 1,2-DCP (ƐC = −13.6 ± 1.4 ‰ and ƐCl = −27.4 ± 5.2 ‰) and 1,2,3-TCP (ƐC = −3.8 ± 0.6 ‰ and ƐCl = −0.8 ± 0.5 ‰) were obtained resulting in distinct dual isotope slopes (Λ12DCP = 0.5 ± 0.1, Λ123TCP = 4 ± 2). However direct comparison of ΛC-Cl among different substrates is not possible and investigation of the C and Cl apparent kinetic isotope effects lead to the hypothesis that concerted dichloroelimination mechanism is more likely for both compounds. In fact, whole cell activity assays using cells suspensions of the Dehalogenimonas-containing culture grown with 1,2-DCP and methyl viologen as electron donor suggest that the same set of reductive dehalogenases was involved in the transformation of 1,2-DCP and 1,2,3-TCP. This study opens the door to the application of isotope techniques for evaluating biodegradation of 1,2-DCP and 1,2,3-TCP, which often co-occur in groundwaters near agricultural fields.

Evapotranspiration partitioning through water stable isotopic measurements in a subtropical coniferous forest

AbstractEvapotranspiration (ET) partitioning distinguishes the soil evaporation (E) and plant transpiration (T) components and is crucial for understanding the land‐atmosphere interactions and ecosystem water budget. However, the mechanism and controls of ET partitioning for subtropical forests in heterogeneous environments remain poorly understood. Here, we present δ18O and δ2H of about 1,527 isotope samples including atmospheric water, soil and plant water during different seasons in 2 years of 2020–2021 from a coniferous forest across Southeast China. We used the isotopic mass balance of ecosystem water pools, the Craig‐Gordon model and the Keeling‐Plot method to partition T from ET (T/ET) and quantify the controls on T/ET. Results indicated that the uncertainty in the T/ET was principally from the soil water evaporation (δE) value, about 20–30 cm was found to be a reasonable evaporating front depth for estimating δE in this coniferous forest. T/ET presented a “U” shape diurnal pattern and varied from 66.7% to 89.9%. Isotope‐based T/ET in autumn with high temperatures and little rain was higher than those in the summer and winter seasons. Relative humidity (or vapour pressure deficit) dominated the diurnal T/ET variations (relative contributions of > 40%) in summer and autumn, while air temperature and soil water content were the main controls in winter. Our study also showed that δ18O‐derived T/ET was consistent with that of δ2H, although δ2H was found to be more stable in ET partitioning, the dual stable isotope approach should be employed in future studies for the uncertainties brought by samplings or measurements. The agreement between the isotope‐based T/ET and ET partitioning approach that uses eddy covariance and sap flux data was stronger at midday. These isotope‐inferred ET partitioning can inform land surface models and provide more insights into water management in subtropical forests.

Hydrochemical and dual-isotope approach to the identification of denitrification in arable field drainage in the Wensum catchment, eastern England

The global pool of reactive nitrogen has doubled in the last century in response to the need to increase food production with the consequent increase in fertiliser-derived reactive nitrogen detrimentally affecting aquatic ecosystems. This study investigates the spatial distribution and significance of denitrification in the lowland, agriculturally-impacted River Wensum catchment in eastern England as a natural attenuation process. To investigate the evidence for denitrification, the hydrochemical characteristics and dual stable isotope composition of nitrate (15N and 18O) were measured over a 15-month period, 2015–2017, in 63 samples of field drainage in predominantly clay loam and sandy clay loam soils under mainly arable cultivation. Microbially-mediated denitrification in field drainage was indicated by the gradient of the linear regression of 15NNO3 and 18ONO3 compositions with a value of 0.58. Dual fractionation of the nitrate isotopes yielded enrichment factors for δ15NNO3 (−4.52‰) and δ18ONO3, (−4.51‰) within the reported ranges for denitrification in aquatic studies. Soil type influenced denitrification, with a positive relationship between percentage clay and δ15NNO3 and δ18ONO3 values. The same relationship was observed for denitrification rates calculated via a simple mass balance approach, which ranged from 11.0 to 26.3 kg N ha−1 and accounted for 30–73% of the leached soil nitrogen. Higher denitrification rates were recorded in drainage areas with a greater soil clay content (>20% by weight). Comparing calculated dentification rates for individual drain areas with median δ15NNO3 values of drain samples demonstrated that an isotopic enrichment of +1‰ is associated with a denitrification rate of 2.6 kg N ha−1. In conclusion, sustainable agricultural practices that maintain natural attenuation processes such as denitrification, for example by preserving and increasing the soil organic carbon content, are desirable to improve overall soil health to support ecosystem services that reduce nitrate pollution.

Cryptic kin discrimination during communal lactation in mice favours cooperation between relatives

Breeding females can cooperate by rearing their offspring communally, sharing synergistic benefits of offspring care but risking exploitation by partners. In lactating mammals, communal rearing occurs mostly among close relatives. Inclusive fitness theory predicts enhanced cooperation between related partners and greater willingness to compensate for any partner under-investment, while females are less likely to bias investment towards own offspring. We use a dual isotopic tracer approach to track individual milk allocation when familiar pairs of sisters or unrelated house mice reared offspring communally. Closely related pairs show lower energy demand and pups experience better access to non-maternal milk. Lactational investment is more skewed between sister partners but females pay greater energetic costs per own offspring reared with an unrelated partner. The choice of close kin as cooperative partners is strongly favoured by these direct as well as indirect benefits, providing a driver to maintain female kin groups for communal breeding.

Validation of a clinically applicable device for fast and accurate quantification of blood volume.

Determination of blood volume (BV) using the dual-isotope (e.g., 99m Tc-labeled red blood cells [99m Tc-RBC] and 125 I-labeled human serum albumin [125 I-HSA]) injection method is limited in medicine due to the long isotope half-life. However, BV has been determined in laboratory settings for 100 years using the carbon monoxide (CO)-rebreathing-based procedure, which allows frequent BV measurements. We investigated the reliability and accuracy of a semi-automated CO-rebreathing device by comparing it against the dual-isotope methodology and its ability to detect a known blood removal. In study A, BV was determined three times in ~2 h; twice using the device with rebreathing protocols lasting 2 (CO2min ) and 10 min (CO10min ) and once with the dual-isotope technique. In study B, the accuracy of the device was assessed by its ability to detect a 2% removal of BV. A good correlation was observed between both the CO-rebreathing protocols (r2 = 0.89-0.98; p < 0.001) and the dual-isotope approach (r2 = 0.89-0.95; p < 0.001). In absolute terms BV was 425 ± 263 mL and 491 ± 388 mL lower (p < 0.001) when quantified with the dual-isotope compared to the CO-rebreathing protocols. When reducing BV by 132 ± 25 mL (2%), the device quantified a lower (p < 0.001) BV of 150 ± 45 mL. This study emphasizes that the semi-automated device accurately determines small changes (i.e., 2%) in BV and that a high correlation with the dual-isotope methodology exists. The findings are clinically relevant owing to the method's simple and fast nature (the absence of radioactive tracers and reduced time requirements, i.e., ~15 min vs. ~180 min) and the possibility for repeated measurements within a single day.

National-scale investigation of dual nitrate isotopes and chloride ion in South Korea: Nitrate source apportionment for stream water

Nitrate sources in surface water have been identified using dual-isotope compositions of nitrate with various tools to efficiently manage the water quality at the local scale. Correlation between Cl and NO3 has also been used to identify NO3. In this study, we assess the reliability of the dual-isotope approach and Cl in terms of nitrate source apportionment. To this end, we collected stream water samples throughout South Korea to estimate nitrate sources in streams and determine whether the land-use pattern was closely related to nitrate sources. The δ15N–NO3 ranging from −1.3 to 14.8‰ showed a spatial distribution that was lower in mountain ranges (<7‰) than plain areas (>8‰). The Cl concentration in this national-scale distribution was also assessed. The relationship between the proportion of Cl and δ15N–NO3 classifies nitrate sources into areas characterized by three land-use patterns: (1) agricultural and business areas, (2) forests in highlands, and (3) lowland forests, of which (1) had proportions of Cl >50%, while (2) and (3) were <50%. The samples in (3) showed δ15N–NO3 values > 6‰, similar to those of (1). Deuterium excess of samples was negatively correlated (R2 = 0.53) with δ15N–NO3, accounting for the fact that δ15N–NO3 reflected land-use patterns. Samples were dominantly affected by agriculture-derived sources and domestic sewage showed NO3/Cl of <0.4 and δ15N–NO3 of >6‰. These results suggest that nitrate source apportionment should be comprehensively evaluated considering the dual-isotope approach, land-use patterns, and Cl proportions.

Isotopic characterisation and mobile detection of methane emissions in a heterogeneous UK landscape

Characterising methane (CH4) sources and their stable isotope values at the regional level is important for taking effective mitigation actions as well as more accurately constraining global atmospheric CH4 budgets. We performed dual stable isotope (13C, 2H) analysis of CH4 emission sources as well as mobile 13C measurements in North-West England, in a region with a mix of natural and anthropogenic emission sources as well as potentially exploitable shale gas deposits. Dual isotope analysis was performed for enteric fermentation, animal waste, landfill gas, wetlands, and natural gas from the regional distribution network. Microbial emission sources’ δ13C values ranged from −72.1 ± 0.31‰ to −53.1 ± 1.17‰ with agricultural sources and landfills showing partially overlapping values (−65.3 ± 0.41‰ to −72.1 ± 0.31‰ and −59.2 ± 0.26‰ to −70.4‰, respectively). However, the use of a dual isotope approach with δ2H provided additional separation between agricultural (−340 ± 0.8‰ to −322 ± 19.5‰) and landfill (−312 ± 0.3‰ to −282‰) CH4. All microbial sources were clearly distinct from natural gas with mean values of −39.5 ± 1.38‰ and −184 ± 4.9‰ for δ13C and δ2H, respectively. Mobile measurements conducted over a distance of 557 km detected emissions from two out of four surveyed managed landfills in the region. Multiple gas leaks were detected, which may confound emissions from other thermogenic sources. When separating the surveyed area by land-use into agricultural and urban, we found that background levels of CH4 were more depleted by around 1‰ in areas with agricultural land use compared to urban areas, but emissions from gas leaks and landfills are present in both categories. Our findings highlight the complexity of isoscapes in regions with multiple types of emission sources and the value of dual-isotope measurements in source attribution.

Mapping the effects of Melinis minutiflora invasion on soil nitrogen dynamics in the Brazilian savanna: A dual-isotope approach

The invasion of exotic grasses in the neotropical savannas is closely linked to the conversion of the native landscape into agriculture and cultivated pastures. Molasses grass (Melinis minutiflora P.Beauv.) is one of the main invasive species in abandoned fields and native vegetation areas with the potential to alter both the structure and functioning of these ecosystems. We used the dual-isotope approach to evaluate the impact of molasses grass invasion on nitrogen dynamics in the soil of a savanna formation located in the Cerrado region of Central Brazil. We divided three plots (70×80 m) in 300 sampling units (7×8 m each) classified by predominant vegetation type: native grasses (NG), native cerrado sensu stricto (CSS), or molasses grass (MG). We interpolated the soil δ15N and δ13C (0–10 cm depth) in the three plots to continuous surfaces using semivariogram fit and ordinary kriging models. We also compared the aboveground biomass, litter decomposition rates, and soil N pools among vegetation types. MG and NG had higher litter decomposition rates than CSS. Soil pH was higher under MG compared to CSS and NG. The local soil δ15N isoscapes show the presence of MG in areas with higher soil δ15N. Soil δ13C under all vegetation types indicates a mixture between the C3 and C4 sources present in the soil organic matter, with the highest soil δ13C under MG. The dual-isotope approach showed the altered processes in the invaded areas with an intensification of the soil N dynamics in the long term compared to the areas dominated by the wood strata and by native grasses. The C and N isoscapes indicated that plant-soil interactions yielded different patterns and showedthe effect of the molasses grass invasion. Therefore, the spatial distribution must be accounted for when assessing the effects and outcome of species interactions and invasion pressure.

A national isotope survey to define the sources of nitrate contamination in New Zealand freshwaters

A national survey identifies the extent and origin of nitrates in New Zealand’s freshwater resources using nitrogen (δ15N) and oxygen (δ18O) isotopes. A comprehensive database with 1042 samples investigates freshwater type, land-use, geology, soil type and geographic effects on nitrate isotopes across New Zealand. Nitrate contamination is the biggest threat to New Zealand’s drinking water resources with almost 60 % of samples in the study having above-baseline nitrate (NO3-N) concentrations >0.9 mg/L, a threshold noted for higher colorectal cancer risk. Groundwater (2.89 mg/L) had higher median NO3-N concentration than surface water (0.65 mg/L). Traditional nitrate isotope biplots based on the Haber-Bosch cycle (which integrates synthetic fertilizers into the food chain), are reinterpreted to place New Zealand’s unique farming nitrogen contributions from urea and ammonia into context. The majority of New Zealand’s freshwater nitrate isotopes lie in a Normal-Nitrogen-Retention (NNR) zone which also acts as a Mixed Urea-Urine-Fertilizer (Mixed UUF) zone, transitioning nitrified fertilizers and animal waste via redox reactions, microbial action and/or dissipation towards a denitrification zone. Nitrogen ‘hot spots’ with strong urea/urine input can be differentiated from natural N cycling in the NNR/Mixed UUF transition zone by a combined NO3-N concentration and dual isotope approach to identify high-risk sites.

Integrating dual C and N isotopic approach to elemental and mathematical solutions for improving the PM source apportionment in complex urban and industrial cities: Case of Tarragona - Spain

Identification of dominant airborne Particulate Matter (PM) sources is essential for maintaining high air quality standards and thus ensuring a good public health. In this study, different approaches were applied for source apportionment of three PM fractions (PM1, PM2.5 and PM10) at the outdoor of 14 schools of a coastal city with a significant land use interweaving such as Tarragona (Spain). PM were collected in 24h-quartz microfiber filters in two seasonal campaigns (cold and warm), together with nine local potential sources, so a total of 84 samples were chemically, mineralogically, and isotopically characterised. Source apportionment was assessed by (i) main chemical components, (ii) Principal Component Analysis (PCA), (iii) dual C and N isotope approach, and (iv) a Bayesian isotope mixing model. When chemical concentrations were grouped into marine, crustal, secondary inorganic aerosols and organic matter + elemental carbon categories, the unaccounted component reached 45% of PM mass. The PCA allowed to identify also traffic and industrial contributions, reducing the unaccounted mass to about 25%. Adding δ13C and δ15N values, secondary organic aerosol could be estimated and a continuous contribution of diesel combustion was identified together with a remarkable use of natural gas in winter. Isotopic values were better understood when considering air masses back trajectories and a possible long-distance contribution from coal-fired electric generating units (EGUs). Finally, using Bayesian dual isotope mixing models, the unaccounted PM mass was reduced up to 5% when adding these EGUs to marine-carbonate related, road traffic, domestic heating, waste incinerator and livestock waste contributions. The added value of the dual isotope approach combined with a Bayesian isotope mixing model, in comparison with conventional chemical approaches, was thus demonstrated for PM source apportionment in an urban and industrial site where many sources and processes converge and can then be applied to other complex cities.

Source Diversity of Intermediate Volatility n-Alkanes Revealed by Compound-Specific δ13C-δD Isotopes.

Intermediate volatility organic compounds (IVOCs) are important precursors of secondary organic aerosols, and their sources remain poorly defined. N-alkanes represent a considerable portion of IVOCs in atmosphere, which can be well identified and quantified out of the complex IVOC pool. To investigate the potential source diversity of intermediate volatility n-alkanes (IVnAs, nC12-nC20), we apportioned the sources of IVnAs in the atmosphere of four North China cities, based on their compound-specific δ13C-δD isotope compositions and Bayesian model analysis. The concentration level of IVnAs reached 1195 ± 594 ng/m3. The δ13C values of IVnAs ranged -32.3 to -27.6‰ and δD values -161 to -90‰. The δD values showed a general increasing trend toward higher carbon number alkanes, albeit a zigzag odd-even prevalence. Bayesian MixSIAR model using δ13C and δD compositions revealed that the source patterns of individual IVnAs were inconsistent; the relative contributions of liquid fossil combustion were higher for lighter IVnAs (e.g., nC12-nC13), while those of coal combustion were higher for heavier IVnAs (e.g., nC17-nC20). This result agrees with principal component analysis of the dual isotope data. Overall, coal combustion, liquid fossil fuel combustion, and biomass burning contributed about 47.8 ± 0.1, 35.7 ± 4.0, and 16.3 ± 4.2% to the total IVnAs, respectively, highlighting the importance of coal combustion as an IVnA source in North China. Our study demonstrates that the dual-isotope approach is a powerful tool for source apportionment of atmospheric IVOCs.

Radiocarbon and Stable Carbon Isotope Constraints on the Propagation of Vent CO 2 to Fluid in the Acidic Kueishantao Shallow Water Hydrothermal System

We report radiocarbon and stable carbon isotope measurements from vent gas (CO2(g)), dissolved inorganic carbon (DIC), and particulate organic carbon (POC), from two vents of the Kueishantao (KST) shallow-water hydrothermal system, offshore northeast Taiwan. The purpose of this research is to investigate how magmatic-sourced carbon enters various carbon pools in the hydrothermal system. We utilize a precipitation method to eliminate sulfur compounds from CO2 samples to facilitate Accelerator Mass Spectrometry (AMS) analysis, and evaluate radiocarbon background levels during processing to characterize hydrothermal-sourced CO2 that contains negligible radiocarbon. The result shows that both CO2(g) and DIC in the fluids below two vent orifices fall within a narrow range of fraction of modern carbon (F14C) from 0.013 to 0.136 and δ13C from −8.3‰ to −5.1‰. The F14C values correspond to approximately 90% magmatic-sourced carbon in CO2(g) and DIC. A combination of equilibrium and kinetic isotopic fractionation can adequately explain relatively high CO2(g) δ13C to DIC, beneath vent orifices. Above the vent orifices, DIC becomes enriched in both 14C and 13C as a result of physical mixing with ambient seawater. POC F14C values confirm a significant magmatic carbon contribution into the POC pool within the KST system, with rapid hydrothermal circulation. Our results identify the physiochemical processes responsible for magmatic carbon migration from CO2(g) into the DIC pool, and demonstrate how a dual carbon isotope approach can serve as an effective tool in understanding carbon flow in high temperature-low pH hydrothermal systems.

Climate signals in stable carbon and hydrogen isotopes of lignin methoxy groups from southern German beech trees

Abstract. Stable hydrogen and carbon isotope ratios of wood lignin methoxy groups (δ13CLM and δ2HLM values) have been shown to be reliable proxies of past temperature variations. Previous studies showed that δ2HLM values even work in temperate environments where classical tree-ring width and maximum latewood density measurements are less successful for climate reconstructions. Here, we analyse the annually resolved δ13CLM values from 1916–2015 of four beech trees (Fagus sylvatica) from a temperate site near Hohenpeißenberg in southern Germany and compare these data with regional- to continental-scale climate observations. Initial δ13CLM values were corrected for the Suess effect (a decrease of δ13C in atmospheric CO2) and physiological tree responses to increasing atmospheric CO2 concentrations considering a range of published discrimination factors. The calibration of δ13CLM chronologies against instrumental data reveals the highest correlations with regional summer (r=0.68) and mean annual temperatures (r=0.66), as well as previous-year September to current-year August temperatures (r=0.61), all calculated from 1916–2015 and reaching p&lt;0.001. Additional calibration trials using detrended δ13CLM values and climate data (to constrain effects of autocorrelation on significance levels) returned rsummer=0.46 (p&lt;0.001), rannual=0.25 (p&lt;0.05) and rprev.September-August=0.18 (p&gt;0.05). The new δ13CLM chronologies were finally compared with the previously produced δ2HLM values of the same trees in order to evaluate the additional gain of assessing past climate variability using a dual-isotope approach. Compared to δ13CLM, δ2HLM values correlate substantially more strongly with large-scale temperatures averaged over western Europe (rprev.September-August=0.69), whereas only weak and mainly insignificant correlations are obtained between precipitation and both isotope chronologies (δ13CLM and δ2HLM values). Our results indicate the great potential of using δ13CLM values from temperate environments as a proxy for local temperatures and, in combination with δ2HLM values, to assess regional- to sub-continental scale temperature patterns.

Dual Isotopic (O &amp; N) Approach in the Assessment of NO3− Pollution in an Urban River

Dual Isotopic (O &amp; N) Approach in the Assessment of NO3− Pollution in an Urban River

Migration, transformation and nitrate source in the Lihu Underground River based on dual stable isotopes of δ15N-NO3- and δ18O-NO3.

Nitrate (NO3-) pollution is a common phenomenon in karst underground rivers, which are important water sources in karst landscapes. For drinking water safety and environmental protection, it is crucial to accurately identify NO3- sources and their migration and transformation processes in the Lihu Underground River. In this study, water samples of the Lihu Underground River in Guangxi were collected in May 2014, October 2014, January 2015, and July 2015, and water chemical and dual isotopic (δ15N-NO3- and δ18O-NO3-) approaches were used to evaluate the NO3- characteristics and sources in the Lihu Underground River. The concentration of NO3- in the Lihu Underground River ranged from 1.16 to 19.78mg·L-1, with an average of 9.30mg·L-1, which is more than 37% of the WHO standard (10mg·L-1). The concentrations of NO3- in the wet season (May 2014 and July 2015) were slightly lower than those in the dry season (from October 2014 to January 2015) at most sampling sites due to dilution effects. The migration and transformation processes of NO3- were analyzed by comparing the measured and calculated concentrations of NO3- in the Lihu Underground River. In the dry season (from October 2014 to January 2015), the variation in NO3- concentration upstream and midstream of the Lihu Underground River was affected by exogenous input and nitrification. From midstream to the outlet of Xiaolongdong, it is affected by self-purification factors, including physical processes, chemical processes, and biological processes. In the wet season (May 2014 and July 2015), the dilution and mixing effects were the main factors controlling the variation in NO3- concentration in the Lihu Underground River. The contribution rates of potential NO3- sources (incl. atmospheric precipitation (AP), NO3- fertilizer (NF), NH4+ in fertilizer and rainfall (NFA), soil organic nitrogen (SON), and manure and sewage (M&S)) were quantitatively evaluated by using the IsoSource model. The results showed that in May 2014, the main sources of NO3- were M&S and NF, with contribution rates of 46% and 41%, respectively. In October 2014, NO3- sources were M&S with a contribution rate of 47%, followed by NFA with a contribution rate of 31%. In January 2015, NO3- sources in groundwater were M&S, with a contribution rate of 53%, followed by NFA (34%). In July 2015, the main NO3- sources were M&S and NF, whose contribution rates were 54% and 39%, respectively.

Using the dual isotope method to assess cecal amino acid absorption of goat whey protein in rats, a pilot study.

Measurement of ileal amino acids (AA) bioavailability is recommended to evaluate protein quality. A dual isotope tracer method, based on plasma isotopic enrichment ratios, has been proposed to determine true digestibility in humans. In a pilot study, we aimed to evaluate whether this method could be implemented in rats to determine AA bioavailability based on isotopic enrichment ratios measured in cecal digesta or plasma samples. Goat milk proteins were intrinsically labeled with 15N and 2H. Wistar rats were fed a meal containing the doubly labeled goat whey proteins and a tracer dose of 13C-spirulina. Blood samples were collected 0, 1h and 3h after meal ingestion from the tail vein. The rats were euthanized 4h (n = 6) or 6h (n = 6) after meal to collect plasma and intestinal contents. True orocecal protein digestibility and AA bioavailability were assessed by means of 15N and 2H enrichment in cecum content and compared with absorption indexes determined at the plasma or cecum level using isotopic ratios. Plasma kinetics of isotopic enrichment could not be completed due to the limited quantity of plasma obtained with sequential blood collection. However, the absorption indexes determined from cecal 15N or 2H/13C ratios gave coherent values with true orocecal AA bioavailability. This dual isotope approach with measurements of isotopic ratios in digestive content could be an interesting strategy to determine true AA bioavailability in ileal digesta of rats.

Reservoir NO3- pollution and chemical weathering: by dual isotopes of δ15N-NO3-, δ18O-NO3- and geochemical constraints.

Reservoir dams alter the nutrient composition and biogeochemical cycle. Thus, dual isotopes of δ18O-NO3- and δ15N-NO-3 and geochemical signatures were employed to study the NO3- pollution and chemical weathering in the Three Gorges Reservoir (TGR), China. This study found that the TGR dam alters the δ15N-NO3- composition and is enriched in the recharge period. Values of δ15N-NO3- varied from 4.5 to 12.9‰ with an average of 9.8‰ in the recharge period, while discharge period δ15N-NO3- ranged from 3.2 to 12.5‰, with an average of 9.3‰. δ18O-NO3- varies (1.2-11.3‰) with an average of 6.5‰ and (2.4-12.4‰) with an average of 7.5‰, in the recharge and discharge periods, respectively. Stable isotopic values sharply decreased fromupstream to downstream, indicating thedamming effects. δ18O-NO3- and δ15N NO3- confirm that sewage effluents, nitrification of soil organic material, and NH4+ fertilizers were the primary sources of NO3- in the reservoir. Carbonate weathering mainly provides ions to the reservoir. HCO3- + SO42- and Ca2+ + Mg2+ represent 90% of major ions in theTGR. Downstream sampling sites showed low solute concentration during the recharge period, indicating the dam effect on solute concentration. Ca-Mg-Cl-, Ca-HCO3- and Ca-Cl- were the main water types in theTGR. The average percentage of solutes contribution revealed the carbonate weathering, evaporites dissolution, silicate weathering, and atmospheric input were 51.9%, 41%, 7.8%, and 1.7% for the recharge period. In contrast, the discharge period contributed 66.4%, 29.2%, 10%, and 4.3%, respectively. TGR water is moderately suitable for irrigation, and hardness is high in drinking water. This study provides new insight into the dual isotopic approach and geochemical signatures to interpret the NO3- cycle and chemical weathering process under dam effects in the TGR. However, this isotopic application has some limitations in source identification, isotope fractionation, and transformation mechanisms of nitrate. Thus, further studies need to be done on these topicsfor a better undestanding.