Stable Hydrogen Isotope Analysis Research Articles

Effect of Water‐Rock Ratio on the Stable Isotope Record of Fluid‐Rock‐Deformation Interactions in Detachment Shear Zone

AbstractOxygen and hydrogen stable isotope analyses of quartz and muscovite veins from the footwall of the Raft River detachment shear zone (Utah) provide insight into the hydrology and fluid‐rock interactions during ductile deformation. Samples were collected from veins containing 90%–100% quartz with orientations either at a high angle or sub‐parallel to the surrounding quartzite mylonite foliation. Stable isotope analysis was performed on 10 samples and compared with previous quartzite mylonite isotope data sets. The results indicate that the fluid present during deformation of the shear zone was meteoric in origin, with a δ2H value of approximately −100‰ and a δ18O value of approximately −13.7‰. Oxygen stable isotope O18O depletion correlates with the muscovite content of the analyzed rocks. Many of the analyzed samples in this and other studies show an apparent lack of equilibrium between the oxygen and hydrogen isotope systems, which can be explained by hydrogen and oxygen isotope exchange at varying fluid‐rock ratios. Our results suggest that the Raft River detachment shear zone had a low static fluid‐rock ratio (<0.1), yet experienced episodic influxes of fluids through semi‐brittle structures. This fluid was then expelled out into the surrounding mylonite following progressive shearing, causing further 18O‐depletion and fluid‐related embrittlement.

Holocene hydroclimate in highland Costa Rica: new evidence from hydrogen and carbon isotopes in n‐alkanes of terrestrial leaf waxes in a 10 000‐year sediment profile

ABSTRACTWe conducted compound‐specific stable hydrogen (δD) and carbon (δ13C) isotope analysis on n‐alkanes from terrestrial leaf waxes preserved in a 10 000‐year sediment profile from Lago de las Morrenas 1 (9.4925° N, 83.4848° W, 3480 m), a glacial lake on the Chirripó massif of the Cordillera de Talamanca in Costa Rica. Our results demonstrate millennial‐scale variations in hydroclimate across the Holocene, with drier than average conditions in the highlands during the early Holocene, but with gradually increasing precipitation; mesic conditions during the middle Holocene with a gradual drying trend; and highly variable conditions during the late Holocene. This general pattern is punctuated by several centennial‐scale manifestations of global climate events, including dry conditions during the 8200, 5200 and 4200 cal a bp events and the Terminal Classic Drought (1200–850 cal a bp). Our δ13C analyses demonstrate that carbon isotope signals are responding to changes in hydroclimate at the site and reinforce prior interpretations of a stable páramo plant community that established following deglaciation and persisted throughout the Holocene. The shifts in hydroclimate inferred from analyses of n‐alkanes in Lago de las Morrenas 1 sediments show correspondence with charcoal records in multiple lakes, with fires most common during drier intervals.

Preservation of bone organic fraction is not predictive of the preservation of bone inorganic fraction when assessing stable isotope analysis sample quality control measures

Stable isotope analysis of carbon (C), nitrogen (N), hydrogen (H), and oxygen (O) of archaeological bone has become an increasingly common research method for interpreting human behavior in the past. However, diagenesis of skeletal material can invalidate stable isotope ratios, thereby compromising interpretations. We examine patterns of bone diagenesis using infrared spectroscopy of bone bioapatite samples in relation to indicators of organic preservation quality indicators. We assess crystallinity, an indicator of bioapatite preservation, using the infrared splitting factor (IR-SF) and carbonate content (carbonate to phosphate ratio, C/P) calculated from infrared spectra. We then test the assumption that if the organic fraction of bone is preserved, the mineral fraction will also be unaffected by postmortem chemical alteration. We analyzed 454 bone bioapatite and extracted bone organic sample pairs from modern, historic, and prehistoric humans. Consistent with previous studies, we observed a strong, statistically significant negative linear relationship between IR-SF and C/P (r = −0.855, p < 0.001). Modern bone bioapatite samples unaltered by diagenesis have low IR-SF and high C/P values. There was no significant association between the collagen yield or atomic C:N ratio and IR-SF or C/P values. The range of variation in IR-SF and C/P values for samples with organic yields between 0 and >20 percent spanned the range of modern bone bioapatite unaltered by diagenesis as well as bone bioapatite significantly affected by diagenesis. The lack of predictive patterning between bone inorganic and organic diagenesis suggests that the depositional context and site formation history play critical and independent roles in the organic and mineral fraction of bone. Thus, the preservation of the organic fraction of bone is not predictive of the preservation of the inorganic fraction (e.g., bioapatite).

A passive method for sampling water in the soil-plant-atmosphere continuum for stable hydrogen and oxygen isotope analyses.

Hydrogen and oxygen isotopes in water molecules are powerful tools to constrain the dynamics of water cycling within the soil-plant-atmosphere continuum (SPAC). However, the recovery of water from the SPAC requires logistical arrangements and implementation of different time- and cost-consuming techniques in either the field or the laboratory. We developed a passive method to sample water from the three compartments of the SPAC by using a hygroscopic salt of a high water absorbance capacity (CaCl2 ). This method allows either H2 O(V) -H2 O(L) isotope equilibration in the case of infinite water reservoir (atmospheric water vapor (WV)) or quantitative absorption of water from a finite water reservoir (e.g. soil and plants). The water absorbed by CaCl2 was distilled first and subsequently processed for hydrogen and triple oxygen isotope mass spectrometry analyses. The distillation step can be bypassed when employing isotope analytical techniques that are based on equilibration. Our experiments show that anhydrous CaCl2 absorbs WV of 210 ± 6% and 130 ± 6% of its dry weight from an infinite WV reservoir at relative humidity of 60% and 30%, respectively. Chemical and isotope equilibrations between WV and absorbed water were attained within 3 days at room temperature, enabling the back-calculation of the isotope composition of atmospheric WV. Preliminary experiments to extract water from plant and sand (i.e. finite WV reservoir) demonstrate a quasi-complete recovery of water in these matrices without significant isotope fractionation. The reproducibility of our method is better than 1.6‰, 0.32‰, 0.17‰ and 6‰ per meg for δ2 H, δ18 O, δ17 O and 17 O-excess. The CaCl2 -H2 O absorption (passive) method requires very limited logistics in the field facilitating spatial and temporal water vapor/water sampling from atmosphere and soil at low resolution (i.e. average of 3-5 days). Moreover, it allows high sample throughput for the extraction of plant water in the laboratory. The reproducibility of this method is similar to the analytical uncertainty in mass spectrometry analyses.

Miocene surface uplift and orogenic evolution of the southern Andean Plateau (central Puna), northwestern Argentina

We present stable hydrogen-isotope analyses of volcanic glass ([Formula: see text]Dg) and radiometric ages (U-Pb zircon, U-Th calcite, AMS14C) from deformed sedimentary deposits in the vicinity of the intermontane Pocitos Basin in the central Puna of the Andean Plateau at about 24.5°S. Our results demonstrate 2-km surface uplift since the middle to late Miocene and protracted shortening that persists until the present day, while other sectors of the Puna show evidence for tectonically neutral and/or extensional settings. These findings are at odds with previous studies suggesting near-modern elevations (4 km) of the Puna Plateau since the late Eocene and formation of the intermontane Miocene Arizaro-Pocitos Basin associated with gravitational foundering of a dense lithosphere. Geophysical and geochemical data support the removal of continental lithosphere beneath the Puna, but the timing and mechanisms by which this removal occurs have remained controversial. We hypothesize that intermontane basin formation in the central Puna is the result of crustal shortening since about 20 Ma, followed by rapid surface uplift, likely related to lithospheric delamination.

Migration of Eastern North American monarch butterflies via the South-east and the Atlantic: evidence from stable isotopes, thin layer chromatography, DNA and phenotype

Abstract Monarch butterflies, Danaus plexippus (L.), from eastern North America are well known for their incredible autumn migration to Mexico; however, not all monarchs follow this route. There is evidence of monarchs overwintering and reproducing in Florida, arriving to insular and continental Caribbean, and roosting by the thousands in the Yucatán, Mexico. This work aims to present evidence that these monarchs are part of two current migratory routes, that we consider as the south-eastern and the Atlantic routes, routes that were probably more prominent in the past. Monarchs were collected for 12 months in south Florida, for 4 years in Cuba in November and once in March, in the Yucatán and Guatemala at different times, and once in northern Venezuela. We used two independent techniques, stable hydrogen isotope (δ2H) analyses of the wings and/or thin layer chromatography (TLC), to trace the monarch’s natal grounds. We analysed the DNA of monarchs collected in St. Marks in the Florida Panhandle, Cuba and Guatemala, and compared those data against previously-analysed DNA data from monarchs in the Americas to characterize their genetic structure and to assess the possible movement and presence of North American monarchs and/or their alleles outside the USA. Our results support the existence of south-eastern and Atlantic migratory routes. TLC, isotope and DNA analyses showed the arrival of likely North American monarchs in Cuba, Yucatán, Guatemala, Venezuela and other areas of the Americas. North American monarchs found in these areas have different natal grounds, phenotypic traits and DNA signature than Mexican migrants. Monarchs from the south-eastern route mostly originated in the south-east USA and fed on local Asclepias spp., such as Asclepias viridis, Asclepias humistrata, Asclepias perennis and Asclepias asperula. Butterflies from this migratory route move east, enter the Florida Peninsula, pass to Cuba, fly to the Yucatán and then to Guatemala where they appear to overwinter in the high mountains of Guatemala where Abies guatemalensis occurs. Monarchs that are part of the Atlantic route move east of the Appalachians, enter the Florida Peninsula, and from there pass to the insular and continental Caribbean. The main host plants for the Atlantic monarchs are A. perennis and A. humistrata; in contrast, Mexican monarchs mainly feed on Asclepias syriaca. Some monarchs from these two proposed migratory routes, south-eastern and Atlantic, will stay in the places where they travelled and others will return via Florida and Mexico. We propose a scenario for how the different migratory routes evolved.

宁夏河东沙区刺槐和丝绵木水分利用策略

PDF HTML阅读 XML下载 导出引用 引用提醒 宁夏河东沙区刺槐和丝绵木水分利用策略 DOI: 10.5846/stxb202202100330 作者: 作者单位: 作者简介: 通讯作者: 中图分类号: 基金项目: 国家自然科学基金项目（31760236，42161013）；宁夏自然科学基金项目（2022AAC03094） Water use strategies of Robinia pseudoacacia and Euonymus bungeanus in the east sandy land of the Yellow River in Ningxia, China Author: Affiliation: Fund Project: The National Natural Science Foundation of China (31760236,42161013);The National Natural Science Foundation of Ningxia,China(2022AAC03094) 摘要 | 图/表 | 访问统计 | 参考文献 | 相似文献 | 引证文献 | 资源附件 | 文章评论 摘要:刺槐和丝绵木混交林是宁夏河东沙区防护林建设的主要模式，了解刺槐和丝绵木的水分利用策略，能为区域植被恢复和防护林林分结构调整提供科学依据。以宁夏河东沙区刺槐（Robinia pseudoacacia）和丝绵木（Euonymus bungeanus）混交林为研究对象，通过监测微气象、树干液流和土壤质量含水量，结合大气降水、土壤水、植物木质部水同位素组成，采用Granier及其校正公式，运用贝叶斯混合模型（MixSIAR）和相似性比例指数（PS）研究2个树种的蒸腾耗水、水分来源和水分利用关系。结果表明：刺槐和丝绵木的蒸腾耗水量在生长季中期较高，前期和后期较小，刺槐的蒸腾耗水量是丝绵木的1.55倍；影响刺槐蒸腾耗水的主要环境因子为饱和水汽压差、太阳辐射、0-40 cm土壤质量含水量和40-120 cm土壤质量含水量；影响丝绵木蒸腾耗水的主要环境因子为饱和水汽压差、太阳辐射、平均气温、0-40 cm土壤质量含水量和40-120 cm土壤质量含水量；蒸腾耗水较高时，刺槐主要吸收利用中层土壤水，丝绵木主要吸收利用浅层土壤水，蒸腾耗水较低时，刺槐主要吸收利用浅层土壤水，丝绵木主要吸收利用中层土壤水；在土壤水分含量较小的月份，刺槐和丝绵木主要通过水分利用空间上的差异来应对干旱，维持自身的蒸腾耗水；土壤水分含量较高的月份，刺槐和丝绵木的相似性比例指数最大，存在较强的水分竞争关系；浅层土壤水分含量较高可能反映了沙区植物根系对土壤水分再分配作用下植物在水分和养分需求之间的平衡。 Abstract:The mixed forest of Robinia pseudoacacia and Euonymus bungeanus is the typical shelterbelt construction mode in the east sandy land of the Yellow River in Ningxia, China. Research on the water use strategies of Robinia pseudoacacia and Euonymus bungeanus could provide scientific basis for restoration regional vegetation and stand structure optimization allocation of shelter forest. In this study, the sap flow of Robinia pseudoacacia and Euonymus bungeanus was monitored continuously to clarify the characteristics of water consumption by transpiration which calculated by Granier and its correction formula, as well as simultaneous records of micro-meteorological factors and gravimetric soil water content. Combined with stable hydrogen and oxygen isotope analysis of rainfall, soil water and plant xylem water, the water source and water use relationship among symbiotic trees were quantitatively analyzed by Bayesian mixture model (MixSIAR) and the proportional similarity index (PS). The results showed that the water consumption of Robinia pseudoacacia and Euonymus bungeanus were higher in the middle growing season, but lower in the early and late growing season. The water consumption of Robinia pseudoacacia was 1.55 times larger than Euonymus bungeanus. The main environmental factors affecting water consumption of Robinia pseudoacacia were vapour pressure deficit, solar radiation, 0-40 cm gravimetric soil water content and 40-120 cm gravimetric soil water content. The main environmental factors affecting water consumption of Euonymus bungeanus were vapour pressure deficit, solar radiation, average temperature, 0-40 cm gravimetric soil water content and 40-120 cm gravimetric soil water content. Robinia pseudoacacia mainly used the middle layer soil water and Euonymus bungeanus mainly used the shallow layer soil water in the season with high water consumption. While the shallow layer soil water and the middle layer soil water were ultilized by Robinia pseudoacacia and Euonymus bungeanus separately in the season with lower tree water consumption. In addition, Robinia pseudoacacia and Euonymus bungeanus was able to deal with drought and maintain their own water consumption mainly through the spatial difference of water use strategy under drought seasons. In the seasons when gravimetric soil water content was higher, the proportional similarity index (PS) of Robinia pseudoacacia and Euonymus bungeanus was the highest, and there was a strong water competition relationship. The higher of shallow layer gravimetric soil water content might reflect a trade-off between water and nutrient requirements of plants under the effect of soil water redistribution by plant roots in the sandy land. 参考文献 相似文献 引证文献

The metabolic sensitivity of hydrogen isotope fractionation differs between plant compounds

Hydrogen stable isotope analyses (δ2H) of plant derived organic compounds are a useful tool for ecological, environmental, and palaeoclimatological research. However, during organic compound synthesis, variable biosynthetic 2H-fractionation has been suggested to occur as a result of changes in plant carbon fluxes. So far, inference has been based on examining the δ2H patterns of plant compounds along environmental gradients, among plant species, and between plant organs. In an alternative approach, we used four plant species with four different types of mutations that cause impaired starch synthesis to assess whether variability in carbon metabolism affects the biosynthetic 2H-fractionation during cellulose, phytol, and acetogenic lipid synthesis. We found that mutants with impaired starch synthesis always had higher cellulose and phytol δ2H values compared to the wild type. By contrast, 2H-fractionation during acetogenic lipid biosynthesis generally did not show strong metabolic sensitivity. We rationalise these differences by considering the biosynthetic pathway of each compound and the likely source of the variable isotope fractionation. In different organic compounds, the sensitivity of variable biosynthetic 2H-fractionation to changes in C-metabolism depends on incorporation of specific H atoms from precursor molecules. As such, we determined that the similar increase in cellulose and phytol δ2H values as an effect of impaired starch synthesis most likely originates in triose-phosphates.

The application of a CART model for forensic human geolocation using stable hydrogen and oxygen isotopes

The utility of stable hydrogen and oxygen isotope analysis of human tissues for geolocation is an important area of study within forensic science. This study aimed to first validate the latitudinal relationship between stable hydrogen and oxygen isotopes in drinking water and human keratinous tissues through the analysis of human samples with known geographical origin. And secondly, to explore the use of classification and regression tree (CART) models to geographically classify individuals based on the stable isotope values of tissues themselves. Human hair and toenails were collected from four distinct study sites across Canada. The comparison of stable isotope values in drinking water and human tissues produced low R2 values indicating that linear models may not fully explain the variation observed for both hydrogen and oxygen values. Additionally, large intrapopulation variations were observed for Canadian cities and highlights the importance of understanding the regional isotopic spread of human values. Further, this study demonstrated that a closed group of unknown individuals known to have originated from a limited number of geographically distinct regions may be classified into their respective groups through the use of CART models. The potential for the CART model approach for human geolocation presents a promising new tool.

Common carp (Cyprinus carpio) obtain omega-3 long-chain polyunsaturated fatty acids via dietary supply and endogenous bioconversion in semi-intensive aquaculture ponds

Omega-3 long-chain polyunsaturated fatty acids (n-3 LC-PUFA) are essential micronutrients for aquatic consumers. Synthesized by aquatic primary producers, n-3 LC-PUFA are transferred across trophic levels and may eventually end up accumulating in fish. However, if short in dietary supply, fish may also biosynthesize n-3 LC-PUFA from dietary precursors (i.e., n-3 C18-PUFA). We applied compound-specific hydrogen stable isotope analysis (CSIA) of fatty acids to investigate sources and metabolic processes of n-3 LC-PUFA, and in particular of docosahexaenoic acid (22:6n-3, DHA), in common carp (Cyprinus carpio) raised in semi-intensive aquaculture ponds. Carp were feeding on natural pond zooplankton and benthic macroinvertebrates rich in n-3 LC-PUFA and cereal-based pellet feeds rich in C18-PUFA. Results provide isotopic evidence that carp obtained a significant amount of dietary lipids and nitrogen from added cereal-based feeds, while n-3 LC-PUFA were generally acquired by feeding on benthic macroinvertebrates and zooplankton. However, DHA retained in carp was also generated endogenously via bioconversion from dietary PUFA precursors, such as EPA. DHA was isotopically lighter than EPA and likely not supplied in sufficient quantities to meet the physiological requirements for DHA in carp. Our data show that depending on the natural abundance of dietary DHA in these eutrophic ponds, farmed carp can obtain DHA by two different pathways; i.e., directly via dietary uptake and indirectly via bioconversion. This field study highlights the importance of dietary LC-PUFA supply in eutrophic aquatic ecosystems and the ability of carp to biosynthesize highly valuable LC-PUFA, eventually also benefiting human health.

Extensive Carbon Contribution of Inundated Terrestrial Plants to Zooplankton Biomass in a Eutrophic Lake.

Organic carbon derived from terrestrial plants contributes to aquatic consumers, e.g., zooplankton in lakes. The degree of the contribution depends on the availability of terrestrial organic carbon in lake organic pool and the transfer efficiency of the carbon. Terrestrial organic carbon is poor-quality food for zooplankton with a mismatch of nutrition content and was incorporated to zooplankton with much lower efficiency than phytoplankton. Contributions of terrestrial carbon to zooplankton generally decrease with an increase in phytoplankton production, indicating a preferential incorporation of phytoplankton in previous investigations. However, in eutrophic lakes, the dominating cyanobacteria were of poor quality and incorporated to consumers inefficiently too. In that case, zooplankton in eutrophic wetlands, where cyanobacteria dominate the phytoplankton production and massive terrestrial plants are inundated, may not preferentially incorporate poor food-quality phytoplankton resource to their biomass. Therefore, we hypothesize that carbon contributions of terrestrial vegetation to zooplankton and to lake particulate organic pool should be similar in such aquatic ecosystems. We tested this hypothesis by sampling zooplankton and carbon sources in Ming Lake (Jinan University Campus, southern China) which was overgrown by terrestrial plants after drying and re-flooded. After 60days of observations at weekly (or biweekly) intervals, applying stable carbon (13C), nitrogen (15N), and hydrogen (2H) isotopic analysis and a stable isotope mixing model, we estimated the occurrence of extensive carbon contribution (≥ 50%) of flooded terrestrial plants to cladocerans and copepods. Contribution of inundated terrestrial plants to cladocerans was similar to that to lake particulate organic pool. Thus, our study quantified the role of terrestrial carbon in eutrophic wetlands, enhancing our understanding of cross-ecosystem interactions in food webs with an emphasis on the resource quality.

The contribution of autochthonous resource to the diet of aquatic consumers is unrelated to its spatial distribution in tank bromeliads

Autochthonous biomass is heterogeneously distributed within freshwater ecosystems, shaping community structure and ecosystem functioning, yet few studies have evaluated how the spatial heterogeneity in the availability of the autochthonous resource affects its contribution to the diets of aquatic consumers. To fill this gap, we conducted a field survey to test whether the spatial heterogeneity of the autochthonous resource within freshwater ecosystems formed in tank bromeliads determines its contribution to the diet of aquatic consumers. Tank bromeliads are Neotropical plants with densely arranged leaves in a rosette shape that accumulate rainwater and terrestrial plant material, providing suitable habitat for a diversity of aquatic invertebrates. We sampled 3 regions (north, central, and south) of the bromeliad ecosystem to provide a natural gradient in the availability of the autochthonous resource (i.e., algae biomass). To trace the diets of aquatic consumers, we used stable isotope analysis of hydrogen coupled with Bayesian stable isotope mixing models. The availability of the autochthonous resource varied among the tank-bromeliad regions with light availability, but it was not related to its relative contribution to the diets of aquatic consumers. Instead, aquatic consumers from all regions showed similarly high degrees of autochthony. The capacity of aquatic consumers to move within the plant did not affect the contribution of the autochthonous resource to their diets. We reason that the contribution of the autochthonous resource to the diets of consumers is not related to its spatial distribution because aquatic consumers preferentially feed on this resource, even when its stocks are limited. In addition, water flow among tanks could provide a subsidy of the autochthonous resource from more productive to less productive regions. We conclude that spatial heterogeneity in the availability of the autochthonous resource does not limit its contribution to the diet of aquatic consumers because of active foraging on the autochthonous resource and the flux of this resource among compartments in freshwater tank-bromeliad ecosystems.

Analysis of Carbon and Hydrogen Stable Isotope Ratios of Phenolic Compounds: Method Development and Biodegradation Applications

Phenolic compounds are priority water pollutants of both natural and anthropogenic origins. Distinguishing the sources and degradation pathways of phenolic compounds in the environment is essential for sustainable water management. In this study, we have developed and validated methods based on gas chromatography–isotope ratio mass spectrometry for analysis of hydrogen and carbon isotope ratios of phenol and cresols. For carbon stable isotope analysis, solid-phase extraction was applied, whereas liquid–liquid extraction, followed by derivatization with trifluoroacetic anhydride, was used for hydrogen stable isotope analysis. The methods were verified in biodegradation experiments using p-cresol and phenol as substrates. Methyl group oxidation of p-cresol by Pseudomonas pseudoalcaligenes and Aromatoleum aromaticum resulted in the strong hydrogen (−76 ± 2 and −103 ± 2 mUr, respectively) and varying carbon isotopic fractionation (−2.1 ± 0.1 and −1.0 ± 0.1 mUr, respectively), leading to distinguishable two-dimensional plots for hydrogen versus carbon isotope ratios, indicating slightly different enzymatic reactions. For anaerobic phenol degradation by Desulfosarcina cetonica, the absence of hydrogen isotopic fractionation indicates adenosine triphosphate-dependent carboxylation as the initial step of the biodegradation pathway. The methods developed in this study are useful to detect biological degradation of phenolic compounds in highly contaminated aqueous environmental systems.

Stable isotope analysis of an aberrant Painted Bunting (Passerina ciris) feather suggests post-molt movements

We present the first record of plumage color aberration and the occurrence of slow-growing feather tissue in the Painted Bunting (Passerina ciris), a colorful songbird breeding in the southern United States during summer and migrating to Central America in winter. We took advantage of this rare sampling opportunity and performed hydrogen stable isotope analysis on 12 cross-sections of 2 primary feathers to compare isotopic values in normal and aberrant tissue sampled from the same individual. We used feather hydrogen stable isotope variation as an informative environmental marker to track the movements of the bird across its annual cycle. Spatial probability density estimates suggest further movements after this bunting arrived at molting stopover sites in northern coastal Mexico, either migrating toward southern coastal latitudes or toward higher elevations. Although we are unable to definitively assign a cause to the aberrant feather and its slow growth rate, we highlight how combining the observation of an atypical morphological trait with a modern molecular approach offers an opportunity to advance our understanding of avian movement behavior.

Compound-specific stable carbon and hydrogen isotope analyses of late-Holocene vegetation and precipitation change at Laguna Los Mangos, Costa Rica

New compound-specific isotope analyses of a sediment core from Laguna Los Mangos in southern Pacific Costa Rica improves understanding of late-Holocene precipitation change in a region with limited paleoprecipitation records that is vulnerable to future climate change. We established paleoprecipitation and paleovegetation records from compound-specific stable hydrogen and carbon isotopic compositions of terrestrially-derived n-alkanes (δ2Halkane and δ13Calkane) to assess paleohydrologic variability and potential linkages to paleoecological change and human activity as revealed by prior analyses of the Los Mangos core. The δ2Halkane values were corrected for isotopic fractionation using pollen counts from the same core. The Los Mangos record extends to 4200 cal yr BP and small increases in δ13C values of C29, +0.6‰, and C31 alkanes, +0.3‰, (δ13CC29, 31) indicate a slight increase in C4 vegetation after initial introduction of maize agriculture to the watershed at ca. 3360 cal yr BP. This slight increase in C4 vegetation is followed by the largest positive carbon isotope excursions in the record, as compared to record averages (δ13CC29 = +3.2‰, δ13CC31 = +5.0‰). Paleohydrologic variability likely influenced vegetation and human activity at Los Mangos. Lake desiccation during the late-Terminal Classic Drought (TCD) resulted in a sedimentary hiatus in the Los Mangos record from ca. 950 to 450 cal yr BP. Positive excursions in comparison to record averages occur for both δ2HC29 and δ2HC31 proxies (δ2HC29 = +25.3 to +13.4‰ and δ2HC31 = +6.5‰) during the middle Little Ice Age (LIA) and indicate drier than average conditions, but there is no evidence of desiccation during this period. Thus, drought conditions during the LIA were apparently not as severe at Los Mangos as during the TCD, possibly because of differing forcing mechanisms for LIA climate that originated, or were more clearly expressed, in the Atlantic basin.

Compound-specific stable hydrogen isotope (δ2 H) analyses of fatty acids: A new method and perspectives for trophic and movement ecology.

Compound-specific stable isotope analysis (CSIA) is a powerful tool for a better understanding of trophic transfer of dietary molecules in and across ecosystems. Hydrogen isotope values (δ2 H) in consumer tissues have potential to more clearly distinguish dietary sources than 13 C or 15 N values within and among habitats, but have not been used at the fatty acid level for ecological purposes. Here we demonstrate a new online high-capacity gas chromatography-isotope ratio mass spectrometry technique (2 H-CSIA) that offers accurate and reproducible determination of δ2 H values for a range of fatty acids from organisms of aquatic food webs. We show that lipid extracts obtained from aquatic sources, such as biofilms, leaves, invertebrates, or fish muscle tissue, have distinctive δ2 H values that can be used to assess sources and trophic interactions, as well as dietary allocation and origin of fatty acids within consumer tissue. The new 2 H-CSIA method can be applied to evaluate sources and trophic dynamics of fatty acids in organisms ranging from food web ecology to migratory connectivity.

Migratory connectivity then and now: a northward shift in breeding origins of a long-distance migratory bird wintering in the tropics.

Temporal variation in the connectivity of populations of migratory animals has not been widely documented, despite having important repercussions for population ecology and conservation. Because the long-distance movements of migratory animals link ecologically distinct and geographically distant areas of the world, changes in the abundance and migratory patterns of species may reflect differential drivers of demographic trends acting over various spatial scales. Using stable hydrogen isotope analyses (δ2H) of feathers from historical museum specimens and contemporary samples obtained in the field, we provide evidence for an approximately 600 km northward shift over 45 years in the breeding origin of a species of songbird of major conservation concern (blackpoll warbler, Setophaga striata) wintering in the foothills of the eastern Andes of Colombia. Our finding mirrors predictions of range shifts for boreal-breeding species under warming climate scenarios and habitat loss in the temperate zone, and underscores likely drivers of widespread declines in populations of migratory birds. Our work also highlights the value of natural history collections to document the effects of global change on biodiversity.

Detection of exogenous sugars in pineapple juice using compound-specific stable hydrogen isotope analysis

An improved procedure for determining 2H/1H isotope ratios, using gas chromatography-isotope ratio mass spectrometry, has been used to detect the addition of exogenous C4-plant-derived sugars to pineapple juice. Isotopic techniques are commonly used to identify the addition of low-cost sugars to fruit juices and are difficult to subvert as it is not economically viable to change the isotopic ratios of the sugars. However, the addition of cane sugar to pineapple juice has presented a significant challenge that is only detected by site-specific 13C analysis of the methyl and methylene positions of ethanol derived from pineapple sugars, measured by nuclear magnetic resonance. This new GC-IRMS-based procedure utilises the trifluoroacetate derivative of sucrose to allow direct measurement of the carbon-bound non-exchangeable hydrogen. This provides advantages over alternative isotopic methods in terms of analysis time and sensitivity. This feasibility study has demonstrated the potential to reliably differentiate between authentic pineapple juices and those adulterated with commercial beet and cane sucrose.

Evaluation of a quick one-step sample preparation method for the determination of the isotopic fingerprint of rapeseed (Brassica napus): Investigation of the influence of the use of 2,2-dimethoxypropane on compound-specific stable carbon and hydrogen isotope analyses by gas chromatography combustion/pyrolysis isotope ratio mass spectrometry.

Gas chromatographic analyses for vegetable oils require transesterification, which generally involves multiple steps, mainly to generate fatty acid methyl esters (FAMEs). A quick method based on acid-catalyzed transesterification using 2,2-dimethoxypropane (DMP) enables the conversion in one step, in a single reactor. For compound-specific stable carbon and hydrogen isotope analyses (C- and H-CSIA) of individual fatty acids (FAs) in oil, the verification of this one-step method has not yet been reported. In this study, we evaluated the feasibility of the one-step method for C- and H-CSIA of individual FAMEs in rapeseed samples. The focus was on the investigation of the influence of methanol, which was produced from the reactions of DMP with glycerol and water during transesterification, on the accuracy of isotope composition of FAMEs, consequently of the FAs. The reproducibility of the one-step method was assessed by the measurement of the FAMEs from rapeseed and rapeseed oil. For the C- and H-CSIA of individual FAMEs, a gas chromatography combustion/pyrolysis isotope ratio mass spectrometry system was used. Our results showed that no significant differences arise in the carbon and hydrogen isotope compositions of the selected main FAMEs produced with and without DMP except for the H-CSIA value of C18:3. The reproducibility of the one-step method for rapeseed was in the range of ±0.1 mUr to ± 0.3 mUr for C-CSIA and ±1 mUr to ±3 mUr for H-CSIA of the main FAMEs. DMP improves the transesterification efficiency without influencing the accuracy of the C- and H-CSIA of FAMEs. The performance of the one-step method for rapeseed samples for the determination of C- and H-CSIA values of FAMEs is satisfactory. Thus, the applicability of the one-step method for isotopic fingerprint analyses of FAs in oilseeds is reported for the first time.

Surface geochemical survey in the vicinity of decommissioned coal mine shafts.

Methane observed in soil atmosphere above active and abandoned bituminous coal mines has a thermogenic (coalbed) and/or microbial (produced by anaerobic bacteria or resulted from in situ coal biodegradation) origin or it may be a mixture of gases generated from various sources. Identification of the origin of methane may support or refute the thesis on the uncontrolled migration of mine gases in rock formations followed by their emission to the atmosphere at coal extraction sites. Surface geochemical surveys were carried out in the vicinity of the decommissioned mine shafts at the Murcki-Staszic Coal Mine, located in the Upper Silesian Coal Basin (southern Poland). Over a 3-month period, measurements were carried out cyclically at 2 locations. Totally, 43 fixed geochemical probes were installed in the area of the Murcki II "Stanisław" Shaft, in which measurements were carried out in six sessions. Next 29 probes were installed in the area of the Staszic III Shaft, where measurements were taken twice. Each measurement included concentrations of 5 components (methane, non-methane volatile organic compounds, total hydrocarbons, carbon dioxide and oxygen), which provided a total number of 1405 individual analytical determinations. For measurements, portable EcoProbe 5 instrument was used. The stable carbon isotope composition of methane and carbon dioxide was analyzed in selected 10 samples. The isotopic composition of hydrogen in methane was also measured in one sample. The comparative material consisted of eight samples of soil gases and two samples of mine gases, which were used as reference 'soil' gases. The isotopic analyses were conducted using a mass spectrometry method. Based on the results of our analyses, it is stated that both the Murcki II "Stanisław" and the Staszic III shafts were properly decommissioned. The successful sealing of mine shafts prevented mine gases from migration through the shaft into the atmosphere. However, at a single geochemical probe located more than 100m from the former shaft center, methane concentration in soil gases reached over 1vol%. This confirms the general observation that mine gas migrates from coal seams and/or gobs through crushed rocks into the atmosphere. The stable carbon isotope analysis of methane and carbon dioxide as well as stable hydrogen isotope analysis of methane suggest that methane in the soil atmosphere is of thermogenic origin with minor contribution of microbial component.