Stable carbon isotopic evidence for differences in the dietary origin of bone cholesterol, collagen and apatite: implications for their use in palaeodietary reconstruction     

Susan Jim  Richard P. Evershed 《Geochimica et cosmochimica acta》2004,68(1):61-72

Rats were raised on a variety of isotopically controlled diets comprising 20% C₃, C₄ or marine protein and C₃ and/or C₄ non-protein or energy (i.e. sucrose, starch and oil) macronutrients. Compound specific stable carbon isotope (δ¹³C) analysis was performed on the cholesterol isolated from the diet (n=7 ) and bone (n=15 ) of these animals and the values compared with bulk δ¹³C measurements of bone collagen and apatite. The dietary signals reflected by these three bone biochemical components were investigated using linear regression analysis. δ¹³C values of bone cholesterol were shown to reflect whole diet δ¹³C values, collagen to reflect mainly dietary protein values and apatite to reflect whole diet values. Further correlations between dietary protein-to-energy spacings (Δ¹³C_prot-engy = δ¹³C_protein - δ¹³C_energy) and whole diet-to-bone component fractionations (Δ¹³C_bcomp-wdiet = δ¹³C_{bone component} - δ¹³C_{whole diet}) indicates that for hypothetical diets where protein δ¹³C values are equal to energy values, fractionations between whole diet and bone biochemical fractions are -3.3‰ for cholesterol, +5.4‰ for collagen and +9.5‰ for apatite. Moreover, the narrow range of variation observed in apatite-to-cholesterol spacings (Δ¹³C_apat-bchol) suggests that cholesterol δ¹³C values can potentially also be used as an independent test for the isotopic integrity of apatite δ¹³C values. These insights into bone cholesterol, collagen and apatite dietary signals, diet-to-bone fractionations and bone component-to-bone component spacings provide the basis for more accurate interpretations of the dietary behaviour of archaeological populations and food webs when the δ¹³C analysis of bone is employed.  相似文献   

Diet and habitat of toxodont megaherbivores (Mammalia, Notoungulata) from the late Quaternary of South and Central America     

Bruce J. MacFadden 《Quaternary Research》2005,64(2):113-124

The toxodont megaherbivores Toxodon and Mixotoxodon were endemic to South and Central America during the late Quaternary. Isotopic signatures of 47 toxodont teeth were analyzed to reconstruct diet and ancient habitat. Tooth enamel carbon isotope data from six regions of South and Central America indicate significant differences in toxodont diet and local vegetation during the late Quaternary. Toxodonts ranged ecologically from C₃ forest browsers in the Amazon (mean δ¹³C = −13.4‰), to mixed C₃ grazers and/or browsers living either in C₃ grasslands, or mixed C₃ forested and grassland habitats in Honduras (mean δ¹³C = −9.3‰), Buenos Aires province, Argentina (δ¹³C = −8.7‰), and Bahia, Brazil (mean δ¹³C = −8.6‰), to predominantly C₄ grazers in northern Argentina (δ¹³C = −4.4‰), to specialized C₄ grazers in the Chaco of Bolivia (δ¹³C = −0.1‰). Although these toxodonts had very high-crowned teeth classically interpreted for grazing, the isotopic data indicate that these megaherbivores had the evolutionary capacity to feed on a variety of dominant local vegetation. In the ancient Amazon region, carbon isotope data for the toxodonts indicate a C₃-based tropical rainforest habitat with no evidence for grasslands as would be predicted from the Neotropical forest refugia hypothesis.  相似文献   

Paired δ13Ccarb and δ13Corg records of the Ordovician on the Yangtze platform,South China     

B.-Y. Li  D.-W. Zhang  X.-Q. Pang  P. Gao  D.-Y. Zhu  K.-Z. Guo 《Australian Journal of Earth Sciences》2018,65(6):809-822

During the Ordovician, huge biological revolutions and environmental changes happened in Earth’s history, including the Great Ordovician Biodiversification Event, global cooling and so on, but the cause of these events remains controversial. Herein, we conducted a paired carbon isotopic analysis of carbonate (δ¹³C_carb) and organic matter (δ¹³C_org) through the Ordovician in the Qiliao section on the Yangtze platform of South China. Our results showed that the δ¹³C_carb trend of the Qiliao section can be correlated with local and global curves. The δ¹³C_org trend seems is less clear than the δ¹³C_carb trend for stratigraphic correlations, but some δ¹³C_org positive excursions in the Middle and Upper Ordovician may be used for correlation studies. These carbon isotopic records may have global significance rather than local significance, revealing several fluctuations to the global carbon cycle during the Ordovician. Several known δ¹³C_carb and δ¹³C_org negative and positive excursions have been recognised in this study, including the early Floian Negative Inorganic Carbon (δ¹³C_carb) Excursion (EFNICE), as well as the early Floian Positive Organic Carbon (δ¹³C_carb) Excursion, the mid-Darriwilian Inorganic Carbon (δ¹³C_carb and δ¹³C_org) Excursion (MDICE), and the early Katian Guttenberg Inorganic Carbon (δ¹³C_carb and δ¹³C_org) Excursion (GICE). These positive excursions and a smooth decline trend of δ¹³C_org values during the early to mid-Floian may imply multiple episodes of enhanced organic carbon burial that began at the early Floian stage, probably resulting in further decline in atmospheric pCO₂ and then global cooling.  相似文献   

The use of a finite mixture distribution model in bottled water characterisation and authentication with stable hydrogen,oxygen and carbon isotopes — Case study from Slovenia     

Mihael Brenčič  Polona Vreča 《Journal of Geochemical Exploration》2010

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Physiological and isotopic responses of scleractinian corals to ocean acidification   总被引：1，自引：0，他引：1  

Shani Krief  Erica J. Hendy  Maoz Fine  Ruth Yam  Gavin L. Foster 《Geochimica et cosmochimica acta》2010,74(17):4988-301

Uptake of anthropogenic CO₂ by the oceans is altering seawater chemistry with potentially serious consequences for coral reef ecosystems due to the reduction of seawater pH and aragonite saturation state (Ω_arag). The objectives of this long-term study were to investigate the viability of two ecologically important reef-building coral species, massive Porites sp. and Stylophora pistillata, exposed to high pCO₂ (or low pH) conditions and to observe possible changes in physiologically related parameters as well as skeletal isotopic composition. Fragments of Porites sp. and S. pistillata were kept for 6-14 months under controlled aquarium conditions characterized by normal and elevated pCO₂ conditions, corresponding to pH_T values of 8.09, 7.49, and 7.19, respectively. In contrast with shorter, and therefore more transient experiments, the long experimental timescale achieved in this study ensures complete equilibration and steady state with the experimental environment and guarantees that the data provide insights into viable and stably growing corals. During the experiments, all coral fragments survived and added new skeleton, even at seawater Ω_arag < 1, implying that the coral skeleton is formed by mechanisms under strong biological control. Measurements of boron (B), carbon (C), and oxygen (O) isotopic composition of skeleton, C isotopic composition of coral tissue and symbiont zooxanthellae, along with physiological data (such as skeletal growth, tissue biomass, zooxanthellae cell density, and chlorophyll concentration) allow for a direct comparison with corals living under normal conditions and sampled simultaneously. Skeletal growth and zooxanthellae density were found to decrease, whereas coral tissue biomass (measured as protein concentration) and zooxanthellae chlorophyll concentrations increased under high pCO₂ (low pH) conditions. Both species showed similar trends of δ¹¹B depletion and δ¹⁸O enrichment under reduced pH, whereas the δ¹³C results imply species-specific metabolic response to high pCO₂ conditions. The skeletal δ¹¹B values plot above seawater δ¹¹B vs. pH borate fractionation curves calculated using either the theoretically derived α_B value of 1.0194 (Kakihana et al. (1977) Bull. Chem. Soc. Jpn.50, 158) or the empirical α_B value of 1.0272 (Klochko et al. (2006) EPSL248, 261). However, the effective α_B must be greater than 1.0200 in order to yield calculated coral skeletal δ¹¹B values for pH conditions where Ω_arag ? 1. The δ¹¹B vs. pH offset from the seawater δ¹¹B vs. pH fractionation curves suggests a change in the ratio of skeletal material laid down during dark and light calcification and/or an internal pH regulation, presumably controlled by ion-transport enzymes. Finally, seawater pH significantly influences skeletal δ¹³C and δ¹⁸O. This must be taken into consideration when reconstructing paleo-environmental conditions from coral skeletons.  相似文献   

Rayleigh distillation and the depth profile of C/C ratios of soil organic carbon from soils of disparate texture in Iron Range National Park, Far North Queensland, Australia     

Jonathan G. Wynn 《Geochimica et cosmochimica acta》2005,69(8):1961-1973

A depth- and particle size-specific analysis of soil organic carbon (SOC) and its isotopic composition was undertaken to investigate the effects of soil texture (or particle size) on the depth profile of stable carbon isotopic composition of SOC (δ¹³C_SOC) in two tropical soils. Depth-specific samples from two soil profiles of markedly different texture (coarse grained and fine grained) were separated into particle size classes and analyzed for the (mass/mass) concentration of SOC (C) and δ¹³C_SOC. Within 1 m of the soil surface, δ¹³C_SOC in the coarse-textured soil increases by 1.3 to 1.6‰, while δ¹³C_SOC from the fine-textured soil increase by as much as 3.8 to 5.5‰. This increasing depth trend in the coarse-textured soil is approximately linear with respect to normalized C, while the increase in the fine-textured soil follows a logarithmic function with respect to normalized C. A model of Rayleigh distillation describing isotope fractionation during decomposition of soil organic matter (SOM) accounts for the depth profile of δ¹³C_SOC in the fine-textured soil, but does not account for the depth profile observed in the coarse-textured soil despite their similar climate, vegetation, and topographic position. These results suggest that kinetic fractionation during humification of SOM leads to preferential accumulation of ¹³C in association with fine mineral particles, or aggregates of fine mineral particles in fine-textured soils. In contrast, the coarse-textured soil shows very little applicability of the Rayleigh distillation model. Rather, the depth profile of δ¹³C_SOC in the coarse-textured soil can be accounted for by mixing of soil carbon with different isotopic ratios.  相似文献   

Microscale Simultaneous Measurement of Carbon and Nitrogen Isotopes on Natural Diamond     

Akizumi Ishida  Kouki Kitajima  Ko Hashizume  Michael J. Spicuzza  Alexander Zaitsev  Daniel J. Schulze  John W. Valley 《Geostandards and Geoanalytical Research》2023,47(3):569-578

Simultaneous analysis of carbon and nitrogen isotope ratios by SIMS was applied for the first-time to a natural diamond from the Kelsey Lake kimberlite, State Line Distinct, Colorado (UWD-1). This in situ procedure is faster, reduces sample size for analysis, and measures both isotope ratios from a single ~ 10 μm diameter pit, a critical advantage for zoned diamonds. The carbon isotope ratio (expressed as δ¹³C_VPDB) of the bulk UWD-1 crystal, determined by the conventional combustion method in the present study, is -5.9‰ ± 0.2‰ (VPDB, 2s). Nitrogen mass fraction ([N]) and isotope ratio (expressed as δ¹⁵N_Air) were determined by stepwise combustion and gas-source mass-spectrometry, resulting in 553 ± 64 μg g^-1 and -6.7‰ ± 1.1‰ (Air, 2s), respectively. Secondary ions of ¹²C₂^-, ¹²C¹³C^-, ¹²C¹⁴N^-, and ¹²C¹⁵N^- were simultaneously measured by SIMS using three Faraday cups and one electron multiplier. The spot-to-spot reproducibility of δ¹³C and δ¹⁵N values for the UWD-1 (178 spots on sixteen chips, 10 μm spots), were 0.3‰ and 1.6‰, respectively (2s). While ¹²C¹⁴N^-/¹²C₂^- ratios, which are an indicator for [N], varied up to 12% among these sixteen chips, such variation did not correlate with either δ¹³C or δ¹⁵N values. We propose that UWD-1 is a suitable reference sample for microscale in situ analysis of δ¹³C and δ¹⁵N values in diamond samples.  相似文献   

Assessing scleractinian corals as recorders for paleo-pH: Empirical calibration and vital effects   总被引：2，自引：0，他引：2  

B. Hönisch  N.G. Hemming  A.G. Grottoli  G.N. Hanson 《Geochimica et cosmochimica acta》2004,68(18):3675-3685

Laboratory experiments on the branching, symbiont-bearing coral genus Porites and Acropora have been carried out to determine the dependence of the skeletal boron isotopic composition (δ¹¹B) on the pH of seawater. The results show a clear relationship similar to previously established empirical calibrations for planktonic foraminifera and inorganic calcite. A −0.6‰ offset exists between P. cylindrica and A. nobilis which is systematic over the pH range of 7.7-8.2. To test whether the δ¹¹B of coral skeletons changes with physiological processes such as photosynthesis and respiration, corals were grown along a depth transect in their natural environment and under controlled conditions in the laboratory at varying light intensities and food supply. Although we also observe an isotopic offset between P. compressa and Montipora verrucosa, neither experimental treatment systematically changed the δ¹¹B of the two species. These findings are encouraging for using the boron isotope paleo-pH proxy in corals, because it appears that seawater pH is the dominant control on the boron isotopic composition in corals.  相似文献   

Stable carbon isotope ratios in Astrangia danae: evidence for algal modification of carbon pools used in calcification     

C.E Cummings  H.B McCarty 《Geochimica et cosmochimica acta》1982,46(6):1125-1129

Stable carbon isotope ratios have been measured in skeletons of the temperature shallow water scleractinian coral, Astrangia danae. δ¹³C values ranging from ?5.42 to ?7.30%. revealed the expected depletion of ¹³C in skeletal carbonate relative to sea water bicarbonate. Differences among the ratios could not be attributed to collection site and were not correlated to skeletal morphology. Values of δ¹³C were directly related to zooxanthellae density for all colonies, so that as zooxanthellae concentration increased, δ¹³C valued increased. Colonies maintained under high temperature conditions were offset from the normal, exhibiting ratios less enriched in ¹³C than similar colonies from natural conditions. These trends supported the models of Weber and Goreau in which the carbon pools used in calcification are modified by algal photosynthesis. Direct evidence of physiological differences between symbiotic and asymbiotic colonies of A. danae has also been provided.  相似文献   

Carbon,oxygen and sulphur isotope variations in concretions from the Upper Lias of N.E. England     

M.L Coleman  R Raiswell 《Geochimica et cosmochimica acta》1981,45(3):329-340

Carbon, oxygen and sulphur isotope data for transects across two pyrite-bearmg carbonate concretions, and their host sediments, from the Upper Lias of N.E. England show symmetrical zonation. δ¹³C_PDB values of the calcite cement (?12.9 to ?15.4%.) indicate that most of it originated from organic matter by bacterial reduction of sulphate, augmented with marine and, to a lesser extent, fermentation derived carbonate. Organic carbon (δ¹³C_PDB = ?26.1 to ?37.0%.). reflects the admixture of allochtho-nous terrestrial organic matter with marine material and the selective preservation of isotopically light organic material through microbiological degradation.Two phases of pyrite are present in each concretion. The earlier framboidal pyrite formed throughout the sediment prior to concretionary growth and has δ³⁴S_CD values of ?22 to ?26%. indicating formation by open system sulphate reduction. The later euhedral phase is more abundant and reaches values of ? 2.5 to ? 5.5%. at concretion margins. This phase of sulphate reduction provided the carbonate source for concretionary growth and occurred in a partially closed system. The δ¹³C and δ³⁴S data are consistent with mineralogical and chemical evidence which suggest that both concretions formed close to the sediment surface. The δ₁₈O values of the calcite in one concretion (δ¹⁸O_PDB = 2.3 to ?4.8%.) indicate precipitation in pore waters whose temperature and isotopic composition was close to that of overlying seawater. The other concretion is isotopically much lighter (δ¹⁸O_PDB?8.9 to ?9.9%.) and large δ¹⁸O differences between concretions in closely-spaced horizons imply that local factors control the isotopic composition of pore waters.  相似文献   

Isotopic and geochemical evolution of ground and surface waters in a karst dominated geological setting: a case study from Belize,Central America     

《Applied Geochemistry》2004,19(6):937-946

Analysis of stable isotopes and major ions in groundwater and surface waters in Belize, Central America was carried out to identify processes that may affect drinking water quality. Belize has a subtropical rainforest/savannah climate with a varied landscape composed predominantly of carbonate rocks and clastic sediments. Stable oxygen (δ¹⁸O) and hydrogen (δD) isotope ratios for surface and groundwater have a similar range and show high d-excess (10–40.8‰). The high d-excess in water samples suggest secondary continental vapor flux mixing with incoming vapor from the Caribbean Sea. Model calculations indicate that moisture derived from continental evaporation contributes 13% to overhead vapor load. In surface and groundwater, concentrations of dissolved inorganic carbon (DIC) ranged from 5.4 to 112.9 mg C/l and δ¹³C_DIC ranged from −7.4 to −17.4‰. SO₄², Ca²⁺ and Mg²⁺ in the water samples ranged from 2–163, 2–6593 and 2–90 mg/l, respectively. The DIC and δ¹³C_DIC indicate both open and closed system carbonate evolution. Combined δ¹³C_DIC and Ca²⁺, Mg²⁺, and SO₄²⁻ suggest additional groundwater evolution by gypsum dissolution and calcite precipitation. The high SO₄²⁻content of some water samples indicates regional geologic control on water quality. Similarity in the range of δ¹⁸O, δD and δ¹³C_DIC for surface waters and groundwater used for drinking water supply is probably due to high hydraulic conductivities of the karstic aquifers. The results of this study indicate rapid recharge of groundwater aquifers, groundwater influence on surface water chemistry and the potential of surface water to impact groundwater quality and vise versa.  相似文献   

Hydrogen and carbon isotopes of petroleum and related organic matter     

Hsueh-Wen Yeh  Samuel Epstein 《Geochimica et cosmochimica acta》1981,45(5):753-762

$\text{D}\text{H}$ and ${}^{13}\text{C}{}^{12}\text{C}$ ratios were measured for 114 petroleum samples and for several samples of related organic matter. δD of crude oil ranges from ?85 to ?181‰, except for one distillate (?250‰) from the Kenai gas field; δ¹³C of crude oil ranges from ?23.3 to ?32.5‰, Variation in δD and δ¹³C values of compound-grouped fractions of a crude oil is small, 3 and 1.1%., respectively, and the difference in δD and δ¹³C between oil and coeval wax is slight. Gas fractions are 53–70 and 22.6–23.2‰ depleted in D and ¹³C, respectively, relative to the coexisting oil fractions.The δD and δ¹³C values of the crude oils appear to be largely determined by the isotopic compositions of their organic precursors. The contribution of terrestrial organic debris to the organic precursors of most marine crude oils may be significant.  相似文献   

Carbon,hydrogen and nitrogen isotopes in solvent-extractable organic matter from carbonaceous chondrites     

Richard H Becker  Samuel Epstein 《Geochimica et cosmochimica acta》1982,46(1):97-103

Solvent extractions were done on the carbonaceous chondrites Murray, Murchison, Orgueil and Renazzo, using CCl₄ and CH₃OH. Between 2 and 10% of the total carbon in these meteorites is extractable by ordinary techniques, most of it in CH₃OH. After demineralization with HF, perhaps as much as 30% of the total carbon in Murray may be extractable with CH₃OH. The extracts from Renazzo have isotopic ratios which suggest that they are mainly terrestrial organic matter, with lesser contributions from indigenous organics. The CH₃OH-soluble organic matter from Murchison and both untreated and HF-treated Murray has δ¹³C values of about +5 to + 10%. and δ¹⁵N values of about +90 to +100%., both of which are significantly higher than the bulk meteorite values. The Orgueil CH₃OH-extract also has a δ¹⁵N value well above the value in residual organic matter. Values for δD of +300 to +500%. are found for the CH₃OH-soluble organic matter. The combined data for C, H and N isotopes makes it highly unlikely that the CH₃OH-soluble components are derivable from, or simply related to, the insoluble organic polymer found in the same meteorites. A relationship is suggested between the event that formed hydrous minerals in CI1 and CM2 meteorites and the introduction of water-soluble (methanol-soluble) organic compounds. Organic matter soluble in CCl₄ has essentially no nitrogen, and δ³C and δD values are lower than for CH₃OH-soluble phases. Either there are large isotopic fractionations for carbon and hydrogen between different soluble organic phases, or the less polar components are partially of terrestrial origin.  相似文献   

Biogeochemical characterization of a Mediterranean shallow lake using stable isotopes: Laguna del Cristo (NW Iberian Peninsula)     

Margarita Jambrina-Enríquez  Clemente Recio  Ildefonso Armenteros 《Environmental Earth Sciences》2018,77(2):49

The present multi-isotopic study (δ¹⁸O–δD_water, δ³⁴S–δ¹⁸O_{dissolved-sulphate}, δ¹³C_{dissolved-inorganic-carbon}, δ¹³C–δ¹⁸O_{shells-modern-gastropods}, δ¹³C_plants, and δ¹³C_{sedimentary-organic-matter}) is aimed at assessing the hydrogeochemical changes and biogeochemical dynamics in a Mediterranean shallow lake fed by a Quaternary–Tertiary aquifer, the “Laguna del Cristo” (NW Iberian Peninsula), a system sensitive to climate fluctuations, between 2010 and 2011. Lake water is of the bicarbonate type, and there are no major pollutants. δ¹⁸O-δD_water values plot on a local evaporation line (δD=5.29δ¹⁸O–12.29) indicating that evaporative enrichment had a significant impact on lake water isotopic features. Periods of high water levels are characterized by lower δ³⁴S–δ¹⁸O_{dissolved-sulphate} and δ¹³C_{dissolved-inorganic-carbon} values and suggest sulphate derived from weathering of sulphides in the catchment area, delivered to the lake by surface run-off or via groundwater, and in situ decay of organic matter. During lower water levels, sulphate reduction and enhanced primary productivity lead to higher δ³⁴S_{dissolved-sulphate} and δ¹³C_{dissolved-inorganic-carbon} values. Evaporation induced enrichment in ¹⁸O_sulphate, ¹³C_{dissolved-inorganic-carbon} and ¹³C–¹⁸O_{shells-Galba-Gyraulus}. δ¹³C_plant confirms the C3 photosynthetic pathway. Enrichment in ¹³C submerged aquatic plants indicates that HCO₃^? is the main carbon source, except for ¹³C-depleted Potamogeton. The TOC, δ¹³C_org values, and TC/TN ratios in sediments all confirm the autochthonous character of organic matter contribution. This study provides a baseline for isotopic research into shallow, flow-through lakes fed by siliciclastic aquifers, and stresses the importance of evaporation and refilling (direct precipitation and groundwater discharge) in controlling the solute chemistry and stable isotopic composition in temperate regions with contrasting seasonal climates. The results also provide a snapshot of modern lake isotope variability that can be applied to paleoenvironmental reconstructions.  相似文献   

A large metabolic carbon contribution to the δC record in marine aragonitic bivalve shells     

David P. Gillikin  Anne Lorrain  Frank Dehairs 《Geochimica et cosmochimica acta》2007,71(12):2936-2946

It is well known that the incorporation of isotopically light metabolic carbon (C_M) significantly affects the stable carbon isotope (δ¹³C) signal recorded in biogenic carbonates. This can obscure the record of δ¹³C of seawater dissolved inorganic carbon (δ¹³C_DIC) potentially archived in the shell carbonate. To assess the C_M contribution to Mercenaria mercenaria shells collected in North Carolina, USA, we sampled seawater δ¹³C_DIC, tissue, hemolymph and shell δ¹³C. All shells showed an ontogenic decrease in shell δ¹³C, with as much as a 4‰ decrease over the lifespan of the clam. There was no apparent ontogenic change in food source indicated by soft tissue δ¹³C values, therefore a change in the respired δ¹³C value cannot be the cause of this decrease. Hemolymph δ¹³C, on the other hand, did exhibit a negative relationship with shell height indicating that respired CO₂ does influence the δ¹³C value of internal fluids and that the amount of respired CO₂ is related to the size or age of the bivalve. The percent metabolic C incorporated into the shell (%C_M) was significantly higher (up to 37%, with a range from 5% to 37%) than has been found in other bivalve shells, which usually contain less than 10%C_M. Interestingly, the hemolymph did contain less than 10%C_M, suggesting that complex fractionation might occur between hemolymph and calcifying fluids. Simple shell biometrics explained nearly 60% of the observed variability in %C_M, however, this is not robust enough to predict %C_M for fossil shells. Thus, the metabolic effect on shell δ¹³C cannot easily be accounted for to allow reliable δ¹³C_DIC reconstructions. However, there does seem to be a common effect of size, as all sites had indistinguishable slopes between the %C_M and shell height (+0.19% per mm of shell height).  相似文献