Stable calcium isotopic composition of meteorites and rocky planets

New measurements of mass-dependent calcium isotope effects in meteorites, lunar and terrestrial samples show that Earth, Moon, Mars, and differentiated asteroids (e.g., 4-Vesta and the angrite and aubrite parent bodies) are indistinguishable from primitive ordinary chondritic meteorites at our current analytical resolution (± 0.07‰ SD for the ⁴⁴Ca/⁴⁰Ca ratio). In contrast, enstatite chondritic meteorites are slightly enriched in heavier calcium isotopes (ca. + 0.5‰) and primitive carbonaceous chondritic meteorites are depleted in heavier calcium isotopes (ca. ? 0.5‰). The calcium isotope effects cannot be easily ascribed to evaporation or intraplanetary differentiation processes. The isotopic variations probably survive from the earliest stages of nebular condensation, and indicate that condensation occurred under non-equilibrium (undercooled nebular gas) conditions. Some of this early high-temperature calcium isotope heterogeneity is recorded by refractory inclusions (Niederer and Papanastassiou, 1984) and survived in planetesimals, but virtually none of it survived through terrestrial planet accretion. The new calcium isotope data suggest that ordinary chondrites are representative of the bulk of the refractory materials that formed the terrestrial planets; enstatite and carbonaceous chondrites are not. The enrichment of light calcium isotopes in bulk carbonaceous chondrites implies that their compositions are not fully representative of the solar nebula condensable fraction.     

Stable isotopic analysis on ancient human bones in Jiahu site

Palaeodietary analysis is one of important topics in bioarchaeology field and has been paid great at- tention to by Chinese archaeometrists recently. Ancient human bones in Jiahu Site were analyzed by means of stable isotopes of C, N and O. 13 human bones were excluded from 28 bones for dietary re- construction due to their unusual collagen contents, C and N contents, and C/N atomic ratios espe- cially. δ 13C (-20.37±0.53‰) in collagen of remaining samples showed that C3 food were consumed mainly, which is consistent of the archaeological findings that rice was the staple in Jiahu. According to the difference of δ 15N and δ 13C values in bone collagen, the samples can be classified into four clusters. The changes of δ 15N values in bone collagen and δ 13C values in hydroxylapatite through whole cultural phases indicated the transition from hunting to gathering and fishing to rice agriculture and animal domestication ultimately. Meanwhile, the δ 18O change in hydroxylapatite showed that pa- laeoclimate was relatively constant during Jiahu culture.     

Stable isotopic studies of dinosaur eggshells from the Nanxiong Basin, South China

Stable carbon and oxygen isotopes have been observed in dinosaur eggshell samples,identified as Macroolithus yaotunensis,collected in two sections of the Nanxiong Basin,Guangdong Province,South China.Multiple positiveδ18O perturbations that occurred during the K/T transition of about 150 ka suggest that there may have been at least three periods of the extreme dry climate with a mean annual air temperature over 27℃.δ13C ranges from -8.37‰ to -11.60‰ of the dinosaur eggshells,added to the metabolic enrichment of 16‰,may indicate that the dinosaurs represented by this type of eggshells probably consumed the plant species of C3 type with the δ13C values of -24.3‰- -27.6‰.Moreover,the trend toward more negative δ13C values of the eggshells during the K/T transition could be an indirect consequence of a lasting increase in atmospheric CO2 concentration.     

Stable isotopic records of the glacial deep-water properties in the South China Sea

Based on the oxygen and carbon stable isotopic records of benthic foraminifera in nine deep-sea cores of the South China Sea (SCS), the bathymetric profiles of δ¹⁸O and δ¹³C since the last glacial maximum (LGM) are preliminarily established. The bathymetric gradients of deep-water δ¹⁸O and δ¹³C in the SCS are obviously greater during the LGM than during the Holocene, showing the existence of the deep thermocline and nutricline at water depth of about 2 000 m. Particularly, the differences in δ¹⁸O and δ¹³C between the LGM and Holocene, from which the ice-volume effect and the global mean shift have been subtracted respectively, are positive values at water depths of 1 000–2 500 m in the SCS. This indicates the existence of deep-water mass with relatively cool temperature or higher salinity, better ventilation and more δ¹³C within the water depth range of the SCS during the LGM, which is distinctly different from that at present. These changes further confirm the existence of the glacial “North Pacific Deep Water” which, however, is possibly confined to the water depth range of 1 000–2 500 m. Project supported by the National Natural Science Foundation of China (Grant Nos. 49576286 and 49732060).     

Mg isotopic composition of carbonate: insight from speleothem formation

Simultaneous high-precision measurement of ²⁴Mg, ²⁵Mg and ²⁶Mg isotopic compositions were made by multiple collector inductively coupled mass spectrometry (MC-ICP-MS) relative to the international standard SRM980. Data are presented on low-Mg calcite speleothems and their associated host rocks and waters from four caves, one in the French Alps and three in Israel, covering various climate conditions. In addition, data are presented on three dolostones and three limestones from the Himalaya. The overall variation is 4.13‰ and 2.14‰ in δ²⁶Mg and δ²⁵Mg, respectively. This is 35 times the uncertainty of the measurements and clearly demonstrates that the terrestrial isotopic composition of Mg is not unique. Each speleothem shows a characteristic range of δ²⁶Mg values that are attributed to the isotopic composition of the local water. Differences between the isotopic composition of Mg in the water dripping from stalactites and that of the modern speleothem are interpreted as being due to Mg isotopic fractionation during carbonate precipitation in the temperature range of 4-18°C. The low-Mg calcite is enriched in light isotopes by 1.35‰/AMU and the dependence on temperature has been found to be less than 0.02‰/AMU/°C. Despite various geological settings, the δ²⁶Mg of the studied dolostones is 2.0±1.2‰ higher than the δ²⁶Mg of the limestones. All together, these results suggest a strong mineralogical control and a weak temperature effect on the Mg isotopic composition of carbonate.     

Stable isotopic characteristic of Taiwan's precipitation: A case study of western Pacific monsoon region

The stable oxygen and hydrogen isotopic features of precipitation in Taiwan, an island located at the western Pacific monsoon area, are presented from nearly 3,500 samples collected during the past decade for 20 stations. Results demonstrate that moisture sources from diverse air masses with different isotopic signals are the main parameter in controlling the precipitation's isotope characteristics. The air mass from polar continental (Pc) region contributes the precipitation with high deuterium excess values (up to 23‰) and relatively enriched isotope compositions (e.g., ? 3.2‰ for δ¹⁸O) during the winter with prevailing northeasterly monsoon. By contrast, air masses from equatorial maritime (Em) and tropical maritime (Tm) supply the precipitation with low deuterium excess values (as low as about 7‰) and more depleted isotope values (e.g., ? 8.9‰ and ? 6.0‰ for δ¹⁸O of Tm and Em, respectively) during the summer with prevailing southwesterly monsoon. Thus seasonal differences in terms of δ¹⁸O, δD, and deuterium excess values are primarily influenced by the interactions among various precipitation sources. While these various air masses travel through Taiwan, secondary evaporation effects further modify the isotope characteristics of the inland precipitation, such as raindrop evaporation (reduces the deuterium excess of winter precipitation) and moisture recycling (increases the deuterium excess of summer precipitation). The semi-quantitative estimations in terms of evaluation for changes in the deuterium excess suggest that the raindrop evaporation fractions for winter precipitation range 7% to 15% and the proportions of recycling moisture in summer precipitation are less than 5%. Additionally, the isotopic altitude gradient in terms of δ¹⁸O for summer precipitation is ? 0.22‰/100 m, greater than ? 0.17‰/100 m of winter precipitation. The greater isotopic gradient in summer can be attributed to a higher temperature vs. altitude gradient relative to winter. The observed spatial and seasonal stable isotopic characteristics in Taiwan's precipitation not only contribute valuable information for regional monsoon research crossing the continent–ocean interface of East Asia, but also can serve as very useful database for local water resources management.     

Stable carbon and nitrogen isotopic composition of gas hydrate-bearing sediment from Hydrate Ridge,Cascadia Margin

Serious interest has been directed toward natural gas hydrate as a potential energy resource; factor in global climate change, and submarine geohazard since naturally occurring gas-hydrate deposits were found in the 1960s. Hydrate Ridge, Cascadia convergent mar- gin, is characterized by abundant methane hydrates at and below the seafloor, active venting of fluids and gases, chemosynthetic communities, and some of the highest methane oxidation rates ever found in the ma-rine environment. All of…     

Stable isotopic compositions and controlling factors of precipitation and atmospheric vapour in the headwaters of the Shule River

Stable isotopic compositions of precipitation (δ¹⁸O_p, δ²H_p and d-excess_p) and atmospheric vapour (δ¹⁸O_v, δ²H_v and d-excess_v) with high spatial–temporal resolution are crucial in revealing hydrologic cycle. Based on the variation characteristics of δ¹⁸O_p/δ¹⁸O_v, δ²H_p/δ²H_v and d-excess_p/d-excess_v in the headwaters of the Shule River (HSR) on hourly and daily scales from June to September 2018, this study analysed the relationships between δ¹⁸O_p/δ²H_p and δ¹⁸O_v/δ²H_v combined with the equilibrium fractionation model, as well as δ¹⁸O_p/δ¹⁸O_v and meteorological factors. The slopes of local meteoric water line (LMWL) and the δ²H_v-δ¹⁸O_v fitting equation were similar (7.96 and 7.94) with both intercepts exceeding 10, reflecting the great contribution of recycling moisture. The values of δ¹⁸O_v/δ²H_v were lower than δ¹⁸O_p/δ²H_p but with consistent variation patterns throughout the period. The equilibrium simulation results suggested that precipitation and atmospheric vapour almost approached isotopic equilibrium state, especially during monsoon intrusion period. Affected by monsoon intrusion, the slopes and intercepts of the LMWLs and the δ²H_v-δ¹⁸O_v fitting equations were smaller than those during non-monsoon period and d-excess and δ¹⁸O were negatively correlated. Relative humidity had significant negative correlations with δ¹⁸O_p and δ¹⁸O_v in the whole period, however, the positive correlations between δ¹⁸O_p/δ¹⁸O_v and temperature were observed during non-monsoon and monsoon intrusion period, respectively. Our results demonstrated that precipitation and atmospheric vapour isotopic compositions exhibited consistency under the influence of diverse moisture sources, while more complex relationships were found between δ¹⁸O_p/δ¹⁸O_v and meteorological factors. This research provided evidence for using the isotopic compositions of atmospheric vapour to indicate moisture sources, and can improve understanding of the water cycle and eco-hydrological process from the perspective of the interaction between water and gas phases of the inland river basin in northwest China.     

Stable isotopic and geochemical identification of groundwater evolution and recharge sources in the arid Shule River Basin of Northwestern China

Stable isotopic (δD_VSMOW and δ¹⁸O_VSMOW) and geochemical signatures were employed to constrain the geochemical evolution and sources of groundwater recharge in the arid Shule River Basin, Northwestern China, where extensive groundwater extraction occurs for agricultural and domestic supply. Springs in the mountain front of the Qilian Mountains, the Yumen‐Tashi groundwater (YTG), and the Guazhou groundwater (GZG) were Ca‐HCO₃, Ca‐Mg‐HCO₃‐SO₄ and Na‐Mg‐SO₄‐Cl type waters, respectively. Total dissolved solids (TDS) and major ion (Mg²⁺, Na⁺, Ca²⁺, K⁺, SO₄^2?, Cl^? and NO₃^?) concentrations of groundwater gradually increase from the mountain front to the lower reaches of the Guazhou Basin. Geochemical evolution in groundwater was possibly due to a combination of mineral dissolution, mixing processes and evapotranspiration along groundwater flow paths. The isotopic and geochemical variations in melt water, springs, river water, YTG and GZG, together with the end‐member mixing analysis (EMMA) indicate that the springs in the mountain front mainly originate from precipitation, the infiltration of melt water and river in the upper reaches; the lateral groundwater from the mountain front and river water in the middle reaches are probably effective recharge sources for the YTG, while contribution of precipitation to YTG is extremely limited; the GZG is mainly recharged by lateral groundwater flow from the Yumen‐Tashi Basin and irrigation return flow. The general characteristics of groundwater in the Shule River Basin have been initially identified, and the results should facilitate integrated management of groundwater and surface water resources in the study area. Copyright © 2015 John Wiley & Sons, Ltd.     

Uplift and submarine formation of some Melanesian porphyry copper deposits: Stable isotope evidence

Hydrogen and oxygen isotope analyses of sericites and kaolinites from four young porphyry copper deposits (Ok Tedi (1.2 Ma) and Yandera (6.5 Ma), Papua New Guinea; Koloula (1.5 Ma), Solomon Islands; and Waisoi (<5 Ma), Fiji) indicate that the fluids from which these minerals precipitated were of mixed magmatic and non-magmatic sources. The non-magmatic component of the fluid from the island arc deposits (Koloula, Waisoi) was ocean water.For Ok Tedi, the non-magmatic component was a meteoric water with an isotopic composition different from that of the present meteoric water in the region. The isotopic signature of the former meteoric water is consistent with a surface elevation of 200 m a.s.l. or less at the time of mineralization. The deposit was later exposed and supergene kaolinitization commenced at approximately 1200 m a.s.l. Uplift and erosion has continued to the present at which time the elevation of the exposed deposit is 1800 m a.s.l. This rate of uplift is consistent with that known from other geological evidence. If the rate of uplift were approximately constant during the last 1.2 Ma, the age of supergene enrichment can be dated at approximately 0.4 Ma B.P.Similarly, influx of meteoric water at Yandera occurred when the ground surface above the deposit was at an elevation of approximately 600 m a.s.l. The deposit's present elevation is 1600 m a.s.l. In this case a total uplift of approximately 2.2 km is indicated, with removal of 1.2 km of overburden by erosion.     

Sm-Nd isotopic evolution of chondrites

The¹⁴³Nd/¹⁴⁴Nd and¹⁴⁷Sm/¹⁴⁴Nd ratios have been measured in five chondrites and the Juvinas achondrite. The range in¹⁴³Nd/¹⁴⁴Nd for the analyzed meteorite samples is 5.3 ε-units (0.511673–0.511944) normalized to¹⁵⁰Nd/¹⁴²Nd= 0.2096. This is correlated with the variation of 4.2% in¹⁴⁷Sm/¹⁴⁴Nd (0.1920–0.2000). Much of this spread is due to small-scale heterogeneities in the chondrites and does not appear to reflect the large-scale volumetric averages. It is shown that none of the samples deviate more than 0.5 ε-units from a 4.6-AE reference isochron and define an initial¹⁴³Nd/¹⁴⁴Nd ratio at 4.6 AE of0.505828 ± 9. Insofar as there is a range of values of¹⁴⁷Sm/¹⁴⁴Nd there is no unique way of picking solar or average chondritic values. From these data we have selected a new set of self-consistent present-day reference values for CHUR (“chondritic uniform reservoir”) of (¹⁴³Nd/¹⁴⁴Nd)_CHUR⁰ = 0.511836and(¹⁴⁷Sm/¹⁴⁴Nd)_CHUR⁰ = 0.1967. The new¹⁴⁷Sm/¹⁴⁴Nd value is 1.6% higher than the previous value assigned to CHUR using the Juvinas data of Lugmair. This will cause a small but significant change in the CHUR evolution curve. Some terrestrial samples of Archean age show clear deviations from the new CHUR curve. If the CHUR curve is representative of undifferentiated mantle then it demonstrates that depleted sources were also tapped early in the Archean. Such a depleted layer may represent the early evolution of the source of present-day mid-ocean ridge basalts. There exists a variety of discrepancies with most earlier meteorite data which includes determination of all Nd isotopes and Sm/Nd ratios. These discrepancies require clarification in order to permit reliable interlaboratory comparisons. The new CHUR curve implies substantial changes in model ages for lunar rocks and thus also in the interpretation of early lunar chronology.     

Nickel isotopic studies in meteorites

We have analyzed the nickel isotopic composition of meteoritic materials by high-precision mass spectrometry. The samples analyzed include almost all meteorite types for which large isotopic anomalies have been reported for oxygen, silver, magnesium and titanium. These samples are C₁, C₃, L, LL, H and E chondrites, IVB irons, Eagle Station pallasite and inclusion, matrix and “whole rock” samples of the Allende meteorite. The result is that we have not found any anomaly for nickel isotopic compositions within our accuracy of 0.7‰ for⁶¹Ni/⁶⁰Ni, 0.4-0.08‰ for⁶²Ni/⁶⁰Ni and 1–1.5‰ for⁶⁴Ni/⁶⁰Ni.     

Nd isotopic variations of Phanerozoic paleoceans

The size of various Phanerozoic paleoceans, determined from paleogeographic maps, provides a framework for assigningε_Nd measurements of primary authigenic marine minerals to individual paleoceans and for establishing theirε_Nd versus age curves. We report newε_Nd data (in the range from 80 to 750 Ma) for the largest Phanerozoic and Late Precambrian paleocean, the Pacific/Panthalassa Ocean (PPO), and limited data on some small Paleozoic paleoceans. These new data and all other published data on paleoceanε_Nd values are used to determine the trends through time ofε_Nd in seven Phanerozoic paleoceans. The variations in paleoceanε_Nd curves are due to changes in the rate of crustal additions and in paleoceanic geometry. From these data we can calculate a meanε_Nd curve and a mean Nd model age curve for Phanerozoic seawater. These curves show large variations with age and reflect the variations ofε_Nd in erosion products from the continents as a function of age. The high erosion rates of young, uplifted areas enhanceε_Nd and Nd model age variations of Phanerozoic seawater. This makes it difficult to quantitatively recover crustal addition rates from these curves; however, it makes the episodic nature of continental additions more evident.     

Revised phosphate-water isotopic temperature scale

The oxygen-isotope data obtained from BiPO₄ samples fluorinated in silver-soldered metal lines are systematically more negative than those obtained by fluorination in a line assembled with flareless fittings. Because of this the phosphate-water isotopic temperature scale has been revised by studying 27 samples of shells of living marine organisms from different areas. The slope of the calculated equation is practically identical to that of the carbonate equation.     

Graphical characterisation of probability distribution tails

 The purpose of this paper is to present a graphical method to characterise the nature of a distribution (exponential or algebraic). In the algebraic case, this statistical tool provides an estimation procedure of the parameter characterising the decrease of the survival function. The realizations of the random variable under study being available in the form of time series, this method is based on the relationship between the duration of exceeding an intensity threshold and the accumulation of the realizations of the random variable during this length of time. The behaviour of the duration-accumulation graphs (when the threshold of reference increases indefinitely) results in a function, the limit of which only depends on the parameter characterising the algebraic decrease of the probability distribution. The estimate of this parameter is biased but can be corrected effectively by numerical methods. We applied this method to two rainfall series differing by their geographical origin (Dédougou in Burkina Faso and a station on the Island of La Réunion) and their time step (respectively 1 day and 76 seconds). For both of them, the behaviour of tail distributions is shown to be algebraic and the values of the parameter characterizing the algebraic decrease of the probability distribution of the two series are very close. This would tend to justify the assumption of a multifractal nature for these series. This work was achieved as part of the National Programme of Research in Hydrology of the INSU (project 99 PNRH 27). The authors are grateful to A. Barcello for providing them the data of the Island of La Réunion Island.     

A non-mass-dependent isotopic fractionation effect

Isotopic fractionation is discussed in terms of collision cross sections. Under thermal equilibrium conditions, isotopically non-reactive collisions and collisions involving indistinguishable isotopes have no effect on the concentration of isotopic species: isotopic exchange reactions give rise to the well known mass-dependent isotopic fractionation (MDF). Under non-thermal equilibrium conditions, the non-reactive and indistinguishable cross sections must be taken into account since they participate in the loss of energy (thermalisation) of the hot species. If an isotope exchange between hot and cold species occurs during the thermalisation, the relative isotopic abundances contribute to the reaction rates and the MDF rule is not valid anymore. A general formulation of the isotopic fractionation, accounting for thermal and non-thermal situations, is proposed. The experimental results obtained during the synthesis of ozone [1] are well explained by the present treatment, which could be extended to other isotopic anomalies observed in meteorites.     

Neodymium isotopic variations in seawater

New data for the direct measurement of the isotopic composition of neodymium in Atlantic Ocean seawater are compared with previous measurements of Pacific Ocean seawater and ferromanganese sediments from major ocean basins. Data for Atlantic seawater are in excellent agreement with Nd isotopic measurements made on Atlantic ferromanganese sediments and are distinctly different from the observed compositions of Pacific samples. These results clearly demonstrate the existence of distinctive differences in the isotopic composition of Nd in the waters of the major ocean basins and are characteristic of the ocean basin sampled. The average ε_Nd(0) values for the major oceans as determined by data from seawater and ferromanganese sediments are as follows: Atlantic Ocean,ε_Nd(0) ? ?12 ± 2; Indian Ocean,ε_Nd(0) ? ?8 ± 2; Pacific Ocean,ε_Nd(0) ? ?3 ± 2. These values are considerably less than ε_Nd(0) value sources with oceanic mantle affinities indicating that the REE in the oceans are dominated by continental sources. The difference in the absolute abundance of¹⁴³Nd between the Pacific and Atlantic Oceans corresponds to ～10⁶ atoms¹⁴³Nd per gram of seawater. The correspondence between the¹⁴³Nd/¹⁴⁴Nd in seawater and in the associated sediments suggests the possible application of this approach to paleo-oceanography.Distinctive differences in ε_Nd(0) values are observed in the Atlantic Ocean between deep-ocean water associated with North Atlantic Deep Water and near-surface water. This suggests that North Atlantic Deep Water may be relatively well mixed with respect to Nd isotopic composition whereas near-surface water may be quite heterogeneous, reflecting different sources for surface waters relative to deep water. This suggests that it may be possible to distinguish the sources of water masses within an ocean basin on the basis of Nd isotopic composition.The Nd isotopic variations in seawater are used to relate the residence time of Nd and mixing rates between the oceans.     

Fracture characterisation using geoelectric null-arrays

The term “geoelectric null-array” is used for direct current electrode configurations yielding a potential difference of zero above a homogeneous half-space. This paper presents a comparative study of the behaviour of three null-arrays, midpoint null-array (MAN), Wenner-γ null-array and Schlumberger null-array in response to a fracture, both in profiling and in azimuthal mode. The main objective is to determine which array(s) best localise fractures or best identify their orientation.Forward modelling of the three null-arrays revealed that the Wenner-γ and Schlumberger null-arrays localise vertical fractures the most accurately, whilst the midpoint null-array combined with the Schlumberger null-array allows accurate orientation of a fracture. Numerical analysis then served as a basis to interpret the field results. Field test measurements were carried out above a quarry in Les Breuleux (Switzerland) with the three null-arrays and classical arrays. The results were cross-validated with quarry-wall geological mapping. In real field circumstances, the Wenner-γ null-array proved to be the most efficient and accurate in localising fractures. The orientations of the fractures according to the numerical results were most efficiently determined with the midpoint null-array, whilst the Schlumberger null-array adds accuracy to the results. This study shows that geoelectrical null-arrays are more suitable than classical arrays for the characterisation of fracture geometry.     

Oxygen isotopic composition of low-temperature authigenic clinoptilolite

Oxygen isotope ratios were obtained from authigenic clinoptilolites from Barbados Accretionary Complex, Yamato Basin, and Exmouth Plateau sediments (ODP Sites 672, 797, and 762) in order to investigate the isotopic fractionation between clinoptilolite and pore water at early diagenetic stages and low temperatures. Dehydrated clinoptilolites display isotopic ratios for the zeolite framework (δ¹⁸O_f) that extend from +18.7‰ to +32.8‰ (vs. SMOW). In combination with associated pore water isotope data, the oxygen isotopic fractionation between clinoptilolite and pore fluids could be assessed in the temperature range from 25°C to 40°C. The resulting fractionation factors of 1.032 at 25°C and 1.027 at 40°C are in good agreement with the theoretically determined oxygen isotope fractionation between clinoptilolite and water. Calculations of isotopic temperatures illustrate that clinoptilolite formation occurred at relatively low temperatures of 17°C to 29°C in Barbados Ridge sediments and at 33°C to 62°C in the Yamato Basin. These data support a low-temperature origin of clinoptilolite and contradict the assumption that elevated temperatures are the main controlling factor for authigenic clinoptilolite formation. Increasing clinoptilolite δ¹⁸O_f values with depth indicate that clinoptilolites which are now in the deeper parts of the zeolite-bearing intervals had either formed at lower temperatures (17–20°C) or under closed system conditions.