Nitrogen abundances and isotopic compositions in stony meteorites

Nitrogen contents range from a few parts per million in ordinary chondrites and achondrites to several hundred parts per million in enstatite chondrites and carbonaceous chondrites. Four major isotopic groups are recognized: (1) C1 and C2 carbonaceous chondrites have δ¹⁵N of+30to+50%.; (2) enstatite chondrites have δ¹⁵N of?30to?40‰; (3) C3 chondrites have low δ¹⁵N with large internal variations; (4) ordinary chondrites have δ¹⁵N of?10to+20‰. The major variations are primary, representing isotopic abundances established at the time of condensation and accretion. Secondary processes, such as spallation reactions, solar wind implantation and metamorphic loss may cause small but observable isotopic variations in particular cases. The large isotopic difference between enstatite chondrites and carbonaceous chondrites cannot be accounted for by equilibrium condensation from a homogeneous nebular gas, and requires either unusually large kinetic effects, or a temporal or spatial variation of isotopic composition of the nebula. Nitrogen isotopic heterogeneity in the nebula due to nuclear processes has not been firmly established, but may be required to account for the large variations found within the Allende and Leoville meteorites. The unique carbonaceous chondrite, Renazzo, has δ¹⁵N of+170%., which is well beyond the range of all other data, and also requires a special source. It is not yet possible, from the meteoritic data, to establish the mode of accretion of nitrogen onto the primitive Earth.     

Deuterium in carbonaceous chondrites

Hydrogen isotopic compositions in seven carbonaceous chondrites lie in the range ?70 to +771‰ relative to SMOW. These values decrease, to a range from ?145 to +219‰, after low-temperature oxidation in an oxygen plasma. Deuterium enrichment is therefore concentrated in the organic matter, the hydrous silicates probably lying close to the terrestrial range for such material. Calculated values for δD of the organic fraction are +450 ‰ for Orgueil and Ivuna and up to +1600‰ for Renazzo. These enrichments, at least for Orgueil and Ivuna, suggest equilibration with protosolar hydrogen at very low temperatures. Assuming a value of 2.5 × 10^?5 for the protosolar D/H ratio, nominal equilibration temperatures of 230°K for silicates and 180°K for organic matter may be derived.     

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.     

Extraction of soluble collagen and its feasibility in the palaeodietary research

In current palaeodietary research, gelatinization is the main method to extract insoluble collagen(ISC) from ancient bones. However, the degradation products of ISC, i.e., soluble collagen(SC), is often neglected and abandoned. In this work, we try to separate the extracts of ancient bones using gel chromatography and compare the contents of carbon and nitrogen, atomic C/N ratio, and stable carbon and nitrogen isotopic values of the extracts from three peaks to determine which peak can be attributed to SC. At last, the potential application of SC in palaeodietary research is discussed based on the comparison of stable isotopic values between ISC and SC. Among the three peaks, the second with the retention time between 17.5 min and 27.5 min had the most broad peak shape, indicating that the molecular weights of proteins collected were most variable. Besides, the contents of carbon and nitrogen and atomic C/N ratio of extracts in this peak were closest to the corresponding ISC. Based on the above, we conclude that the extract in second peak is SC. More important, the δ 13C and δ 15N values of ISC and SC are very similar. For ISC and SC with atomic C/N ratios within the normal range(2.9–3.6), the mean difference of δ 13C value was only(0.3±0.2)‰(n=2) while δ 15N value was(0.6±0.1)‰(n=2). Although the atomic C/N ratios of some SC are slightly beyond the normal range, the mean differences of δ 13C and δ 15N values were still only(0.4±0.1)‰ and(0.3±0)‰(n=2) respectively. These isotopic differences are quite below the isotope fractionation in one trophic level(δ 13C values of 1‰–1.5‰ and δ 15N values of 3‰–5‰), suggesting that SC had great application potentials in palaeodietary research.     

Sources and distribution of organic matter in northern Patagonia fjords,Chile (∼44–47°S): A multi-tracer approach for carbon cycling assessment

We investigated the provenance of organic matter in the inner fjord area of northern Patagonia, Chile (～44–47°S), by studying the elemental (organic carbon, total nitrogen), isotopic (δ¹³C, δ¹⁵N), and biomarker (n-alkanoic acids from vascular plant waxes) composition of surface sediments as well as local marine and terrestrial organic matter. Average end-member values of N/C, δ¹³C, and δ¹⁵N from organic matter were 0.127±0.010, ?19.8±0.3‰, and 9.9±0.5‰ for autochthonous (marine) sources and 0.040±0.018, ?29.3±2.1‰, and 0.2±3.0‰ for allochthonous (terrestrial) sources. Using a mixing equation based on these two end-members, we calculated the relative contribution of marine and terrestrial organic carbon from the open ocean to the heads of fjords close to river outlets. The input of marine-derived organic carbon varied widely and accounted for 13–96% (average 61%) of the organic carbon pool of surface sediments. Integrated regional calculations for the inner fjord system of northern Patagonia covered in this study, which encompasses an area of ～4280 km², suggest that carbon accumulation may account for between 2.3 and 7.8×10⁴ ton C yr^?1. This represents a storage capacity of marine-derived carbon between 1.8 and 6.2×10⁴ ton yr^?1, which corresponds to an assimilation rate of CO₂ by marine photosynthesis between 0.06 and 0.23×10⁶ ton yr^?1. This rate suggests that the entire fjord system of Patagonia, which covers an area of ～240,000 km², may represent a potentially important region for the global burial of marine organic matter and the sequestration of atmospheric CO₂.     

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.     

Siliceous productivity changes in Gulf of Ancud sediments (42°S, 72°W), southern Chile,over the last ∼150 years

We evaluated changes in siliceous export production and the source of organic matter preserved in sediment core MD07-3109H recovered from the Gulf of Ancud, Chiloé Inner Sea (42°S, 72°W, water column depth: 328 m), southern Chile. We analyzed the abundance of siliceous microfossils (diatoms, silicoflagellates, sponge spicules, Chrysophyte cysts, phytoliths), geochemical proxies (weight percent silicon %Si_OPAL, organic carbon, total nitrogen, C/N molar), and sediment stable isotopes (δ¹³C_org, δ¹⁵N). Chronology based on ²¹⁰Pb and ¹⁴C provided an accumulated age of 144 years at the base of the core.Sediments of core MD07-3109H are predominantly marine in origin, averaging δ¹³C_org=–20.75‰±0.82, δ¹⁵N=8.7±0.35‰, and C/N=8.76±0.36. Marine diatoms compose 94% of the total assemblage of siliceous microfossils. Our record of productivity based on the mass accumulation rates of organic carbon, total nitrogen, Si_OPAL, and total diatoms showed high values between 1863 and 1869 AD followed by a declining trend until 1921 AD, a transition period from 1921 to 1959 AD with fluctuating values, and a clear decreasing pattern from 1960 AD to the present. This marked reduction in productivity was associated with decreased precipitation and Puelo River streamflow (41°S), as well as a warmer and more stratified water column, especially since the 1980s.     

Investigating the distribution and sources of organic matter in surface sediment of Coombabah Lake (Australia) using elemental,isotopic and fatty acid biomarkers

Extensive physical and biological measurements were made of the surface sediments within the shallow, semi-urbanised Coombabah Lake in southern Moreton Bay, Australia. Sediment bulk parameters (C/N ratios, δ¹³C and δ¹⁵N) and fatty acid biomarkers were used to determine distributions and sources of organic matter in the intertidal sediments. The determination of organic matter sources within coastal and estuarine settings is important in understanding the roles of organic matter as energy and nutrient sources. Spatial variability of biomarker values within the sediments were interpreted by thematic maps employing the Krigging algorithm. Grain size analysis indicated the lake was dominated by mud (<63 μm) in the southern (landward) and sand (>63 μm) in the northern (seaward) lake regions, respectively. Surface sediment organic C and N values ranged from 0.12% to 1.76% and 0.01% to 0.12% dry weight, respectively, and C/N ratios averaged 16.3±3.19%. Sedimentary δ¹³C values ranged from −26.1‰ to −20.9‰, with an average value of −23.9±1.0‰. Sedimentary δ¹⁵N values ranged from +1.7‰ to +4.8‰, with an average value of +2.8±0.8‰. Bulk sediment parameters suggested that sedimentary organic matter is provided predominantly by allochthonous sources in the form of fringing mangroves. Thirty-nine individual fatty acids were identified using gas chromatography–mass spectrometry. The mean contributions of long chain fatty acids (LCFAs), polyunsaturated fatty acids (PUFAs), saturated fatty acids (SAFAs) and bacterial fatty acids (BAFAs) were, respectively, 13.9±11.4%, 7.6±4.1%, 53.6±8.6% and 18.2±4.6% of the identified fatty acid methyl esters (FAMEs), with BAFAs occurring in all sampled sediments. Fatty acid compositions varied throughout lake sediments, which indicated spatial differences in autochthonous and allochthonous organic matter sources, including terrestrial and planktonic (i.e. zooplankton, diatoms and other algal species) sources. The contribution of organic matter from shoreline mangroves was confirmed by the presence of LCFAs and 18:2ω6 and 18:3ω3, which are markers for mangroves in this ecosystem. BAFAs were identified in increased proportions in sediments adjacent to urban developments and dominated by mud. Grain size was identified as a dominant factor in the fatty acid compositions and contributing values to FAME pool. Spatial patterns of C/N ratios, δ¹³C and δ¹⁵N values, and fatty acid biomarker contributions illustrated that there is a greater contribution of autochthonous and labile organic matter to the sedimentary organic matter pool in the northern (marine entrance) sediments compared to the more allochthonous sourced organic matter of the southern region of the lake. This study details the distribution and sources of organic matter within Coombabah Lake and illustrates the usefulness of a multiple biomarker approach in discriminating organic matter sources within estuarine environments.     

Geologic controls on the chemical behaviour of nitrate in riverside alluvial aquifers,Korea

To investigate the origin and behaviour of nitrate in alluvial aquifers adjacent to Nakdong River, Korea, we chose two representative sites (Wolha and Yongdang) having similar land‐use characteristics but different geology. A total of 96 shallow groundwater samples were collected from irrigation and domestic wells tapping alluvial aquifers. About 63% of the samples analysed had nitrate concentrations that exceeded the Korean drinking water limit (44·3 mg l^?1 NO₃^?), and about 35% of the samples had nitrate concentrations that exceeded the Korean groundwater quality standard for agricultural use (88·6 mg l^?1 NO₃^?). Based on nitrogen isotope analysis, two major nitrate sources were identified: synthetic fertilizer (about 4‰ δ¹⁵N) applied to farmland, and animal manure and sewage (15–20‰ δ¹⁵N) originating from upstream residential areas. Shallow groundwater in the farmland generally had higher nitrate concentrations than those in residential areas, due to the influence of synthetic fertilizer. Nitrate concentrations at both study sites were highest near the water table and then progressively decreased with depth. Nitrate concentrations are also closely related to the geologic characteristics of the aquifer. In Yongdang, denitrification is important in regulating nitrate chemistry because of the availability of organic carbon from a silt layer (about 20 m thick) below a thin, sandy surface aquifer. In Wolha, however, conservative mixing between farmland‐recharged water and water coming from a village is suggested as the dominant process. Mixing ratios estimated based on the nitrate concentrations and the δ¹⁵N values indicate that water originating from the village affects the nitrate chemistry of the shallow groundwater underneath the farmland to a large extent. Copyright © 2003 John Wiley & Sons, Ltd.     

The impact of pipe flow in riparian peat deposits on nitrate transport and removal

The effect of preferential flow in soil pipes on nitrate retention in riparian zones is poorly understood. The characteristics of soil pipes and their influence on patterns of groundwater transport and nitrate dynamics were studied along four transects in a 1‐ to >3‐m deep layer of peat and marl overlying an oxic sand aquifer in a riparian zone in southern Ontario, Canada. The peat‐marl deposit, which consisted of several horizontal layers with large differences in bulk density, contained soil pipes that were generally 0.1 to 0.2 m in diameter and often extended vertically for 1 to >2 m. Springs that produced overland flow across the riparian area occurred at some sites where pipes extended to the peat surface. Concentrations of NO₃^?–N (20–30 mg L^?1) and dissolved oxygen (DO) (4–6 mg L^?1) observed in peat pipe systems and surface springs were similar to values in the underlying sand aquifer, indicating that preferential flow transported groundwater with limited nitrate depletion. Low NO₃^?–N concentrations of <5 mg L^?1 and enriched δ¹⁵N values indicated that denitrification was restricted to small areas of the peat where pipes were absent. Groundwater DO concentrations declined rapidly to <2 mg L^?1 in the peat matrix adjacent to pipes, whereas high NO₃^?–N concentrations of >15 mg L^?1 extended over a larger zone. Low dissolved organic carbon values at these locations suggest that supplies of organic carbon were not sufficient to support high rates of denitrification, despite low DO conditions. These data indicate that it is important to develop a greater understanding of pipes in peat deposits, which function as sites where the transport of large fluxes of water with low biogeochemical reaction rates can limit the nitrate removal capacity of riparian zones. Copyright © 2011 John Wiley & Sons, Ltd.     

Distribution and sources of sedimentary organic matter in a tropical estuary,south west coast of India (Cochin estuary): A baseline study

Surface sediments samples were collected from 9 stations of the Cochin estuary during the monsoon, post-monsoon and pre-monsoon seasons and were analyzed for grain size, total organic carbon (OC), total nitrogen (TN) and stable isotopic ratios of carbon (δ¹³C) and nitrogen (δ¹⁵N) to identify major sources of organic matter in surface sediments. Sediment grain size is found to be the key factor influencing the organic matter accumulation in surface sediments. The δ¹³C values ranges from ?27.5‰ to ?21.7‰ in surface sediments with a gradual increase from inner part of the estuary to the seaward side that suggest an increasing contribution of marine autogenous organic matter towards the seaward side. The δ¹⁵N value varies between 3.1‰ and 6.7‰ and it exhibits complex spatial and seasonal distributions in the study area. It is found that the dynamic cycling of nitrogen through various biogeochemical and organic matter degradation processes modifies the OC/TN ratios and δ¹⁵N to a considerable degree. The fraction of terrestrial organic matter in the total organic matter pool ranges from 13% to 74% in the surface sediments as estimated by δ¹³C based two end member mixing model.     

A classification of meteorites based on oxygen isotopes

On the basis of¹⁸O/¹⁶O and¹⁷O/¹⁶O ratios, meteorites and planets can be grouped into at least six categories, as follows: (1) the terrestrial group, consisting of the earth, moon, differentiated meteorites and enstatite chondrites; (2) types L and LL ordinary chondrites; (3) type H ordinary chondrites; (4) anhydrous minerals of C2, C3, C4 carbonaceous chondrites; (5) hydrous matrix minerals of C2 carbonaceous chondrites; (6) the ureilites. Objects of one category cannot be derived by fractionation or differentiation from the source materials of any other category.     

Land–ocean distribution of allochthonous organic matter in surface sediments of the Chiloé and Aysén interior seas (Chilean Northern Patagonia)

We investigated the relative distribution of allochthonous (i.e., terrigenous) organic matter in the complex, continuous, river–fjord–sound–channel–gulf system of Chile’s North Patagonia (41.5–46.5°S) in order to establish whether this organic matter can reach the open ocean or whether it is largely retained near its fluvial sources. Grain size distribution, total organic carbon and total nitrogen contents, and carbon stable isotope contents (δ¹³C) were quantified in 53 surface sediment samples collected during the CIMAR Fiordos cruises 1, 4, 8, and 10, as were salinity and silicic acid concentrations in the surface waters. A principal component analysis segregated the Chiloé and Aysén interior seas into two zones: (i) the continental fjords, with sediment enriched in allochthonous organic matter, having higher C:N molar ratios (10–14) and lower δ¹³C composition (?23‰ to ?27‰); and (ii) the channels and gulfs, with a prevalent autochthonous marine source, having lower C:N values (6–10) and higher δ¹³C composition (?20‰ to ?23‰). Estuarine waters with low salinity (2–30) and high silicic acid (10–90 μM) were associated with high C:N ratios and low δ¹³C in surface sediments, meaning that terrestrial organic matter was transported up to the mouth of the continental fjords. A two-source mixing model confirmed that allochthonous (terrestrial) organic matter contents (50–90%) associated with local river discharges were present within the continental fjords. On the contrary, autochthonous (marine) organic matter was prevalent (50–90%) at the sites in the marine influenced channels, sounds, and gulfs.     

Lu-Hf and Sm-Nd isotopic systematics in chondrites and their constraints on the Lu-Hf properties of the Earth

Sm-Nd and Lu-Hf isotopic data are presented for 19 chondritic meteorites: six carbonaceous chondrites, five L-chondrites, seven H-chondrites, and a single enstatite chondrite. The primary goal of the study is to better define the Bulk Silicate Earth (BSE) reference values for Hf isotopes. Except for one sample with lower Sm/Nd, the Sm-Nd data define a cluster around the accepted reference values for chondrites and terrestrial planets, giving a mean ¹⁴⁷Sm/¹⁴⁴Nd of 0.1960±0.0005, and a mean ¹⁴³Nd/¹⁴⁴Nd of 0.512631±0.000010 (uncertainties are two standard errors). It seems appropriate to retain the presently accepted Sm-Nd reference parameters, ¹⁴⁷Sm/¹⁴⁴Nd=0.1966 and ¹⁴³Nd/¹⁴⁴Nd=0.512638 (when fractionation-corrected to ¹⁴⁶Nd/¹⁴⁴Nd=0.7219).Lu-Hf isotopic data are not clustered, but spread along an approximate 4.5-Ga isochron trend, with a range of ¹⁷⁶Lu/¹⁷⁷Hf from 0.0301 to 0.0354. The data are similar to many of the samples of chondrites presented by Bizzarro et al. [Nature 421 (2003) 931], but lack the range to lower Lu/Hf shown by those authors. Our chondrite data define a regression line of 4.44±0.34 Ga when 1.867×10⁻¹¹ year⁻¹ is used for the decay constant of ¹⁷⁶Lu [Science 293 (2001) 683; Earth Planet. Sci. Lett. 219 (2004) 311-324]. Combining our data with the main population of analyses from Bizzarro et al. [Nature 421 (2003) 931] yields 4.51±0.24 Ga. Unless samples of eucrite meteorites and deviating replicates of chondrites with ¹⁷⁶Lu/¹⁷⁷Hf less than 0.030 are employed, no combination of the main population of chondrite Lu-Hf data yields a regression with sufficiently low error to constrain the decay constant of ¹⁷⁶Lu. Sample heterogeneity seems to hinder the acquisition of reproducible Lu-Hf analyses from small, manually ground pieces of chondrites, and we suggest that analysis of powders prepared from large volumes of meteorite will be needed to adequately characterize the Lu-Hf isotope systematics of chondritic reservoirs and of BSE. Our results for carbonaceous chondrites show higher average ¹⁷⁶Lu/¹⁷⁷Hf and ¹⁷⁶Hf/¹⁷⁷Hf than ordinary chondrites, and the mean of carbonaceous chondrites also coincides with replicate analyses of a powder representing a large volume of meteorite, the Allende powder from the Smithsonian Institution. Use of the carbonaceous chondrite mean for BSE Lu-Hf characteristics results in a BSE Hf-Nd point that lies well within the array of terrestrial compositions, and leads to plausible initial ε_Hf values for Precambrian rocks. An improved objective resolution of meteorite data and of meteoritic models for the Earth needs to occur before BSE can be established for Lu-Hf.     

Sr and O isotopic characteristics of porphyries in the Qinling molybdenum deposit belt and their implication to genetic mechanism and type

A great deal of Mesozoic hypobatholithic granites and hypabyssal porphyries develop in the Qinling Mountains. The former has long been regarded as transformation type (or S-type), and the latter associated with Mo-mineralization regarded as syntexis type (or I-type) granitoids. Statistics show that Sr₁ and σ¹⁸O of hypabyssal porphyries respectively range from 0.705 to 0.714, and from 7.2‰ to 12.1‰, agreeing with those of hypobatholithes (Sr₁=0.705–0.710, σ¹⁸O=6.1‰–10.4‰), which indicates that they share similar material sources and petrogenic mechanism. Based on analysis of lithological, mineralogical and geochemical characteristics of these granitoids and on study of their petrogenic tectonic background and regional geophysical data, we argue that both the shallow-seated porphyries and deep-seated batholithes were the products of Mesozoic collision between South China and North China paleocontinents. Subsequently, all these grantitoids should be attributed to collision type.     

Changes in carbon and nitrogen cycling in a floodplain lake over recent decades linked to littoral expansion,declining riverine influx,and eutrophication

This study aimed to understand changes in the biogeochemical processing of organic matter (OM) in response to multiple stressors (e.g., littoral area expansion, wastewater input, and hydrological regulation) in East Dongting Lake (Central China) over the past 60 years, using analyses of total organic carbon (TOC), total nitrogen (TN), C/N ratios, δ¹³C, δ¹⁵N, and diatoms from 2 sediment cores collected from the littoral and central parts of the lake. OM mainly originated from phytoplankton and C₃ plant‐derived soil OM based on the ranges of C/N ratios (from 7 to 11) and δ¹³C (between ?27‰ and ?23‰). Littoral area expansion due to siltation caused an increasing influx of terrestrial soil OM in the 1980s and the 1990s, subsequently lowering δ¹³C values and rising C/N ratios in both sediment cores. Meanwhile, higher δ¹⁵N was linked to a high influx of isotopically heavy nitrate from urban and agricultural wastewaters. After 2000, slight decreases in TOC and TN in the littoral area were attributable to reducing inputs of external OM, likely linked to declining sediment influx from the upper reaches resulting from the Three Gorges Dam impoundment. Contrasting increases in TOC, TN, and C/N ratios in the central part indicated a high influx of terrestrial soil OM due to the declining distance from the shoreline with littoral area expansion. Declining δ¹⁵N values after 2000 indicated an increase in N₂‐fixing cyanobacteria with eutrophication. Changes in diatom assemblages in both the littoral and central zones reflected nutrient enrichment and hydrological alterations. These results indicate that littoral expansion, declining riverine influx, and anthropogenic nutrient inputs are potential driving forces for the biogeochemical processing of OM in floodplain lakes. This study provides sedimentary biogeochemical clues for tracking past limnological conditions of floodplain lakes that are subjected to increasing disturbances from hydrological regulation and eutrophication.     

Nickel isotope heterogeneity in the early Solar System

We report small but significant variations in the ⁵⁸Ni/⁶¹Ni-normalised ⁶⁰Ni/⁶¹Ni and ⁶²Ni/⁶¹Ni ratios (expressed as ε⁶⁰Ni and ε⁶²Ni) of bulk iron and chondritic meteorites. Carbonaceous chondrites have variable, positive ε⁶²Ni (0.05 to 0.25), whereas ordinary chondrites have negative ε⁶²Ni (− 0.04 to − 0.09). The Ni isotope compositions of iron meteorites overlap with those of chondrites, and define an array with negative slope in the ε⁶⁰Ni versus ε⁶²Ni diagram. The Ni isotope compositions of the volatile-depleted Group IVB irons are similar to those of the refractory CO, CV carbonaceous chondrites, whereas the other common magmatic iron groups have Ni isotope compositions similar to ordinary chondrites. Only enstatite chondrites have identical Ni isotope compositions to Earth and so appear to represent the most appropriate terrestrial building material. Differences in ε⁶²Ni reflect distinct nucleosynthetic components in precursor solids that have been variably mixed, but some of the ε⁶⁰Ni variability could reflect a radiogenic component from the decay of ⁶⁰Fe. Comparison of the ε⁶⁰Ni of iron and chondritic meteorites with the same ε⁶²Ni allows us to place upper limits on the ⁶⁰Fe/⁵⁶Fe of planetesimals during core segregation. We estimate that carbonaceous chondrites had initial ⁶⁰Fe/⁵⁶Fe < 1 × 10^− 7. Our data place less good constraints on initial ⁶⁰Fe/⁵⁶Fe ratios of ordinary chondrites but our results are not incompatible with values as high as 3 × 10^− 7 as determined by in-situ measurements. We suggest that the Ni isotope variations and apparently heterogeneous initial ⁶⁰Fe/⁵⁶Fe results from physical sorting within the protosolar nebula of different phases (silicate, metal and sulphide) that carry different isotopic signatures.     

Carbon isotopic compositions of organic matter across continental Cretaceous–Tertiary (K–T) boundary sections: Implications for paleoenvironment after the K–T impact event

To assess the environmental perturbation induced by the impact event that marks the Cretaceous–Tertiary (K–T) boundary, concentrations and isotopic compositions of bulk organic carbon were determined in sedimentary rocks that span the terrestrial K–T boundary at Dogie Creek, Montana, and Brownie Butte, Wyoming in the Western Interior of the United States. The boundary clays at both sites are not bounded by coals. Although coals consist mainly of organic matter derived from plant tissue, siliceous sedimentary rocks, such as shale and clay, may contain organic matter derived from microbiota as well as plants. Coals record δ¹³C values of plant-derived organic matter, reflecting the δ¹³C value of atmospheric CO₂, whereas siliceous sedimentary rocks record the δ¹³C values of organic matter derived from plants and microbiota. The microbiota δ¹³C value reflects not only the δ¹³C value of atmospheric CO₂, but also biological productivity. Therefore, the siliceous rocks from these sites yields information that differs from that obtained previously from coal beds.Across the freshwater K–T boundary at Brownie Butte, the δ¹³C values decrease by 2.6‰ (from − 26.15‰ below the boundary clay to − 28.78‰ above the boundary clay), similar to the trend in carbonate at marine K–T sites. This means that the organic δ¹³C values reflect the variation of δ¹³C of atmospheric CO₂, which is in equilibrium with carbon isotopes at the ocean surface. Although a decrease in δ¹³C values is observed across the K–T boundary at Dogie Creek (from − 25.32‰ below the boundary clay to − 26.11‰ above the boundary clay), the degree of δ¹³C-decrease at Dogie Creek is smaller than that at Brownie Butte and that for marine carbonate.About 2‰ decrease in δ¹³C of atmospheric CO₂ was expected from the δ¹³C variation of marine carbonate at the K–T boundary. This δ¹³C-decrease of atmospheric CO₂ should affect the δ¹³C values of organic matter derived from plant tissue. As such a decrease in δ¹³C value was not observed at Dogie Creek, a process that compensates the δ¹³C-decrease of atmospheric CO₂ should be involved. For example, the enhanced contribution of ¹³C-enriched organic matter derived from algae in a high-productivity environment could be responsible. The δ¹³C values of algal organic matter become higher than, and thus distinguishable from, those of plant organic matter in situations with high productivity, where dissolved HCO₃⁻ becomes an important carbon source, as well as dissolved CO₂. As the δ¹³C-decrease of atmospheric CO₂ reflected a reduction of marine productivity, the compensation of the δ¹³C decrease by the enhanced activity of the terrestrial microbiota means that the microbiota at freshwater environment recovered more rapidly than those in the marine environment.A distinct positive δ¹³C excursion of 2‰ in the K–T boundary clays is superimposed on the overall decreasing trend at Dogie Creek; this coincides with an increase in the content of organic carbon. We conclude that the K–T boundary clays include ¹³C-enriched organic matter derived from highly productive algae. Such a high biological productivity was induced by phenomena resulting from the K–T impact, such as nitrogen fertilization and/or eutrophication induced by enhanced sulfide formation. The high productivity recorded in the K–T boundary clays means that the freshwater environments (in contrast to marine environments) recovered rapidly enough to almost immediately (within 10 yr) respond to the impact-related environmental perturbations.     

Stable isotope paleohydrology and chemostratigraphy of the Albian Wayan Formation from the wedge-top depozone,North American Western Interior Basin

Understanding of the role of atmospheric moisture and heat transport in the climate system of the Cretaceous greenhouse world represents a major challenge in Earth system science.Stable isotopic paleohydrologic data from mid-Cretaceous paleosols in North America,from paleoequatorial to paleoArctic latitudes,have been used to constrain the oxygen isotope mass balance of the Albian hydrologic cycle.Over the range from 40°-50°N paleolatitude,sideritic paleosols predominate,indicating paleoenvironments with positive precipitation-evaporation(P-E)balances.Local exceptions occur on leeward side of the Sevier Orogen,where calcic paleosols in the wedge-top depozone record paleoenvironments with negative P-E balances in the orographic rain shadow.Stratigraphic sections in the Wayan Formation of Idaho(WF)were sampled from the wedge-top depozone.The units consist of stacked m-scale mudstone paleosols separated by m-scale sandstone-siltstone beds.Sections were sampled for organic carbon isotope profiles,and B-horizons from 6 well-developed paleosols were sampled for detrital zircons to determine maximum depositional ages.The first of these from the WF has produced a U-Pb concordia age of 101.0±1.1 Ma.This same WF section has produced a stratigraphic trend of upwardly decreasingδ~(13)C values ranging from-24‰upwards to-27‰VPDB,suggesting correlation to the late Albian C15 C-isotope segment.Pedogenic carbonates from the WF principally consist of micritic calcite,with carbon-oxygen isotope values that array along meteoric calcite lines(MCLs)withδ~(18)O values that range from-9.47‰up to-8.39‰VPDB.At approximately 42°N paleolatitude,these MCL values produce calculated paleoprecipitation values of-8.12‰to-7.04‰VSMOW,a range that is consistent with the estimates produced from other proxies at the same paleolatitudes across North America.These results indicate that despite the orographic rain shadow effect,the processes of meridional atmospheric moisture transport in this locale were similar to those in more humid mid-latitude paleoenvironments elsewhere in the continent.     

Classification and origin of natural gases from Lishui Sag,the East China Sea Basin

Natural gases discovered up to now in Lishui Sag, the East China Sea Basin, differ greatly in gaseous compositions, of which hydrocarbon gases amount to 2%–94% while non-hydrocarbon gases are dominated by CO₂. Their hydrocarbon gases, without exception, contain less than 90% of methane and over 10% of C₂ ⁺ heavier hydrocarbons, indicating a wet gas. Carbon isotopic analyses on these hydrocarbon gases showed that δ ¹³C₁, δ ¹³C₂ and δ ¹³C₃ are basically lighter than −44‰, −29‰ and −26‰, respectively. The difference in carbon isotopic values between methane and ethane is great, suggesting a biogenic oil-type gas produced by the mixed organic matter at peak generation. δ ¹³ \( C_{CO_2 } \) values of nonhydrocarbon gases are all heavier than −10‰, indicating a typical abiogenic gas. The simulation experiment on hydrocarbon generation of organic matter in a closed gold-tube system showed that the proportion of methane in natural gases produced by terrigenous organic matter in the Lingfeng Formation marine deposit is obviously higher than that in natural gases derived from the aquatic and terrigenous mixed organic matter in the Yueguifeng Formation lacustrine deposit, consequently the proportion of heavier hydrocarbons of the former is remarkably lower than that of the latter. Moreover, δ ¹³C₁ values of natural gases produced by terrigenous organic matter in the Lingfeng Formation marine deposit are about 5‰ heavier than those of natural gases derived from the aquatic and terrigenous mixed organic matter in the Yueguifeng Formation lacustrine deposit while δ ¹³C₂ and δ ¹³C₃ values of the former are over 9‰ heavier than those of the latter. Currently the LS36-1 oil-gas pool is the only commercial oil-gas reservoir in Lishui Sag, where carbon isotopic compositions of various hydrocarbon components differ greatly from those of natural gases produced by the Lingfeng Formation organic matter but are very similar to those of natural gases derived from the Yueguifeng Formation organic matter, therefore, natural gases in the LS36-1 oil-gas pool are mainly derived from the Yueguifeng Formation lacustrine source rock rather than the Lingfeng Formation marine or Mingyuefeng Formation coal-measures source rocks.