The nature and fate of natural resins in the geosphere Part XI.† Ruthenium tetroxide oxidation of a mature Class Ib amber polymer‡

The results of ruthenium tetroxide (RuO₄) oxidation of a mature Class Ib amber polymer are reported and discussed. These data indicate that the residual double bond present in mature Class I ambers is not located in the A/B ring structure of these materials and that C17 of the original labdanoid precursors is retained in mature Class I ambers as a methyl group. These data also suggest that the reaction which results in formation of the residual unsaturated structure in mature ambers also results in a second covalent connection between the A/B ring system and the polymer backbone, probably through C8 of the original labdanoid structure.     

Heterogeneity of grain-size fractions of nanodiamonds from the Orgueil C1 meteorite

A model for the composition of meteoritic nanodiamonds is suggested based on analysis of the concentrations and isotopic compositions of C, N, and Xe in the nanodiamond-rich grain-size fractions, which were separated for the first time from the Orgueil CI chondrite. According to the model, meteoritic nanodiamond consists of two populations of grains (denoted C_HL and C_N). The size distributions of grains in populations in the C_HL and C_N populations are different: the C_HL population is finer grained than C_N. The grains of the C_HL population are characterized by a radial gradient in the carbon isotopic composition, and they contain implanted anomalous noble gases (HL component) and the heavy nitrogen isotope ¹⁵N. Following (Clayton et al., 1995), the probable astrophysical source of this population of nanodiamond grains is thought to be the mixing helium and hydrogen shells of a Type-II supernova, and the mechanism that produced these grains was the slow CVD process. The C_N population grains have homogeneous isotopic compositions of carbon (δ¹³C ≡–100‰) and nitrogen (δ¹⁵N ≡–400‰) and contain almost all nitrogen of the nanodiamond-rich fractions. This population of nanodiamond grains was likely formed by a fast unequilibrated process, when shock waves affected organic compounds or gas rich in C- and N-bearing compounds during the early evolution of the protosolar nebula. Calculations within the framework of the model show that the nanodiamond-rich fractions separated from the Orgueil meteorite have the C_N/C_HL ratios varying from 1 in the finest grained fraction to 10 in the coarse-grained one. At these proportions of the populations, weighted mean δ¹³C values of C_HL grains in the fractions lie within the range of 42 to 394‰, and the concentrations of ¹³²Xe-HL and ¹⁵N are (49–563) × 10^–8 cm³/gC and (1.1–6.2) × 10^–5 cm³/gC, respectively.     

A golden age for ectoparasitoids of Embiodea: Cretaceous Sclerogibbidae (Hymenoptera,Chrysidoidea) from Kachin (Myanmar), Charentes (France) and Choshi (Japan) ambers

Sclerogibbid wasps are obligate parasitoids of webspinners (Embiodea). Both groups have a particularly scarce geological record and are known since the Cretaceous: there are only four species of webspinners known from Burmese amber, and only two sclerogibbids were described from Barremian Lebanese and Cenomanian Burmese ambers. Here we report transferred genus from Aptian Choshi (Japan) amber and new sclerogibbids from Cenomanian Burmese and Charentese (France) ambers. The taxa described from Burmese amber are: Burmasclerogibba aptera gen. et sp. nov., Cretosclerogibba gen. nov. (with C. antennalis sp. nov., C. contractocollis sp. nov., C. neli sp. nov. and C. rasnitsyni sp. nov.) and Edrossia vetusta gen. et sp. nov. The first European fossil sclerogibbid Gallosclerogibba alnensis gen. et sp. nov. is described from Charentese amber. The holotype of Chosia yamadai Fujiyama, from Choshi amber, is re-described; it appears to be the oldest Laurasian sclerogibbid. The significant abundance and variety of Burmese sclerogibbid wasps (60% of fossil species known worldwide), as proxy of their hosts, were probably caused by the protection granted to them by the silk webs and possibly by the limited predation from ornithuromorph birds or crown-group ants. While all three extant sclerogibbid genera have apterous females, genera with winged females (Cretosclerogibba and Edrossia) dominated in Burmese amber. Small silk galleries from hosts may have favored the preservation of wings in females of Cretaceous sclerogibbids. Most new species described in the present paper, in addition to C. yamadai, are characterized by a very slender neck and a very long frontal process concealing the antennal toruli. These characters disappeared in extant species. We suggest that this loss was caused by a change in the fauna of predators, penalizing species with long neck and rostrum.     

应用稳定同位素示踪琥珀的产地

利用稳定同位素比值质谱仪（IRMS）对波罗的海琥珀、多米尼加琥珀、墨西哥琥珀、缅甸琥珀及不同产地的柯巴树脂的13C,D,18O稳定同位素进行了高精度测定.研究结果表明：（1）不同产地琥珀的δ13C值分布在一个较为稳定的范围内,缅甸琥珀δ13C=-19.38‰～-22.90‰,平均值为-21.15‰;波罗的海琥珀δ13C=-22.76‰～-25.76‰,平均值为-24.35‰;多米尼加琥珀δ13C=-23.57‰～-26.63‰,平均值为-24.99‰,且均值无交叉;（2）不同产地琥珀的δ13C值与琥珀形成的地质时代存在较好的线性关系.具体表征为随着天然树脂石化地质年代（琥珀化程度）的增加,13C值有规律地增大,据此可推断不同产地琥珀成熟度由高到低的相对顺序为缅甸＞波罗的海＞多米尼加、墨西哥;（3）柯巴树脂的δ13C值为-26.82‰～-29.94‰,平均为-28.55‰,比琥珀的明显贫δ13C,依据实验测试统计数据,推荐参考临界值为-27.00‰（＋0.18,-3.00）,这为界定琥珀与柯巴树脂提供了稳定同位素依据;（4）缅甸琥珀δD=-195.90‰～-244.40‰,平均为-226.00‰;波罗的海琥珀δD=-235.90‰～-270.10‰,平均为-25δ.80‰;多米尼加琥珀δD=-202.80‰～239.40‰,平均为-219.90‰;墨西哥琥珀δD=-218.90‰.不同产地琥珀中δD的同位素变异反映了环境水（大气降水）与古纬度之间的变化规律,即随着琥珀产地古纬度的增加,δD逐渐减小;（5）不同产地琥珀在13C-18O,D-18O同位素之间及13C,D,18O同位素在二维图解、三维空间中具有很好的分区性,表明碳、氢、氧稳定同位素综合分析可以示踪琥珀的产地信息.     

High-pressure phase of natural fullerene C60 in iridium-rich Cretaceous-Tertiary boundary layers of Deccan intertrappean deposits, Anjar, Kutch, India

We report here for the first time the presence of the natural, toluene-soluble C₆₀ and the toluene-insoluble high-pressure and temperature phase of fullerene C₆₀ in the carbonaceous matter extracted from the iridium-rich layers of the intertrappean sediments of Anjar, India. The toluene-insoluble form of fullerene is formed at high-temperature and pressure (HPT) and is distinguished from normal fullerene by UV-visible and Fourier-transform infrared (FT-IR) spectroscopic techniques. The C₆₀ fullerene has been identified by high-resolution electron-impact ionization mass spectrometric analysis, as well as by Fourier-transform infrared (FT-IR), UV-visible, and ¹³C-nuclear magnetic resonance (NMR) spectroscopy. In iridium-poor horizons of this section, fullerenes are absent, but complex hydrocarbons are sometimes present. The FT-IR spectroscopic studies on the insoluble fullerenes show strong absorption peaks at about 740 and 509 cm⁻¹ and a number of weak peaks at 1380, 1300, 1205, 1120, 1000, 608, 554, and 441 cm⁻¹, which are characteristic of a high-pressure and temperature C₆₀ fullerene. The UV-visible spectra of the toluene-soluble fullerene, as well as the insoluble fullerene, show strong absorption bands at 270 and 348 nm, which are characteristic of pristine fullerene C₆₀. The toluene-insoluble carbon-rich residue shows additional absorption bands at 710, 640, and 395 nm. These UV-visible bands independently confirm the presence of the high-pressure-temperature (HPT) phase of fullerene C₆₀. Conditions of high-pressure and temperature required for formation of the HPT fullerene phase can be created by an energetic impact event. Therefore, the presence of HPT fullerene in the KT boundary layer at Anjar is linked to the impact event at the KT transition.     

The dynamics of organic matter in soil size and density fractions traced by stable carbon isotopes

1IntroductionSoilorganicmatter (SOM)isakeysourceofnutrientsforplantgrowth ,itisessentialforthemaintenanceofsoilstructureanditcontributestotheabilityofsoiltoretainnutrientsandwater.AnimprovedunderstandingofSOMdynamicsiscentraltothedevelopmentofmoreenvironmentallysoundandsustainablepracticesofagriculturalmanagement (Collinsetal.,2 0 0 0 ) .Avarietyofcon ceptualmethodshavebeenusedtodescribetheprocessesofSOMaccumulationandturnover (Jen kinsonandRayner,1 977;Duxburyetal.1 989;Partonetal.,1 99…     

琥珀的激光拉曼光谱特征研究

采用激光拉曼光谱仪对波罗的海、多米尼加、缅甸三个地区的琥珀样品进行了拉曼光谱测试分析,描述了拉曼光谱的位置、形态、相对强度,分析了振动模式,同时对某些分子基团如ν（C-H）,ν（C-O）做了谱带归属。结果表明,琥珀结构中碳链骨架振动是导致其拉曼光谱形成的主要原因,同一产地不同品种琥珀的拉曼谱峰特征基本一致,不同产地琥珀的拉曼谱峰仅在个别拉曼位移处存在较小差异。另外,对前人提出的用拉曼光谱中ν（C=C）和δ（CH2）的强度比值N（I1645cm-1／I 1450cm-1）来确定天然树脂成熟度的初步设想进行了验证分析。拉曼光谱对于琥珀真伪及其产地的鉴定有一定的辅助作用,但不能作为鉴别产地的唯一指示性依据。     

琥珀优化工艺实验研究

选用俄罗斯加里宁格勒琥珀原料为优化工艺实验研究对象,以市场上常见的琥珀品种为实验目标,通过控制实验过程中的温度、压力及环境气氛,获得了金珀、血珀、金花珀、红花珀及老蜜蜡等实验产品,并探讨了琥珀优化的工艺流程、工艺条件及影响因素。研究结果说明,琥珀优化的工艺流程分为准备阶段、装炉阶段、优化阶段和开炉阶段。通过净化工艺可获得金珀产品,通过烤色工艺可获得血珀产品,通过爆花工艺可获得花珀,在常压、长时间低温加热的缓慢氧化条件下可获得老蜜蜡。总结了影响琥珀优化工艺的因素,包括其原料的颜色、透明度、块度、温压条件、环境气氛等。     

Cyclic terpenoids of contemporary resinous plant detritus and of fossil woods, ambers and coals

Cyclic terpenoids present in the solvent extractable material of fossil woods, ambers and brown coals have been analyzed. The sample series chosen consisted of wood remains preserved in Holocene to Jurassic sediments and a set of of ambers from the Philippines (copalite), Israel, Canada and Dominican Republic. The brown coals selected were from the Fortuna Garsdorf Mine and Miocene formations on Fiji.The fossil wood extracts contained dominant diterpenoid or sesquiterpenoid skeletons, and aromatized species were present at high concentrations, with a major amount of two-ring aromatic compounds. Tricyclic diterpenoids were the predominant compounds in the ambers. Aromatized derivatives were the major components, consisting of one or two aromatic ring species with the abietane and occasionally pimarane skeletons. The saturated structures were comprised primarily of the abietane and pimarane skeletons having from three to five carbon (C₁, C₂, etc.) substituents. Kaurane and phyllocladane isomers were present in only minor amounts. Bicyclic sesquiterpenoids as saturated and partial or fully aromatized forms were also common in these samples, but only traces of sesterterpenoids and triterpenoid derivatives were found.The brown coal extracts were composed of major amounts of one- and two-ring aromatized terpenoids, with a greater proportion of triterpenoid derivatives than in the case of the woods and ambers. This was especially noticeable for the German coal, where the triterpenoids were predominant. Open C-ring aromatized structures were also present in this coal. Steroid compounds were not detectable, but some hopanes were found as minor components in the German brown coal.An overview of the skeletal structure classes identified in each sample, as well as the general mass spectrometric characteristics of the unknown compounds are included in the present paper. It can be concluded from these structural distributions that aromatization is the main process for the transformation of terrestrial cyclic terpenoids during diagenesis, constituting a general pathway for all terpenoids.     

鉴定热处理琥珀的关键证据

在琥珀热处理实验研究的基础上,采用常规宝石学方法和红外光谱仪,测试并跟踪收集和对比分析了实验样品热处理前、后的宝石学参数和红外光谱的变化规律及琥珀内含物的演化、改造与破坏标识,并对获得的琥珀热处理效果进行了成因分析,从而总结出鉴定琥珀热处理的关键证据。研究结果表明：（1）折射率的增加、荧光的弱化或湮灭是热处理琥珀的重要佐证;（2）盘状裂隙、红色流纹、汽化纹、龟裂纹和氧化裂纹是热处理琥珀的重要标识;（3）FTIR光谱中I=2930cm-1/I=1735cm-1比值若≤1,可视为热处理琥珀的红外光谱指纹检测依据;（4）1735,1700cm-1处的羰基（C？O）伸缩振动与1260～1156cm-1处的C—O伸缩振动吸收强度的明显增强及多峰合并的趋势反映出热处理琥珀表面的热氧化反应;C？O浓度的增加可能是热处理琥珀红色的生色团,同时又是热处理琥珀荧光的淬灭剂。     

多米尼加与墨西哥蓝珀光致发光-拉曼光谱及微量元素赋存特征研究

蓝珀主要产于多米尼加共和国、墨西哥与缅甸,其形成机制、组成成分及光谱特征与之特定的产出地理环境有密切的关联.因此,蓝珀的产地研究成为当前珠宝玉石、考古及生物矿物学研究领域的热点课题.前人主要应用红外光谱、X射线荧光光谱、质谱、同位素示踪等技术开展了较系统的蓝珀产地的溯源研究,但限于蓝珀材质的类同,不同产地蓝珀的光谱学等...     

不同产地琥珀有机元素组成及光谱学特征

利用Elementar vario PYRO cube 型元素分析仪器对不同产地琥珀中的元素质量分数完成了高精度测试,分析不同产地琥珀的构成变化规律,并利用IRAffinity-1型傅立叶变换红外光谱仪采用透射法对不同产地琥珀的吸收光谱进行了比较和分析,结果表明石化时琥珀中氢元素和周围环境氢元素并未发生比较明显的交换反应,红外吸收光谱可作为鉴别不同产地琥珀的重要依据.     

The nature and fate of natural resins in the geosphere XIII: a probable pinaceous resin from the early Cretaceous (Barremian), Isle of Wight

Terpenoid resin is produced by all families and most genera of the order Coniferales (the conifers), and the distribution of terpenes present in most conifer resins is characteristic of the originating family. Analyses of early Cretaceous (Barremian) amber (fossil resin) from the English Wealden, Isle of Wight, southern England, by pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS), indicate a terpene distribution dominated by abietane- and labdane-type terpenes. Similar distributions are observed in some species of the extant family Pinaceae. The Pinaceae are well represented within the Wealden deposits of southern England, by only one (known) species, Pityites solmsii (Seward) Seward, whereas the macro-fossil record of these deposits is dominated by the extinct conifer family Cheirolepidiaceae, for which no resin chemistry has been reported. By analogy with modern materials, it is probable that the ambers found in these deposits are derived from an extinct member of the Pinaceae, but given the absence of evidence concerning the chemotaxonomy of the Cheirolepidiaceae, this family cannot be excluded a priori as a possible paleobotanical source. These ambers may therefore be assigned to either the Pinaceae or to the Cheirolepidiaceae. These samples are the oldest ambers to date to yield useful chemotaxonomic data.     

Biting midges of the extinct genus Protoculicoides Boesel from Lower Cretaceous amber of San Just,Spain and new synonymy in recently described fossil genera (Diptera: Ceratopogonidae)

We describe two new species of extinct biting midges in the fossil genus Protoculicoides: Protoculicoides hispanicus Szadziewski and Arillo, sp. nov. and Protoculicodes sanjusti Szadziewski and Arillo, sp. nov., from Albian (101–113 Ma) amber of San Just, Spain. Atriculicoides Remm, 1976 is recognized as a new junior synonym of Protoculicoides Boesel, 1937 (NEW SYNONYM). Devalquia Choufani et al., 2013 is regarded here as a new junior synonym of the extant genus Culicoides Latreille, 1809 (NEW SYNONYM). Metahelea roggeroi Choufani et al., 2013 from Upper Cretaceous French amber, is excluded from the tribe Heteromyiini and placed in the extant genus Stilobezzia Kieffer, 1911, tribe Ceratopogonini: Stilobezzia roggeroi (Choufani et al., 2013), comb. nov. The extinct tribe Atriculicoidini Szadziewski, 1996 is regarded as a new subfamily, Atriculicoidinae, stat. nov., that includes the fossil genus Protoculicoides, with 13 species reported from Albian, Turonian, Cenomanian, Coniacian, Santonian and Campanian ambers (78–113 Ma). Protoculicoides skalskii Szadziewski & Arillo, 1998 from Lower Cretaceous amber of Álava, Spain, Protoculicoides succineus Szadziewski, 1966 from Lower Cretaceous Lebanese amber and Protoculicoides burmiticus Szadziewski & Poinar, 2005 from Upper Cretaceous Burmese amber are transferred to the extinct genus Archiculicoides Szadziewski, 1996, comb. nov. Protoculicoides krzeminskii Choufani et al., 2014 from Lower Cretaceous Lebanese amber is transferred to the extinct genus Archiaustroconops Szadziewski, 1996, comb. nov. The Cretaceous subfamily Atriculicoidinae forms an unresolved trichotomy with the extant subfamilies Forcipomyiinae and Dasyheleinae, both of which date to the Eocene. The fossil record indicates that wings with macrotrichia in biting midges evolved during the mid-Cretaceous greenhouse climate. We suggest that this was an evolutionary adaptation to new atmospheric conditions with higher levels of CO₂ in order for the antennal Johnston's organs of males to receive the vibrational sex signals produced by females during flight.     

Colloidal and polymeric nature of fossil amber

Fossilized ambers from several geographical origins, copal from the Kauri pine tree of New Zealand and modern white spruce tree resin have been analyzed by the following analytical techniques: dynamic light scattering, optical and scanning electron microscopy, gel permeation chromatography, IR spectroscopy, rheology and viscometry. The results dispute the prevailing view that amber is largely an insoluble, continuously crosslinked, integral polymer network. Rather, the data indicate that a large portion of amber consists of insoluble though solvent-swellable colloidal particles, ranging from submicron to multimicron in size, which can be dispersed in organic solvents such as N,N-dimethyl-formamide. The presence of colloidal particles in fossil amber, copal and even fresh resin suggests a mechanism for resin exudation involving the presence or formation of discrete ‘packets’ of resin, where the surface of each packet has been modified by the interaction with oxygen and water.     

New species of fossil oribatid mites (Acariformes,Oribatida), from the Lower Cretaceous amber of Spain

Mites are relatively common and diverse in fossiliferous ambers, but remain essentially unstudied. Here, we report on five new oribatid fossil species from Lower Cretaceous Spanish amber, including representatives of three superfamilies, and five families of the Oribatida. Hypovertex hispanicus sp. nov. and Tenuelamellarea estefaniae sp. nov. are described from amber pieces discovered in the San Just outcrop (Teruel Province). This is the first time fossil oribatid mites have been discovered in the El Soplao outcrop (Cantabria Province) and, here, we describe the following new species: Afronothrus ornosae sp. nov., Nothrus vazquezae sp. nov., and Platyliodes sellnicki sp. nov. The taxa are discussed in relation to other fossil lineages of Oribatida as well as in relation to their modern counterparts. Some of the inclusions were imaged using confocal laser scanning microscopy, demonstrating the potential of this technique for studying fossil mites in amber. A table, including all the known Mesozoic oribatid mites preserved in amber, is included.     

Terpenoid composition and origin of amber from the Cape York Peninsula,Australia

The terpenoid composition of fossil resin from the Cape York Peninsula, Australia has been analysed by pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) to determine its origin. The pyrolysis products were dominated by cadalene-based C₁₅ bicyclic sesquiterpenoids including some C₃₀–C₃₁ bicadinanes and bicadinenes typical of Class II resin derived from angiosperm plants of Dipterocarpaceae. This observation contrasts with the Araucariaceae (Agathis sp.) source previously suggested for the resin based on Fourier transform infrared (FTIR) analyses. Dipterocarpaceae are not known in Australian vegetation but grow abundantly in Southeast Asia including New Guinea, indicating that the geological origin of the amber is not the Australian mainland but could be traced to Southeast Asia.     

Structural features of humic acids from a sedimentary sequence in the Guadiana estuary (Portugal–Spain border)

The structural characteristics of humic acids (HAs) from two different depths of a sedimentary sequence representing the last 13 kyr in the valley of Guadiana river estuary (SW Portugal/Spain border) have been approached using a combination of spectroscopic techniques, wet chemical degradation methods (sequential oxidation with sodium persulfate followed by KMnO₄, and oxidation with RuO₄) and analytical pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) in the presence and absence of tetramethylammonium hydroxyde (TMAH). The aim was to obtain complementary information on the sources and alteration of the organic matter (OM) provided by a previous study on the vertical distribution of terrestrial and phytoplankton biogeochemical markers in the sequence. Both the FT-IR (Fourier transformed infrared) and ¹³C NMR (nuclear magnetic resonance) spectra showed a close similarity with the structural characteristics of the HA samples. NMR signals in the alkyl region (0–45 ppm) as well as FT-IR band patterns typical for methoxyl-substituted aromatic rings pointed to the presence of an important aliphatic domain, as well as to lignin-derived compounds. This finding was confirmed using analytical pyrolysis. In addition, the main TMAH thermochemolysis products were typical lignin-derived methoxyphenols with both guaicyl and syringyl nuclei. The detection of methoxyphenol units with three to six carbon atom (C₃–C₆) side chains suggests that lignin and possibly suberin were only partially degraded. Compounds arising from proteins and polysaccharides were also detected, although in lesser and varying amount. The major products from persulfate oxidation were series of n-alkanes (C₁₆–C₃₃ with clear odd/even predominance) and n-fatty acids, both saturated (C₁₀–C₂₆ with strong even/odd predominance) and unsaturated, which may arise from the above aliphatic biomacromolecules. The major products from permanganate oxidation of the persulfate residue were α,ω-diacids (C₆–C₁₁) originating from oxidation of the ether bonds linking the building blocks constituting the core of the HA structure. Aromatic compounds (phenols, methoxy-dimethoxybenzene carboxylic acid and benzene di-, tri-, tetra- and pentacarboxylic acids), most probably derived from the aromatic backbone of the HAs, that may also include lignin moieties as well as other polyphenols (flavonoids and tannins) were also detected. The RuO₄ oxidation also released series of n-alkanes (C₁₆–C₃₃), linear saturated fatty acids (C₁₀–C₂₈) and α,ω-diacids (C₇–C₂₅), as well as traces of benzene polycarboxylic acids. Regarding the usefulness of the various techniques used, they provide complementary information. Indeed, spectroscopic techniques and analytical pyrolysis provide information on the backbone of the HAs, and on their origin, whereas the oxidative degradations provide different information on the structural features of the HA, particularly the nature of the linking between the building blocks. In general, the data support the idea that the HAs still contain information about the signature of aliphatic and aromatic biomacromolecules contributing to the OM deposited. The presence of lignin-derived residues suggests a large input from terrestrial carbon throughout the core.     

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

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.     

Paleoceanographic Indicators for Early Cambrian Black Shales from the Yangtze Platform,South China: Evidence from Biomarkers and Carbon Isotopes

The lower Cambrian Niutitang Formation, a widespread black shale deposition, is of geological interest because of its polymetallic beds, Cambrian explosion, depositional ages, dramatic environmental changes and so on. Previous study focused mainly on inorganic geochemistry and few studies have investigated the organic fractions of upper Neoproterozoic-lower Cambrian strata in South China. Here we report a study of biomarkers plus organic carbon isotopes for black shales from Ganziping, Hunan Province (China). All the saturated hydrocarbon fractions have a unimodal distribution of n-alkanes, a high content of short-chain alkanes and maximize at C 19 or C 20 (C 23 for sample Gzh00-1). The C 27 /C 29 sterane ratio ranges from 0.77 to 1.20 and 4-methylsteranes are in low abundance. These parameters indicate that algae and bacteria are the important primary producers. Furthermore, biomarker maturity proxies show the samples to be higher maturity. The low Pr/Ph values (<0.7) suggest that the samples were deposited under anoxic conditions and, likely, under stratified water columns. In addition, 25-norhopanes and gammacerane are present as diagnostic indicators of normal marine salinity and dysoxic to anoxic conditions. During the Early Tommotian, known to coincide with a transgression event, small shelly fossils increased in abundance and diversity. Moreover, positive δ 13 C org excursions close to 1.4‰ occur at the base of the Tommotian stage. In summary, the Early Cambrian black shales were deposited under dramatic paleoenvironmental changes, including oceanic anoxia, higher primary productivity and sea-level rise.