The effect of tissue structure and soil chemistry on trace element uptake in fossils

Trace element profiles for common divalent cations (Sr, Zn, Ba), rare-earth elements (REE), Y, U, and Th were measured in fossil bones and teeth from the c. 25 ka Merrell locality, Montana, USA, by using laser-ablation ICP-MS. Multiple traverses in teeth were transformed into 2-D trace element maps for visualizing structural influences on trace element uptake. Trace element compositions of different soils from the fossil site were also analyzed by solution ICP-MS, employing progressive leaches that included distilled H₂O, 0.1 M acetic acid, and microwave digestion in concentrated HCl-HNO₃. In teeth, trace element uptake in enamel is 2-4 orders of magnitude slower than in dentine, forming an effective trace element barrier. Uptake in dentine parallel to the dentine-enamel interface is enhanced by at least 2 orders of magnitude compared to transverse, causing trace element “plumes” down the tooth core. In bone, U, Ba and Sr are nearly homogeneous, implying diffusivities ∼5 orders of magnitude faster than in enamel and virtually complete equilibration with host soils. In contrast all REE show strong depletions inward, with stepwise linear segments in log-normal or inverse complementary error function plots; these data require a multi-medium diffusion model, with about 2 orders of magnitude difference in slowest vs. fastest diffusivities. Differences in REE diffusivities in bone (slow) vs. dentine (fast) reflect different partition coefficients (K_d’s). Although acid leaches and bulk digestion of soils yield comparable fossil-soil K_d’s among different elements, natural solutions are expected to be neutral to slightly basic. Distilled H₂O leachates instead reveal radically different K_d’s in bone for REE than for U-Sr-Ba, suggest orders of magnitude lower effective diffusivities for REE, and readily explain steep vs. flat profiles for REE vs. U-Sr-Ba, respectively. Differences among REE K_d’s and diffusivities may explain inward changes in Ce anomalies. Acid washes and bulk soil compositions yield misleading K_d’s for many trace elements, especially the REE, and H₂O-leaches are preferred. Patterns of trace element distributions indicate diagenetic alteration at all scales, including enamel, and challenge the use of trace elements in paleodietary studies.     

Diagenetic cycling of trace elements in the bottom sediments of the Swan River Estuary,Western Australia

Teflon strips were used in-situ in the bottom sediments at two sites in the Swan River Estuary to collect diagenetic Fe–Mn oxyhydroxides and monitor monthly changes in their morphology and trace element geochemistry. This study demonstrates that substantial concentrations of trace elements accumulate at the redox front during the formation of diagenetic Fe–Mn oxyhydroxides. It is likely that the Fe–Mn oxyhydroxides initially nucleate and grow on the Teflon strips via bacterial activity. Trace element geochemistry of the diagenetic Fe–Mn oxyhydroxides is influenced by changes in the supply of trace elements from either the bottom sediments and/or water column or changes in the physico-chemical status of bottom and porewaters. If sufficient diagenetic Fe–Mn oxyhydroxides are preserved in the upper layer(s) of the bottom sediment it is possible that diagenetic (secondary) trace element enrichment profiles may be produced which modify the historical input of natural or anthropogenic trace element sources. Alternatively, partial or complete dissolution of the diagenetic Fe–Mn oxyhydroxides in response to temporal changes in the redox status of the bottom sediment may lead to a substantial underestimate of trace element fluxes in historical bottom sediment profiles. This study highlights that considerable care must be taken when interpreting short- to long-term geochemical profiles in bottom sediments due to the possible occurrence of rapid, seasonally mediated diagenetic processes.     

甘肃北山白山堂铜矿外围找矿靶区地球化学评价方法示范

在甘肃北山白山堂铜矿及其外围,以1:20万营盘幅区域化探数据为基础,探讨了综合利用富集贫化两类指标形成的正、负异常圈定找矿靶区并进行靶区评价的可行性示范研究。结果表明,在1:20万区域尺度上,已知白山堂铜矿产出位置出现了成矿元素(Cu)及伴生元素(Zn、Au、Ag、As、Sb、Mo)、常量组分(Fe2O3、MgO)的正异常和亲石分散元素(Ba、Sr)、常量组分(Al2O3、Na2O)的负异常,构成白山堂铜矿整体异常结构模式。以是否出现异常结构模式为标准,利用岩石裂隙充填物测量或岩屑测量结果,对白山堂铜矿外围出现的地球化学异常成矿前景进行了评价。根据示范研究结果认为,利用异常结构模式进行找矿靶区评价是行之有效的,较单纯利用成矿元素及伴生元素异常进行靶区评价证据更系统、充分。     

浙江省恶性肿瘤的环境地球化学研究

利用区域地球化学资料开展浙江省恶性肿瘤的地球化学环境影响因素研究.恶性肿瘤标化死亡率受地球化学综合因素影响,应用微量元素对各类恶性肿瘤标化死亡率的相关阵和逐步回归方程定量地研究各类恶性肿瘤与地质环境中微量元素的关系.胃癌、肝癌、肺癌、肠癌、食管癌、白血病与铁族元素及Ba、Zr、Mo的背景密切相关,宫颈癌、鼻咽癌、乳腺癌与Cu、Pb、zn元素的背景相关,稀土元素对恶性肿瘤有压抑作用.浙江省恶性肿瘤的流行受区域地质构造控制和地球化学环境制约,具明显的地域性分布特征.     

Nd and Sr isotope compositions in modern and fossil bones - Proxies for vertebrate provenance and taphonomy

Rare earth elements (REE), while not essential for the physiologic functions of animals, are ingested and incorporated in ppb concentrations in bones and teeth. Nd isotope compositions of modern bones of animals from isotopically distinct habitats demonstrate that the ¹⁴³Nd/¹⁴⁴Nd of the apatite can be used as a fingerprint for bedrock geology or ambient water mass. This potentially allows the provenance and migration of extant vertebrates to be traced, similar to the use of Sr isotopes. Although REE may be enriched by up to 5 orders of magnitude during diagenesis and recrystallization of bone apatite, in vivo¹⁴³Nd/¹⁴⁴Nd may be preserved in the inner cortex of fossil bones or enamel. However, tracking the provenance of ancient or extinct vertebrates is possible only for well-preserved archeological and paleontological skeletal remains with in vivo-like Nd contents at the ppb-level. Intra-bone and -tooth REE analysis can be used to screen for appropriate areas. Large intra-bone Nd concentration gradients of 10¹-10³ are often measured. Nd concentrations in the inner bone cortex increase over timescales of millions of years, while bone rims may be enriched over millenial timescales. Nevertheless, ε_Nd values are often similar within one ε_Nd unit within a single bone. Larger intra-bone differences in specimens may either reflect a partial preservation of in vivo values or changing ε_Nd values of the diagenetic fluid during fossilization. However, most fossil specimens and the outer rims of bones will record taphonomic ¹⁴³Nd/¹⁴⁴Nd incorporated post mortem during diagenesis. Unlike REE patterns, ¹⁴³Nd/¹⁴⁴Nd are not biased by fractionation processes during REE-uptake into the apatite crystal lattice, hence the ε_Nd value is an important tracer for taphonomy and reworking. Bones and teeth from autochthonous fossil assemblages have small variations of ±1 ε_Nd unit only. In contrast, fossil bones and teeth from over 20 different marine and terrestrial fossil sites have a total range of ε_Nd values from -13.0 to 4.9 (n = 80), often matching the composition of the embedding sediment. This implies that the surrounding sediment is the source of Nd in the fossil bones and that the specimens of this study seem not to have been reworked. Differences in ε_Nd values between skeletal remains and embedding sediment may either indicate reworking of fossils and/or a REE-uptake from a diagenetic fluid with non-sediment derived ε_Nd values. The latter often applies to fossil shark teeth, which may preserve paleo-seawater values. Complementary to ε_Nd values, ⁸⁷Sr/⁸⁶Sr can help to further constrain the fossil provenance and reworking.     

鄂尔多斯盆地东南缘延长组石油充注对砂岩储层成岩演化的影响

综合运用岩石学、矿物学和地球化学方法,对石油充注鄂尔多斯盆地东南缘三叠系延长组砂岩储层后的成岩反应系 统进行了研究,揭示了石油充注对储层成岩环境的改变在一定程度上影响了本区储层成岩作用的演化。研究表明,该区延 长组长石砂岩储层在石油充注后有机酸和CO2大量出现,pH值降低,促进了岩石骨架颗粒长石的溶解,导致了次生孔隙的发 育,增强了储层的储集性能,但未能增加石英的溶解度;但是由于含油饱和度偏低,石油的充注使成岩环境的变化仅在很 小程度上抑制伊利石的生长,并没有完全阻止伊利石的生长,伊利石“搭桥”胶结孔隙,一定程度上降低了储层的储集性 能;同时石油的充注也使成岩早期形成的碳酸盐胶结物出现溶解,当成岩温度>100℃时,有机质热演化产生较高的CO2分 压,缓冲了pH值使含铁碳酸盐大量沉淀从而使储层致密化。石油充注对储层的这些影响对下一步的储层评价提供了重要依 据。     

Timescales and mechanisms of REE and Hf uptake in fossil bones

Rare earth element (REE) patterns of fossil bones and teeth are widely used as proxies for provenance, taphonomy, and palaeoenvironment. In order to investigate if fossil bones behave as closed systems over geologic time, REE profiles were analysed by LA-ICPMS along cross sections of 54 bones from various well-characterised and well-dated settings. These include terrestrial and marine diagenetic environments, covering Early Triassic to Holocene ages. In general, all fossil bones exhibit the highest REE concentrations at the outer rim, gradually decreasing by up to four orders of magnitude toward the inner bone cortex. Intra-bone REE concentration gradients decrease significantly from Quaternary via Tertiary to Mesozoic specimens, suggesting long term REE uptake and open system behaviour of fossil bone. This view is further corroborated by ¹⁷⁶Lu-¹⁷⁶Hf dating of selected samples, all yielding significantly younger ages than the known chronostratigraphic ages. Hence, there is clear evidence for long term open system behaviour of fossil bones with respect to REE, which is in marked contrast to currently accepted models suggesting that REE uptake is only early diagenetic. Although unexpected, statistically significant four to seven point isochrons are observed for four fossil dinosaur bone samples and one Upper Triassic Mastodonsaurus tooth with MSWDs ranging from 0.083 to 4.5. Notably, mobility of Lu alone cannot account for the observed age patterns. Assuming constant Lu uptake rates over time, the radiometric ages should only be as low as half of the chronostratigraphic age. However, a six-point isochron defined by subsamples of a single Upper Triassic Mastodonsaurus tooth yields an age of 65.2 ± 1.1 Ma (MSWD = 0.68), much younger than half of the stratigraphic age (ca. 234 Ma). Hence, Hf must also undergo late diagenetic exchange. Likely mechanisms to account for the presence of statistically meaningful isochrons as well as for the late diagenetic exchange of both REE and Hf are diffusion, adsorption, and dissolution-reprecipitation processes.     

四川峨眉山地区二叠系与三叠系界线微量元素地球化学研究

通过对峨眉山地区地层剖面的实地观察和测量,采集界线附近的粘土岩,分析了该区微量元素地球化学的组成特征,并通过对稀土元素标准化图解和其它微量元素的研究,利用微量元素的示踪作用以及微量元素地球化学异常,初步探讨了界线粘土岩的来源,为全球二叠一三叠界线研究工作提供依据。     

Geochemistry and Sedimentology of Jhill Limestone of Gaj Formation,in Cape Monze and Adjoining Area,Karachi

Among several lithostratigraphic subdivisions of the Gaj Formation of Miocene age, the Jhill limestone is entirely different with respect to its colour, texture and structures. This limestone unit has been evaluated to elaborate its geochemical and sedimentological characteristics. The distribution of various elements in the acid-soluble fraction has been studied in order to determine their mineralogy, sedimentary environment, facies and diagenesis. Mineralogy, recrystallization and other diagenetic changes are the main factors affecting the distribution of trace elements and their mutual relationships in the limestones. Samples of the Jhill limestone show depletion in large-sized ions (Sr, Pb & K) and also in the ions that are not compatible with calcite space group. Elements (Fe, Mn, Zn, Cu & Co) having distribution coefficient (D) above unity for natural calcites, are more enriched. Microscopic and X-ray studies revealed nearly complete conversion of aragonite into stable low-Mg calcite. An attempt has also been made to verify the reefal conditions for these limestones on the basis of geochemical studies. The plots of Sr and other facies-indicator elements show that the majority of the beds belong to forereef flank facies with some algal banks. Low Mg/Ca and Sr/Ca ratios suggest that a phreatic diagenetic environment prevailed after the deposition. High concentrations of Cr, Ni, and Co in the Jhill limestone show a positive correlation with a higher amount of insoluble residue, which reflects a relatively high rate of influx of terrigenous material.     

滇黔北坳陷寒武系碳酸盐岩古海洋环境特征及地质意义

为厘定滇黔北坳陷寒武系碳酸盐岩古海洋环境,揭示成岩流体与岩溶作用的潜在联系,并预测有利储层发育层段,基于镇雄羊场碳酸盐岩剖面实测及系统取样基础上,采用微量元素、碳氧锶同位素及铸体薄片等分析手段,地球化学与岩石学方法相结合,探讨碳酸盐岩古海洋环境及地质意义。研究结果表明:滇黔北坳陷寒武系清虚洞组-娄山关组整体为海相环境,古海洋温度处于12.82℃~32.84℃之间,主体为温暖或炎热的亚热带气候。海平面具有主体震荡下降的趋势,存在8期海平面变化旋回,发育对应的岩相组合,其同位素演化曲线可作为地层划分依据。微量元素、同位素地球化学及岩石学特征证实娄山关组岩溶作用相对发育,成岩流体混入强氧化性低温大气水,有利储层纵向上主要分布在海平面下降旋回的高部位。     

In Praise of Phosphates,or Why Vertebrates Chose Apatite to Mineralize Their Skeletal Elements

The geochemical abundance of phosphorus belies its importance as phosphate to life forms. As we explore the roles of microorganisms and humans in biogeochemical cycles, we are also enhancing our understandings of the phosphate control and the continuum that to a biomineralogist begins and ends in apatite. Well-crystallized apatite is utilized in geochemical studies for dating geologic events, and apatitic materials, such as marine phosphate deposits, contribute to the construction of the global phosphate cycle. The apatitic mineral in bones and teeth is a reservoir of information on diet, climate, and the environment. A unique group of samples that integrate biogeochemical information, the detailed chemical investigations of teeth and bone, are now utilized to investigate geochemical events and environments, but they also are sources of information in medical diagnosis and treatment. As we question the mechanisms of disease induction and hazards, both natural and anthropologically created or induced on a global scale over time, the record is being preserved in apatitic mineralized tissues.     

Geochemical migration of impurity trace elements and resultant fractal distribution patterns in source rocks

The migration of trace elements from the inner part of solid cells to the weaknesses is the bottleneck in the migration of these elements from their initial positions in the source rock to the final deposition site in ore bodies. Diffusion may play a key role in the reactivation of trace elements. The overall migration pattern of trace elements in source rocks is a fractal structure. There are two general tendencies for trace elements to migrate. One is from within solid cells toward sinks, and the other is from high temperature fields toward low temperature ones. High temperature enhances these two tendencies. Conjugate geochemical anomalies are the inevitable result of a closed geochemical system.     

鄂尔多斯盆地东北部纳岭沟铀矿床元素地球化学特征及其地质意义

纳岭沟铀矿床位于鄂尔多斯盆地北部,是我国目前已发现的可地浸砂岩型铀矿床之一。其受古层间氧化带控制,呈板状产于中侏罗统直罗组下段辫状河砂体中。笔者从元素地球化学分析入手,通过对不同蚀变砂岩的地球化学特征进行对比,认为蚀变砂岩主要化学成分的变化受成岩作用、水-岩作用,以及油气二次还原作用等影响,并且有机碳含量在矿化砂岩中较高,说明铀矿化与有机质关系密切。矿化砂岩中的微量元素相对富集或亏损明显,可能与成岩后期(热液)的改造作用有关。蚀变砂岩均表现出壳型花岗岩的微量和稀土元素特征,LREE相对富集,说明盆地北部的阴山、大青山古陆壳富铀花岗岩体是直罗组的主要物源。此外,δEu和δCe特征也表明纳岭沟铀矿床是在弱氧化-弱还原过渡性环境下形成。这些特征可作为找矿勘探的重要指示或标志。     

Application of multivariate statistical analysis and a geographic information system to trace element contamination in the Chungnam Coal Mine area,Korea

In order to examine contamination in the Chungnam Coal Mine area, rock, stream sediment and water samples were collected and analyzed for trace elements. In order to compile the drainage-based geochemical maps, catchment basins were calculated using aspects of DEM (data elevation model) and stream-line segments. The constructed DEMs with 3 types of resolution were examined, these need to be properly used for well-shaped and accurate catchment basins. The stream-line segments and sampling points were also considered as a target image for watershed segments and it was found that the stream-line segments as target images were better role at reflecting the catchment area rather than the sampling points. It is important that the geochemical databases were manipulated to present the various phenomena. Factor analysis in R-mode was used to integrate geochemical data, and the input data for factor analysis were the concentrations of 12 trace elements in stream sediment and 3 anion concentrations and pH values in stream water. Using a maximum likelihood scheme, eigenvalues that explained about 90% of total variance were established and 4 factors were selected. Factors 1 and 2 indicated relative enrichment of trace elements, factor 3 was explained by human activities of residents and factor 4 was related to the pH of stream water. The drainage-based geochemical maps with 4 kinds of factor scores were compiled.     

湖北郧西黄龙洞骨化石表面改造痕迹研究

湖北黄龙洞遗址出土有距今约10万年的7枚晚期智人牙齿化石,以及大量哺乳动物化石,并发掘出石制品和骨制品等。本研究使用光学显微镜、超景深数码显微镜以及三维扫描仪等对该遗址骨化石表面具有明显改造痕迹的标本进行形态学观察,并参考国内外关于标本表面改造痕迹的认识,对痕迹性质(种类)进行鉴定。然后以鉴定工作为基础,对痕迹在骨骼表面的分布组合特征进行量化分析。痕迹研究结果支持了发掘者此前提出的关于黄龙洞骨骼堆积属于原地埋藏的研究结论,并表明:黄龙洞内古人类的狩猎与屠宰等活动,是造成洞穴内骨骼堆积的主要原因;当时古人类可能在居址附近猎获动物后,将动物集中到洞穴内进行过较细致的屠宰。居住在黄龙洞的古人类屠宰技术行为主要有:切割、刮切、砍斫和砸击等。大多数切割痕迹主要是为了剥取肉食,部分位于骨骺端的切割痕迹以及砍斫痕迹是肢解行为的结果,而砸击痕迹则与取食骨髓以及骨器制作的行为有关。与人工痕迹同时出现的动物改造痕迹还反映出食肉动物和啮齿动物对人类遗留在洞穴内的骨骼有一定程度的再利用。     

Combined statistical and petrological analysis of provenance and diagenetic history of mudrocks: Application to Alpine Tethydes shales (Sicily,Italy)

Mineralogical (X-ray diffraction) and geochemical (X-ray fluorescence) compositional data of Alpine Tethyde mudrocks from Sicily were used to unravel the interplay of provenance and diagenesis by means of multivariate statistical methods (PCA, discriminant function analysis) designed for non-negative constant-sum data. The Sicilian Alpine Tethydes comprise Cretaceous–Eocene scaly shales (Mt. Soro and Upper Scagliose Shales Units), Eocene–Oligocene variegated shales (Troina and Nicosia Units), and Miocene Numidian shales (Nicosia Unit). The use of biplots of clr-transformed variables allows discrimination of two different groups of shales. High CIA values reveal a strongly weathered source area especially for the Numidian shales. The analyses of mixed-layered clay minerals indicate that the behaviour of K2O and geochemical affine elements is controlled by the diagenetic grade, which increases from south-west to north-east in response to tectonic loading. Ratios of selected elements (Zr, Y, La, Nb, Ti, Co, Cr, Ni), considered essentially unchanged with respect to the source rocks, are similar in the scaly and variegated shales, and resemble the Variscan Peloritani metamorphic basement. In contrast, the distinct geochemical signature of the Numidian shales reveals a source similar to the average cratonic sandstone, suggesting derivation from external sources located in the foreland. Multivariate discriminant analysis performed on selected trace elements confirms the previous suggestions.     

龙门山地区早泥盆世古海洋环境——来自腕足类壳体的地球化学证据

四川龙门山地区泥盆系是解决我国华南区与西北区及国外泥盆系对比的纽带,也是全球古生代气候变化对比研究的一个重要地区。但该地区早泥盆世古海洋环境研究一直缺乏同位素地球化学方面的证据,影响到该地区泥盆纪地球化学记录与世界其他地区的对比,进而影响全球范围内的古生代气候变化对比研究。针对这一问题,我们通过龙门山地区早泥盆世保存完好的腕足化石稳定同位素地球化学研究,对该地区早泥盆世海洋的古地理环境特征进行了探讨。保存鉴定结果显示:腕足化石壳体结构保存完整;阴极射线照射下壳体不发光或部分壳体呈微弱橙黄色;大多数壳体微量元素Mn < 250 μg/g、Sr > 400 μg/g。表明腕足化石保存完好,后期成岩作用影响微弱。同位素结果揭示龙门山地区δ18O值在-4.5‰ ~ -9.9‰(PDB下同)之间,明显低于该时期世界其他相同纬度地区的δ18O值 (-1.7‰ ~ -6.9‰);微量元素Fe、Mn含量变化与氧同位素组成变化呈反相关系。这说明龙门山海域当时处于海水同开阔海水交流不畅,海水化学成分受陆源淡水注入控制。这一发现从同位素地球化学角度对龙门山古海洋环境做出了判别,为龙门山地区同位素及微量元素研究在世界范围内进行短尺度对比提供依据。     

Positive Eu anomaly development during diagenesis of the K/T boundary ejecta layer in the Agost section (SE Spain): implications for trace-element remobilization

K/T boundary geochemical anomalies have been used previously to support the impact event at the end of the Cretaceous. However, impact models and assessment of the extraterrestrial contribution to the boundary sediments should also consider the diagenetic alteration of the impact signatures. Mineralogical and geochemical studies centring on redox proxies reveal differences in trace-element concentrations at Agost and Caravaca (SE Spain), two of the most complete K/T boundary sections. These differences probably derive from variations in the diagenetic evolution of the ejecta layer. Several redox proxies, such as extensive pyrite formation, high authigenic uranium concentration and positive Eu anomalies, indicate very strong reducing conditions at Agost. Positive Eu anomalies are extremely unusual in sediments, and in this case are interpreted to indicate a highly reducing environment. In such conditions, certain trace elements such as Ir, may have been remobilized, thereby masking the original signature of the impact.     

Taphonomic analysis of small mammal bone remains preyed upon by wildcats (Carnivora: Felidae) from the central Monte Desert (Mendoza,Argentina)

The present study analysed the taphonomic characteristics of small mammal bone accumulations produced by small felids in an area from the central Monte Desert (Mendoza, Argentina). In order to provide criteria to identify the role that these predators had in the formation of zooarchaeological assemblages, the anatomical representation, bone breakage patterns and degrees of digestive corrosion were evaluated. The main taphonomic results are: low average values for the relative abundance of skeletal elements; greater representation of mandibles, maxillae, isolated incisors, humeri and femora than the remaining elements; preponderance of cranial elements with high proportion of isolated teeth; elevated frequencies of proximal limb bones compared with distal parts; high degree of breakage in all skeletal elements and digestive corrosion on almost all diagnostic bones (mainly moderate and heavy). The values of the studied taphonomic variables indicate that small felids in this area made severe alterations to the bones of their prey (mainly rodents), attributable to the category of extreme modifier, while preserving enough skeletal elements to allow their taphonomic characterization. Tooth marks or grooves on bone surfaces produced by scratching and chewing were not detected. The low relative abundance of skeletal elements, the high degree of breakage and the elevated frequency of elements with digestion traces represent general taphonomic patterns that fall within those reported for other South American small carnivores.