Electron spin resonance dating in paleoanthropology

Many archeological and paleoanthropological sites cannot be dated by well established and common dating techniques such as uranium series (U-series) or argon-argon (⁴⁰Ar/³⁹Ar) because of the lack of materials that are suitable for these techniques. Most sites, however, contain bones and teeth, and the latter can be used to obtain electron spin resonance (ESR) age estimates. The theoretical age range of ESR dating accuracy lies between a few thousand and more than a million years. In practice, continuing uranium accumulation increases the uncertainty of ESR age assessments in such a way that most age assignments beyond 300,000 years are very uncertain.     

Predicting protein decomposition: the case of aspartic-acid racemization kinetics

The increase in proportion of the non-biological (D-) isomer of aspartic acid (Asp) relative to the L-isomer has been widely used in archaeology and geochemistry as a tool for dating. the method has proved controversial, particularly when used for bones. The non-linear kinetics of Asp racemization have prompted a number of suggestions as to the underlying mechanism(s) and have led to the use of mathematical transformations which linearize the increase in D-Asp with respect to time. Using one example, a suggestion that the initial rapid phase of Asp racemization is due to a contribution from asparagine (Asn), we demonstrate how a simple model of the degradation and racemization of Asn can be used to predict the observed kinetics. A more complex model of peptide bound Asx (Asn + Asp) racemization, which occurs via the formation of a cyclic succinimide (Asu), can be used to correctly predict Asx racemization kinetics in proteins at high temperatures (95-140 degrees C). The model fails to predict racemization kinetics in dentine collagen at 37 degrees C. The reason for this is that Asu formation is highly conformation dependent and is predicted to occur extremely slowly in triple helical collagen. As conformation strongly influences the rate of Asu formation and hence Asx racemization, the use of extrapolation from high temperatures to estimate racemization kinetics of Asx in proteins below their denaturation temperature is called into question. In the case of archaeological bone, we argue that the D:L ratio of Asx reflects the proportion of non-helical to helical collagen, overlain by the effects of leaching of more soluble (and conformationally unconstrained) peptides. Thus, racemization kinetics in bone are potentially unpredictable, and the proposed use of Asx racemization to estimate the extent of DNA depurination in archaeological bones is challenged.     

巢县人年代位置新证据及其意义

本文银山地点钟乳石和骨石样的铀系年代。根据位于第２层顶部一钙板样３次分析的平均值,巢县人的上限年龄应为３１万年,据此似可将这一人类化石从目前分类的早期智人改划为晚期直立人。讨论了钟乳石铀系年代的可信度。银山下部地层骨化石样的分析结果,可引为二法一致的骨化石铀系年龄不足以保证数据真实的例证。     

铀子系法测定骨化石年龄的可靠性研究及华北地区主要旧石器地点的铀子系年代序列

本文报告测定骨化石~(231)Pa/~(235)U比值的实验方法,并根据骨化石样品的铀子系法年龄与~(14)C年龄的对比,讨论了铀子系法测定哺乳动物骨化石年龄的可靠性。作者实际测定了华北地区周口店、丁村等十个重要旧石器地点的年代,尝试提出华北地区旧石器文化年表。     

Neandertals,competition, and the origin of modern human behavior in the Levant

The East Mediterranean Levant is a small region, but its paleoanthropological record looms large in debates about the origin of modern humans and the fate of the Neandertals. For most of the twentieth century, the Levantine paleoanthropological record supported models of continuity and evolutionary transition between Neandertals and early modern humans. Recent advances in radiometric dating have challenged these models by reversing the chronological relationship between Levantine Neandertals and early modern humans. This revised chronostratigraphy for Levantine Middle Paleolithic human fossils raises interesting questions about the evolutionary relationship between Neandertals and early modern humans. A reconsideration of this relationship moves us closer to understanding the long delay between the origin of morphologically modern‐looking humans during the Middle Paleolithic (>130 Kyr) and the adaptive radiation of modern humans into Eurasia around the time of the transition from the Middle to Upper Paleolithic (50 to 30 Kyr).     

Geochemical evolution of amino acids in dentine of Pleistocene bears

A linear correlation was established between aspartic acid racemization ratio from cave bear dentine collagen and absolute dating. The high correlation coefficient obtained allowed age calculation through amino acid racemization. Aspartic acid and glutamic acid racemization kinetics have also been explored in dentine from a North American black bear (Ursus americanus Pallas). Three sample sets were prepared for kinetic heating experiments in nitrogen atmosphere: one water soaked, one with a water-saturated nitrogen atmosphere, and one without any moisture. It was possible to show that the presence of water is a factor controlling amino acid racemization rate. The aspartic acid in a heating experiment at 105 degrees C shows an "apparent kinetics reversal" which can be explained by a progressive hydrolysis of amino acid chains (proteins and polypeptides). Because of the low potential of collagen preservation over long periods of time, the apparent kinetics reversal phenomenon will not affect the dating of old material where no traces of collagen remain. An apparent kinetics reversal was not observed in glutamic acid, which racemizates more slowly.     

泥河湾盆地板井子晚更新世遗址古人类对动物资源的消费策略

本文以泥河湾盆地板井子遗址（约90 kaBP）2015年出土的动物骨骼为材料,通过骨骼表面痕迹分析、骨骼单元出现频率研究及长骨破碎方式的统计,辨识自然作用与人类行为对动物骨骼造成的不同影响,讨论深海氧同位素5阶段(MIS 5)中国北方古人类获取、搬运及处理动物资源的综合性策略。研究结果显示：1)遗址出土的动物遗存为古人类活动所遗留,自然营力对动物骨骼有改造作用,但并未影响我们对古人类行为的辨识;2)古人类在捕获马科动物之后,将其完整地带回了遗址并肢解;3)在处理猎物遗骸时,肌肉和骨髓富集的部位是古人类利用的重点。结合河南许昌灵井遗址的动物遗存研究结果,我们认为,在MIS 5阶段前后,中国北方已经出现了可以高效利用动物资源的人类群体;稳定、充沛的能量来源,或是他们应对北半球中高纬度干旱草原环境气候波动的重要生存策略。     

广西一些第四纪洞穴堆积中化石的氨基酸地质年龄

利用化石中氨基酸的外消旋程度随化石年龄增加而增大的原理,本文分别用“校正法”和“高温法”测定了广西柳州早更新世巨猿洞、中更新世笔架山洞、晚更新世一全新世白莲洞、大龙潭及桂林Chen皮岩的一此处第四纪洞穴堆积物中牙化石、骨化石或贝壳化石的氨基酸年龄,测年结果与其它地质证据或^14C年龄基本一致。     

Border Cave revisited: a revised ESR chronology

In view of a decade of progress in ESR dating we have revised the ESR chronology of Border Cave. A detailed gamma ray survey in 1994 and newly calculated beta attenuation data led to total dose rate estimations that are between 0 and 30% smaller than previously estimated. Accordingly, the resulting ESR age estimates are between 0 and 30% older. The ESR dates are now in good agreement with independent age estimates, particularly(14)C and amino acid racemization. New ESR dates for the lowermost dated sedimentary layer, 5 WA (white ash), indicate that the sedimentation of the sequence started around 200 ka ago.     

A systematic study of the amino acid compositions and D/L ratios in fossil bones from two french neanderthalian sites

The reaction of racemization in which the L amino acids are reversibly converted into the corresponding D amino acids, proceeds in geological environment at such a slow rate that it may be used as a geochronometer. However, in fossils several parameters may affect the rate of racemization, i.e. moisture, surface, pH buffer and metal cations. This work consists of a systematic study of total amino acid content in fossil bones from two neanderthalian sites. The amino acid distributions of all specimens were determined and compared to that of fresh bone. The D/L amino acid were quantified and expressed in terms of age as a function of the temperature. The results led us to consider the «La Roquette» site older than «Les Canalettes» site.     

Immunochemical detection and characterisation of osteocalcin from moa bone

Osteocalcin (the 6,000 dalton Mr gamma-carboxyglutamate-containing protein of bone) has been detected in acid extracts of bones of the extinct class of New Zealand ratite birds, the moas, using a radioimmunoassay for sheep osteocalcin. The immunoreactive osteocalcin of the extracts of two of these bones (the fibulae from two specimens of Pachyornis elephantopus found in South Island swamps) has been fractionated by gel filtration chromatography and reversed-phase high performance liquid chromatography, and behaves in a manner characteristic of osteocalcin from modern bones. Carbon-14 dating of bones and gizzard contents found in association with these specimens indicates approximate ages of 3,600 and 7,400 years respectively.     

Histidine racemization in the synthesis of an analog of the luteinizing hormone releasing factor. Investigation by HPLC and enzymatic methods

To investigate histidine racemization in the synthesis of a LHRH analog, (D-Trp)6-LHRH2-10 was built up by stepwise elongation of the sequence 3-10 using the solid phase technique on a 1% cross-linked chloromethyl polystyrene. For the whole synthesis the tert.-butyloxycarbonyl (BOC) group was used for temporary N-terminal protection. To protect the pi-nitrogen in histidine the benzyl-oxymethyl (BOM) group was utilized. The condensation position in the (D-Trp)6-LHRH analog was chosen so as to be able to investigate the racemization of histidine. We coupled BOC-His(BOM) with the (D-Trp)6-LHRH3-10 fragment using three different activating agents, mixed anhydride, carbonyldiimidazole (1 equiv.)/1-hydroxybenzotriazole (2 equiv.) and dicyclohexylcarbodiimide/1-hydroxybenzotriazole. The racemization was investigated by enzymatic digestion and by HPLC. For HPLC, (D-His(BOM)2-(D-Trp)6-LHRH2-10 was also synthesized. It could be proved that practically no racemization occurs during the actual peptide synthesis. The small amount (1%) of D-histidine found is due to racemization in the synthesis of BOC-His(BOM).     

Uranium-series dating and the origin of modern man.

Uranium-series dating is based on measurement of the radioactivity of short-lived daughter isotopes of uranium formed in samples which initially contained only the parent uranium. Materials suitable for U-series dating are found in many prehistoric archaeological sites, and include stalagmitic layers (flowstones), and spring-deposited travertines. Some marls and calcretes are also datable using isochron methods, whereas dates on molluscan shells, bones and teeth are less reliable. Ages obtained using alpha counting to determine isotope ratios have errors greater than 5%, and can range from 1 to 350 ka. Mass spectrometric methods slightly increase the range (0.1-500 ka) but greatly decrease the error to less than 1%, making this the optimal method for high-precision dating of the origin of modern man.     

许家窑-侯家窑遗址地层穷究

许家窑-侯家窑遗址是中国旧石器时代中期一处重要的考古遗址, 出土的化石"许家窑人"属于早期智人。按照现行地层古生物学常规判断, 其地层应该属于上更新统。目前, 许家窑组是泥河湾盆地乃至东亚地区发现的上更新统包含古人类及其旧石器文化遗物和古哺乳动物化石相当丰富的一个地层剖面, 但断代存在理念误区。     

The current state of korean paleoanthropology

The hominid fossil and Paleolithic archaeology records from the Korean Peninsula are extensive, but relatively little is known about the Korean human evolutionary record outside this region. The Korean paleoanthropological record is reviewed here in light of major research issues, including the hominid fossil record, relative and chronometric dating, lithic analysis, hominid subsistence, and the presence of bone tools, art and symbolism. Some of the major conclusions drawn from this review include: (1) hominid fossils have been found in nine separate sites on the Korean Peninsula; (2) possible Homo erectus fossils are present in North Korea; (3) Ryonggok Cave, in North Korea, has exposed the remains of at least five archaic Homo sapiens individuals; (4) a possible burial of an anatomically modern Homo sapiens child, discovered in Hungsu Cave in South Korea, has been tentatively dated to roughly 40,000 years ago; (5) handaxes and cleavers have been found at a number of sites near Chongokni and they appear to date to at least 100,000 years ago; and (6) taphonomic studies are necessary for addressing issues related to determining the nature of hominid-carnivore interaction over similar resources (e.g. carcasses and shelter); and the presence/absence of Early Paleolithic bone tools, art, and symbolism in Korea.     

The kinetics of diastereomeric amino acids with o-phthaldialdehyde.

The kinetics of the reaction of the amino acid epimers L-isoleucine, D-allo-isoleucine, L-threonine, and D-allo-threonine with o-phthaldialdehyde and mercaptoethanol were determined at 25 degrees C. L-Isoleucine reacts faster than its D-epimer whereas L-threonine reacts slightly slower than its D-epimer. In the case of isoleucine, the consequence can be an allo/iso ratio which in the worst case is 25% too low if these amino acids are quantified by liquid chromatography and o-phthaldialdehyde fluorescence detection. The effect on dating of fossils by amino acid racemization is discussed.     

An Integrated Experimental and Computational Approach for Characterizing the Kinetics and Mechanism of Triadimefon Racemization

Enantiomers of chiral molecules commonly exhibit differing pharmacokinetics and toxicities, which can introduce significant uncertainty when evaluating biological and environmental fates and potential risks to humans and the environment. However, racemization (the irreversible transformation of one enantiomer into the racemic mixture) and enantiomerization (the reversible conversion of one enantiomer into the other) are poorly understood. To better understand these processes, we investigated the chiral fungicide, triadimefon, which undergoes racemization in soils, water, and organic solvents. Nuclear magnetic resonance (NMR) and gas chromatography / mass spectrometry (GC/MS) techniques were used to measure the rates of enantiomerization and racemization, deuterium isotope effects, and activation energies for triadimefon in H₂O and D₂O. From these results we were able to determine that: 1) the alpha‐carbonyl carbon of triadimefon is the reaction site; 2) cleavage of the C‐H (C‐D) bond is the rate‐determining step; 3) the reaction is base‐catalyzed; and 4) the reaction likely involves a symmetrical intermediate. The B3LYP/6–311 + G** level of theory was used to compute optimized geometries, harmonic vibrational frequencies, nature population analysis, and intrinsic reaction coordinates for triadimefon in water and three racemization pathways were hypothesized. This work provides an initial step in developing predictive, structure‐based models that are needed to identify compounds of concern that may undergo racemization. Chirality 28:633–641, 2016. © 2016 Wiley Periodicals, Inc.     

Association between ancient bone preservation and dna yield: A multidisciplinary approach

Ancient molecular typing depends on DNA survival in archaeological bones. Finding valuable tools to predict DNA presence in ancient samples, which can be measured prior to undertaking a genetic study, has become an important issue as a consequence of the peculiarities of archaeological samples. Since the survival of DNA is explained by complex interrelations of multiple variables, the aim of the present study was to analyze morphological, structural, chemical, and biological aspects of a set of medieval human bones, to provide an accurate reflection of the state of preservation of the bony components and to relate it with DNA presence. Archaeological bones that yielded amplifiable DNA presented high collagen content (generally more than 12%), low racemization values of aspartic acid (lesser than 0.08), leucine and glutamic acid, low infrared splitting factor, small size of crystallite, and more compact appearance of bone in the scanning electron micrographs. Whether these patterns are characteristic of ancient bones or specific of each burial site or specimen requires further investigation. Am J Phys Anthropol 151:102–109, 2013. © 2013 Wiley Periodicals, Inc.