Cross dating (Th/U-C) of calcite covering prehistoric paintings in Borneo

We present the first application of cross-dating (Th/U measured by thermo-ionization mass spectrometry (TIMS) and ¹⁴C measured by accelerator mass spectrometry (AMS)) of calcite covering prehistoric paintings. Th/U age estimates of cave drapery range from 9800 to 27,300 yr B.P. while conventional ¹⁴C age is estimated between 9900 and 7610 yr B.P. depending on the dead carbon correction. The age discrepancy is attributed to a disturbance of Th/U and/or ¹⁴C geochemical systems, showing the limits of the geochronological approach applied to this kind of material. For the Th/U system, the poor consistency of U data (U content, ²³⁴U/²³⁸U activity ratios) and apparent ages argue for open system conditions. For ¹⁴C system, variation of the dead carbon fraction (dcf) and a possible mixing of successive generations of calcite could account for age discrepancy. Nevertheless, one sample shows concordant ages for the two methods. Compatible ages through corrections for open system conditions are assumed for other samples. Then, the cross-dating suggests 9900 yr as the minimum age of the piece of drapery; the underlying painting must be older. This study of rock art demonstrates the presence of a Pleistocene population before 9900 yr in the southeast of Borneo, whereas previously the only population in evidence in this area was of Austronesian type from ∼5000 to 6000 yrs ago.     

海南岛万泉河口沉积物有机碳、 氮同位素的特征及其环境意义*

对海南岛万泉河口沙美内海柱样K3和K4沉积物进行生物地球化学指标总有机碳(TOC)、总氮(TN)、有机碳同位素(δ¹³ C)、氮同位素(δ¹⁵ N)的分析,以及²¹⁰ Pb定年了解其近代变化特征,追踪沉积物有机质来源的变化,提取沉积环境演变及人类活动的信息。K3中TOC的变化介于0.51 ％ ~1.12 ％ ,K4变化介于0.43 ％ ~1.49 ％ ,而其随时间的变化反映了流域内人类活动的历史。17世纪TOC含量明显增加记录了明末清初开始流域内广泛种植农作物的活动,19世纪以来TOC含量逐渐增加,至现代达最高值,对应了工业革命以来人类活动的增强。K3和K4的δ¹³ C值变化分别在-24.38 ‰ ~-21.02 ‰ 之间和-24.74 ‰ ~-20.17 ‰ 之间,δ¹⁵ N值变化分别在2.20 ‰ ~4.62 ‰ 之间和2.39 ‰ ~5.02 ‰ 之间,映证了本区沉积物有机质是陆源物质和海洋物质混合的特点。明末清初开始流域内广泛种植玉米等农作物造成δ¹³ C值增加和δ¹⁵ N值减少; 自19世纪以来至现在,该区的经济活动增加,人口的持续增长,尤其是近50年来化肥农药的大量使用,造成陆源输入的有机碳含量大幅增加,使δ¹³ C值减少和δ¹⁵ N比值增加。 δ¹³ C值自19世纪以来就逐渐变轻,说明陆源和海洋有机碳的比例发生了变化,较轻的陆源有机碳比例相对增加,较重的海洋有机碳比例相对减少,反映了玉带滩沙坝的增长、沙美内海封闭、海水交换作用减少的状况。C/N比值分别从底部的16.19和17.36到顶部减小为11左右,自19世纪以来呈明显减小的趋势也反映了沙美内海泻湖自生的藻类有机质供应越来越多,也说明了其逐渐封闭、水动力条件越来越弱,与外海的交换作用逐渐减少的状况。     

Composition of organic matter in subducted and unsubducted sediments off the Nicoya peninsula, Costa Rica (ODP Leg 170, Sites 1039 and 1040)

Investigation of sediment samples from Sites 1039 and 1040 (ODP Leg 170) drilled off the Nicoya peninsula (Costa Rica) by organic geochemical and organic petrological methods has revealed that subduction has only little influence on the composition of the sedimentary organic matter. Organic carbon contents reached 1.5% in the Pleistocene samples but Miocene and Pliocene sediments had an average organic carbon content of less than 0.5%. Organic carbon/sulfur ratios are generally below 2.8, reflecting an intense sulfate reduction in the uppermost sediments which was enhanced by sulfate supply both from sea water and deeper strata. Microscopical examinations indicate that the organic matter is mainly derived from marine sources. A small amount of terrigenous organic matter is, however, present as well according to n-alkane and fatty acid distributions. The alkenone unsaturation index U₃₇^k′ shows only a slight decrease during the Miocene and Pliocene, and stronger variations in the Pleistocene, probably indicating more stable sea surface temperatures during the Miocene and Pliocene. Variations in the Pleistocene can possibly be related to glacial/interglacial changes.     

天然放射性碳同位素在海洋有机地球化学中的应用

天然放射性碳（¹⁴C）是年代测定的有效手段，它在考古学和地质学的应用已有几十年的历史。过去10年中，伴随着加速器质谱仪（AMS）技术和检测灵敏度的提高，AMS已经能够检测少于mg C量级样品中自然丰度水平的¹⁴C，这大大扩展了¹⁴ C在自然科学，特别是地球科学研究中的应用范畴。简要评述了利用天然¹⁴ C进行海洋地球化学研究的应用，重点介绍了前景广阔、并已取得显著成果的应用领域。     

AMS~(14)C测年揭示的渤海湾沿海低地第Ⅱ海相层年龄(Ⅱ)

在初步获得渤海湾海河南部沿海低地第Ⅱ海相层年龄大于43.5ka BP的基础上,在沧州北部和海河北部的沿海低地又利用6个新的机械钻孔岩心,建立了2条垂直于现代岸线的长剖面。根据沉积物岩性和有孔虫查明了第Ⅱ海侵层在剖面中的空间分布,并获得一组新的AMS~(14)C年龄数据。结果显示,在第Ⅱ海相层中新获得的9个AMS~(14)C年龄同样均大于43.5ka BP。至此,渤海湾3条垂直现代岸线剖面10个钻孔的第Ⅱ海相层的21个AMS~(14)C年龄均大于43.5ka BP,进一步证实了普遍发育于渤海湾沿海低地的第Ⅱ海相层形成于MIS 3阶段早期或MIS 5阶段,而不是前人认为的23~39ka BP。     

Suitability of biogenic carbonate of Lithospermum fruits for C dating

Lithospermum (Boraginaceae) belongs to a small group of plant taxa that accumulate biogenic carbonate in their fruits. In this genus, carbonate incrustations form in the cells of the epidermis and sclerenchyma of the pericarp. Fossil Lithospermum fruits (nutlets) with well-preserved calcified tissues commonly occur in Quaternary sediments and cultural layers. We tested the suitability of biogenic carbonate of Lithospermum fruits for radiocarbon dating using a total of 15 AMS measurement results from four modern and 11 fossil samples. The ¹⁴C data from modern samples suggest that Lithospermum utilises only atmospheric carbon to synthesise calcite in the nutlets. In general, the ages determined through ¹⁴C dating of fossil fruitscorresponded well with the absolute-age intervals for archaeological sites over the last 5000 yr. Biogenic carbonate of Lithospermum fruits, like that of Celtis, represents a new source of chronological information for late Quaternary studies.     

Pyrolysis-combustion C dating of soil organic matter

Radiocarbon (¹⁴C) dating of total soil organic matter (SOM) often yields results inconsistent with the stratigraphic sequence. The onerous chemical extractions for SOM fractions do not always produce satisfactory ¹⁴C dates. In an effort to develop an alternative method, the pyrolysis-combustion technique was investigated to partition SOM into pyrolysis volatile (Py-V) and pyrolysis residue (Py-R) fractions. The Py-V fractions obtained from a thick glacigenic loess succession in Illinois yielded ¹⁴C dates much younger but more reasonable than the counterpart Py-R fractions for the soil residence time. Carbon isotopic composition (δ¹³C) was heavier in the Py-V fractions, suggesting a greater abundance of carbohydrate- and protein-related constituents, and δ¹³C was lighter in the Py-R fractions, suggesting more lignin- and lipid-related constituents. The combination of ¹⁴C dates and δ¹³C values indicates that the Py-V fractions are less biodegradation resistant and the Py-R fractions are more biodegradation resistant. The pyrolysis-combustion method provides a less cumbersome approach for ¹⁴C dating of SOM fractions. With further study, this method may become a useful tool for analyzing unlithified terrestrial sediments when macrofossils are absent.     

Biogeochemical processes of carbon and sulfur cycles in sediments of the outer shelf of the Black Sea (Russian Sector)

Within the mass of recent (unit-I) and ancient Black Sea (unit-II) sediments on the outer shelf of the Russian sector of the Black Sea, the rates of anoxic processes participating in diagenetic transformations of carbon and sulfur compounds were first measured using ³⁵S and ¹⁴C radioactive tracers. The main energy source for biogeochemical processes in (unit-I) sediments is the organic matter (OM) supplied to the bottom from the water mass. In (unit-II) sediments, this is methane in a migratory form proved by the excess of its oxidation rate over that of its generation. In recent silt, the primary microbial process is sulfate reduction; in unit-II, this is methane anoxic oxidation by the consortium of archeides and sulfate reductants. The organic matter produced in methane oxidation, in turn, acts as an energy source for the community of anaerobic heterotrophic microorganisms in the bottom sediments, which are remote from the water-sediment interface.     

Observations and simulations of water-sediment heat exchange in a shallow coastal lagoon

Water and sediment temperatures from Florida's Indian River Lagoon are used to investigate water-sediment heat energy exchanges and the resulting sub-bottom temperature fluctuations in a shallow-water estuarine environment. A 132-day study documents the response to cold-air outbreaks and spring warming. A one-dimensional, 120-layer numerical model simulates temperatures in the top 24 m of the sediment in response to observed water temperatures. Model simulations supplement sediment temperatures measured 50 and 95 cm below the water-sediment interface approximately weekly. Simulated water-sediment heat fluxes are generally between +0.075 (into the sediment) and −0.050 cal cm⁻² min⁻¹. The average simulated water-sediment heat flux is +0.003 cal cm⁻² min⁻¹. Over the course of an average day, heat entering the sediment reaches a maximum rate of 0.037 cal cm⁻² min⁻¹ at 1700, and fluxes out of the sediments reach −0.021 cal cm⁻² min⁻¹ at 0700. The standard deviations of sediment temperatures simulated for the 0–20, 80–100, and 180–200 cm layers are 85%, 41%, and 14%, respectively, of the standard deviation of the water temperature.     

The great 1950 Assam Earthquake revisited: Field evidences of liquefaction and search for paleoseismic events

Extensive field investigations were carried out for the first time in the meizoseismal area of the great 1950 Assam Earthquake aimed at exploring the paleoseismic history of the NE Indian region through documentation of liquefaction features and radiocarbon (¹⁴C) dating. Trenching at more than a dozen locations along the Burhi Dihing River valley and within the alluvial fans adjoining the Brahmaputra and Dibang Rivers resulted in the identification of more than a dozen very prominent liquefaction features (sand dykes, sills, sand blows etc.) as evidences of large to great earthquakes. ¹⁴C dating of the organic material associated with some of the features indicates a paleoseismic record of about 500 yrs archived by the sediments in this region. Compelling geological evidence(s) of the great 1950 earthquake are well constrained by ¹⁴C dating. Out of the two historically reported seismic events (1548 AD and 1697 AD) from this region, ¹⁴C dating could constrain the 1548 AD event though not distinctly. Further studies using combined ¹⁴C and OSL dating may better constrain the seismo-chronology of the study region.     

C chronology for ice retreat and inception of Champlain Sea in the St. Lawrence Lowlands, Canada

AMS radiocarbon cross-dating of plant debris and marine shells trapped in a lake basin on Mount St. Hilaire (Québec, Canada) provides a direct assessment of a reservoir effect totaling ca. 1800 ¹⁴C years during the early stage of Champlain Sea. Pollen-based extrapolation of bottommost ages on terrestrial plant macrofossils in sediments of this lake, and of another lake nearby support an estimate of 11,100 ± 100 ¹⁴C yr B.P. for marine invasion in the Central St. Lawrence River Lowlands. Results indicate a 400–1000 years younger regional chronology of ice retreat, now congruent with the one inferred from the New England varve chronology. This is a summary of a longer paper to be published in French.     

Precise radiocarbon dating of Late-Glacial cooling in mid-latitude South America

Variability of atmospheric ¹⁴C content often complicates radiocarbon-based chronologies; however, specific features such as periods of constant ¹⁴C age or steep changes in radiocarbon ages can be useful stratigraphic markers. The Younger Dryas event in the Northern Hemisphere is one of those periods, showing conspicuous ¹⁴C wiggles. Although the origin of those variations is not fully understood, we can make practical use of them and determine: (i) whether the Younger Dryas was global in extent; if so, (ii) were the initial cooling and the final warming synchronous worldwide; and (iii) what are the implications of these similarities/differences? Here we report high-resolution AMS ¹⁴C chronologies from the mid-latitudes of South America that pinpoint a cool episode between 11,400 and 10,200¹⁴C yr B.P. The onset of the final cool episode of the Late Glacial in the southern mid-latitudes, i.e., the Huelmo/Mascardi Cold Reversal, preceded the onset of the Younger Dryas cold event by ∼550 calendar years. Both events ended during a radiocarbon-age plateau at ∼10,200¹⁴C yr B.P. Thus, the Huelmo/Mascardi Cold Reversal encompasses the Younger Dryas, as well as a couple of short-term cool/warm oscillations that immediately preceded its onset in the North Atlantic region.     

The radiocarbon age of organic carbon in marine surface sediments

Long-term carbon cycling and climate change are strongly dependent on organic carbon (OC) burial in marine sediments. Radiocarbon (¹⁴C) has been widely used to constrain the sources, sinks, and processing of sedimentary OC. To elucidate the dominant controls on the radiocarbon content of total organic carbon (¹⁴C_TOC) accumulating in surface sediments we construct a box model that predicts ¹⁴C_TOC in the sediment mixed layer (measured as fraction modern, Fm). Our model defines three distinct OC pools (“degradable,” “semi-labile,” and “refractory”) and assumes that ¹⁴C_TOC flux to sediments is exclusively derived from surface ocean primary productivity, and hence follows a “generic” surface ocean dissolved inorganic carbon (DIC) bomb curve. Model predictions are compared to a set of 75 surface sediment samples, which span a wide geographic range and reflect diverse water column and depositional conditions, and for which sedimentation rate and mixed-layer depth are well characterized. Our model overestimates the Fm value for a majority (65%) of these sites, especially at shallow water depths and for sites characterized by depleted δ¹³C_TOC values. The model is most sensitive to sedimentation rate and mixed-layer depth. Therefore, slight changes to these parameters can lead to a match between modeled and measured Fm values at many sites. Yet, in some cases, we find that measured Fm values cannot be simulated without large and unrealistic changes to sedimentation rate and mixed-layer depth. These results point to sources of pre-aged OC to surface sediments and implicate soil-derived terrestrial OC, reworked marine OC, and/or anthropogenic carbon as important components of the organic matter present in surface sediments. This approach provides a valuable framework within which to explore controls on sedimentary organic matter composition and carbon burial over a range of spatial and temporal scales.     

Elucidation of the Alum Shale kerogen structure using a multi-disciplinary approach

The significance and validity of integrating data obtained from a variety of analytical techniques to understand, elucidate and model kerogen's complex chemical structure is reported here using degradative (open and closed system pyrolysis, chemical oxidation), non-degradative (¹³C CP/MAS NMR) and optical (incident white light and blue light) methods. Seven Cambrian Alum Shale samples, ranging in maturity from immature to post-mature with respect to petroleum generation, were studied and were chosen for their simple geological history, uniform organic matter type and high organic carbon content. The Alum Shale kerogens, which primarily consist of algal organic matter, liberate low molecular weight gaseous and aromatic compounds on pyrolysis and give mostly branched dicarboxylic acids on chemical oxidation. ¹³C NMR spectroscopy shows that the Alum Shale kerogens are anomalously rich in oxygen-bearing functional groups (such as C = O, ArCO, CHO, CH_xO), most of which apparently remain intact within the kerogen macro-molecule (KMM) through the diagenetic and catagenetic stages. Fragments released by different degradative techniques are quantified and the aromaticity (f_a), O/C and relative proportions of various carbon types estimated by ¹³C NMR. A synthesis of these data has allowed us to better understand the chemistry of the Alum Shale kerogen.     

Middle and late Pleistocene glaciations in the Campo Felice Basin (central Apennines, Italy)

The present paper refers to research conducted in the tectonic-karst depression of Campo Felice in the central Apennines (Italy), in which glacial, alluvial and lacustrine sediments have been preserved. Stratigraphic interpretations of sediments underlying the Campo Felice Plain are based on evidence obtained from nine continuous-core boreholes. The boreholes reach a depth of 120 m and provide evidence of five sedimentation cycles separated by erosion surfaces. Each cycle is interpreted as an initial response to a mainly warm stage, characterized by low-energy alluvial and colluvial deposition, pedogenesis, and limited episodes of marsh formation. In turn, a mainly cold stage follows during which a lake formed, and glaciers developed and expanded, leading to deposition of glacial and fluvioglacial deposits. The chronological framework is established by eleven accelerator mass spectrometer ¹⁴C ages and three ³⁹Ar-⁴⁰Ar ages on leucites from interbedded tephra layers. These age determinations indicate five glacial advances that respectively occurred during marine oxygen isotope stages 2, 3-4, 6, 10 and 14.     

藏南定日地区白垩纪中期地球化学异常对海平面上升的响应

西藏南部定日地区在白垩纪中期为一套浅灰色-深灰色的陆源碎屑岩（钙质页岩）及碳酸盐岩（泥灰岩及微晶灰岩）的混积型沉积物，其中的地球化学特征变化反映了古海洋发生的重大变革。δ¹³ C的同位素曲线变化具有明显的低-高-低旋回变化，δ¹³ C正偏与有机碳大量埋藏、海平面上升及缺氧事件密切相关。铀、钍、钾的含量变化及Th/U比值的变化特征表明由海平面上升所形成的全球大洋缺氧的重要时期，由于有机物质及粘土矿物的增多，它们的含量均比标准平均值偏高。而⁸⁷Sr/ ⁸⁶Sr比值在该时期偏低，这也与当时的构造背景及海平面发生重大变化相一致。     

Younger Dryas to mid-Holocene environmental history of the lowlands of NW Transylvania, Romania

Pollen, micro-charcoal and total carbon analyses on sediments from the Turbuta palaeolake, in the Transylvanian Basin of NW Romania, reveal Younger Dryas to mid-Holocene environmental changes. The chronostratigraphy relies on AMS ¹⁴C measurements on organic matter and U/Th TIMS datings of snail shells. Results indicate the presence of Pinus and Betula open woodlands with small populations of Picea, Ulmus, Alnus and Salix before 12,000 cal yr BP. A fairly abrupt replacement of Pinus and Betula by Ulmus-dominated woodlands at ca. 11,900 cal. yr BP likely represents competition effects of vegetation driven by climate warming at the onset of the Holocene. By 11,000 cal yr BP, the woodlands were increasingly diverse and dense with the expansion of Quercus, Fraxinus and Tilia, the establishment of Corylus and the decline of upland herbaceous and shrubs taxa. The marked expansion of Quercus accompanied by Tilia between 10,500 and 8000 cal yr BP could be the result of low effective moisture associated with both low elevation of the site and with regional change towards a drier climate. At 10,000 cal yr BP, Corylus spread across the region, and by 8000 cal yr BP it replaced Quercus as a dominant forest constituent, with only little representation of Picea abies. Carpinus became established around 5500 cal yr BP, but it was only a minor constituent in local woodlands until ca. 5000 cal yr BP. Results from this study also indicate that the woodlands in the lowlands of Turbuta were never closed.     

New radiocarbon age constraints for the 120 km-long Toomba flow,north Queensland,Australia

The Toomba flow is the youngest flow of the Nulla volcanic province, located in north Queensland. This 120?km-long flow has yielded a published ⁴⁰Ar/³⁹Ar age of 21,000?±?3000 years. In contrast, seven published conventional radiocarbon (¹⁴C) analyses of carbon-bearing material beneath the flow yielded radiocarbon ages of 16,000 to <2500?BP. These radiocarbon ages are younger than the ⁴⁰Ar/³⁹Ar age, potentially due to contamination of the charcoal by younger carbon that was not removed by the acid–base pre-treatment. We have re-examined the radiocarbon age of Toomba flow using newly sampled charcoal buried beneath the Toomba flow in combination with hydrogen pyrolysis pre-treatment and accelerated mass spectrometer (AMS) measurements. We determined a calibrated radiocarbon age of 20,815–19,726?cal BP (2σ) for the material beneath the Toomba flow. Our radiocarbon age, therefore: (1) is older than previous radiocarbon ages for the Toomba flow, (2) provides the most precise age yet available for the Toomba flow, (3) is in agreement with the ⁴⁰Ar/³⁹Ar age, and (4) validates that hydrogen pyrolysis is a robust and effective pre-treatment method, for subtropical conditions where samples are susceptible to contamination by younger carbon. The Toomba flow erupted during the Last Glacial Maximum, but the preserved surface suggests that the rate of weathering and soil formation has been almost negligible in this region, despite being situated in a subtropical climate that experiences highly variable often intense rainfall.     

Uranium isotopic disequilibrium for groundwater classification: first results on complexe terminal and continental intercalaire aquifers in Southern Tunisia

A fractionation of uranium (U) series into parent–daughter pairs – ²³⁴U and ²³⁸U – always occurs in natural waters, and the disequilibria between these is commonly used as a tracer of groundwater flow. We report here an interpretation of the U-content and U isotope disequilibria in groundwater sampled from the deep Complexe Terminal and Continental Intercalaire aquifers of southern Tunisia. Variations in both the contents of these isotopes (0.006–2.4 ppb) and ²³⁴U/²³⁸U activity ratios (ARs) (1.7–15.4) were observed. The data could be plotted in two distinct fields of reciprocal U concentration versus ²³⁴U/²³⁸U AR according to groundwater flow and regional bedrock differences. An initial assessment aimed at verifying whether the results of this investigation support those of previous hydrogeological and isotope studies, thereby suggesting that the disequilibrium between U isotopes in groundwater may represent a useful tool for hydrogeological investigations of deep and fossil groundwater. In addition, the disequilibrium can be used for quantifying the recharge or mixing rates between different formations with the aim of delineating the preferential outflow pattern or determining residence times of waters.     

Transformation of particulate organic matter at the water-bottom boundary in the Russian Arctic seas: Evidence from isotope and radioisotope data

Complex biogeochemical studies including the determination of isotopic composition of C_org in both suspended particulate matter and surface horizon (0–1 cm) of sediments (more than 260 determinations of δ¹³C-C_org) were carried out for five Arctic shelf seas: White, Barents, Kara, East Siberian, and Chukchi. The aim of this study is to elucidate causes that change the isotopic composition of particulate organic carbon at the water-sediment boundary. It is shown that the isotopic composition of C_org in sediments from seas with a high river runoff (White, Kara, and East Siberian) does not inherit the isotopic composition of C_org in particles precipitating from the water column, but is enriched in heavy ¹³C. Seas with a low river runoff (Barents and Chukchi) show insignificant difference between the value of δ¹³C-C_org in both suspended load and sediment because of a low content of the isotopically light allochthonous organic matter (OM) in particulates. Complex biogeochemical studies with radioisotope tracers (¹⁴CO₂, ³⁵S, and ¹⁴CH₄) revealed the existence of specific microbial filter formed from heterotrophic and autotrophic organisms at the water-sediment boundary. This filter prevents the mass influx of products of OM decomposition into water column, as well as reduces the influx of a part of OM contained in the suspended particulate matter from water into sediment.