Identifying “free” and “bound” lipid fractions in stalagmite samples: An example from Heshang Cave,Southern China

Stalagmites are good archives for paleoecological change, as they are easy to date, and contain multiple environmental proxy records, including climatic records from oxygen isotopes. Lipid biomarkers preserved within stalagmites have recently been used to investigate changes in the overlying soil and vegetation. However, the understanding of lipid records from stalagmites is still at an early stage, and is hindered by the low abundances of lipids preserved and the complexity of the organic matter signal. Here the first results of a sequential extraction procedure are presented, that enables examination of the distribution patterns of “free” (solvent extraction) and “bound” (including physically bound within the calcite matrix and chemically bound to macromolecules) lipids in a stalagmite from southern China. In both groups the dominant compounds are saturated fatty acids, which are an order of magnitude more abundant in the “bound” phase. n-alkanes and n-alcohols chiefly appear in the “free” lipids. In contrast, 3-hydroxy acids are predominantly released under strong acid reflux conditions, suggesting a principal input from bacterial membrane compounds. A direct comparison between the present results and the published data from an Ethiopian stalagmite shows significant differences in the lipid signals from separate sites, with a stronger microbial signal in the Chinese sample. This preliminary investigation of lipid distributions in different modes highlights the importance of microbial geochemical processes in karst systems and supports the use of stalagmites in paleoecological reconstruction.     

石笋微层物质组成的二次离子质谱初步分析及其气候意义

我国北方洞穴石笋中发育双重光性微层(透光微层和发光微层),两种微层可以相互对应,但也存在不相匹配的现象。运用二次离子质谱分析微层内物质组分,发现透光微层的浅色段含有相对丰度较高的Mg和Sr元素以及小分子有机质,而Ba和Fe及大分子有机质主要赋存于微层内暗色段,层内暗色物质包含有机质和粘土物质。微层物质组成和成因等方面的研究可以反映气候变化的高分辨率信息。     

文石石笋发生矿物重结晶的影响因素及其古气候意义

洞穴沉积物—石笋已成为研究岩溶区环境气候变化历史的重要载体。在我国湘西地区,某些洞穴石笋原始沉积多为不稳定的文石矿物,极易发生重结晶,可能使石笋中相关化学元素含量最终偏离原生矿物的特征,限制了文石石笋某些代用指标在古气候研究中的应用。文章以前人研究成果为基础,总结梳理了文石石笋发生重结晶的影响因素及其对石笋记录古气候的影响:（1）石笋剖面特征、XRD结果、显微镜观察和地球化学元素特征等可作为石笋发生重结晶的判别依据;（2）洞穴滴水和石笋孔隙水饱和度、文石晶体缺陷和晶体之间的方解石胶结物以及岩溶水体中Mg2+浓度等均会影响文石石笋的矿物转变;（3）在文石向方解石转变过程中,石笋铀含量会有一定程度的流失,可导致放射性铀系定年的异常或年代倒序;（4）矿物重结晶可导致δ18O、δ13C及石笋微量元素浓度（或比值）等指标发生改变,其变化特征因洞穴而异,从而影响其作为环境指示器的可靠性;（5）湖南龙山惹迷洞石笋（RM2）发生了不均一的矿物重结晶,自顶部至20.3 cm以放射状为主,20.3 cm至底部主要为糖粒状,并结合年代结果发现文石重结晶对石笋铀系定年产生了影响,而重结晶作用对该石笋其他指标的影响还有待进一步研究。      

A 2000‐year lipid biomarker record preserved in a stalagmite from north‐west Scotland

Previous studies on lipid biomarkers preserved in Chinese stalagmites have indicated that ratios of low‐molecular‐weight (LMW) to high‐molecular‐weight (HMW) n‐alkanes, n‐alkan‐2‐ones, n‐alkanols and n‐alkanoic acids can be used as an index of vegetation versus microbial organic matter input to the system and, by extension, a marker of climatic changes, with increases in the proportion of LMW compounds coinciding with colder periods. Here we test whether this hypothesis is equally applicable to a different geographical region (north‐west Scotland), by examining a stalagmite record of the past 200 years, and a wider range of lipid markers. We also test the applicability of other lipid proxies in this context, including the use of n‐alkane ratios, to interpret vegetation changes, and unsaturated alkanoic acid ratios as climatic indicators. The results show that lipid proxies preserved in stalagmites, and especially those related to vegetation, are potentially extremely useful in palaeoenvironmental research. Of particular value is the use of C₂₇/C₃₁ n‐alkane ratios as a proxy for vegetation change, clearly indicating variations between herbaceous and arboreal cover. This proxy has now been successfully applied to samples from diverse environments, and can be considered sufficiently robust to be of use in analysing future stalagmite records. It will be of particular value in areas where reliable pollen records are not available, as is often the case with deeper cave deposits. However, the division between LMW and HMW aliphatic compounds is not a clear‐cut case of microbial versus plant activity, with the changes in LMW compounds relating more closely to those in their HMW analogues than in specific bacterial biomarkers. The use of unsaturated alkanoic acid ratios here gives conflicting results, with the observed variation through time depending on the isomer measured. The discrepancies between the findings of this study and previous work are likely to be due to the varying controls on the lipids (original organic matter input, and compound degradation), which in turn will be affected by whether the main climatic limiting factor on the soil is temperature or precipitation. This suggests that lipid proxies preserved in stalagmites must be interpreted with care, particularly in the case of bacterial compounds which may be derived from within the cave or from the soil. However, many of these issues can be resolved by the use of multi‐proxy studies. Copyright © 2011 John Wiley & Sons, Ltd.     

Composition and origin of organic matter in surface sediments of Lake Sarbsko: A highly eutrophic and shallow coastal lake (northern Poland)

We present an organic geochemical study of surface sediments of Lake Sarbsko, a shallow coastal lake on the middle Polish Baltic coast. The aim was to provide evidence concerning the origin of the organic matter (OM) and its compositional diversity in surface deposits of this very productive, highly dynamic water body. The content and composition of the OM in the bottom sediments were investigated at 11 sampling stations throughout the lake basin. OM sources were assigned on the basis of bulk indicators [total organic carbon (TOC), total nitrogen (TN), δ¹³C_TOC and δ¹⁵N and extractable OM yield], biomarker composition of extractable OM and compound-specific C isotope signatures. The source characterization of autochthonous compounds was verified via phytoplankton analysis. The distribution of gaseous hydrocarbons in the sediments, as well as temporal changes in lake water pH, the concentration of DIC (dissolved inorganic carbon) and δ¹³C_DIC were used to trace OM decomposition.The sedimentary OM is composed mainly of well preserved phytoplankton compounds and shows minor spatial variability in composition. However, the presence of CH₄ and CO₂ in the bottom deposits provides evidence for microbial degradation of sedimentary OM. The transformation of organic compounds in surface, bottom and pore waters via oxidative processes influences carbonate equilibrium in the lake and seasonally favours precipitation or dissolution of CaCO₃.The data enhance our understanding of the relationships between the composition of sedimentary OM and environmental conditions within coastal ecosystems and shed light on the reliability of OM proxies for environmental reconstruction of coastal lakes.     

Hyperspectral imaging of speleothems

Proxy records from speleothems are used in palaeoclimatic reconstructions, as the factors controlling their growth rate, nature of their internal structure and chemical composition respond to changes in surface climate. Optical analyses of stalagmites include visual observation of stalagmite images obtained from flatbed scanners or digital cameras. Hyperspectral imaging has not been used in stalagmite research, but potentially has many advantages over standard optical imaging techniques. Hyperspectral images of a set of stalagmites have been obtained in order to demonstrate the application of hyperspectral imaging in speleothem research. Our results highlight the following: (1) Spectra obtained for these calcite stalagmites are similar between a group of stalagmites of different ages, hydrological setting within a cave and from different caves. (2) The largest differences in relative reflectance between areas of dark compact calcite (DCC) and white porous calcite (WPC) are in the range 470–590 nm (this may extend to 680 nm for some of the stalagmites). (3) Imaging in the near infrared (NIR) demonstrates a decrease in reflection at water absorbance wavelengths, suggesting there is potential for mapping H₂O.     

Preserved organic matter in a fossil Ocean Continent Transition in the Alps: the example of Totalp,SE Switzerland

Evidence from ultraslow spreading mid-ocean ridges and both fossil and present-day Ocean–Continent Transitions (OCT) demonstrates that mantle serpentinization resulting from the interaction of mantle rock and water during tectonic exhumation is widespread. Observations at white smokers in modern ocean settings suggest that methane produced by serpentinization can support methanotrophic bio-systems, which use methane as the only source of carbon. An important question is whether such bio-systems are more generally pervasive in their association with serpentinized mantle in the subsurface. In this study, we examined whether there is evidence for such a methanotrophic system in exhumed serpentinized mantle at a magma-poor rifted continental margin, by probing for characteristic biological markers in these and associated sedimentary rocks in the Totalp unit of SE Switzerland. This unit represents a remnant of the former OCT of the southern Alpine Tethyan margin and was chosen because of its mild Alpine tectonic and low-grade metamorphic overprint during Alpine orogeny, hence giving potential for the preservation of indigenous organic matter (OM). Totalp samples are characterized by low organic carbon contents of 11–647 ppm. The majority of the samples contain hydrocarbons in the form of n-alkanes in the range C₁₇–C₃₆. Some sediments contain isoprenoids, for example pristane and phytane and a suite of steranes that are consistent with a marine origin for the OM preserved in the rocks. Traces of marine planktonic and bacterial OM are preserved in the serpentinized mantle and overlying sediments of this ancient Tethyan OCT, but there is no evidence that the OM has been generated from methanotrophic bio-systems.     

Association of specific organic matter compounds in size fractions of soils under different environmental controls

Inherent chemical recalcitrance and association of organic matter (OM) with minerals are mechanisms responsible for the long term preservation of OM in soils. The structural characteristics of OM are also believed to control specific interactions between OM and soil minerals. However, the extent of the relationship between recalcitrance and mineral protection and the specificity of these chemically driven interactions are not clearly understood at the molecular level. To measure chemical patterns of OM sequestration in sand-, silt-, clay-size and light fractions, we analyzed three soils, which mainly differed in carbon content and overlying vegetation, but have similar clay mineralogy, using biomarker analysis and nuclear magnetic resonance (NMR). Despite differences in environmental controls, long chain aliphatic compounds generally accumulated in the fine fractions of all soils. This accumulation is likely due to the strong interaction between recalcitrant forms of OM and soil minerals. For example, polymethylene and >C₂₀ organic acids accumulated in fine fractions, while lignin-derived phenols were protected from oxidation in silt-size fractions. Diffusion edited solution state ¹H NMR suggested that contributions from microbial-derived OM was greater in finer fractions, which is likely due to the accumulation of microbial-derived compounds or higher microbial activity in clay micro-sites. Our data suggest that, for these Prairie soils, the specific structure of OM and not environmental factors is responsible for long term preservation of OM in mineral fractions. Further research is necessary to understand the interplay between these preservation mechanisms such that the long term fate of OM can be further elucidated.     

中国南方发现大型文石笋

中国南方大量石笋剖面研究表明,石笋矿物组成有方解石、文石、方解石-文石三种类型。石笋沉积纹(微)层结构构造特征大同小异,但是文石石笋的放射状纹(微)层构造更显著。文石石笋沉积生长的气候环境是滴水多而稳定,水温低、气温略高的冷、湿的洞穴气候条件。文石转变为方解石常保留文石的针状、柱状晶形,并存在于石笋沉积生长的始终。文石结构构造转化在常温或低温、常压或低压下自调整作用的成晶成岩环境进行,其强度取决于所在洞穴气候环境、滴水在石笋的渗流和石笋的含水度。转化作用不影响同位素分馏,石笋同时全面记录古气候环境信息。研究文石石笋对重建古气候环境、成岩成矿作用都有重要理论和实践意义。     

Stalagmites from western Thailand: preliminary investigations and challenges for palaeoenvironmental research

Locating suitable caves and stalagmites for palaeoenvironmental and palaeoclimatic studies can be challenging. Isotopic geochemical analyses, albeit commonly performed for palaeoclimatic reconstruction, are also time consuming and costly. Therefore, petrographic and non‐destructive morphological studies on speleothems are desirable to facilitate sample selection for further analysis. In this study, 20 caves were surveyed in Ban Rai district, Uthai Thani province in western Thailand. After external physical observations in the field, three stalagmite samples were collected from Tham Nam Cave to test their potential for palaeoclimatic research. Firstly, the stalagmites were scanned by X‐ray computed tomography (CT scanning) and subsequently the CT images were compared with petrographic inspections. Columnar fabrics show the highest density, whereas closed and open dendritic fabrics have medium and the lowest densities, respectively. Layers near the top and bottom of the three stalagmites were dated by U‐Th mass spectrometric techniques. All three samples were deposited between c. 87 and c. 105 ka ago; therefore, they are probably the oldest stalagmites that have been reported so far from mainland Southeast Asia. However, their physical features indicate that all the samples have suffered from postdepositional dissolution, and are unlikely to be suitable for palaeoclimatic research. The internal dissolution feature of stalagmites, however, cannot be identified by visual inspection of uncut samples. We hereby argue that CT images are useful to characterize stalagmite petrography, in particular fabric, porosity and density. Such features can be used to select the ideal plane of a stalagmite for sectioning, to maximize the chances of robust climatic reconstruction.     

Atmospheric sources and soil filtering of PAH content in karst seepage waters

The analysis of PAHs (polycyclic aromatic hydrocarbons) in karst environments has provided an assessment of the vulnerability of karst water and the study of PAH records in stalagmites. The major source of PAHs has generally been considered to be the soil. In this study, we report the quantification of PAHs in the ecosystem compartments of a mountain karst system over a snow-melting period and the spring to summer dry period. PAH profiles in karst seepage waters were consistently similar to those in wet deposits, following the change in PAH profiles between winter and summer periods. However, PAH signatures of atmospheric wet deposits were modulated by a loss of the high molecular weight PAHs, which appear to accumulate in soils. A PAH mass balance was calculated during a summer storm event. This mass balance suggests that dry deposits and canopy throughfall could account for the PAH abundance in karst seepage waters. This study demonstrates the ability of organic hydrophobic compounds to be directly transferred from the atmosphere or canopy into seepage waters, giving new emphasis to the study of PAHs recorded in stalagmites.     

Organic matter preservation in the carbonate matrix of a recent microbial mat – Is there a ‘mat seal effect’?

Phototrophic mats (microbial mats with a phototrophic top layer) are complex systems in terms of microbial diversity, biogeochemical cycles and organic matter (OM) turnover. It has been proposed that these mats were a predominant life form in Proterozoic shallow water settings, prior to the emergence of bioturbating organisms in the Ediacaran–Cambrian transition. For most of the Precambrian, microbial mats were not only quantitative important carbon fixing systems, but also influenced the transfer and transformation of OM before it entered the geosphere. The profound alteration of compound inventories during transit through microbial mats, implying substantial consequences for OM preservation in the Proterozoic, was recently proposed as a “mat-seal effect” [Pawlowska et al. (2012) Geology 41, 103–106]. To obtain a better understanding of the early diagenetic fate of primary produced OM in microbial mats, we studied a recent calcifying mat from a hypersaline lake in Kiritimati, which showed in the deeper mat layers a maximum ¹⁴C_carbonate age of ∼1500 years. We particularly focused on OM entrapped in the carbonate matrix, because of the better potential of such biomineral-encapsulated OM to reach the geosphere before degradation (and remineralization). Our data indicate that selective preservation is important in phototrophic mats. While a diagenetic transformation of lipid fatty acids (FAs) was evident, their fatty acyl-derived hydrocarbon moieties were not introduced into protokerogen, which was instead mainly comprised of cyanobacterial and/or algal biomacromolecules. Our data support the proposed major impact of the “mat-seal effect” on OM turnover and preservation; i.e. the suppression of biosignatures derived from the upper mat layers, while signals of heterotrophic microbes thriving in deeper mat layers become preferentially preserved (e.g. high hopane/sterane ratios). This mechanism may have broad consequences for the interpretation of biomarkers from Proterozoic shelf environments, because biosignatures of phototrophic mat dwellers as well as planktonic signals may have become heavily biased by the production and turnover of OM in microbial mat systems.     

Sulfur isotopic composition of individual organic compounds from Cariaco Basin sediments

Reactions between reduced inorganic sulfur and organic compounds are thought to be important for the preservation of organic matter (OM) in sediments, but the sulfurization process is poorly understood. Sulfur isotopes are potentially useful tracers of sulfurization reactions, which often occur in the presence of a strong porewater isotopic gradient driven by microbial sulfate reduction. Prior studies of bulk sedimentary OM indicate that sulfurized products are ³⁴S-enriched relative to coexisting sulfide, and experiments have produced ³⁴S-enriched organosulfur compounds. However, analytical limitations have prevented the relationship from being tested at the molecular level in natural environments. Here we apply a new method, coupled gas chromatography – inductively coupled plasma mass spectrometry, to measure the compound-specific sulfur isotopic compositions of volatile organosulfur compounds over a 6 m core of anoxic Cariaco Basin sediments. In contrast to current conceptual models, nearly all extractable organosulfur compounds were substantially depleted in ³⁴S relative to coexisting kerogen and porewater sulfide. We hypothesize that this ³⁴S depletion is due to a normal kinetic isotope effect during the initial formation of a carbon–sulfur bond and that the source of sulfur in this relatively irreversible reaction is most likely the bisulfide anion in sedimentary porewater. The ³⁴S-depleted products of irreversible bisulfide addition alone cannot explain the isotopic composition of total extractable or residual OM. Therefore, at least two different sulfurization pathways must operate in the Cariaco Basin, generating isotopically distinct products. Compound-specific sulfur isotope analysis thus provides new insights into the timescales and mechanisms of OM sulfurization.     

The use of three physico-chemical methods in the study of the organic matter associated with the sedimentary phosphorites in Djebel Onk Basin, Algeria

The study of the organic matter (OM) associated with the phosphate ore of Kef Essennoun deposit (Djebel Onk mining basin, Algeria) was with a view to determine the decomposition degree of the OM within the pellets and the matrix, and the conditions of diagenesis. The sedimentary phosphates of this deposit are constituted of sub-rounded, phosphate-rich grains (pellets) dispersed in a surrounding, much poorer than pellets in P, matrix (or gangue). The survey of the OM associated with both pellets and matrix used several types of analyses: scanning electron microscopy (SEM), scanning electron microscope with energy-dispersive X-ray analysis, Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. The results show the OM, dispersed approximately homogeneously, in the form of large flat particles, within the gangue and within the phosphatic pellets in the form of small particles. The O/C ratio showed that the OM is more oxidised in the matrix than within the pellets. The oxidation increased with the phosphatisation rate of the pellets and more with the carbonation rate of the matrix, but it decreased with the silicification degree in the siliceous carbonated matrix. Two major functional classes were distinguished within pellets: aliphatic and oxygenated ones, the latter being fundamentally present in humic OM. The presence and abundance of these humic compounds in pelletal phosphorites are known from the 1980s and considered as witnessing a formation of apatite in a strictly closed environment, inside the pellet.     

东海盆地长江坳陷美人峰组烃源岩沉积环境与生烃潜力评价

利用东海盆地长江坳陷古新统美人峰组烃源岩的元素、热解、干酪根δ13C、镜质体反射率、岩石薄片、X射线衍射等资料,对长江坳陷美人峰组不同层段烃源岩进行沉积环境分析及生烃潜力评价。研究结果表明:美人峰组烃源岩的沉积环境整体表现为温暖潮湿的弱氧化淡水环境,古盐度和古气候是控制美人峰组烃源岩发育的主要环境因素。美人峰组第一段和第二段沉积时期,气候温暖潮湿,有大量陆源有机质输入,水体盐度相对较高,有机质保存条件较好,有机质丰度高,有机质类型以Ⅲ型为主,含少量II型,有机质已进入低成熟—成熟演化阶段,是美人峰组最具生烃潜力的层段;第三段和第四段沉积时期,气候相对干热,陆源碎屑及有机质输入少于第一段和第二段,水体盐度较低,不利于有机质保存,有机质丰度较低,有机质类型以Ⅲ型为主,有机质以低成熟演化阶段为主,生烃潜力不大;第五段和第六段沉积时期,气候恢复为温湿状态,有机质丰度较第三段和第四段高,有机质类型为Ⅲ型,但有机质热演化程度低,处于未熟状态,为无效烃源岩。随着埋深增加,美人峰组烃源岩的有机质成熟度变高,具有更大的生烃潜力。     

石笋生长直径的测定及其在古气候重建中的应用

石笋是第四纪陆地气候重建的良好信息载体,对了解过去气候和环境的演变十分重要。中国石笋具有生长相对连续,年代准确,信息丰富等特点,为全球季风及其长期演化提供了不可多得的视窗。基于石笋而开发了一系列气候替代指标,如δ18O、δ13C、微量元素及其同位素组成、有机化合物及其同位素组成、生长速率等,在石笋古气候重建中得到广泛的应用。但是,作为石笋形貌学的基本特征,对石笋的生长直径及其对气候变化的指示意义却鲜有报道。本研究中,作者首先提出一种测定石笋生长直径的方法,然后利用该方法测定了湖北清江和尚洞HS4石笋顶部35 cm的石笋生长直径,并与研究区的气温和洪涝频率记录进行比较,探讨石笋生长直径对气候变化的响应。研究表明,通过纹层的识别和不同深度上纹层宽度的测定而建立的指数回归法较好地表征了石笋的生长直径,适合于一些具有明显纹层的石笋直径测定。HS4石笋的实际生长直径比理论计算值偏小,可能与洞穴结构有关;高的落差增加了岩溶滴水的冲力,水滴飞溅而导致有效水量的损失,即滴水的有效体积减少,石笋直径偏小。与温度相比,降水对石笋直径的影响更加显著,因而石笋直径是一个有效降水的替代指标,有望在石笋古气候的研究中得到应用。      

文石-方解石石笋U/Th体系的封闭性判断及意义

湖南省龙山县莲花洞两根大型石笋LLl(文石-方解石型)和LL5(文石型)ICP-MS230Th结果表明,82个年龄数据并不完全符合石笋生长层序律.根据U/Th同位素比值、沉积和矿物学特征,分析了同位素体系开放度对建立石笋正确年代学模式的影响.莲花洞LLl石笋全新世以来234U/238U对230Th/238U的比值具有谐和性特征并且230Th年龄层序正常,说明文石矿物基本接近U/Th同位素封闭系统,实测年龄基本可靠.10～40 ka期间234U/238U与230Th/238U离散度较大和矿物具有溶蚀、风化现象,表明体系发生U加入/流失作用.LL5石笋60～80 ka期间封闭性较好,实测年龄可信.上述结果表明,同一洞穴中文石石笋U/Th同位素体系开放度与时间的关系并不是线性关系,沉积时水文和物理化学性质以及随后的保存状况是决定洞穴文石石笋同位素封闭性的关键因素.     

桂林水南洞石笋的沉积学特征

利用组成石笋的方解石成分、岩石化学、微量元素含量以及结构、层面构造、沉积间断或风化壳等特征标志,阐述桂林水南洞石笋的沉积特征以及古滴水动态变化.经铀系法测年,确定石笋形成于中更新世晚期至晚更新世早期,其年龄为8.07万年至22.91万年,经历了14.84万年,沉积速率为2.08~2.82mm/100a(未扣除间断时间).     

洞穴碳酸盐微层研究及其发展方向

近几年,在分辨率气候－环境变化研究中,洞穴碳酸盐微层逐渐受到人们重视。洞穴碳酸盐微层的类型较多,主要为年层。微层是在沉积条件发生高频率的周期性改变时形成的,要受到供水条件和碳酸钙浓度等多因素的控制。洞穴碳酸盐微层的稳定同位素组成,生长速率,微层结构与物质组分,微层厚度与灰度和光学特征等可以反映降水,温度,土壤成分及植被变化等信息。