Quantitative X-Ray diffraction of carbonate sediments: mineralogical analysis through fitting of Lorentzian profiles to diffraction peaks

A new automatic method for quantitative mineralogical analysis of carbonate sediments by X-Ray diffraction is described. Percentage analysis has been carried out by means of the reference intensities method from integrated areas of the diffraction peaks. Diffraction peaks were fitted by means of Lorentzian profiles. The addition of an internal standard allows the determination of data on the stoichiometric disequilibrium of the carbonate phases and the existence of non-carbonate phases and/or non-crystalline phases simultaneously. Relative errors of the quantitative estimates of carbonate phases are always less than 15%, even though real percentage differences between actual and calculated values are less than 3·8% in all cases.     

蛇纹石物相的X射线衍射定量分析方法

X射线衍射分析法虽然是部分国家测定蛇纹石的标准方法,但由于现有方法缺乏试验数据的支撑,其检测质量的监控得不到保证,我国目前仍未采用X射线衍射法作为蛇纹石物相定量分析的标准方法。应用X射线衍射仪,根据不同含量分别采用标准曲线法和K值法定量测定蛇纹石含量,通过精密度试验及其协作试验、准确度（包括加标回收）试验等一系列测试,对结果进行统计分析。研究成果可为分析质量的监控及分析方法的评价等提供依据,为建立我国蛇纹石物相定量分析标准方法提供技术支撑。     

Quantitative determination of cerussite (lead carbonate) by X-ray powder diffraction and inferences for lead speciation and transport in stream sediments from a former lead mining area in Scotland

Most current investigations of sites contaminated with heavy metals (e.g. Pb, Zn, Cu) emphasise the importance of determining the amounts of physical and chemical forms of metals rather than just the total amounts present. Chemical extraction techniques used for this purpose are inevitably operationally defined. A more direct approach to the identification of crystalline forms can be made by mineralogical techniques such as X-ray powder diffraction (XRPD), but quantitative determination of a particular form is not often attempted. Recent advances in methods of analysis and sample preparation for XRPD mean that it is now a relatively simple matter to obtain quantitative XRPD data. Here, it is applied to the quantitative determination of the forms of Pb in different size-fractions of stream sediment samples from Leadhills/Wanlockhead, SW Scotland, an historic Pb mining area. Comparison of the XRPD analyses with determinations of Pb by atomic absorption spectrophotometry demonstrates that a large proportion of the Pb present in the stream sediments is in the form of cerussite (PbCO₃). Furthermore, the cerussite tends to be concentrated in the silt fraction and is even a minor component of the clay-size fraction. However, quantitative analysis of fractions <6 μm indicates that cerussite alone cannot account for all the Pb in this size range. Indirectly, this result suggests that Pb adsorbed to clay minerals, organic matter and/or amorphous Fe and Mn oxides may be proportionally more important for the <6 μm materials. Sediment in this size range, however, typically accounts for no more than 1% by weight of the total stream bed sediment samples collected in the study area. In relation to its size distribution, the mobility of Pb within the wider environment is most likely to occur principally through physical transport of fine particles.     

The mineralogical composition of precursor sediments of calcareous rhythmites: a new approach

Previous studies in Silurian carbonates from Gotland (Sweden) have led to a model for the development of limestone-marl alternations. This model postulates that early diagenesis of precursor sediments without strong primary differences can result in a differentiation by selective dissolution of aragonite in marl beds and reprecipitation of calcite cement in limestone beds. This model is described as a set of mathematical equations that quantify the diagenetic processes (aragonite dissolution and calcite reprecipitation) that occur during the formation of limestone-marl interbeds from a hypothetical homogeneous precursor sediment. The calculations demonstrate that resulting hypothetical limestone-marl alternations show characteristic mathematical relationships between the ratios of the bed thicknesses of limestones and marls on one side, and the carbonate contents, on the other. By reversing this model, the original mineralogical composition of the precursor sediment of real-world rhythmic successions can be determined. In this study, alternations from the Silurian of Gotland, the Cambrian, Devonian, and Mississippian of North America, the Jurassic of France and Germany, and the Cretaceous of France are shown to exhibit mathematical relationships similar to those calculated for hypothetical precursor sediments without primary differences. Therefore, the mineralogical composition of their precursor sediments can be estimated. In contrast, the clear mismatch shown by the Lower Jurassic Belemnite Marls from Dorset indicates that these rhythms did not suffer an early diagenetic overprint. Our model helps to differentiate between rhythmites with strong depositional variations and those without; however, it cannot indicate whether a given alternation is the product of rhythmic diagenesis of a homogeneous precursor sediment or the result of diagenetic enhancement of subtle underlying sedimentary rhythms. For horizontally correlated patterns, such as laterally extensive beds and layers of nodules, an a priori unknown external signal has to be assumed.     

Comparison of neutron and X-ray diffraction in texture analysis of deformed carbonate rocks

The paper compares pole figure determinations with neutron diffraction and X-ray diffraction on experimentally deformed carbonate rocks, a coarse grained marble and fine grained limestone. Neutron diffraction enables determination of complete pole figures on a single spherical specimen and is advantageous for coarse grained materials. Results obtained with both diffraction techniques agree satisfactorily, although uncertainties introduced by counting statistics are more serious for neutrons than for X-rays. Continuous detectors add new possibilities which are still little explored.     

Quantitative analysis of calcite and Mg-calcite by X-ray diffraction: effect of grinding on peak height and peak area

Mineralogical analysis of calcite and Mg-calcite by X-ray diffraction requires that the samples be ground to a powder. Such grinding determines the particle size of the powder and the structural damage of the minerals. Both of these in turn affect the peak intensities recorded by the X-ray machine. Most carbonate sediments are inhomogeneous; they contain both calcite and Mg-calcite which are affected differently by grinding. Such differences cause quantitative analytical results to be inconsistent with the true mineralogical abundance. The two acceptable methods of analysis—(1) measurement of peak height from the base and (2) measurement of the area under the peak—were compared to determine if sample preparation affects the quantitative results. In samples with variable and relatively small amounts of calcite and Mg-calcite the measurement of peak height yields more reproducible results than does the measurement of peak areas. Different proportions of particle size of the mineralogical components in a sample powder, affect proportionally more the peak areas than the peak heights. Extensive grinding causes structural damage of the component minerals which affects much more the peak areas than the peak heights. Thus for quantitative analyses of calcite and Mg-calcite in inhomogeneous carbonate samples which require differing grinding times and have greatly variable amounts of calcite and Mg-calcite, the peak height measurement seems to be a better method than peak area measurement.     

安徽宿松上石炭统碳酸盐岩台地沉积物定量分析与海平面变化

安徽宿松地区上石炭统碳酸盐岩发育,厚约100m,化石丰富,属于比较典型的浅海碳酸盐岩台地沉积。定量分析显示,研究区岩石类型主要为颗粒灰岩和泥粒灰岩,颗粒平均含量分别为81.2％和69.6％,以浅海生物碎屑为主;其次为粒泥灰岩和泥晶灰岩,颗粒平均含量分别为26.4％和4.1％。依据岩石学特征,研究区主要发育开阔台地相和潮坪相,并可进一步划分出5种沉积亚相,分别是台内滩、台内盆、台内坪、潮间坪和潮上坪。在研究区上石炭统中共识别出3个长期的海进—海退旋回,其表现出在海平面变化总体呈下降趋势的背景之上叠加了短期的高频海平面波动的特征。这3个旋回与扬子板块其他地区及欧美板块同时代地层中的长期海进—海退旋回相当,表明海平面的变化可能受到晚古生代冈瓦纳大陆冰川的冰期和间冰期交替活动的影响。     

Marbles and carbonate rocks from central Morocco: a petrographic,mineralogical and geochemical study

Petrographic, mineralogical, and stable isotopes (δ¹³C, δ¹⁸O values) compositions were used to characterise marbles and sedimentary carbonate rocks from central Morocco, which are considered to be a likely source of ornamental and building material from Roman time to the present day. This new data set was used in the frame of an archaeometric provenance study on Roman artefacts from the town of Thamusida (Kenitra, north Morocco), to assess the potential employment of these rocks for the manufacture of the archaeological materials. A representative set of samples from marbles and other carbonate rocks (limestone, dolostone) were collected in several quarries and outcrops in the Moroccan Meseta, in a region extending from the Meknes–Khenifra alignment to the Atlantic Ocean. All the samples were studied using a petrographic, mineralogical and geochemical methods. The petrographic and minerological investigations (optical microscopy, electron microscopy, X-ray diffraction) allowed to group the carbonate rocks in limestones, foliated limestone, diagenetic breccias and dolostone. The limestones could be further grouped as mudstones, wackestones–packstones, crinoid grainstones, oolitic grainstone and floatstones. Textural differences allowed to define marbles varieties. The stable carbon and oxygen isotope composition proved to be quite useful in the discrimination of marble sources, with apparently less discriminatory potential for carbonate rocks.     

一种新的适合富有机质沉积岩的Re-Os同位素分析方法初探

虽然富有机质沉积岩中的Re和Os主要都富集在有机质中,但其中碎屑部分中的Re和Os也会影响其Re-Os等时线的准确度和精度。目前最常用的Cr O3-H2SO4溶样法虽然能尽量避免碎屑物质中Re和Os的溶出,但该方法具有Re流程空白高和环境污染严重等问题。因此,本研究尝试在富有机质沉积岩Re-Os同位素分析中使用H2O2-HNO3溶样来代替Cr O3-H2SO4溶样。本研究利用国际油页岩标样SGR-1b(USGS)为实验研究对象,分别对HCl-HNO3溶样、Cr O3-H2SO4溶样和H2O2-HNO3溶样3种溶样方法进行了对比研究。研究表明,H2O2与HNO3的体积比约为5﹕1的H2O2-HNO3溶液,不仅能保证样品和稀释剂的Re、Os同位素达到同位素交换平衡而且尽可能地避免碎屑物质中Re和Os的溶出。本方法相比于HCl-HNO3溶样,能尽量避免碎屑物质中Re和Os的溶出;而相比于Cr O3-H2SO4溶样,该方法具有本底低、无污染的优点。最后利用H2O2-HNO3溶样方法对广西金秀地区的泥岩样品和广东大宝山地区的碳质页岩样品进行了Re-Os同位素定年分析,分别得到了(404±5)Ma(IOs=1.57±0.13,n=8,MSWD=50)和(211±11)Ma(IOs=0.67±0.09,n=5,MSWD=11.1)的等时线年龄,这一结果与HCl-HNO3溶样得到的结果((412±11)Ma,IOs=1.18±0.38,n=8,MSWD=311;(223±18)Ma,IOs=0.59±0.14,n=5,MSWD=63)在误差范围内一致,但更为精确。     

碳酸盐岩生屑颗粒定量研究*——点计数法的理论分析与应用

碳酸盐岩中的生屑丰度数据为研究化石类群分异度、重建古生态环境提供了重要依据。点计数法易于定量统计各类生屑颗粒的丰度,比目估法、图像分析方法更适于碳酸盐岩组分的定量研究。在实际应用过程中,点计数法的最佳计点数常不易确定,往往会造成统计结果的精度不足,或统计工作耗时多、工作量大。应用点计数法和图像分析方法分别对视觉百分含量对比图和碳酸盐岩显微图像进行定量统计,分析沉积组分特征对点计数法测量误差的影响,以确定点计数法在碳酸盐岩生屑丰度统计时的最佳计点数。研究结果表明,点计数法适用于碳酸盐岩生屑颗粒丰度研究。对于大部分碳酸盐岩薄片定量分析工作,500点的计点数量基本可以将点计数法的测量误差控制在±2.5％以内。但是点计数法统计结果的精度受到薄片中生屑颗粒丰度、粒径大小、分选性甚至生屑分异度等沉积组分特征的影响。因此在实际工作中,应根据具体情况,适度调整计点数,从而在统计工作量和统计数据误差之间获得平衡。     

Petrofabric analysis of Saxony Granulites by optical and X-ray diffraction methods

The regional development of distinct patterns of preferred orientation of quartz c-axes in the Saxony Granulites has been well documented in the literature. A suite of specimens representative of these fabrics has been examined both by optical universal stage, to determine quartz c-axis orientation, and by X-ray diffraction, to obtain orientation data from r, z, m and a. The data are combined to yield inverse pole figures of schistosity and lineation.The finite strain of the Saxony Granulites is thought to be essentially a flattening and there is no evidence that the deformation path is other than one of continuous flattening. Elongation in the plane of the schistosity is local and not extreme. Because of this apparently simple deformation picture, and because preliminary transmission electron microscopy reveals the presence of dislocation structures similar to those found in deformed metals, an attempt is made to interpret the quartz orientation in terms of dislocation slip mechanisms. There is some evidence that the activation of different mechanisms is perhaps primarily controlled by temperature. At least some of the patterns of preferred orientation of quartz were probably produced by deformation in the field of stability of α-quartz.     

Authigenic carbonate precipitates from the NE Black Sea: a mineralogical,geochemical, and lipid biomarker study

Carbonate precipitates recovered from 2,000 m water depth at the Dolgovskoy Mound (Shatsky Ridge, north eastern Black Sea) were studied using mineralogical, geochemical and lipid biomarker analyses. The carbonates differ in shape from simple pavements to cavernous structures with thick microbial mats attached to their lower side and within cavities. Low δ¹³C values measured on carbonates (−41 to −32‰ V-PDB) and extracted lipid biomarkers indicate that anaerobic oxidation of methane (AOM) played a crucial role in precipitating these carbonates. The internal structure of the carbonates is dominated by finely laminated coccolith ooze and homogeneous clay layers, both cemented by micritic high-magnesium calcite (HMC), and pure, botryoidal, yellowish low-magnesium calcite (LMC) grown in direct contact to microbial mats. δ¹⁸O measurements suggest that the authigenic HMC precipitated in equilibrium with the Black Sea bottom water while the yellowish LMC rims have been growing in slightly ¹⁸O-depleted interstitial water. Although precipitated under significantly different environmental conditions, especially with respect to methane availability, all analysed carbonate samples show lipid patterns that are typical for ANME-1 dominated AOM consortia, in the case of the HMC samples with significant contributions of allochthonous components of marine and terrestrial origin, reflecting the hemipelagic nature of the primary sediment.     

Quantitative compositional analysis of a Triassic carbonate platform (Southern Alps,Italy)

We have estimated abundance and distribution of automicrite, marine cements and skeletal grains in the Triassic Sella massif, an isolated platform flanked by steep (25–35°) clinoforms. 108 samples were taken at constant intervals from measured sections of the major zones of the platform edifice: the platform top, margin–upper slope, and lower slope. In a first step, carried out in the field and on hand specimen, purely detrital deposits were separated from automicrite facies, i.e. beds with automicrite, cement-filled, primary vugs and admixtures of skeletal carbonate and lithoclasts. In the second step, samples with automicrite facies were thin-sectioned and point counted. The categories used for point counting were (a) automicrite, (b) vugs and cement, (c) microspar or neomorphic spar, (d) skeletal grains and (e) internal sediments. At the platform top 46% of samples are pure detrital deposits, 27% consist of automicrite facies and 27% are too strongly altered by dolomitization to allow classification. At the margin–upper slope 68% of samples consist of automicrite facies, 22% are pure detrital sediments and 10% are strongly altered. At the lower slope 63% are detrital deposits, 10% automicrite facies and 27% are extensively dolomitized. The most important contributors to the automicrite facies are automicrite (41% on the platform top, 29% on the margin–upper slope, 28% on the lower slope) and early marine cement (35% on the platform top, 48% on the margin–upper slope, 27% on the lower slope). The amount of skeletal grains is less than 10%.The automicrite facies stabilized the platform margin and upper slope. Automicrite, abundant early marine cements and micro-organisms such as Tubiphytes, formed a rigid framework, thus substituting for the lack of a metazoan reef. On the upper slopes, the framework of automicrite facies stabilized the slope but intermittently. The automicrite layers are frequently dissected by sediment-filled fractures or are broken into clasts. We assume that they slid on the layers of loose detritus. Bigger slides turned into rubbly debris flows that formed metre-thick breccias at the lower slope and the proximal basin floor. The planar shape and steep angle of the clinoforms indicate that the large-scale geometry of the slope was not controlled by the automicrite but rather by non-cohesive layers of sand and rubble piled up to the angle of repose.The production mode of the Sella is comparable of that of a (mud) mound factory. This factory was highly productive: in 1 Ma, the platform aggraded over 300 m and prograded over 2000 m in all directions.     

Element fractionation by sequential extraction in a soil with high carbonate content

The influence of carbonate and other buffering substances in soils on the results of a 3-step sequential extraction procedure (BCR) used for metal fractionation was investigated. Deviating from the original extraction scheme, where the extracts are analysed only for a limited number of metals, almost all elements in the soils were quantified by X-ray fluorescence spectroscopy, in the initial samples as well as in the residues of all extraction steps. Additionally, the mineral contents were determined by X-ray diffractometry. Using this methodology, it was possible to correlate changes in soil composition caused by the extraction procedure with the release of elements. Furthermore, the pH values of all extracts were monitored, and certain extraction steps were repeated until no significant pH-rise occurred. A soil with high dolomite content (27%) and a carbonate free soil were extracted. Applying the original BCR-sequence to the calcareous soil, carbonate was found in the residues of the first two steps and extract pH-values rose by around two units in the first and second step, caused mainly by carbonate dissolution. This led to wrong assignment of the carbonate elements Ca, Mg, Sr, Ba, and also to decreased desorption and increased re-adsorption of ions in those steps. After repetition of the acetic acid step until extract pH remained low, the carbonate was completely destroyed and the distributions of the elements Ca, Mg, Sr, Ba as well as those of Co, Ni, Cu, Zn and Pb were found to be quite different to those determined in the original extraction. Furthermore, it could be shown that the effectiveness of the reduction process in step two was reduced by increasing pH: Fe oxides were not significantly attacked by the repeated acetic acid treatments, but a 10-fold amount of Fe was mobilized by hydroxylamine hydrochloride after complete carbonate destruction. On the other hand, only small amounts of Fe were released anyway. Even repeated reduction steps did not destroy the amorphous Fe oxides completely, showing that 0.1 mol L⁻¹ hydroxylamine hydrochloride was not strong enough to attack these oxides effectively.The extraction sequences were carried out not only on the soil samples, but also on their coarse and fine fractions (> or <2 μm). The fine fraction of the calcareous soil contained only 10% dolomite, but was enriched in organic matter and clay minerals, which also resulted in increased extract pH-values during the sequential extraction. Hence, the effects on ion release in the fine fraction were similar to those of the whole soil. Since the destruction of the organic matter was incomplete after regular oxidation, the H₂O₂-treatment of the fine fraction had to be repeated. The addition of the extractable amounts of the two fractions showed good agreement to the results obtained for extraction of the whole soils. Likewise the pH-values of the carbonate-free soil extracts did not increase significantly, therefore it was concluded that repetitions of extraction steps for this soil were not necessary.Extract-pHs should always be controlled so that extraction conditions are comparable; to be able to use the BCR extraction scheme or similar ones for carbonate- and organic-rich samples this is mandatory. Single extraction steps should be repeated if pH rises too much; additionally the oxidizing step should be performed more than twice for samples rich in organic substances, depending upon the violence of the reaction with H₂O₂. If these precautions are neglected the validity of the extraction data is likely to be questionable.     

Evaluation of a wide range laser diffraction grain size analyser for use with sediments

The qualities of a laser diffraction grain size analyser, the Coulter LS-100 (range claimed by the manufacturer: 0·4–900 μm in a single measurement), are evaluated on sediments of fluvial and lacustrine origin. Accuracy and resolution of measurement on standard latex spheres are excellent. Reproducibility of the results on natural sediments appears to be satisfactory, but the method underestimates the fraction of clay particles with an efficiency of detection (36–70%) proportional to the clay content determined from pipette analysis. This efficiency is somewhat higher than those reported from other instruments of the same generation. Comparison of the Coulter LS-100 with other sizing techniques shows good agreement with the sieving method but some differences appear with the electroresistance particle technique: median and mean size values measured by the Coulter Counter TA1 are systematically lower than those obtained by the Coulter LS-100. Analyses show good correlation with those of a Malvern Laser particle analyser but a discrepancy appears with very fine silt and clay sized sediments. The Coulter LS-100 detects a higher clay content than that measured with the Malvern Laser Sizer 2600. Except when precise measurements of clay content are needed, the Coulter LS-100 produces precise and accurate results in size ranges required for geological and environmental studies.     

利用XRD法探讨邢台隆东井田煤变质规律

邢台隆东井田煤变质情况复杂,直接影响煤的工业利用。利用X-射线衍射(XRD)法探讨了区内不同变质程度煤的基本结构单元特征及煤变质规律。结果显示:垂向上,随着煤层埋藏深度的增加,层片间距d₀₀₂值逐渐减小,层片堆积高度L_c和层片直径L_a值逐渐增大;平面上,离岩浆侵入体越近,煤层的层间距d₀₀₂值越小,反之d₀₀₂值越大。在煤种分布上,因受岩浆热源的影响,井田内煤种以旧城为中心向外呈带状分布,旧城附近为无烟煤,向外逐渐过渡为贫煤、瘦煤、焦煤、肥煤和气煤。区内煤变质作用主要受区域变质作用影响,并叠加了岩浆热变质作用。     

Petrographic thin sections of archaeologial sediments: A new method for paleobotanical studies

The use of petrographic thin sections to examine archaeological sediments has centered on the study of detrital and chemical components of the material. There has been relatively little effort made to study botanical remains—particularly charcoal—with this technique. This paper illustrates that millimeter-size or even smaller fragments examined in undisturbed, artificially indurated samples, which normally would escape collection with standard flotation and sieving techniques, can furnish significant paleobotanical information about the types of vegetal matter found in a site. Samples from cave sediments in Israel and an open-air site in Canada are presented. © 1994 John Wiley & Sons, Inc.     

Salinity reflux and dolomitization of southern Australian slope sediments: the importance of low carbonate saturation levels

Anomalously saline waters in Ocean Drilling Program Holes 1127, 1129, 1130, 1131 and 1132, which penetrate southern Australian slope sediments, and isotopic analyses of large benthic foraminifera from southern Australian continental shelf sediments, indicate that Pleistocene–Holocene meso‐haline salinity reflux is occurring along the southern Australian margin. Ongoing dolomite formation is observed in slope sediments associated with marine waters commonly exceeding 50‰ salinity. A well‐flushed zone at the top of all holes contains pore waters with normal marine trace element contents, alkalinities and pH values. Dolomite precipitation occurs directly below the well‐flushed zone in two phases. Phase 1 is a nucleation stage associated with waters of relatively low pH (ca 7) caused by oxidation of H₂S diffusing upward from below. This dolomite precipitates in sediments < 80 m below the sea floor and has δ¹³C values consistent with having formed from normal sea water (? 1‰ to + 1‰ Vienna Pee Dee Belemnite). The Sr content of Phase 1 dolomite indicates that precipitation can occur prior to substantial metastable carbonate dissolution (< 300 ppm in Holes 1129 and 1127). Dolomite nucleation is interpreted to occur because the system is undersaturated with respect to the less stable minerals aragonite and Mg‐calcite, which form more readily in normal ocean water. Phase 2 is a growth stage associated with the dissolution of metastable carbonate in the acidified sea water. Analysis of large dolomite rhombs demonstrates that at depths > 80 m below the sea floor, Phase 2 dolomite grows on dolomite cores precipitated during Phase 1. Phase 2 dolomite has δ¹³C values similar to those of the surrounding bulk carbonate and high Sr values relative to Phase 1 dolomite, consistent with having formed in waters affected by aragonite and calcite dissolution. The nucleation stage in this model (Phase 1) challenges the more commonly accepted paradigm that inhibition of dolomitization by sea water is overcome by effectively increasing the saturation state of dolomite in sea water.