酸碱滴定法测定天然石膏中碳酸盐的不确定度评定

对酸碱滴定法测定天然石膏中碳酸盐的结果进行不确定度评定。测量过程中的不确定度主要来源于样品制备过程引入的不确定度、滴定导致的不确定度、标定NaOH标准滴定溶液和HCl标准溶液引起的不确定度及重复性实验引起的不确定度等。合成各不确定度分量,并乘以扩展因子2得到扩展不确定度。对于CO₂平均含量为8.66%（质量分数）的天然石膏样品,其扩展不确定度为0.17%。     

基于聚丙烯扩散皿的碱解扩散分离-酸碱滴定法测定土壤中水解性氮

传统的碱解扩散分离-酸碱滴定法测定土壤样品中的水解性氮,通常采用玻璃扩散皿进行碱解扩散分离。但是使用该法对样品进行前处理和碱解扩散分离过程中,操作者常会面临如下三种困扰：一是玻璃扩散皿内室溶液极易被氢氧化钠溶液和碱性胶液污染;二是玻璃扩散皿和盖子之间容易出现氨气泄漏,而且发现时往往无法解决;三是玻璃扩散皿比较笨重易碎,实验操作不方便;最终导致测定结果不稳定性和操作者对该法体验不佳。本文采用聚丙烯扩散皿,通过改进扩散皿清洗方法和提升扩散皿密封性、统一还原剂加入量和氢氧化钠溶液浓度(1.8mol/L)、适当增加氢氧化钠溶液的加入体积和降低盐酸标准溶液浓度,提高了水解性氮测定的稳定性和准确性。该方法中发生的污染明显降低,避免了发生氨气泄漏,操作便捷。应用于分析土壤有效态标准物质的测定值与标准值一致,如水解性氮测定值< 50mg/kg的标准物质GBW07416a,其绝对偏差为0.2~1.8mg/kg;水解性氮测定值在50~200mg/kg的标准物质GBW07415a、NSA-1、NSA-4、NSA-5、NSA-6,其绝对偏差为0~4.0mg/kg。还原剂对硝态氮转化为铵态氮的加标回收率在89.6%~96.4%之间。该方法可满足测定土壤样品中水解性氮含量的要求。     

钾长石-石膏-石灰(石)热分解体系研究

在钾长石-石膏-石灰(石)热分解体系中可能发生的7类反应的ΔGT0进行重新计算的基础上,利用纯物质摩尔配比,分别在1 273 K,1 323 K,1 373 K和1 423 K条件下进行物料焙烧实验,通过对烧成物可溶K2O含量测定,得出反应KAS6 CaSO4 14CaO=K2SO4 C3A 6C2S是7类分解反应中最容易发生的反应,与计算的该反应ΔGT0值最负相当吻合。对7类反应的烧成物进行XRD和EPMA分析,得出了这7类反应中只有反应式KAS6 CaSO4 12CaO=K2SO4 CA 6C2S和KAS6 CaSO4 14CaO=K2SO4 C3A 6C2S正确,其他均需要重新修正,修正后的反应可以更加合理的解释该体系的分解机理,从而为利用该体系焙烧生产钾肥提供理论指导。     

利用谱睿(Pre)在线样品前处理技术检测高碳酸盐基体中阴离子

利用戴安公司全新的谱睿(Pre)在线样品前处理技术,开发了一种柱前在线去除高碳酸盐基体中碳酸盐的方法,解决了以往高碳酸盐基体对其他阴离子测定的影响问题。利用该方法对钢铁洗涤液碳酸钠溶液、固体碳酸钠试剂、商品化碳酸钠淋洗液浓缩液等不同类型的样品分别进行了检测。选择的色谱条件为高容量氢氧化物选择性IonPac AS15阴离子交换色谱柱,淋洗液自动发生装置在线产生KOH进行梯度淋洗,抑制电导检测。该方法在常规离子色谱基础上增加一个输液泵、一个六通阀和一个在线二氧化碳去除器(CRD),提出了不使用浓缩柱作为前处理设备与离子色谱主机之间的接口,而采用大定量环,选取合适的时间窗口这一先进理念。该方法可实现5000 mg/L碳酸盐溶液的在线去除,同时检测出浓度低于50μg/L的氯离子、硝酸根离子、硫酸根离子等阴离子。采用外标法和外延法进行定量,标准曲线线性较好,标准加入回收率为92%~108%。方法具有操作简单、可重复性强、方法新颖等特点,并解决了碳酸根离子对其他阴离子的测定干扰这一离子色谱技术难题。     

基体分离-电位滴定法测定高硫金属矿中的微量氯

使用碳酸钠-氧化锌混合碱焙烧样品,将硫化物矿中的低价硫转化为硫酸盐或高价硫,过滤分离基体,采用电位滴定法测定硫化物矿(铜精矿、锌精矿、硫铁矿)中的微量氯,消除由于硫化银沉淀的产生对氯化银测定结果的干扰。通过电位突越,确定滴定终点,消除色度和浊度对滴定终点的影响。采用电极电位-浓度二次微商滴定曲线,计算滴定终点。对混合碱的选择及加入量、焙烧温度、溶液酸度、测定温度、滴定介质以及基体和共存元素的干扰进行了试验。方法精密度(RSD,n=9)均小于9%,回收率为94.1%~105.6%。     

碳酸盐(岩)的锂同位素组成:一种潜在的古海水pH替代性指标

地球演化历史中海水的pH值发生了明显变化,海水pH值可能是控制海相碳酸盐岩能否形成及其成分演化的重要因素,对了解地球早期白云岩的成因和一些矿产的形成等均有重要指示意义.然而,记录海洋pH值变化的替代性指标非常稀少,常用的主要是碳酸盐(岩)的硼同位素.古老碳酸盐的硼同位素往往受到后期地质作用的影响,δ11B-pH转化过程中需要基于多种假设,硼酸和硼酸根之间的分馏系数(αB)、硼酸表观电离常数(pKB*)以及 δ11BSW的不确定性,使硼同位素分析结果具有多解性、不确定性.亟需多个独立指标对海水pH值进行限制,碳酸盐(岩)锂同位素是一个潜在的替代性指标,Roberts et al.(2018)发现有孔虫碳酸盐壳体的δ7Li与海水pH值呈显著负相关关系,认为6Li和7Li水合离子在进入碳酸盐晶格时要脱去溶剂水,这个过程的去溶能与pH值相关,导致锂离子进入有孔虫方解石壳体的过程中存在显著的同位素分馏.在对蓟县剖面中—新元古代海相碳酸盐岩碳酸盐相的硼、锂同位素进行研究时发现,纯净原始碳酸盐岩的锂同位素组成(4.9‰~13.4‰,平均8.03‰)明显低于现代海洋碳酸盐的锂同位素组成,中元古以来碳酸盐(岩)的锂同位素组成总体呈上升趋势.纯净原始碳酸盐岩的锂同位素组成与硼同位素组成及海水的pH值(δ11Bsw=25‰)呈明显反相关关系;硅质条带白云岩的硼、锂同位素组成也呈明显反相关关系,说明碳酸盐(岩)的锂同位素确实有可能成为一种潜在的pH值替代性指标.若碳酸盐(岩)锂同位素可以对海水pH值施加独立约束,那硼、锂同位素联合研究将对重建古海洋的pH值演化具有重大意义.     

电感耦合等离子体发射光谱法多向观测同时测定碳酸盐中常量和微量元素

采用偏硼酸锂熔矿分解试样,稀盐酸提取,电感耦合等离子体发射法同时测定碳酸盐中二氧化硅、氧化钙、氧化镁、三氧化二铝、三氧化二铁、氧化钾、氧化钠、氧化锰、二氧化钛、五氧化二磷、三氧化硫等多种常量和微量组分。各元素选择光谱干扰少、准确度高的多向观测方式(轴向、径向衰减),改善方法的检出限和精密度。方法回收率为94.7%~104.6%,相对标准偏差(RSD,n=10)低于3.0%。方法经国家一级标准物质验证,测定值与标准值基本相符。     

广东高凤金矿形成时代的Rb-Sr、~(40)Ar-~(39)Ar年龄测定

用含金石英脉流体包裹体Rb-Sr和~(40)Ar-~(39)Ar方法测定了广东高凤金矿的形成时代为印支期(215×10~6a)。两种方法的结果在误差范围内完全一致,两种测定方法相互验证,结果准确可靠。研究表明含金石英脉流体包裹体Rb-Sr和~(40)Ar-~(39)Ar年代方法对于解决石英脉型金矿的成矿时代具有很好的应用前景。     

氢化物发生—原子荧光光谱法测定地质样品中的锑(Ⅲ)和锑(Ⅴ)

提出了一种氢化物发生—原子荧光光谱法测定地质样品(水系沉积物)中Sb(Ⅲ)和Sb(Ⅴ)的方法.选取4.8 mol/L HC1为提取剂,采用超声波辅助提取,以6 g/mL柠檬酸钠作为Sb(Ⅴ)的掩蔽剂,在0.24 mol/L的HC1介质中选择性测定Sb(Ⅲ),用差减法求得Sb(Ⅴ).Sb(Ⅲ)的方法检出限为0.075×10-6,Sb(Ⅴ)的方法检出限为0.097×10-6.对40 ng/mL的Sb(Ⅲ)和Sb(Ⅴ)分别连续测定11次,得到相对标准偏差分别为1.1％和0.64％.应用该方法对地质样品中的Sb(Ⅲ)和Sb(Ⅴ)进行分析测定,并与王水溶解值相比较,该方法测定的总Sb提取率在80％以上,Sb(Ⅲ)和Sb(Ⅴ)的加标回收率分别为83％ ～ 107％和98％ ～ 114％.     

碳酸盐岩中烃类包裹体的人工合成实验研究

运用Sterner和Bodnar在1984年提出的愈合裂隙的实验技术,利用冰洲石作为主矿物,进行了烃类包裹体的合成实验研究.并将实验产物磨制成双面抛光的薄片,在普通光学显微镜和荧光显微镜下对合成的包裹体进行了岩相学观察.结果表明本次研究在冰洲石中成功地合成了含液态烃类的包裹体,这也是国内外首次在碳酸盐岩矿物中成功合成的烃类包裹体,它为研究碳酸盐岩中油气藏的形成机理提供了一种新的手段,也为正确理解和解释自然界碳酸盐岩油气藏中烃类包裹体的资料提供了重要的参考.     

Facies and sedimentology of a carbonate delta drift (Miocene,Maldives)

The identification of sediment drifts typically relies on interpretation of reflection seismic data sets. This study sedimentologically analyzed an example of a carbonate delta drift previously identified in seismics in order to provide a catalogue of characteristic features at core and seismic scale for allowing testing the occurrence of this poorly known type of deposit elsewhere. Cores and downhole logs recovered during International Ocean Discovery Program Expedition 359 to the Maldives, in combination with seismic data, were analyzed with this objective. The diagnostic criteria for the sedimentological recognition of a delta drift are: (i) the development of sigmoidal clinoforms that thin out towards proximal and distal settings; (ii) a proximal part characterized by coarse‐grained facies with abundant shallow‐water components and distal areas dominated by fine‐grained facies with rare to absent shallow‐water components; (iii) winnowing of the finer fraction in proximal facies; (iv) extensive fragmentation of most of the bioclasts with minor intervals of well‐preserved components; (v) bigradational intervals in the proximal part and large channels in proximal to distal settings; and (vi) the lobe to delta shaped outline of the sediment accumulation. The characteristic shallow‐water fossil assemblage of the Mid to Upper Miocene delta drift consists of large benthic foraminifera (Amphistegina, Cycloclypeus, Lepidocyclina, Operculina and Heterostegina), fragmented red algae and bryozoans, equinoid debris, and Halimeda plates. The deeper‐water part of the drift bodies consists of fine‐grained planktonic foraminifera‐rich wackestone. Condensed intervals may occur as result of enhanced bottom‐current activity. In contrast to siliciclastic drift bodies, the carbonate delta drift has an important contribution by in situ shallow‐water carbonate production reminiscent of a shoal. In situ carbonate production is proposed as a major controlling factor which is as important as the pelagic settling or the shaping by density and bottom currents in siliciclastic drifts. In the absence of three‐dimensional data and in two‐dimensional views the carbonate delta drift sediment bodies resemble carbonate ramps, which indicates that there may be the need to re‐evaluate various cases of such systems described from the geological record.     

Geotechnical evaluation of Miocene gypsum from Sivas (Turkey)

Gypsum is widely distributed in Sivas (Turkey), occurring chiefly in the formations of Miocene age. The gypsum is generally of the alabastrine type with a little of the porphiroblast type and contains traces of clay minerals, anhydrite and calcite. It is a moderately strong rock in terms of its unconfined compressive strength which is related to the crystal size. Strength increases as the crystal size decreases. The strength of gypsum was reduced by approximately 55%, when the samples were kept in the water for 20 days. Most samples exhibit plastic–elastic–plastic deformation. The gypsum has a high modulus ratio, and is a moderately deformable rock. High lateral deformations and low vertical deformations are observed under the vertical stress conditions in accordance with the relationship between modulus ratio and strain.     

Continuity and facies heterogeneities of shallow carbonate ramp cycles (Sinemurian,Lower Jurassic,North‐east Spain)

The lateral continuity and facies heterogeneities of metre‐scale cycles in a greenhouse Lower Jurassic (Sinemurian) carbonate ramp from the northern Iberian Basin (Spain) was evaluated from extensive field analysis carried out on a well‐exposed 12 km long outcrop. Eleven high‐frequency continuous cycles and their bounding surfaces are traceable laterally through the entire outcrop. However, three of these cycles are found to split laterally into discontinuous cycles of more limited distribution (up to 3 to 5 km of lateral extent). The continuous and discontinuous cycles have a similar field expression in one‐dimensional logs. As a consequence, the number of cycles that can be differentiated is variable along the logged sections (i.e. from 11 to 16). Cycles have variable facies heterogeneities and sedimentary trends depending on the environment of formation: shallowing‐upward and symmetrical cycles occur in protected lagoon–tidal flat areas and in the open‐marine, high‐energy domain. These cycles show significant facies heterogeneities, which were controlled mainly by lateral migration of a mosaic of facies over an irregular topography. Deepening‐upward and aggradational cycles are generated in low‐energy, sub wave‐base, open‐marine areas. Facies are laterally homogeneous, reflecting low potential for carbonate accumulation and inability to fill the created accommodation space in this low‐relief and relatively deep area. Cycle boundaries are generated by stages of rapid accommodation gain, involving the flooding of the carbonate ramp; they are more likely to originate from regional tectonic pulses (related to the extensional tectonics operating in the northern Iberian Basin) rather than greenhouse low‐amplitude eustacy. Discontinuous cycles tend to occur in thickened areas and are interpreted as originating from the infill of wedge‐shaped accommodation space resulting from differential subsidence (i.e. local tectonic pulses). In conclusion, where thickness variations occur in extensional settings lateral continuity of cycles should not be expected. In less well‐exposed, or in one‐dimensional sections and in wells, it would not be possible to distinguish continuous from discontinuous cycles, or to understand such two‐dimensional heterogeneities. Identification of unique cycle‐forming mechanisms or attempting cyclostratigraphic long‐distance correlation of cycles is unrealistic without a detailed analysis of the architecture of cycles in laterally continuous outcrops.     

Evolution of karst in Messinian gypsum (Monferrato,Northern Italy)

In the Tertiary Basin of Piedmont (Northern Italy) a 100-150 m thick Messinian sedimentary succession crops out, composed of pre-evaporitic clays, gypsum beds and post-evaporitic lacustrine-marine fine-grained sediments. In the Monferrato area the thickness of the evaporite sequence is highly variable (0-140 m) due to an important erosion surface formed at the end of the evaporite cycle and carved in the gypsum beds. Epigenic caves probably formed during this short intra-Messinian phase of emersion. Cave sediments contain benthonic and planctonic foraminiferal associations ranging in age from Burdigalian to Upper Pliocene. These sediments have probably been deposited in recent times, although it cannot be completely ruled out that they accumulated in caves developed in Upper Messinian times. The formation of the most important caves of this area probably started at the end of the Messinian under epigenic conditions. Possibly, those inherited caves enlarged slowly during the Quaternary in an intrastratal and confined hypogene karst system.     

中国西部三大盆地海相碳酸盐岩台地边缘类型及特征

在回顾经典的碳酸盐沉积模式类型研究和我国学者对碳酸盐岩台地边缘特征研究的基础上,以构造控盆、盆地控相、相控生储盖组合为指导思想,依据中国西部三大海相盆地碳酸盐岩发育的特殊性,从中国西部三大盆地海相碳酸盐岩发育特征和地质实际情况出发,系统建立了5种碳酸盐岩台地边缘类型及沉积模式和12种亚类类型。以中国西部三大盆地不同时期发育的碳酸盐沉积特征为主线,从盆地构造演化、岩性特征、相带变化以及模式演化等方面详细分析了各个碳酸盐岩台地边缘类型及沉积模式特征。不同类型台地边缘及其沉积模式演化特征研究对分析生烃、储烃和盖烃物质等油气要素的时间和空间匹配关系具有重要的指导意义。     

The start‐up of the Dolomia Principale/Hauptdolomit carbonate platform (Upper Triassic) in the eastern Southern Alps

Wide carbonate platform environments developed on the western passive margin of the Tethys during the Late Triassic, after a major climate change (Carnian Pluvial Episode) that produced a crisis of high‐relief microbial carbonate platforms. The peritidal succession of this epicontinental platform (Dolomia Principale/Hauptdolomit, Dachstein Limestone) is widespread in the Mediterranean region. However, the start‐up stage is not fully understood. The original platform to basin depositional geometries of the system have been studied in the north‐eastern Southern Alps, close to the Italian/Slovenian boundary where they are exceptionally preserved. Sedimentological features have been investigated in detail by measuring several stratigraphic sections cropping out along an ideal depositional profile. The analysis of the facies architecture allowed reconstruction of the palaeoenvironments of the Dolomia Principale platform during its start‐up and early growth stages in the late Carnian. The carbonate platform was characterized by an outer platform area, connected northward to steep slopes facing a relatively deep basin. Southward, the outer platform was connected to inner sheltered environments by a narrow, often emerged shelf crest. Behind this zone, carbonate sedimentation occurred in shallow lagoons and tidal flats, passing inward to a siliciclastic mudflat. The Dolomia Principale platform was initially aggrading and able to keep pace with a concomitant sea‐level rise, and then prograding during the late Carnian. This stratigraphic interval was correlated with the Tuvalian succession of the Dolomites, allowing depiction of the depositional system on a wide scale of hundreds of kilometres. This large‐scale depositional system presents features in common with some Palaeozoic and Mesozoic carbonate build‐ups (for example, the Permian Capitan Reef complex, Anisian Latemar platform), both in terms of architecture and prevailing carbonate producers. A microbial‐dominated carbonate factory is found in the outer platform and upper slope. The recovery of high‐relief microbial carbonate platforms marks the end of the Carnian Pluvial Episode in the Tuvalian of Tethys.     

Flotation Separation of Trace Elements from Alkaline-Earth Matrices by Co(III) Hexamethylenedithiocarbamate before ICP-AES Determination

A method for the selective separation of Ag, Cd, Cr, Cu, Ni, Pb and Zn in traces from solutions of calcite (CaCO₃), dolomite (CaMg(CO₃)₂) and gypsum (CaSO₄.2H₂O) before their determination by inductively coupled plasma-atomic emission spectrometry (ICP-AES) is presented. The expected interferences of Ca and Mg on intensities of trace analytes were removed by collecting the elements of interest with cobalt(III) hexamethylenedithiocar-bamate, Co(HMDTC)₃. The flotation of aqueous solutions (1 l) of calcite, dolomite and gypsum was performed at pH 6.0, by 1.5 mg l⁻¹ Co and 0.6 mmol l⁻¹ HMDTC⁻. To minimise the effect of the reaction between Ca/Mg, which restrains the function of the surfactant, careful selection of the most suitable foaming reagent was necessary. The accuracy of the method was established by analysing natural alkaline-earth minerals by the standard addition method as well as using the dolomite reference materials GBW 07114 and GSJ JDo-1. The ICP-AES limits of detection following flotation on different minerals were found to be 0.080 μg g⁻¹ for Cd, 0.105 μg g⁻¹ for Ag, 0.142 μg g⁻¹ for Cu, 0.195 μg g⁻¹ for Cr, 0.212 μg g⁻¹ for Ni, 0.235 μg g⁻¹ for Zn and 0.450 μg g⁻¹ for Pb.     

基于生物诱导碳酸钙沉淀的土体固化研究进展

基于微生物或脲酶诱导碳酸钙沉淀（MICP/EICP）的土体固化技术是近年来岩土和地质工程领域的研究热点之一。在系统回顾基于生物诱导碳酸钙沉淀的土体固化技术发展历程的基础上,重点阐述了MICP/EICP固化机制、土体孔隙结构、菌液和脲酶性质、胶凝液性质和固化方式等方面对碳酸钙特性影响的研究进展。研究结果表明：土体孔隙越小,越不利于微生物或脲酶入渗,固化均匀性越差;土颗粒接触点越多,可为碳酸钙提供的沉积点位越多,碳酸钙与土颗粒间的黏结和桥接作用越强,固化效果越好;一定菌液或脲酶浓度或脲酶活性范围内,碳酸钙的生成速率和生成总量随浓度及活性的增大而增大,但过高的浓度或活性易导致碳酸钙生成速率过快,从而在土体注入端发生堵塞;低浓度胶凝液得到的碳酸钙晶体更小,在土体中的分布更均匀;采用合适的注浆饱和度可提高具有黏结作用的碳酸钙的占比;采用多层交替注入或单相低pH值注入可提高碳酸钙在试样中分布的均匀性。基于碳酸钙沉淀特性的影响因素,提高固化土体的均匀性,验证其耐久性,室内试验结果在现场尺度的适应性和改进方案应该成为以后研究的重点。