湖相原生白云石的微生物成因机理探讨*

近年来,随着对微生物白云石模式研究的不断深入,为解释“白云石问题”提供了新思路。前人对微生物白云石成因研究侧重于微生物对未固结沉积物的改造,即有机准同生白云石化作用,这与实验室中以微生物为媒介形成的“有机原生白云石”在成因机理上存在差异。笔者将微生物白云石机理引入湖相原生白云石成因解释中,认为在湖水—沉积物交界处也会发生微生物成因的原生白云石沉淀,即有机原生白云石。湖水与沉积物交界处的微环境存在明显区别,总体可分为有氧和缺氧2种亚环境,不同亚环境中生活有不同的微生物群落。根据湖泊亚环境特性和微生物种类及其在白云石形成过程中所发挥的作用,可以区分出细菌有氧氧化模式、硫酸盐还原模式和产甲烷模式3种微生物白云石模式。不同模式对应于不同的湖泊环境: 细菌有氧氧化模式主要发生于有氧、高Mg/Ca值的咸水/盐湖环境;硫酸盐还原模式主要发生于缺氧、高Mg/Ca值的咸水/盐湖环境;产甲烷模式主要发生于缺氧、低Mg/Ca值的淡水/咸水湖环境。另外,还探讨了pH值变化、SO42-的存在和硫化物对镁水合物脱水的影响以及微生物白云石沉淀的环境因子。对微生物成因的原生白云石模式的深入认识,将为湖相白云石成因研究提供新的理论基础和研究思路。     

湖相原生白云石的微生物成因机理探讨

近年来,随着对微生物白云石模式研究的不断深入,为解释"白云石问题"提供了新思路。前人对微生物白云石成因研究侧重于微生物对未固结沉积物的改造,即有机准同生白云石化作用,这与实验室中以微生物为媒介形成的"有机原生白云石"在成因机理上存在差异。笔者将微生物白云石机理引入湖相原生白云石成因解释中,认为在湖水—沉积物交界处也会发生微生物成因的原生白云石沉淀,即有机原生白云石。湖水与沉积物交界处的微环境存在明显区别,总体可分为有氧和缺氧2种亚环境,不同亚环境中生活有不同的微生物群落。根据湖泊亚环境特性和微生物种类及其在白云石形成过程中所发挥的作用,可以区分出细菌有氧氧化模式、硫酸盐还原模式和产甲烷模式3种微生物白云石模式。不同模式对应于不同的湖泊环境:细菌有氧氧化模式主要发生于有氧、高Mg/Ca值的咸水/盐湖环境;硫酸盐还原模式主要发生于缺氧、高Mg/Ca值的咸水/盐湖环境;产甲烷模式主要发生于缺氧、低Mg/Ca值的淡水/咸水湖环境。另外,还探讨了pH值变化、SO_4~(2-)的存在和硫化物对镁水合物脱水的影响以及微生物白云石沉淀的环境因子。对微生物成因的原生白云石模式的深入认识,将为湖相白云石成因研究提供新的理论基础和研究思路。     

松科1井嫩江组湖相含铁白云石的准确定名和矿物学特征

通过XRD衍射和电子探针分析,从矿物学命名的角度出发,提出松科1井嫩江组湖相白云岩的主要矿物是白云石和铁白云石之间的过渡类型——含铁白云石,而不是长期认为的铁白云石。矿物学特征表明:精测后的晶胞参数a、c、V值均大于标准白云石,更接近标准铁白云石,说明含铁白云石和铁白云石具有相同晶体结构,但在同一结构位置上,Fe2+和Mg2+的数量比存有差异,且结构中Fe2+对Mg2+的部分替代是导致晶胞轴长和体积增大的原因,从晶体结构的角度再次证实样品为含铁白云石。另外,通过计算,含铁白云石的有序度均值为0.40,CaCO3摩尔含量均值为55.48g/mol,表明较富钙的、低有序度的含铁白云石形成于结晶速度较快、不稳定的成岩环境中。     

柴西下干柴沟组湖相白云岩特征及成因分析

对柴达木盆地西部地区下干柴沟组湖相白云岩的岩石组构、矿物成分、主微量元素地球化学及碳氧同位素特征进行研究,并分析白云岩成因。研究区白云岩沉积环境为浅水相对封闭湖相环境,白云岩以泥晶白云岩为主,层状、块状分布,见藻云岩、膏质白云岩及颗粒云岩,有序度普遍较低。主量元素中Mg2+/Ca2+比值低,Mn、Fe、Na、Sr元素含量高,指示沉积环境水体盐度较高和相对封闭;微量元素中稀土元素具有轻稀土相对富集、Eu负异常特征,反映低温浅埋藏的成岩环境;氧同位素为较低的负值,反映整体咸化水体特征,碳同位素为较低的正值或负值,主要是受到大气水影响和生物的影响。研究认为白云石形成于准同生期相对封闭咸化环境中,白云石化流体中Mg2+主要来源于大气水的淋滤和深部卤水,少数来自于藻类的分解;Mg2+通过蒸发、盐类矿物沉淀而富集,富Mg2+流体通过回流渗透交代方解石发生白云石化。     

三株嗜盐古菌诱导形成白云石

白云石成因问题是地质学上长期悬而未决的难题之一.近年来,微生物诱导白云石沉淀逐渐成为白云石成因的重要理论之一,但其中微生物的作用机理远未探明.现生白云石主要分布于高盐环境,该环境中的优势菌群为嗜盐菌,包括嗜盐细菌和嗜盐古菌.因而此次选取三株嗜盐古菌Natrinema sp.J7-1、Natrinema sp.J7-3和Natrinema sp.LJ7,研究其诱导白云石沉淀的能力,并对比不同细胞浓度对白云石沉淀的影响,以期更深入地了解微生物在白云石形成中的作用.通过X射线衍射 (XRD) 检测沉淀物的物相,利用扫描电子显微镜 (SEM) 观察所得矿物形态,同时辅以能量色散谱分析 (EDS) 分析矿物的元素组成.实验结果表明三株嗜盐古菌皆可诱导球型、哑铃型、花椰菜型以及球形聚集体等白云石的形成,且在较高细胞浓度下诱导形成的矿物中白云石含量增多.分析表明细胞浓度的增加会导致细胞表面羧基含量的增加,从而为白云石的沉淀提供更多的成核位点,有利于Mg进入矿物晶格,从而诱导白云石沉淀,本结果进一步提高了对微生物白云石成因机理的认识.      

白云凹陷第三系储层中铁白云石的成因机理及与CO2活动的关系

白云凹陷第三系储层中发育大量的铁白云石,受研究区热流背景的影响,铁白云石主要见于高地温梯度地区埋深1000～3000m、地层温度60～130℃的浅—中部地层中及CO_2热流体活动区域。铁白云石的δ~(13)C值(-2.83‰～-1.83‰)具有无机成因的特征,与研究区气藏中幔源岩浆成因CO_2的δ~(13)C值较为一致,铁白云石的δ~(18)O值(-9.45‰～-5.37‰)和~(87)Sr/~(86)Sr值(0.7101～0.7161)也反映了其沉淀受到深部热流体活动的影响。以两口典型CO_2气井为例,储层中流体包裹体均一温度及蒙脱石向伊利石的演化特征证明储层经历了热流体侵入;CO_2热流体活动区域不仅是铁白云石集中分布地带,并出现片钠铝石+铁白云石+菱铁矿等示踪CO_2运移、聚集的自生矿物组合。地层中铁白云石、高岭石含量与气藏中CO_2的含量呈正相关关系,绿泥石含量与CO_2、铁白云石含量呈反消长关系。高地温梯度地区丰富的CO_2热流体活动是该地区储层中铁白云石沉淀与含量高的重要原因,无机岩浆成因CO_2是铁白云石沉淀的主要碳源,CO_2热流体充注造成绿泥石等黏土矿物异常转化,为铁白云石沉淀提供了所需的Fe~(2+)、Mg~(2+)离子。     

铁白云石矿物学特征及原生次生成因机制

长期以来,铁白云石的命名划分标准混乱,一直被当成高温及次生的产物.综述了国内外铁白云石的研究进展,详细探讨了铁白云石的矿物学特征,特别在其成因中加入了微生物因素,运用地质微生物学探讨原生铁白云石的成因机制.研究认为:（1）铁白云石命名划分依据应遵照国际矿物学会的原则,以铁是否替代白云石晶格中半数镁的位置为标准,分为白云石和铁白云石;（2）详述铁白云石矿物学及其晶体特征;（3）铁白云石成因分为原生沉淀及次生两种,微生物介导形成原生白云石的过程中,有助于铁进入到白云石晶格中,增加晶格中铁的含量.      

青海湖底沉积物中球状白云石集合体的发现及其地质意义

青海湖为盐度低于海水的微咸水湖。为了探索白云石的成因,在青海湖二浪尖以北约15 km的湖底采集了长25 cm的沉积物柱状样品。对样品所做的X-衍射矿物物相定量分析表明其中含有2.2％的白云石。文献中也曾报道青海湖底沉积物中含有高达10％的白云石矿物。对这些含白云石矿物的湖底沉积物所进行的扫描电镜研究发现了其中呈球状、椭球状,大小1~2 μm的白云石集合体及其伴生的草莓状黄铁矿的存在。其特征与文献中报道的现代近海高盐度泻湖和萨勃哈中发现的微生物成因的白云石极为相似。这是内陆低盐度环境中此类白云石的首次发现,对于探讨不同盐度环境中白云石的形成机理,促进“白云石问题”的深入研究具有重要的理论意义。     

“白云石问题”及其实验研究

“白云石问题”无疑是地质学上最有趣最长久的难题之一。作为一种常见的碳酸盐矿物,白云石在地质历史时期大量 发育,却在现代海洋沉积环境中鲜少沉积,并且在实验室模拟海水条件下也几乎无法低温合成。白云石[CaMg(CO3)2]不同于 Ca2+、Mg2+无序的高镁方解石,具有阳离子有序超结构,空间群为R-3,在地表条件下为热力学稳定相。尽管人们尝试模拟 自然界中白云石存在的物理化学条件,但却几乎没有从实验中成功合成有序白云石。在已有的实验室研究中,有序白云石 仅能通过高温水热实验形成。这说明白云石的形成极可能是一个动力学控制过程。而近些年被人们广泛接受的白云石微生 物成因模式认为微生物活动是低温白云石形成的关键,相关的微生物矿化实验也证实微生物的存在能够促进高镁方解石的 形成。对白云石问题的探讨不仅对理解白云岩成因具有重要意义,还能够促进矿物学理论研究发展。此次研究从高温合成 实验、低温合成实验、微生物协同沉淀实验等方面综述了有关白云石问题的实验室研究进展,阐明了目前对于白云石问题 认识的局限,有助于更好的理解“白云石问题”和其中所包含的矿物学和物理化学问题,乃至于帮助寻找到它的答案。     

不同状态嗜盐古菌细胞及羧基微球诱导白云石沉淀

白云石是沉积岩中广泛存在的碳酸盐矿物,其成因机制一直备受关注.野外调研发现现生白云石多分布于高盐环境,模拟实验也表明嗜盐微生物能诱导形成白云石,但微生物诱导白云石沉淀的机理仍不明确.分别用嗜盐古菌Natrinema sp.J7-1对数后期的活细胞、失去代谢活性的J7-1完整细胞（经线粒体氧化磷酸化解偶联剂处理）、表面蛋白质变性的J7-1细胞（经多聚甲醛和戊二醛处理）和表面富含羧基的微球,在盐度为280‰的沉淀体系中诱导白云石沉淀.分别利用X射线衍射（XRD）分析矿物的物相,扫描电子显微镜（SEM）分析矿物、微生物以及羧基微球的形貌,傅立叶红外光谱（FT-IR）分析细胞变性前后表面的官能团.结果表明,失去代谢活性的J7-1细胞与正常的对数后期细胞均能够诱导原白云石形成;经过多聚甲醛/戊二醛固定后,细胞表面羧基含量降低,不能诱导白云石沉淀;羧基微球能够诱导形成原白云石.以上研究证实细胞表面的羧基可能是微生物促进白云石沉淀的一种关键因素,而细胞的生长代谢在本研究的条件下不是控制白云石沉淀的主要因素.      

Origin and diagenetic evolution of Ca–Mg–Fe carbonates in some coalfields of Japan

Carbonate concretions, lenses and bands in the Pleistocene, Palaeogene and Upper Triassic coalfields of Japan consist of various carbonate minerals with varied chemical compositions. Authigenic carbonates in freshwater sediments are siderite > calcite > ankerite > dolomite >> ferroan magnesite; in brackish water to marine sediments in the coal measures, calcite > dolomite > ankerite > siderite >> ferroan magnesite; and in the overlying marine deposits, calcite > dolomite >> siderite. Most carbonates were formed progressively during burial within a range of depths between the sediment-water interface and approximately 3 km. The mineral species and the chemical composition of the carbonates are controlled primarily by the initial sedimentary facies of the host sediments and secondarily by the diagenetic evolution of pore water during burial. Based on the regular sequence and burial depth of precipitation of authigenic carbonates in a specific sedimentary facies, three diagenetic stages of carbonates are proposed. Carbonates formed during Stage I (< 500 m) strongly reflect the initial sedimentary facies, e.g. low Ca-Mg siderite in freshwater sediments which are initially rich in iron derived from lateritic soil on the nearby landmass, and Mg calcite and dolomite in brackish-marine sediments whose pore waters abound in Ca²⁺ and Mg²⁺ originating in seawater and calcareous shells. Carbonates formed during Stage II (500–2000 m) include high Ca-Mg siderite, ankerite, Fe dolomite and Fe–Mg calcite in freshwater sediments. The assemblage of Stage II carbonates in brackish-marine sediments in the coal measures is similar to that in freshwater sediments. This suggests similar diagenetic environments owing to an effective migration and mixing of pore water due to the compaction of host sediments. Carbonates formed during Stage III (> 2000 m) are Fe calcite and extremely high Ca-Mg siderite; the latter is exclusively in marine mudstones. The supply of Ca is partly from the alteration of silicates in the sediments at elevated burial temperatures. After uplift, calcite with low Mg content precipitates from percolating groundwater and fills extensional cracks.     

Secondary Ion Mass Spectrometry Bias on Isotope Ratios in Dolomite–Ankerite,Part I: δ18O Matrix Effects

We document the development of a suite of carbonate mineral reference materials for calibrating SIMS determinations of δ¹⁸O in samples with compositions along the dolomite–ankerite solid solution series [CaMg(CO₃)₂–CaFe(CO₃)₂]. Under routine operating conditions for the analysis of carbonates for δ¹⁸O with a CAMECA IMS 1280 instrument (at WiscSIMS, University of Wisconsin‐Madison), the magnitude of instrumental bias along the dolomite–ankerite series decreased exponentially by ~ 10‰ with increasing Fe content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mol% Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the sample matrix effect) was calibrated using the Hill equation, which relates bias to the Fe# of dolomite–ankerite [i.e., molar Fe/(Mg+Fe)] for thirteen reference materials (Fe# = 0.004–0.789); for calibrations employing either 10 or 3 μm diameter spot size measurements, this yielded residual values ≤ 0.3–0.4‰ relative to CRM NBS 19 for most reference materials in the suite. Analytical precision was ± 0.3‰ (2s, standard deviations) for 10‐μm spots and ± 0.7‰ (2s) for 3‐μm spots, based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses. Analytical uncertainty for individual sample analyses was approximated by a combination of precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 0.5‰ (2s) for 10‐μm spots and ± 1‰ (2s) for 3‐μm spots.     

微生物白云石模式评述

Vasconcelos等在实验室模拟巴西Lagoa Vermelha潟湖条件,成功地沉淀出白云石,由此提出了微生物白云石模式。该模式在南澳大利亚、阿拉伯海湾、西印度外陆棚边缘以及意大利南部等地区得到了不同研究者的肯定,我国鄂尔多斯盆地奥陶系马家沟组五段白云岩也可以解释为微生物成因。此模式对白云石形成机理的研究具有突破性的意义。当硫酸盐还原细菌利用SO42-时,也吸收了Mg2+,因为Mg2+与SO42-形成了很强的离子对。微生物由于其新陈代谢作用利用SO42-而克服了动力障碍,同时从离子对中释放出Mg2+。在白云石形成的化学反应中,微生物因素把硫酸根离子从反应的抑制剂变成了催化剂。白云石一旦成核,就会在埋藏过程中长大。尽管不是所有的白云石都可以用微生物白云石模式来解释,但野外研究和模拟实验都证明这一模式是有说服力和生命力的。     

Calcium and magnesium‐limited dolomite precipitation at Deep Springs Lake,California

Dolomite [Ca,Mg(CO₃)₂] precipitation from supersaturated ionic solutions at Earth surface temperatures is considered kinetically inhibited because of the difficulties experienced in experimentally reproducing such a process. Nevertheless, recent dolomite is observed to form in hypersaline and alkaline environments. Such recent dolomite precipitation is commonly attributed to microbial mediation because dolomite has been demonstrated to form in vitro in microbial cultures. The mechanism of microbially mediated dolomite precipitation is, however, poorly understood and it remains unclear what role microbial mediation plays in natural environments. In the study presented here, simple geochemical methods were used to assess the limitations and controls of dolomite formation in Deep Springs Lake, a highly alkaline playa lake in eastern California showing ongoing dolomite authigenesis. The sediments of Deep Springs Lake consist of unlithified, clay‐fraction dolomite ooze. Based on δ¹⁸O equilibria and textural observations, dolomite precipitates from oxygenated and agitated surface brine. The Na‐SO₄‐dominated brine contains up to 500 mm dissolved inorganic carbon whereas Mg²⁺ and Ca²⁺ concentrations are ca 1 and 0·3 mm , respectively. Precipitation in the subsurface probably is not significant because of the lack of Ca²⁺ (below 0·01 mm ). Under such highly alkaline conditions, the effect of microbial metabolism on supersaturation by pH and alkalinity increase is negligible. A putative microbial effect could, however, support dolomite nucleation or support crystal growth by overcoming a kinetic barrier. An essential limitation on crystal growth rates imposed by the low Ca²⁺ and Mg²⁺ concentrations could favour the thermodynamically more stable carbonate phase (which is dolomite) to precipitate. This mode of unlithified dolomite ooze formation showing δ¹³C values near to equilibrium with atmospheric CO₂ (ca 3‰) contrasts the formation of isotopically light (organically derived), hard‐lithified dolomite layers in the subsurface of some less alkaline environments. Inferred physicochemical controls on dolomite formation under highly alkaline conditions observed in Deep Springs Lake may shed light on conditions that favoured extensive dolomite formation in alkaline Precambrian oceans, as opposed to modern oceans where dolomites only form diagenetically in organic C‐rich sediments.     

Double carbonate breakdown reactions at high pressures: an experimental study in the system CaO–MgO–FeO–MnO–CO2

The pressure–temperature conditions of the reactions of the double carbonates CaM(CO₃)₂, where M = Mg (dolomite), Fe (ankerite) and Mn (kutnohorite), to MCO₃ plus CaCO₃ (aragonite) have been investigated at 5–8 GPa, 600–1,100°C, using multi-anvil apparatus. The reaction dolomite = magnesite + aragonite is in good agreement with the results of Sato and Katsura (Earth Planet Sci 184:529–534, 2001), but in poor agreement with the results of Luth (Contrib Mineral Petrol 141:222–232, 2001). The dolomite is partially disordered at 620°C, and fully disordered at 1,100°C. All ankerite and kutnohorite samples, including the synthetic starting materials, are disordered. The P–T slopes of the three reactions increase in the order M = Mg, Fe, Mn. The shallower slope for the reaction involving magnesite is due partly to its having a higher compressibility than expected from unit-cell volume considerations. At low pressures there is a preference for partitioning into the double carbonate of Mg > Fe > Mn. At high pressures the partitioning preference is reversed. Using the measured reaction positions, the P–T conditions at which dolomite solid solutions will break down on increasing P and T in subduction zones can be estimated.     

Dolomite formation within microbial mats in the coastal sabkha of Abu Dhabi (United Arab Emirates)

Microbial mediation is the only demonstrated mechanism to precipitate dolomite under Earth surface conditions. A link between microbial activity and dolomite formation in the sabkha of Abu Dhabi has, until now, not been evaluated, even though this environment is cited frequently as the type analogue for many ancient evaporitic sequences. Such an evaluation is the purpose of this study, which is based on a geochemical and petrographic investigation of three sites located on the coastal sabkha of Abu Dhabi, along a transect from the intertidal to the supratidal zone. This investigation revealed a close association between microbial mats and dolomite, suggesting that microbes are involved in the mineralization process. Observations using scanning electron microscopy equipped with a cryotransfer system indicate that authigenic dolomite precipitates within the exopolymeric substances constituting the microbial mats. In current models, microbial dolomite precipitation is linked to an active microbial activity that sustains high pH and alkalinity and decreased sulphate concentrations in pore waters. Such models can be applied to the sabkha environment to explain dolomite formation within microbial mats present at the surface of the intertidal zone. By contrast, these models cannot be applied to the supratidal zone, where abundant dolomite is present within buried mats that no longer show signs of intensive microbial activity. As no abiotic mechanism is known to form dolomite at Earth surface conditions, two different hypotheses can reconcile this result. In a first scenario, all of the dolomite present in the supratidal zone formed in the past, when the mats were active at the surface. In a second scenario, dolomite formation continues within the buried and inactive mats. In order to explain dolomite formation in the absence of active microbial metabolisms, a revised microbial model is proposed in which the mineral‐template properties of exopolymeric substances play a crucial role.     

Disseminated ‘jigsaw piece’ dolomite in Upper Jurassic shelf sandstones,Central North Sea: an example of cement growth during bioturbation?

Unusual textural and chemical characteristics of disseminated dolomite in Upper Jurassic shelf sediments of the North Sea have provided the basis for a proposed new interpretation of early diagenetic dolomite authigenesis in highly bioturbated marine sandstones. The dolomite is present throughout the Franklin Sandstone Formation of the Franklin and Elgin Fields as discrete, non‐ferroan, generally unzoned, subhedral to highly anhedral ‘jigsaw piece’ crystals. These are of a similar size to the detrital silicate grains and typically account for ≈5% of the rock volume. The dolomite crystals are never seen to form polycrystalline aggregates or concretions, or ever to envelop the adjacent silicate grains. They are uniformly dispersed throughout the sandstones, irrespective of detrital grain size or clay content. Dolomite authigenesis predated all the other significant diagenetic events visible in thin section. The dolomite is overgrown by late diagenetic ankerite, and bulk samples display stable isotope compositions that lie on a mixing trend between these components. Extrapolation of this trend suggests that the dolomite has near‐marine δ¹⁸O values and low, positive δ¹³C values. The unusual textural and chemical characteristics of this dolomite can all be reconciled if it formed in the near‐surface zone of active bioturbation. Sea water provided a plentiful reservoir of Mg and a pore fluid of regionally consistent δ¹⁸O. Labile bioclastic debris (e.g. aragonite, Mg‐calcite) supplied isotopically positive carbon to the pore fluids during shallow‐burial dissolution. Such dissolution took place in response to the ambient ‘calcite sea’ conditions, but may have been catalysed by organic matter oxidation reactions. Bioturbation not only ensured that the dissolving carbonate was dispersed throughout the sandstones, but also prohibited coalescence of the dolomite crystals and consequent cementation of the grain framework. Continued exchange of Mg²⁺ and Ca²⁺ with the sea‐water reservoir maintained a sufficient Mg/Ca ratio for dolomite (rather than calcite) to form. Irregular crystal shapes resulted from dissolution, of both the dolomite and the enclosed fine calcitic shell debris, before ankerite precipitation during deep‐burial diagenesis.     

Secondary Ion Mass Spectrometry Bias on Isotope Ratios in Dolomite–Ankerite,Part II: δ13C Matrix Effects

This study is Part II of a series that documents the development of a suite of calibration reference materials for in situ SIMS analysis of stable isotope ratios in Ca‐Mg‐Fe carbonates. Part I explored the effects of Fe²⁺ substitution on SIMS δ¹⁸O bias measured from the dolomite–ankerite solid solution series [CaMg(CO₃)₂–CaFe(CO₃)₂], whereas this complementary work explores the compositional dependence of SIMS δ¹³C bias (calibrated range: Fe# = 0.004–0.789, where Fe# = molar Fe/(Mg+Fe)). Under routine operating conditions for carbonate δ¹³C analysis at WiscSIMS (CAMECA IMS 1280), the magnitude of instrumental bias increased exponentially by 2.5–5.5‰ (session‐specific) with increasing Fe‐content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mole % Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the matrix effect) was expressed using the Hill equation, yielding calibration residual values ≤ 0.3‰ relative to CRM NBS‐19 for eleven carbonate reference materials (6‐μm‐diameter spot size measurements). Based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses, the analytical precision was ± 0.6–1.2‰ (2s, standard deviations). The analytical uncertainty for individual sample analyses was approximated by combining the precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 1.0–1.5‰ (2s).     

Superstructures in ankerite and calcite

Two rhombohedral carbonates, ferroan dolomite (ankerite) and magnesian calcite from lower Jurassic ammonites, have been studied by transmission electron microscopy. The samples show small domains with the morphology of platelets parallel to (11 \(\bar 2\) 0) which have exceptionally well ordered superstructures and characteristic c-reflections. Diffraction patterns and contrast analysis of atomic resolution images indicate that the domains observed in ankerite are rich in Ca [Ca_0.75(Mg, Fe)_0.25CO₃] and those in calcite rich in Mg, and there is strong evidence that cation ordering is the cause for the observed superstructures which are proposed mainly on diffraction evidence. Rhombohedral carbonates have a close similarity to NaCl, with CO₃-groups substituting for Cl. Cation ordering patterns can therefore be discussed in analogy to f.c.c. alloys. We make use of ordering waves to describe superstructures and to qualitatively interpret kinetic conditions for their formation.