鲕粒原生矿物识别及对海水化学成分变化的指示意义

鲕粒是碳酸盐沉积过程中一类非常特殊的颗粒类型, 为研究当时的沉积背景、水动力条件、气候环境, 甚至储层特征提供了重要线索。然而, 鲕粒的矿物组成及控制因素问题, 长期受到忽视。组成鲕粒的原生矿物类型在地质历史时期呈周期性变化, 在显生宙表现为三个以文石和高镁方解石占主导的时期以及两个以低镁方解石占主导的时期, 这也被称作“文石海”和“方解石海”时期。原生矿物的组成, 制约着鲕粒的纹层结构、保存程度以及成岩特征, 还蕴含着海水化学成分变化的线索。鲕粒原生矿物识别主要依据:①原生纹层结构;②保存程度;③微量元素浓度, 尤其是Sr-Mg的浓度。文石质鲕粒受文石不稳定性的影响, 原生结构保存程度较差;一般保存有典型的文石残余纹层结构(例如砖砌结构、溶解变形结构以及偏心结构等);在封闭成岩环境下原生矿物为文石质的鲕粒Sr浓度往往大于2 000 ppm;纹层结构主要为切线状(占主导)和放射状。方解石质鲕粒包括低镁方解石和高镁方解石两种类型:低镁方解石为稳定矿物, 原生结构一般保存良好。尽管高镁方解石也为亚稳定矿物, 但成岩转换后的保存程度好于文石。两者Sr含量一般均低于1 000 ppm, Mg含量一般在0~20 mol % MgCO₃(两者以4 mol % MgCO₃为界)。高镁方解石受成岩作用影响, 在纹层中往往保留有微粒白云石包裹体;海相地层中保存的方解石质鲕粒为放射状或同心-放射状结构。另外还存在一类由两种矿物共同构成的双矿物鲕粒, 可以通过分析两类纹层在结构和保存特征上的差异进行区分。鲕粒原生矿物成分随时间的波动变化受到海水化学条件, 尤其是Mg/Ca比值, 大气二氧化碳分压以及碳酸盐饱和度的控制。Mg/Ca比值的波动决定着鲕粒原生矿物类型的长期变化规律。一些突发性事件可能会扰动(区域)短时间尺度下鲕粒原生矿物的组成, 造成鲕粒原生矿物的转换。通过研究碳酸盐鲕粒原生矿物特征以及控制因素进而了解海水的化学特征, 是独立于古生物学和地球化学分析之外的一种较为可靠的沉积学方法。     

Constraints on paleowater dissolved loads and on catchment weathering over the past 16 ka from Sr/Sr ratios and Ca/Mg/Sr chemistry of freshwater ostracode tests in sediments of Lake Constance, Central Europe

Sr isotope and Ca/Mg/Sr chemical compositions of freshwater ostracode tests separated from a sediment core represent the last 16 ka of sedimentation in Lake Constance, Central Europe. The chemical evolution of the paleowater's dissolved load of Lake Constance was estimated by correcting the ostracode data for Ca/Mg/Sr fractionation due to biogenic calcification. Since the Late Pleistocene deglaciation, the Ca/Sr molar ratios of paleowaters increased systematically from about 100 (a near marine signature) to about 200. Ca/Mg molar ratios varied in the range of 1–25. The ⁸⁷Sr/⁸⁶Sr ratios indicate Late Pleistocene paleowater compositions of 0.7086–0.7091, significantly more radiogenic than present day waters (0.7085). Sr isotopes and Ca/Mg/Sr chemical data together show that weathering of Mesozoic evaporites consistently dominated the dissolved Sr load (80–90%). Carbonate and silicate weathering were less important (1–10%). Trends of Sr dissolved loads were therefore not related to Mg which was mainly mobilized by carbonate weathering. Biotite weathering was an important source of radiogenic Sr in the paleowaters. The short-term release (duration about 600–800 years) of radiogenic Sr during glacier retreat started 15.2 ka ago and was due to enhanced biotite weathering at the glacier base. Long-term release of radiogenic Sr was due to biotite weathering in glacial soils and silicate rocks, and has gradually declined since the Late Pleistocene/Holocene transition.     

Studies on the phosphorus requirement and proper calcium/phosphorus ratio in the diet of the black sea bream (Sparus macrocephalus)

An expriment on the phosphorus requirement and the proper Ca/P ratio in the diet of the black sea bream using the phosphorus gradient method (with casein as basic diet, sodium dihydrogen phosphate as source of phosphorus, and calcium lactate as source of calcium) showed that growth was greatly affected by the diet's phosphorus content and Ca/P ratio. Inadequate phosphorus in the diet resulted in slow growth and poor food conversion ratio (FCR). Analyses of the fish body showed it contained a high level of lipid but a low level of moisture, ash, calcium and phosphorus. The optimal values of phosphorus and Ca/P ratio in the black sea bream diet are 0.68% and 1∶2 respectively. Phosphorus in excess of this optimum value resulted in slow growth or even death. The results of this experiment clearly indicated that phosphorus is the principal mineral additive affecting black sea bream growth. Contribution No. 1972 from the Institute of Oceanology, Academia Sinica.     

甘氨酸-硝酸盐燃烧法制备Ca0.3Sr0.7TiO3介电质材料

采用甘氨酸-硝酸盐燃烧法,以硝酸锶、硝酸钙、钛酸丁酯和甘氨酸为原料合成了Ca0·3Sr0·7TiO3陶瓷粉体。对影响粉体特性的两个主要因素pH值和原料配比进行了讨论。XRD结果表明,所得粉体结晶好,纯度高。用所得粉体经1420℃烧结成瓷,介电频率特性测试结果表明,介电常数随频率单调递减,50kHz到10MHz范围内,介电常数基本稳定在140~150之间。介电损耗随着频率的增大先减小后增大,最小介电损耗在1MHz下为0·0243。     

Mineralogy and petrology of Al-rich objects and amoeboid olivine aggregates in the CH carbonaceous chondrite North West Africa 739

The aluminum-rich (>10 wt% Al₂O₃) objects in the CH carbonaceous chondrite North West Africa (NWA) 739 include Ca,Al-rich inclusions (CAIs), Al-rich chondrules, and isolated mineral grains (spinel, plagioclase, glass). Based on the major mineralogy, 54 refractory inclusions found in about 1 cm² polished section of NWA 739 can be divided into hibonite-rich (16%), grossite-rich (26%), melilite-rich (28%), spinel-pyroxene-rich (16%) CAIs, and amoeboid olivine aggregates, (AOA's, 17%). Most CAIs are rounded, 25–185 μm (average=70 μm) in apparent diameter, contain abundant, tiny perovskite grains, and typically surrounded by a single- or double-layered rim composed of melilite and/or Al-diopside; occasionally, layers of spinel+hibonite and forsterite are observed. The AOAs are irregularly shaped, 100–250 μm (average=175 μm) in size, and consist of forsterite, Fe,Ni-metal, and CAIs composed of Al-diopside, anorthite, and minor spinel. One AOA contains compact, rounded melilite-spinel-perovskite CAIs and low-Ca pyroxene replacing forsterite. The Al-rich (>10 wt% bulk Al₂O₃) chondrules are divided into Al-diopside-rich and plagioclase-rich. The Al-diopside-rich chondrules, 50–310 μm (average=165 μm) in apparent diameter, consist of Al-diopside, skeletal forsterite, spinel, ±Al-rich low-Ca pyroxene, and ±mesostasis. The plagioclase-rich chondrules, 120–455 μm (average=285 μm) in apparent diameter, are composed of low-Ca and high-Ca pyroxenes, forsterite, anorthitic plagioclase, Fe,Ni-metal nodules, and mesostasis. The isolated spinel occurs as coarse, 50–125 μm in size, subhedral grains, which are probably the fragments of Al-diopside chondrules. The isolated plagioclase grains are too coarse (60–120 μm) to have been produced by disintegration of chondrules or CAIs; they range in composition from nearly pure anorthite to nearly pure albite; their origin is unclear. The Al-rich objects show no evidence for Fe-alkali metasomatic or aqueous alteration; the only exception is an Al-rich chondrule fragment with anorthite replaced by nepheline. They are texturally and mineralogically similar to those in other CH chondrites studied (Acfer 182, ALH85085, PAT91467, NWA 770), but are distinct from the Al-rich objects in other chondrite groups (CM, CO, CR, CV). The CH CAIs are dominated by very refractory minerals, such as hibonite, grossite, perovskite and gehlenitic melilite, and appear to have experienced very low degrees of high-temperature alteration reactions. These include replacement of grossite by melilite, of melilite by anorthite, diopside, and spinel, and of forsterite by low-Ca pyroxene. Only a few CAIs show evidence for melting and multilayered Wark-Lovering rims. These observations may suggest that CH CAIs experienced rather simple formation history and escaped extensive recycling. In order to preserve the high-temperature mineral assemblages, they must have been efficiently isolated from the hot nebular region, like some chondrules and the zoned Fe,Ni-metal grains in CH chondrites.     

Mass‐Independent and Mass‐Dependent Ca Isotopic Compositions of Thirteen Geological Reference Materials Measured by Thermal Ionisation Mass Spectrometry

We report mass‐independent and mass‐dependent Ca isotopic compositions for thirteen geological reference materials, including carbonates (NIST SRM 915a and 915b), Atlantic seawater as well as ten rock reference materials ranging from peridotite to sandstone, using traditional ε and δ values relative to NIST SRM 915a, respectively. Isotope ratio determinations were conducted by independent unspiked and ⁴³Ca‐⁴⁸Ca double‐spiked measurements using a customised Triton Plus TIMS. The mean of twelve measurement results gave ε^40/44Ca values within ± 1.1, except for GSP‐2 that had ε^40/44Ca = 4.04 ± 0.15 (2SE). Significant radiogenic ⁴⁰Ca enrichment was evident in some high K/Ca samples. At an uncertainty level of ± 0.6, all reference materials had the same ε^43/44Ca and ε^48/44Ca values. We suggest the use of δ^44/42Ca to report mass‐dependent Ca isotopic compositions. The precision under intermediate measurement conditions for δ^44/42Ca over eight months in our laboratory was ± 0.03‰ (with n ≥ 8 repeat measurements). Measured igneous reference materials gave δ^44/42Ca values ranging from 0.27‰ to 0.54‰. Significant Ca isotope fractionation may occur during magmatic and metasomatism processes. Studied reference materials with higher (Dy_n/Yb_n) tend to have lower δ^44/42Ca, implying a potential role of garnet in producing magmas with low δ^44/42Ca. Sandstone GBW07106 had a δ^44/42Ca value of 0.22‰, lower than all igneous rocks studied so far.     

泥沙颗粒表面电荷特性及其对干容重影响试验研究

采用黄河及长江中的沙样在不同Ca2+浓度下分别进行电位滴定试验和干容重试验,得到以下结论:①随Ca2+浓度的增加,泥沙颗粒表面负电荷先不断减少然后趋于不变。②Ca2+对泥沙淤积干容重的影响可分为三个阶段:第一阶段干容重减小;第二阶段增加并达到最大值;第三阶段减小最后趋于不变。③在Ca2+浓度相同条件下,泥沙浓度对淤积干容重的影响根据所加Ca2+浓度不同也呈现不同的变化。④Ca2+浓度、泥沙浓度相同时,中值粒径越大干容重越大,且中值粒径大的泥沙干容重达到最大值所需Ca2+少。⑤在不同Ca2+浓度下泥沙颗粒由于表面电荷不同造成静电斥力不同,同时表面水膜作用力也不同,二者共同作用使得干容重体现不同的变化。     

南海北部5万年来的表层海水盐度及东亚季风降水

为了探讨末次冰期以来南海北部区域降水变化对东亚夏季风强度变化的响应,利用南海北部191PC柱状样有孔虫壳体氧同位素和镁钙比值,重建了过去5万以来的表层海水温度和海水氧同位素变化。通过分析南海北部淡水收支的主要影响因素,认为夏季风降水是本研究站位海水盐度的主要影响因素,而海平面变化导致的冲淡效应变化并非主导因素。基于此前提,将剩余海水氧同位素作为区域降水变化的指标,结果表明,南海北部降水量与东亚季风强度在50~10kaB.P.间变化趋势较一致,10kaB.P.以来则呈相反的变化趋势。本文通过对比分析南海和西太平洋相关站位的古盐度变化、东亚陆地的干湿变化,结合数值模拟结果,认为50~10kaB.P.之间,北半球大陆冰盖对东亚夏季风的影响较强,东亚内陆和南海北部降水同时响应北半球高纬气温变化,表现出冷事件时降水少而暖事件时降水多的特点。而在10kaB.P.以来,南海北部和华南地区降水量与东亚季风强度变化趋势相反,表现出东亚-西北太平洋区域降水量分布的海陆差异特征。此现象与中全新世南北半球夏季辐射量不对称变化和海陆热容差异导致的温度、水汽重新分布有关。     

胶州湾海水中的钙和镁

于1989年10月28日在胶州湾的23个站位采集表层水样,对Ca、Mg及盐度、氯度、碱度等化学要素进行了测定,并用崂山水库水进行了稀释实验。结果表明,Ca/s,Mg/s均高于大洋水,其值分别为0.01250±7×10~(-4)和0.03728±1×10~(-4)。湾东北部的Ca,Mg均高于中部及湾口海域,这是湾东北部的工业废水及高盐卤水排放所致;CaCO_3(20℃)呈现过饱和状态。认为,ca,Mg有良好的保守性,低盐混合水样在放置过程中pH的下降可能与空气中CO_2的溶解有关,从而将引起ca,Mg含量的相对增高。     

高温实验模拟Mg/Ca浓度对文石质生物碎屑白云石化过程的影响

高温(150℃以上)合成白云石实验被认为是了解自然条件下白云石成因的有效途径。选择自然条件下对白云石成因有重要影响的Mg/Ca值(摩尔浓度比)指标,分别采用鹿角珊瑚和大琵琶螺两种文石质生物碎屑为先驱反应物,在220℃高温环境下对不同Mg/Ca值(0.5、0.7、1.0、1.2、1.5)和不同反应时间(0.5、1.0、1.5、2、3、6、8、14 h)条件下文石质生物碎屑的白云石化过程开展研究。结果表明,在高温条件下白云石化过程可分为诱导阶段、快速反应阶段和平稳阶段,这一反应过程未明显受到先驱文石质反应物的影响,反映了流体Mg/Ca浓度对白云石化产物具有明显的控制作用。随着反应溶液Mg/Ca值的提高,白云石化的诱导期缩短、速率加快,产物白云石中CaCO₃的摩尔分数降低且有序度提高,表明高Mg²⁺浓度能够促进Mg²⁺快速交代文石中的Ca²⁺并完成白云石的有序化过程。研究结果为解释自然条件下Mg/Ca浓度对白云石化过程的影响提供了基础理论支撑。