Modelling the OH stretch envelope shape and temperature effects in infrared spectra of hydrous silica and silicate glasses

Simple model calculations show that the reversible temperature effects reported for broad OH-stretching bands in infrared spectra of silica, aluminosilicate, and similar glasses can be explained, in essentials, by homogeneous thermal broadening of the ν(OH) envelope constituents and a decrease in intensity with increasing temperature taking place uniformly across the band. This means that these effects are reasonably consistent with the temperature behaviour of narrow ν(OH) bands of crystalline OH-bearing minerals. These findings leave little room for the previously agreed interpretation in terms of a change in hydrogen-bonding strength, although the dependence of integrated intensity on temperature still remains to be understood. Received: 16 April 1999 / Accepted: 4 April 2000     

砂岩中石英胶结物的成因及其研究意义

次生加大石英胶结物是砂岩中最的胶结物之一。石英胶结物的时空分布表现在越年轻的地层石英胶结物的含量越少,随埋深增加石英胶结物的含量增加,而且盆地类型也是控制石英胶结物含量的一个不可忽视的因素。石英胶结物的硅质来源有很多种说法,但是区域上可能以某一种或某几种来源为主。影响石英胶结物沉淀的主要因素有温度流体的ｐＨ值等;而关于孔隙流动与硅质搬运和沉淀有三促假说,即：浅部地下水循环说、压实驱动流体高度集中说     

乌江流域水库沉积物中生物硅的测定方法及其环境意义

采用碱提取法中的单点法与多点法相结合,测定了乌江流域水库沉积物中生物硅的含量,并对多点提取法进行了改良。采用多个离心管分装定量样品进行连续振荡,每小时提取1个样品进行测定。对多个时间点的提取结果,利用线性回归法分析得出最佳提取时间,优化最佳提取液,然后利用单点提取-硅钼蓝检测法测定沉积物中生物硅的含量。该方法既保证了单点法的快速,也减小了多点法的多次提取操作与提取时的体积误差。本文根据测定结果探讨了乌江流域水库沉积物中生物硅含量变化规律及其环境意义。     

北极新奥尔松地区土壤中生物硅含量及形态特征

硅循环与碳循环密切相关,生物硅作为硅的重要载体,在全球硅循环中占有十分重要的地位。目前,人们对陆地生态系统的硅循环做了大量研究,但对极地地区硅的研究却极为少见。利用中国第五次北极考察获得的土壤与植物样品,对北极新奥尔松地区中国黄河站站基表层土壤中生物硅的含量及土壤和植被中生物硅(主要为植硅体)的形态进行了初步研究。主要结论为:北极新奥尔松地区中国黄河站站基附近表层土壤中颗粒有机碳的含量为1.00—69.3 mg·g-1,平均值为13.7 mg·g-1;颗粒有机氮含量为0.11—9.84 mg·g-1,平均值为1.43 mg·g-1;可溶态硅含量为3.90—26.3μg·g-1,平均值为10.7μg·g-1;生物硅含量为5.60—9.97 mg·g-1,平均值为7.56 mg·g-1,且其含量与土壤颗粒态有机碳和颗粒有机氮呈正相关关系,表明三者具有相似来源。北极表层土壤生物硅比温带、热带地区生物硅含量要高。植物样品中植硅体形态以帽形、圆形、平滑棒形、齿形、刺棒形和哑铃形等形态为主,大小在10—100μm之间。土壤样品中的植硅体主要来源于植物,形态分别为平滑棒形、刺棒形、圆形、哑铃形、鞍形、尖形和帽形,另外硅藻也是北极土壤中生物硅的组成部分,其中裸露土壤中藻类(羽纹纲硅藻)占生物硅的多数(93.3%)。对比发现,有植被覆盖的土壤中,土壤有机碳、可溶出态硅、生物硅含量和植硅体形态丰富度往往比无植被覆盖或寡植被区土壤高,这表明尽管该地区植被稀少,但植物生长对该地区土壤硅循环存在显著影响,值得进一步关注。     

应用元素分析仪测定铅锌矿中的高含量硫

目前对铅锌矿中高含量硫的测定主要采用传统的重量法和容量法,但由于铅锌矿基体复杂,干扰较多,造成操作步骤繁琐;而采用湿法仪器分析又受制于样品的前处理等问题使得测定结果的准确度较差。本文建立了应用元素分析仪测定铅锌矿中的高含量硫(1.0%~32.0%)的分析方法。将样品磨制成粒度小于0.075 mm的粉末,样品制备时加入高纯二氧化硅作为稀释剂以降低铅锌矿的含硫量,仪器测量时加入线状氧化铜作为添加剂以提高硫的氧化效果,优先选用与实际测定样品相同性质的铅锌矿国家标准物质GBW07287(硫的标准值为10.76%)建立标准曲线以减小基体效应。方法精密度(RSD,n=12)小于1%,实际样品分析的测定值与重量法的相对误差小于1%。本方法比化学分析方法的操作简单,几乎没有干扰;比湿法仪器分析方法的样品前处理步骤少,待测元素硫的损失少,测定结果可靠度高。     

Exceptional silica speleothems in a volcanic cave: A unique example of silicification and sub‐aquatic opaline stromatolite formation (Terceira,Azores)

Silica stromatolites occur in a number of modern hydrothermal environments, but their formation in caves is very rare. The silica stromatolitic speleothems of the Branca Opala cave (Terceira Island, Azores), however, provide an excellent opportunity for their study. These formations may be analogous to ancient silica stromatolites seen around the world. Petrographic, mineralogical and geochemical analyses were undertaken on the silica speleothems of the above cave, and on the silica‐tufa deposits outside it, with the aim of understanding their genesis. The possible hydrothermal origin of their silica is discussed. X‐ray diffraction analyses showed opal‐A to be the sole silica phase. Negligible ordering of this opal‐A showed ageing to be insignificant, as expected for recent silica deposits. Most of the silica speleothems examined were definable as sub‐aquatic opaline stromatolites that are not currently growing. Optical microscopy clearly revealed a lower microlaminated, an intermediate and an upper microlaminated zone within the stromatolites. Stromatolite types (I, II and III) were classified with respect to their internal structure and distribution throughout the cave. Scanning electron microscopy showed silicified bacterial filaments within the stromatolites, the silicified plant remains and the silica‐tufa deposits. Bacteria therefore played a major role in the precipitation of the opal‐A. Plasma emission/mass spectrometry showed major, minor and rare earth elements to be present in only small quantities. The rare earth elements were mainly hosted within volcanic grains. Rapid silica precipitation from highly super‐saturated water would explain the intense silicification of the plant remains found inside and outside the cave. The opaline stromatolites, the silica‐tufa deposits and the above‐mentioned intense general silicification suggest a local hydrothermal source for the silica. Indeed, these deposits strongly resemble plant‐rich silica sinter associated with low‐temperature hot spring deposits that include bacterial filaments. However, no geochemical signals that might indicate a hydrothermal origin could be found.     

生物硅的测定及其生物地球化学意义

生物硅（BSi）指用化学方法测定的沉积物中的无定形硅含量。生物硅的含量与水体中初级生产息息相关。硅藻、放射虫、海绵骨针和硅鞭毛虫产生的生物硅是地球化学和古海洋学研究的重要参数。重点讨论了目前生物硅测定方法中的化学提取法，评述了提取过程中存在的一些问题，并对BSi测定的生物地球化学意义进行了讨论。     

Processes controlling solubility of biogenic silica and pore water build-up of silicic acid in marine sediments

Dissolution experiments in batch and flow-through reactors were combined with data on sediment composition and pore water silicic acid profiles to identify processes controlling the solubility of biogenic silica and the build-up of silicic acid in marine sediments. The variability of experimentally determined biogenic silica solubilities is due, in part, to variations in specific surface area and Al content of biosiliceous materials. Preferential dissolution of delicate skeletal structures and frustules with high surface areas leads to a progressive decrease of the specific surface area. This may cause a reduction of the solubility of deposited biosiliceous debris by 10–15%, relative to fresh planktonic assemblages. Dissolution of lithogenic (detrital) minerals in sediments releases dissolved aluminum to the pore waters. This aluminum becomes structurally incorporated into deposited biogenic silica, further decreasing its solubility. Compared to Al-free biogenic silica, the solubility of diatom frustules is lowered by as much as 25% when one out of every 70 Si atoms is substituted by an Al(III) ion.The build-up of silicic acid in pore waters of sediments with variable proportions of detrital matter and biogenic silica was simulated in batch experiments using kaolinite and basalt as model detrital constituents. The steady-state silicic acid concentrations measured in the experiments decreased with increasing detrital-to-opal ratios of the mixtures. This trend is similar to the observed inverse relationship between asymptotic pore water silicic acid concentrations and detrital-to-opal ratios in Southern Ocean sediments. Flow-through reactor experiments further showed that in detrital-rich sediments, precipitation of authigenic alumino-silicates may prevent the pore waters from reaching equilibrium with the dissolving biogenic silica. This agrees with data from Southern Ocean sediments where, at sites containing more than 30 wt.% detrital material, the pore waters remain undersaturated with respect to the experimentally determined in situ solubility of biogenic silica.The results of the study show that interactions between deposited biogenic silica and detrital material cause large variations in the asymptotic silicic acid concentration of marine sediments. The production of Al(III) by the dissolution of detrital minerals affects the build-up of silicic acid by reducing the apparent silica solubility and dissolution kinetics of biosiliceous materials, and by inducing precipitation of authigenic alumino-silicate minerals.     

黄河下游营养盐浓度、入海通量月变化及“人造洪峰”的影响

于2009年至2011年在黄河下游采集溶解及颗粒态营养盐样品,分析了黄河下游各形态营养盐的浓度变化及营养盐入海通量,结果表明各形态氮的浓度多呈丰水期低、枯水期高,溶解无机氮是溶解态氮的主要存在形式;受黄河高悬浮颗粒物含量的影响,磷以颗粒态占绝对优势,而溶解态磷以溶解无机磷为主要存在形态;生物硅的含量平均约占硅酸盐与生物硅之和的20％,硅的浓度丰水期高于枯水期.颗粒态磷与生物硅的含量与悬浮颗粒物含量呈正相关.营养盐的组成具有高氮磷比、高硅磷比、低硅氮比的特点.近年来黄河下游溶解无机氮浓度显著升高而溶解无机磷变化不大,硅酸盐的浓度有所下降.黄河下游水沙通量、营养盐入海通量有明显的季节变化,丰水期占全年总入海通量的42％～84％.调水调沙期间,各营养盐的浓度和组成均有明显变化,氮的浓度、DIN/PO4-P下降,磷与硅的浓度、SiO3-Si/DIN、SiO3-Si/PO4-P升高,颗粒态营养盐的比例明显增加.短期内大量水沙及营养盐入海通量对黄河口及渤海生态系统产生重要影响.     

Metalliferous Sediment and a Silica-Hematite Deposit within the Blanco Fracture Zone,Northeast Pacific

A Tiburon ROV dive within the East Blanco Depression (EBD) increased the mapped extent of a known hydrothermal field by an order of magnitude. In addition, a unique opal-CT (cristobalite-tridymite)-hematite mound was discovered, and mineralized sediments and rock were collected and analyzed. Silica-hematite mounds have not previously been found on the deep ocean floor. The light-weight rock of the porous mound consists predominantly of opal-CT and hematite filaments, rods, and strands, and averages 77.8% SiO₂ and 11.8% Fe₂O₃. The hematite and opal-CT precipitated from a low-temperature (≥ 115° C), strongly oxidized, silica- and iron-rich, sulfur-poor hydrothermal fluid; a bacterial mat provided the framework for precipitation.

Samples collected from a volcaniclastic rock outcrop consist primarily of quartz with lesser plagioclase, smectite, pyroxene, and sulfides; SiO₂ content averages 72.5%. Formation of these quartz-rich samples is best explained by cooling in an up-flow zone of silica-rich hydrothermal fluids within a low permeability system. Opal-A, opal-CT, and quartz mineralization found in different places within the EBD hydrothermal field likely reflects decreasing silica saturation and increasing temperature of the mineralizing fluid with increasing silica crystallinity.

Six push cores recovered gravel, coarse sand, and mud mineralized variously by Fe or Mn oxides, silica, and sulfides. Total rare-earth element concentrations are low for both the rock and push core samples. Ce and Eu anomalies reflect high and low temperature hydrothermal components and detrital phases.

A remarkable variety of types of mineralization occur within the EBD field, yet a consistent suite of elements is enriched (relative to basalt and unmineralized cores) in all samples analyzed: Ag, Au, S, Mo, Hg, As, Sb, Sr, and U; most samples are also enriched in Cu, Pb, Cd, and Zn. On the basis of these element enrichments, the EBD hydrothermal field might best be described as a base- and precious-metal-bearing, silica-Fe-oxide-barite deposit. Such deposits are commonly spatially and temporally associated with volcanogenic massive sulfide (VMS) ores. A plot of data for pathfinder elements shows a large hot spot at the northwestern margin of the field, which may mark a region where moderate to high temperature sulfide deposits are forming at depth; further exploration of the hydrothermal field to the northwest is warranted.