Quantification of Water Content and Speciation in Synthetic Rhyolitic Glasses: Optimising the Analytical Method of Confocal Raman Spectrometry

Quantification of water content in silicate glasses is of vital significance in understanding magma evolution and metamorphic anataxis. Here we provide a method for the determination of total dissolved water content and water speciation in silicate melts by confocal laser Raman spectrometry based on a set of hydrous rhyolitic glasses. A series of alumino-silicate glasses with water contents from 0.33 to 9.05% m/m were synthesised in a piston cylinder apparatus. Synchrotron-FTIR mapping shows that these glasses have relatively homogeneous distributions of dissolved water. Total water contents of the glasses were precisely measured by TC/EA-MS and FTIR. Both external and internal calibration were established for the quantitative analysis of water content and water speciation in the silicate glasses based on excellent linear correlation between total dissolved water content and integrated area of the water Raman band. Furthermore, by decomposing the total water Raman bands into four Gaussians components, the relative concentration of water speciation (OH groups and molecules H₂O_m) dissolved in the glasses was determined with a similar trend to water speciation data derived from FTIR. We suggest that the relative concentration of water speciation can be estimated in rhyolitic glasses with 4–8% m/m H₂O. Our work provides an accurate method to determine total water content and a potential tool to limit the relative concentration of water speciation dissolved in silicic glasses.     

莱州湾西南部海域及其毗邻河流水体营养盐的分布特征及长期变化趋势

根据2012年9月对莱州湾西南部海域及其毗邻10条河流的调查结果,以及近30年来关于莱州湾海域表层水营养盐的调查资料,报道了各条河流和近海海域的营养盐状况及该海域营养盐的长期变化趋势,结果表明:(1)10条主要调查河流的总溶解态氮(TDN)平均含量在1.82~10.66mg/L之间,其中有8条河流超过河流总氮劣五类水质标准,6条河流硝态氮(NO3-N)含量高于氨氮(NH4-N)。(2)所调查的5个近海断面中小清河口近海断面、虞河口近海断面及溢洪河口近海断面的DIN平均含量超过海水无机氮第四类水质标准;除小清河口近海断面外其余近海断面活性磷(PO4-P)含量均属一类海水水质。(3)部分断面营养盐含量在河口混合区淡水端升高,可能与咸淡水混合动力作用相关;莱州湾西部区域营养盐含量高于南部区域,南部的堤河氮、磷含量极高;原油开采活动可能是影响附近水体中营养盐含量及形态的重要因素。(4)从20世纪80年代初至90年代中期,莱州湾表层水无机氮平均含量经历了由低到高的变化,到90年代后期已属劣四类海水水质;无机磷平均含量在该时段呈降低趋势,但到90年代后期也保持在较高水平,随后又波动下降。(5)所调查的莱州湾近海区域整体处于磷限制潜在富营养状态;氮磷摩尔比(N∶P)在所考察的大部分时段内高于Redfield阈值(16),净营养盐收支呈磷减少而氮增加的总体变化趋势,近年来磷限制程度有所减缓。     

Sn-Ni化学镀硅酸钙镁矿物晶须的制备与表征

以硅酸钙镁晶须为原料,采用化学镀方法制备一种镀Sn-Ni硅酸钙镁晶须,并用SEM,XRD,EDS和FT-IR对镀Sn-Ni硅酸钙镁晶须进行表征。结果表明:镀Sn-Ni硅酸钙镁晶须是一种针状结构的硅酸盐晶须材料,除有部分聚集增粗外,其形貌几乎没有变化;镀Sn-Ni硅酸钙镁晶须的主要化学组成为:w(O)48.24%,w(Si)10.78%,w(Mg)5.44%,w(Ca)2.26%,w(Sn)22.45%,w(Ni)2.19%,w(Na)4.38%,w(P)2.46%和w(S)1.80%;镀Sn-Ni硅酸钙镁晶须在1100cm-1～850cm-1强吸收区的振动频率的增加值与在750cm-1～600cm-1弱吸收区的振动频率的降低值均为4.98cm-1;镀Sn-Ni硅酸钙镁晶须的主体结构和化学键没有发生根本上改变,Sn-Ni化学镀在本质上是一种物理包覆过程。该研究为提高矿产资源的综合开发和利用水平提供了一种新的思路和方法。     

Determination of Fluorine and Chlorine by Pyrohydrolysis and Ion Chromatography: Comparison with Alkaline Fusion Digestion and Ion Chromatography

A method to determine F and Cl in silicate materials by employing pyrohydrolysis and ion chromatography (IC) is described. Pyrohydrolysis involved mixing a pulverised sample (∼ 40 mg) with V₂O₅ (∼ 160 mg) and heating to 1100 °C under a wet oxygen flow in a quartz tube. Recovery yields of F and Cl were ∼ 97% using a NaF + NaCl standard solution. Detection limits of the pyrohydrolysis-IC method for silicate samples were 0.36 and 0.69 μg g^-1 for F and Cl, respectively. Fluorine and Cl concentrations were determined in the reference materials JB-2, JB-3 and JA-1 from the GSJ; BCR-2, BHVO-1, BHVO-2, AGV-1 and AGV-2 from the USGS; and NIST SRM 610, 612 and 614 glasses. Precisions (RSD) for determinations of F were 1–13% (except NIST SRM 614) and 2–19% for Cl, and were dependent on the concentration and blank correction. Most results obtained in this study were in good agreement with those of previous studies. In comparison, the Na₂CO₃ + ZnO fusion method at 900 °C showed that the yields of F and Cl by alkaline fusion systematically decreased with fusion duration time. The yields were 84% and 83% for JB-3, inferring that F and Cl were lost in this alkaline fusion.     

Boron and Oxygen Isotope Composition of Certified Reference Materials NIST SRM 610/612 and Reference Materials JB-2 and JR-2

We present data on the concentration, the isotope composition and the homogeneity of boron in NIST silicate glass reference materials SRM 610 and SRM 612, and in powders and glasses of geological reference materials JB-2 (basalt) and JR-2 (rhyolite). Our data are intended to serve as references for both microanalytical and wet-chemical techniques. The δ¹¹ B compositions determined by N-TIMS and P-TIMS agree within 0.5% and compare with SIMS data within 2.5%. SIMS profiles demonstrate boron isotope homogeneity to better than δ¹¹ B = 2% for both NIST glasses, however a slight boron depletion was detected towards the outermost 200 μm of the rim of each sample wafer. The boron isotope compositions of SRM 610 and SRM 612 were indistinguishable. Glasses produced in this study by fusing JB-2 and JR-2 powder also showed good boron isotope homogeneity, both within and between different glass fragments. Their major element abundance as well as boron isotope compositions and concentrations were identical to those of the starting composition. Hence, reference materials (glasses) for the in situ measurement of boron isotopes can be produced from already well-studied volcanic samples without significant isotope fractionation. Oxygen isotope ratios, both within and between wafers, of NIST reference glasses SRM 610 and SRM 612 are uniform. In contrast to boron, significant differences in oxygen isotope compositions were found between the two glasses, which may be due to the different amounts of trace element oxides added at ten-fold different concentration levels to the silicate matrix.     

Geochemical processes controlling silica concentrations in groundwaters of the Salado River drainage basin, Argentina

Chemical analyses of dissolved silica in the shallow groundwater of the lower part of the Salado River drainage basin indicate that silica values averaged 60 ppm. The groundwaters are oversaturated in relation to quartz, Na-plagioclase, K-feldspar, and the weathering of quartz and aluminosilicates appear to have little control on silica concentrations in solution. Groundwater is undersaturated with respect to amorphous silica present in the loessic sediments, and these sediments are specially important in the control of the groundwater composition. The sources of amorphous silica are volcanic glass shards and biogenic silica derived from plant (silicophytoliths, diatom frustules) or animal remains (sponge spicules) also present in the Pampean loess. Silicophytoliths and diatoms have also been reported in A soil horizon samples. The dissolution of amorphous silica most likely controls the high dissolved silica concentrations in groundwater.     

Processes of silicate karstification associated with pan formation in the Darwin–Koolpinya area of northern Australia

Lyons Lagoon, one of many small pans near Darwin, Northern Australia, occurs in lateritized terrain. Formation by structurally facilitated silicate karsti?cation of the parent Cretaceous sandy sediments was earlier proposed. This paper presents the results of thin section microscopy and scanning electron microscopy with energy‐dispersive X‐ray study of pan sediments with a view to assessing the extent to which they re?ect the geomorphological/hydrogeological history. Severe corrosion was found to overprint the impact features of the primary sands, attributed to aggressive leaching and consistent with formation of the depression by karsti?cation when the water table was low. Formation of a smectitic matrix is considered to have followed when the water table was high. Upon subsequent lowering of the water level leaching was resumed, altering smectite to kaolinite and resulting in incongruent dissolution of kaolinite to leave a siliceous residuum. At least two cycles of high followed by low water levels are recognized. Such periodic changes of levels are considered essential to pan formation within freely draining lateritic terrain. The processes of pan formation and alteration of pan sediments (essentially residual deposits) is ongoing, biocorrosion being implicated as an important mechanism. Incongruent kaolinite dissolution, to leave a silica residuum, a hitherto apparently unrecognized process, raises the possibility that silcrete may form as a relative accumulation which is synchronous with lateritic leaching in more elevated topographic positions. Copyright © 2004 John Wiley & Sons, Ltd.     

Co-existing fluid and silicate inclusions in mantle diamond

We document the compositions of co-existing silicate macro-inclusions and fluid micro-inclusions in the fibrous coats of eight coated diamonds from the Panda kimberlite (Canada). The mineral inclusions in the diamond coats come from either the peridotite suite (Cr-pyrope, orthopyroxene, olivine and Cr-diopside) or the eclogite suite (omphacite). Therefore, fibrous diamonds grow in the same paragenetic environments as octahedral diamonds. The inclusions document a more fertile source composition (lower Mg# and higher CaO) than for equivalent phases in octahedral diamonds from Panda and worldwide. However, moderate to high Cr₂O₃ contents in garnet and clinopyroxene inclusions suggest that this apparent fertility is due to a secondary process. Geothermometry of the silicate inclusions yields low equilibration temperatures of 930 to 1010 °C. The co-existing fluid micro-inclusions are dominated by H₂O, carbonate and KCl. Fluid inclusions in both the peridotitic and eclogitic samples fall along linear arrays between Fe–Ca–Mg carbonate and KCl. Inclusions in the one eclogitic sample also contain quartz. We suggest that the diamonds have trapped both metasomatised minerals and the metasomatic fluid, and so provide a snap shot of a metasomatic event in the mantle.     

利用天然粉石英制作耐高温硅酸钙保温材料的研究

研究以天然粉石英为硅质原料,普通建筑用石灰为钙质原料生产硬硅钙石型硅酸钙保温材料的基本反应原理、反应过程和可用于工业化生产的工艺技术。用该项新技术所生产的硬硅钙石型硅酸钙保温材料,其性能达到美国和日本同类产品标准。     

GeoPT2. International Proficiency Test for Analytical Geochemistry Laboratories - Report on Round 2

Results from sixty laboratories participating in GeoPT2, the international proficiency testing programme for analytical geochemistry laboratories, are reported. Compared with 71.3% in the last round, 74.6% of the reported data complied with the laboratories' selected fitness for purpose criteria.