高氯酸-盐酸体系-火焰原子吸收光谱法测定铅精粉中的银

采用X射线衍射技术(XRD)对水镁石原矿和不同工艺条件生产的出口镁砂产品进行了物相组成分析,水镁石原矿粉中主相Mg(OH)2含量达到85.9%,杂质主要是Mg3Si2(OH)4O5、CaCO3和CaMg(CO3)2;轻烧镁砂中的Mg(OH)2大部分已经分解为MgO,但还有12.3%的Mg(OH)2未分解,并在低温煅烧的情况下生成了微量的新相Mg2SiO4;重烧镁砂中的Mg(OH)2已经完全分解为MgO,杂质主要存在形式是Mg2SiO4和CaCO3,占总量的18.5%。实验结果将成为提高水镁石矿煅烧生产的镁砂品质而改进提纯工艺的参考依据。     

Disposal of wastewater containing Congo Red by synthesizing layer double hydroxide in-situ

Based on the principle of synthesis, a new method was put forward to dispose Congo Red anion-containing dyestuff from wastewater and its feasibility was also examined. The principle of the method is described as follows： Mg^2＋ and Al^3＋ are hydrolyzed to form Mg/Al-LDH by adding Mg^2＋, Al^3＋ and NaOH in wastewater containing anion dyestuff, which is selectively intercalated with the interlayer of LDH in order to balance positive structural charge. While Mg^2＋ and Al^3＋ are co-precipitated to form LDH, the anion dyestuff in wastewater will be removed by LDH synthesized in-situ, as is confirmed by X-ray diffraction analysis of settlings and chemical analysis of aqueous samples. In this work, we studied the influence of Mg/Al mole ratio, pH value, time and temperature of reaction on the removal of anion dyestuff and the use of Mg and Al. The experimental results showed the maximum removal efficiency of anion dyestuff could be attained when pH value was 9.0, and Mg/Al mol ratio was 2 ： 1, reaction duration was 2 hours, and the effect of temperature was not remarkable, and the removal efficiency could reach 100%. Meanwhile, the Mg and Al added could be made good use of. This technology has the advantage of extraordinary efficiency of wastewater disposal.     

硼掺入Mg(OH)2形式及机理

采用pH=9.5～13.0的无镁合成海水进行了Mg(OH)₂沉积时B的掺入实验,证实了B(OH)₃优先掺入Mg(OH)₂的硼同位素分馏特征。在所研究的pH范围内,Mg(OH)₂沉积的δ11B均高于无镁合成海水的δ11B,它们之间的硼同位素分馏系数α沉积/海水为1.017 7~1.056 9,平均为1.032 9±0.009 32(SD)。硼同位素的这种分馏特征与无机碳酸盐沉积时的硼同位素分馏存在明显差异,表明B掺入Mg(OH)₂沉积具有不同的机理。B在Mg(OH)₂沉积上的吸附以及B(OH)₃与Mg(OH)₂的沉积反应同时存在并相互制约是其主要特征,造成了B(OH)₃优先掺入的总结果,这并不意味B(OH)₃在掺入的分数上占有优势,相反在所研究的pH范围内,Mg(OH)₂沉积的B(OH)₃/B(OH)-₄大都小于1,因此吸附作用决定了Mg(OH)₂沉积中B浓度的变化特征。采用这种模型能很好地解释沉积中B浓度、B在沉积和海水间的分配系数Kd以及沉积与海水间的分馏系数α随海水pH的变化特征。石珊瑚中Mg(OH)₂的普遍存在和Mg(OH)₂中B(OH)₃的优先掺入也许会影响珊瑚的硼同位素组成与海水pH的定量对应关系,给δ11B作为古海水pH的代用指标带来一定的不确定性。     

Magnesium isotopic composition of igneous rock standards measured by MC-ICP-MS

To provide inter-lab comparison for high-precision Mg isotope analysis, Mg isotope compositions (expressed as δ²⁶Mg relative to DSM-3) for commercially accessible peridotite, basalt, andesite, and granite geo-standards have been measured by multi-collector inductively coupled mass-spectrometry (Nu-Plasma) using sample-standard bracketing method. There is a large tolerance of matrix cations during the measurement of Mg isotopes, as intensity ratios of ²³Na/²⁴Mg and ²⁷Al/²⁴Mg of about 20% only change the δ²⁶Mg by less than 0.1‰, and low ⁵⁵Mn/²⁴Mg (<0.1) and ⁵⁸Ni/²⁴Mg (<0.01) do not cause significant mass bias either. Concentration match between samples and standards within 90% is adequate to obtain accurate isotope analysis, which also mitigates the isobaric interference of ¹²C¹⁴N⁺ on ²⁶Mg. Organic matrix from chemical purification can cause significant analytical errors when the mass of Mg processed is small. The long-term reproducibility of δ²⁶Mg_DSM-3 for samples with relatively higher MgO content is about 0.11‰ (2SD), and granites with lower MgO content is about 0.2‰ (2SD). Although the standards in this study have wide ranges of major element compositions with SiO₂ from 40 to 70 wt.% and MgO from 0.75 to 49.6 wt.%, they exhibit a variation of Mg isotopic compositions with δ²⁶Mg from −0.07 to −0.40‰. δ²⁶Mg do not correlate with SiO₂ or MgO contents, suggesting homogenous Mg isotope compositions in igneous rocks at the level of current precision, relative to low temperature samples including sediments and riverine and sea waters. Our data do not support a non-chondritic Mg isotope composition of the Earth.     

荥巩矿区岩溶地下水系统的水文地球化学特征及其指示意义

本文在分析荥巩矿区水文地质条件的基础上,重点对岩溶地下水系统的水化学特征进行分析。结果表明:岩溶水水化学类型自补给区到排泄区,从单一的HCO3型向复杂的HCO3.SO4型和SO4.HCO3型转变,TDS和Sr2+/Ca2+值均增加。地下水氢氧稳定同位素分析结果表明,本区岩溶地下水主要接受大气降水的入渗补给。根据同位素计算的补给高程推断岩溶水补给范围和划分的流动系统与地面调查结果及水化学研究成果一致:矿区处于区域流动系统排泄带,中寒武统张夏组—中奥陶统灰岩在矿区南部出露的范围接受降水补给,以侧向径流的方式进入矿区充水含水层。     

典型岩溶丘陵区地下水水化学特征及地球化学敏感性分析——以武冈东部地区为例

通过对典型岩溶丘陵区地下水进行水化学特征及地球化学敏感性的研究表明,该地下水系统水化学特征阳离子以Ca2+、Mg2+为主,阴离子以HCO3-、NO3-、SO42-为主,受水岩作用及人类活动共同影响;Mg2+/Ca2+受岩性控制,流经白云岩地层最高,灰岩夹白云岩次之,灰岩最低;研究区岩溶地下水表现出较高的地球化学敏感性。阳离子以Ca2+最为敏感,其次为Mg2+,阴离子以HCO3-最为敏感,其次为NO3-,元素的地球化学敏感性大小依次为:HCO3->Ca2+>Mg2+>NO3->SO42->Cl->Na+>K+;以敏感性最强的敏感因子HCO3-对研究区岩溶地下水进行敏感性等级划分。研究区低敏感性的水点仅占7.27%,中敏感性的水点占25.45%,高敏感性的水点占67.28%。通过地球化学敏感性划分统计结果显示,对该地区地下水的保护显得十分重要且迫切。      

室温常压下 Ca2+-Mg2+-HCO31--H2O 体系的试验研究

世界上很多海域中的现代碳酸盐沉积正在形成,如巴哈马滩、美国的佛罗里达湾、古巴的巴塔诺湾、中东的波斯湾等地,以及丹麦的某些近海地区。产于这些海域中的现代碳酸盐沉积物,其矿物组成主要是文石,其次为镁方解石,纯方解石较少,现代白云石沉积更为少见。我国的现代碳酸盐沉积见于南海诸岛及海南岛的沿海地带。作者曾利用粉晶照相鉴定了采自我国南海二十余种珊瑚、瓣鳃类、腹足类、有孔虫等现代海相生物壳体的物相,发现除有孔虫和海胆壳是由镁方解石构成外,其余生物壳体皆由文石构成。     

哀牢山─金沙江裂谷系岩石中镁铁云母成分特征及其岩石学意义

本区的Mg－Fe云母是富镁黑云母及金云母，MF＞1．35，［Mg／（Mg＋Fe3+＋Fe2+＋Mn）］＞0.65，［（Fe3+＋Fe2+）／（Fe3+＋Fe2+＋Mg）］＜0．4，属于富镁、富碱、高硅、贫铁类型云母。根据Mg－Fe云母的成分及形成的物化条件，表明其寄生岩石属于富碱，浅成一超浅成的幔源岩石。     

重庆市南川区南部岩溶地下水水文地球化学特征

以重庆市南川区南部地区岩溶地下水为研究对象,通过野外调查和取样测试分析,对研究区内149件地下水样品进行水化学常规分析和微量重金属元素分析,结果表明:研究区内地下水化学类型以HCO3-Ca·Mg、HCO3-Ca和HCO3-SO4-Ca型为主。地下水中主要阴阳离子HCO3-、SO42-、Ca2+和Mg2+浓度均表现出与含水岩组相对应的关系,即碳酸盐岩类岩溶水＞碳酸盐岩夹碎屑岩水＞碎屑岩水。地下水中Mg2+ /Ca2+摩尔比值表明研究区内绝大部分地下水径流过程中以方解石和白云石的共同溶解为主。地下水中微量重金属元素含量整体偏低,绝大部分水质都在Ⅲ类水标准以内,只有极个别点受到污染导致部分重金属组分偏高      

Analysis on hydrochemical characteristics of groundwater in strongly exploited area in Hutuo River Plain

The Hutuo River alluvial-proluvial fan is located in North China Plain, and groundwater is the main source of water supply for agriculture and domestic water. Shijiazhuang depression funnels due to the long-term excessive exploitation are the bottleneck of the regional economic development. Analyzing the chemical characteristics of groundwater under the condition of strong human activities, can provide a scientific basis for further study of strong groundwater mining area environmental change. 143 groups of shallow groundwater samples are collected during the period of 2007-2008. In this paper, the hydrochemical characteristics of groundwater in the Hutuo River Plain area are analyzed systematically, using hydrogeochemical theory, combined with statistical methods and hydrochemical methods. Results are shown as follows: HCO_3~- and Ca~(2+) are major anion and cation. The variation coefficients of K~+, Ca~(2+), Mg~(2+) and HCO_3~- between 0.25 and 0.52, which means small and stable relatively. The variation coefficient of are Na~+, NO_3~-, Cl-, SO2-4 were large(0.89-1.01). They are sensitive and vulnerable to environmental change affect. Due to the impact of human activities, from the top to the edge of the alluvial-proluvial fan, the hydrochemical types of groundwater change from single to multiple, followed by HCO_3~-Ca·Mg, HCO_3·SO_4-Ca·Mg, HCO_3·SO_4·Cl-Ca·Mg, HCO_3·Cl-Ca·Mg and other types.     

袁复礼石的矿物学新资料及晶体结构

袁复礼石是一种Ｍｇ、Ｆｅ３＋、Ａｌ３＋和Ｔｉ的硼酸盐新矿物。除了与遂安石、硬石膏和磷灰石共生外，还与硼铝镁石、镁橄榄石和方解石等共生，形成两个矿物共生组合。单矿物化学分析表明，后一组合中的袁复礼石更富铁，特别是Ｆｅ３＋，相对贫镁。袁复礼石的晶体结构分析证明，袁复礼石与硼钛镁石的结构类型一致，阳离子的占位为Ｍ（１）＝Ｍｅ３＋，Ｍ（２）＝Ｍｅ２＋。袁复礼石是Ｍ（１）位置上为Ｆｅ端员组分，Ｍ（２）位置上为Ｍｇ端员组分的新矿物。     

Magnesium isotopic composition of the Earth and chondrites

To constrain further the Mg isotopic composition of the Earth and chondrites, and investigate the behavior of Mg isotopes during planetary formation and magmatic processes, we report high-precision (±0.06‰ on δ²⁵Mg and ±0.07‰ on δ²⁶Mg, 2SD) analyses of Mg isotopes for (1) 47 mid-ocean ridge basalts covering global major ridge segments and spanning a broad range in latitudes, geochemical and radiogenic isotopic compositions; (2) 63 ocean island basalts from Hawaii (Kilauea, Koolau and Loihi) and French Polynesia (Society Island and Cook-Austral chain); (3) 29 peridotite xenoliths from Australia, China, France, Tanzania and USA; and (4) 38 carbonaceous, ordinary and enstatite chondrites including 9 chondrite groups (CI, CM, CO, CV, L, LL, H, EH and EL).Oceanic basalts and peridotite xenoliths have similar Mg isotopic compositions, with average values of δ²⁵Mg = −0.13 ± 0.05 (2SD) and δ²⁶Mg = −0.26 ± 0.07 (2SD) for global oceanic basalts (n = 110) and δ²⁵Mg = −0.13 ± 0.03 (2SD) and δ²⁶Mg = −0.25 ± 0.04 (2SD) for global peridotite xenoliths (n = 29). The identical Mg isotopic compositions in oceanic basalts and peridotites suggest that equilibrium Mg isotope fractionation during partial melting of peridotite mantle and magmatic differentiation of basaltic magma is negligible. Thirty-eight chondrites have indistinguishable Mg isotopic compositions, with δ²⁵Mg = −0.15 ± 0.04 (2SD) and δ²⁶Mg = −0.28 ± 0.06 (2SD). The constancy of Mg isotopic compositions in all major types of chondrites suggest that primary and secondary processes that affected the chemical and oxygen isotopic compositions of chondrites did not significantly fractionate Mg isotopes.Collectively, the Mg isotopic composition of the Earth’s mantle, based on oceanic basalts and peridotites, is estimated to be −0.13 ± 0.04 for δ²⁵Mg and −0.25 ± 0.07 for δ²⁶Mg (2SD, n = 139). The Mg isotopic composition of the Earth, as represented by the mantle, is similar to chondrites. The chondritic composition of the Earth implies that Mg isotopes were well mixed during accretion of the inner solar system.     

湖南新田富锶地下水水化学特征与成因分析

研究湖南新田富锶地下水水化学特征及成因,为富锶地下水的可持续利用与开发提供理论依据。对研究区21个下降泉、30个机井富锶地下水样品的水化学类型、化学成分含量特征、成分间相关性以及离子比值的研究。结果表明：下降泉水化学类型全部为HCO3-Ca型,机井水化学类型以HCO3-Ca、HCO3-Ca·Mg型为主。相关分析表明,下降泉和机井中SO42-与Ca2+、Mg2+均表现显著相关或极显著相关,HCO3-与Ca2+、SO42-与NO3-在下降泉与机井中的相关性具有差异,下降泉、机井Sr与Ca2+、Mg2+、HCO3-均表现为极显著相关。Gibbs图表明下降泉和机井的水化学组成主要受水-岩相互作用的控制,下降泉、机井c(Ca2+)/c(Mg2+)、c(HCO3-)/c(SO42-+Cl-)、c(Na+)/c(Cl-)、c(Cl-)/c(Ca2+)系数比值具有差异。结果表明富Sr地下水的形成受碳酸盐岩成分影响显著,赋存条件的差异导致富锶地下水在下降泉、机井中的水化学特征、相关性以及离子系数比值的差异。     

Structure of Cu-bearing orthopyroxene, Mg(Cu.56,Mg.44)Si2O6, and behavior of Cu2+ in the orthopyroxene structure

Cu-bearing pyroxene, Mg(Cu.₅₆,Mg.₄₄)Si₂O₆, has been synthesized by a flux method and crystal structure refinement has been performed by single crystal X-ray diffraction. It is found that the crystal structure is orthorhombic (space group Pbca) with unit cell dimensions of a=18.221(4), b=8.890(1), c=5.2260(7)Å and the cell volume of 846.5( )3ų. In the M2-site one of the M-O bonds(M-O3B) is extremely expanded from 2.444(2) in enstatite to 2.732(2), thus the coordination polyhedron around M2-site is regarded as square pyramidal rather than square planar or octahedral. It is also found that the M1-site in the pyroxene structure is occupied almost exclusively by Mg, while the M2-site is almost evenly occupied by Mg and Cu. The observed extreme site preference shown by Cu²⁺ is unusual among the divalent cations with similar ionic sizes.     

我国北方前寒武区域变质岩区变质作用对镁铁云母成分的影响

辽宁鞍山、冀东、密云和内蒙古地区镁铁云母的寄主岩石类型有变沉积岩和变火山岩。其镁铁云母的Al_2O_3含量和Mg/(Mg+Fe~(2+))比值随寄主岩石类型不同而有明显的差异。而在同类寄主岩石中,镁铁云母的成分,特别是Mg/(Mg+Fe~(2+))比值,则随变质作用强度而出现规律性的变化。 研究表明,从鞍山-冀东-密云、内蒙古、变质作用强度(主要是温度)升高;在翼东水厂矿区,从南至北,变质作用强度也有增加的趋势。镁铁云母成分可为变质岩区的地层对比、确定构造形迹和找矿提供有益的信息。     

Melting of a Hydrous Mantle: II. Geochemistry of Crystals and Liquids Formed by Anatexis of Mantle Peridotite at High Pressures and High Temperatures as a Function of Controlled Activities of Water, Hydrogen, and Carbon Dioxide

The system peridotite-H₂O-CO₂ serves as a simplified model forthe phase relations of mantle peridotite involving more thanone volatile component. Run products obtained in a study ofphase relations of four mantle peridotites in the presence ofH₂O- and (H₂O+CO₂)-bearing vapors and with controlled hydrogenfugacity (f_H2) at high pressures and temperatures have beensubjected to a detailed chemical investigation, principallyby the electron microprobe. Mg/(Mg+Fe) of all phases generally increases with increasingtemperature and with increasing Mg/(Mg+Fe) of the starting material.This ratio appears to decrease with increasing pressure forolivine, and for amphibole coexisting with garnet. DecreasingfH₂from that of IW buffer to that of MH buffer decreases Mg/(Mg+Fe)of the partial melt from approximately 0?85 to approximately0?50, whereas the Fo content of coexisting olivine increasesslightly less than 3 per cent and the Mg/(Mg+Fe) of clinopyroxeneincreases about 4 per cent. However, the variations in Fo contentof olivines are within those observed in olivines from naturalmantle peridotite. The chemistry of other silicate mineralsdoes not significantly reflect variations of fH₂. Consequently,the peridotite mineralogy and/or chemistry is not a good indicatorfor the fH₂ conditions during crystallization. All crystalline phases, except amphibole, and to some extentgarnet, show increasing Cr content with increasing temperatureand increasing Cr content of the starting material, resultingin a positive correlation with Mg/(Mg+Fe). Partial melts aredepleted in Cr₂O₃ relative to the crystalline phases. High Mg/(Mg+Fe)and Cr₂O₃ are thus expected in crystal residues after partialmelting. The absolute values depend on degree of melting andthe composition of the parent peridotite.     

X射线衍射法分析水镁石煅烧制备的镁砂物相组成

研究了离子色谱法同时测定砂岩型铀矿浸出液中阳离子的方法。采用Ionpac CS12A阳离子分离柱,以20 mmol/L甲基磺酸(MSA)为淋洗液,直接电导检测-离子色谱法分离测定铀矿石浸出液中常见的阳离子(Li+、Na+、K+、NH4+、Ca2+、Mg2+),方法检出限为0.012 7~0.194 mg/L,相对标准偏差(RSD,n=5)为1.04%~4.50%,加标回收率为91.5%~106.0%。该方法用于铀矿石浸出液中的阳离子同时测定,具有很好的实用性。     

Disposal of wastewater containing Congo Red by synthesizing layer double hydroxide in-situ

Based on the principle of synthesis, a new method was put forward to dispose Congo Red anion-containing dyestuff from wastewater and its feasibility was also examined. The principle of the method is described as follows: Mg²⁺ and Al³⁺ are hydrolyzed to form Mg/Al-LDH by adding Mg²⁺, Al³⁺ and NaOH in wastewater containing anion dyestuff, which is selectively intercalated with the interlayer of LDH in order to balance positive structural charge. While Mg²⁺ and Al³⁺ are co-precipitated to form LDH, the anion dyestuff in wastewater will be removed by LDH synthesized in-situ, as is confirmed by X-ray diffraction analysis of settlings and chemical analysis of aqueous samples. In this work, we studied the influence of Mg/Al mole ratio, pH value, time and temperature of reaction on the removal of anion dyestuff and the use of Mg and Al. The experimental results showed the maximum removal efficiency of anion dyestuff could be attained when pH value was 9.0, and Mg/Al mol ratio was 2: 1, reaction duration was 2 hours, and the effect of temperature was not remarkable, and the removal efficiency could reach 100%. Meanwhile, the Mg and Al added could be made good use of. This technology has the advantage of extraordinary efficiency of wastewater disposal. Foundation item: Project supported by the National Natural Science Foundation of China (40472026).     

新发现的沂蒙矿类质同象系列矿物──K(Ti_5Fe_3Cr_2Mg_2)_(12)O_(19)及Ba(Ti_5Fe_4Mg_2Cr)_(12)O_(19)

在山东蒙阴金伯利岩中，首次发现了沂蒙矿类质同象系列新的富Ti矿物（变）种。理想的晶体化学式可表达为：K（Ti5Fe3Cr2Mg2）12O19（简称K－Ti沂蒙矿）（Ba，K）（Ti5Fe4Mg2Cr）12O19（简称Ba－Ti沂蒙矿）从而与原来确定的沂蒙矿K（Cr5Ti3Fe2Mg2）12O19和钡钛铁铝矿（Ba，K）（Cr4Fe4Ti3Mg）12O19一起构成了金伯利岩中AM12O19磁铁铅矿型矿物的K-Cr、Ba－Cr、K-Ti、Ba-Ti四种端元类型的复杂类质同象系列。新发现的两个矿物（变）种均产出于具叶片状尖晶石出溶体的镁钛铁矿中。根据结构已知的沂蒙矿中原子的占位和配位多面体情况，分析了K－Ti，Ba－Ti沂蒙矿中各原子的占位和配位多面体，认为新发现的两个（变）种在成分上与沂蒙矿和钡钛铁铬矿有明显的区别。根据镁钛铁矿、尖晶石、沂蒙矿新（变）种、钙钛矿之间的相互关系，探讨了它们的形成环境，从而为这类矿物的地幔成因提供了直接证据。     

杭州湾及其邻近海域沉积物中Fe、Mn、Ca、Mg的地球化学研究

本文通过对杭州湾及其邻近海域29个站位的表层沉积物化学、粘土矿物及碎屑矿物资料的分析,详细研究了开放型海湾沉积物中Fe、Mn、Ca、Mg元素地球化学特征。研究表明,1)与同类型海湾相比,杭州湾显示高Fe、Mn、Mg低Ca的特点。表明物质来源丰富,而生物作用较弱;2)Fe、Mn主要来自长江和钱塘江径流搬运,受粘土控制。Mg主要来自粘土对海水中Mg2+的吸附,同时受上覆水盐度的影响;3)北区元素间关系明显的比南区强烈,表明南区物质来源较北区复杂;4)主断面沉积物中Mg/Ca由河口向海洋增加,并与有机碳呈明显的正相关,显示杭州湾及邻近陆架区可能发生着原始碳酸盐（钙）白云岩化的反应。