Implications of Analcime Hydrothermally Formed from Na-alumino-borosilicate Glasses Containing Cs and Sr for the Stability of High-level Radioactive Waste Form

Abstract. In order to know the behaviors of radioactive elements such as cesium and strontium during a hydrothermal alteration of borosilicate glass of radioactive waste, some alumino-borosilicate glasses belonging to the systems Na₂O-Al₂O₃-B₂O₃-SiO₂-SrO, Na₂O-Al₂O₃-B₂O₃-SiO₂-Cs₂O and Na₂O-Al₂-O₃-B₂O₃-SiO₂-SrO-Cs₂O have been treated hydrothermally at 200C under a vapor pressure of 1.54 MPa. The result shows that all glasses are changed into crystalline phases with running time up to 60 days, and that analcime-type zeolite is formed as a major product. The formed zeolite is shown to contain cesium and/or strontium. Considering the fact that natural zeolite occurs in wide physicochemical conditions including hydrothermal one, the analcime-type zeolite is expected to fix stably the radioactive elements in the disposal site. Since aluminum is necessary for the formation of the analcime-type zeolite, the waste glass should have aluminum as one of major components.     

Determination of the Absolute Hydrogen Isotopic Ratio of V-SMOW and SLAP

By mixing ¹H₂O and ²H₂O, both with accurately known purity, samples were prepared with ²H/¹H ratios close to those of the international isotopic water standards: V-SMOW and SLAP. A mass spectrometrical comparison of these calibration samples with the actual water standards revealed:
²H/¹H of V-SMOW = (155.95 ± 0.08) × 10^−6
2H/¹H of SLAP = (89.12 ± 0.07) × 10⁻⁶
δ²H_V-SMOW(SLAP) =−428.5 ± 0.5 %     

Review of the Study on the Stable Isotopes of Nitrogen and Oxygen in Atmospheric Nitrate

Due to the emissions from intensive human activities and rapid development of industry and agriculture, atmospheric nitrate (NO {}_3^{-} ) contamination is becoming more serious and now is a worldwide environmental problem. The isotopic compositions of NO {}_3^{-} (δ¹⁵N, δ¹⁸O and Δ¹⁷O) can deliver more information than the concentration alone, i.e., the nitrogen and oxygen isotopes can suggest the sources of NO {}_3^{-} and oxidation capability of the atmosphere, providing a powerful tool for investigating atmospheric nitrogen cycling and atmospheric NO {}_3^{-} pollution control. The δ¹⁵N of different sourced NO {}_3^{-} in the atmosphere, as well as the seasonal variation of δ¹⁵N (NO {}_3^{-} ) and the associated mechanisms were reviewed. In addition, the oxygen isotopes of various oxidants and NO {}_3^{-} (δ¹⁸O and Δ¹⁷O) in the atmosphere were summarized, and the global distribution patterns of the oxygen isotopes of NO {}_3^{-} were discussed. Lastly, the available analysis techniques of isotopic compositions of NO {}_3^{-} were reviewed. Based on the research progress of NO {}_3^{-} isotopes in the atmosphere, it was suggested that further investigations should focus on measuring the isotopic compositions of oxidants and NOx from different sources, characterizing the production mechanisms of NO {}_3^{-} , as well as investigating chemical recycling between NOx and NO {}_3^{-} with the aid of atmospheric chemical models.     

Ionic association in H2O–CO2 fluids at mid-crustal conditions

The equilibrium constant, K _a, of the association reaction to form ion pairs from charged solute species in supercritical solutions can be calculated from a model based on published equations. Log K _a at constant pressure is a linear function of the inverse in the dielectric constant of the fluid times temperature. The dielectric properties of H₂O and CO₂ at supercritical pressures and temperatures can also be evaluated using the Kirkwood equation. Using Looyenga mixing rules, the dielectric constant of H₂O–CO₂ mixtures can be obtained and the change in log K _a with addition of CO₂ in aqueous solutions evaluated. These changes in log K _a with addition of CO₂ are consistent with measured changes of log K _a with addition of Ar in supercritical H₂O–Ar solutions.
Log K _a of KCl and NaCl increase to an increasing extent as the mole fraction of CO₂ increases in H₂O–CO₂ solutions. For instance, at 2 kbar and constant temperature between 400 and 600° C, log K _a of KCl increases by about two orders of magnitude whilst that of NaCl increases by over four orders of magnitude as the CO₂ mole fraction increases from 0.0 to 0.35. Such changes in log K _a will have dramatic effects on the solubility of minerals in CO₂-rich environments.     

The (Na–Ca)amphibole–albite–chlorite–epidote–quartz geothermobarometer in the system S–A–F–M–C–N–H2O. 1. An empirical calibration

The proposed geothermobarometer is based on an empirical calibration which takes account of two equilibria involving the tremolite, edenite, pargasite and hastingsite components in amphiboles. It has applications to assemblages found in metabasic rocks of widely different chemical compositions (magnesian to Fe-rich metabasalts), and for metamorphism ranging from lower greenschist to highest amphibolite facies. Knowing the Si_(T1), Al^iv, Al^vi, Fe³⁺, Fe²⁺, Mg, Ca, Na_M4, Na_A and A vacancy in an amphibole, and the Al³⁺ and X _Mg in coexisting epidote and chlorite, it is possible to calculate two values of In K _d for this assemblage. These equilibria involve edenite-tremolite and (pargasite/hastingsite)-tremolite end-members in amphibole (the calculation program is given). For these equilibria, the isopleths (iso-values of K _d) have been calculated for 0.27 < X _Mg < 0.75 and 0 < X _Fe3+= Fe³⁺/(Fe³⁺+ Al^vi) < 0.8. It is then possible to determine pressure and temperature directly when X _Mg, X _Fe3+, In K _d for tremoliteedenite and In K _d for (pargasite/hastingsite)-tremolite are known. Application of this geothermobarometer is limited to Ca-free plagioclase assemblages, and complete P–T paths can be drawn only if all the minerals are considered together. Phase relations at successive stages of crystallization can be constrained by studying the relationships between the coexisting minerals, their zoning and the metamorphic fabrics.     

Effect of Fe on garnet–melt trace element partitioning: experiments in FCMAS and quantification of crystal-chemical controls in natural systems

Garnet–melt trace element partitioning experiments were performed in the system FeO–CaO–MgO–Al₂O₃–SiO₂ (FCMAS) at 3 GPa and 1540°C, aimed specifically at studying the effect of garnet Fe²⁺ content on partition coefficients (D^Grt/Melt). D^Grt/Melt, measured by SIMS, for trivalent elements entering the garnet X-site show a small but significant dependence on garnet almandine content. This dependence is rationalised using the lattice strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454], which describes partitioning of an element i with radius r_i and valency Z in terms of three parameters: the effective radius of the site r₀(Z), the strain-free partition coefficient D₀(Z) for a cation with radius r₀(Z), and the apparent compressibility of the garnet X-site given by its Young's modulus E_X(Z). Combination of these results with data in Fe-free systems [Van Westrenen, W., Blundy, J.D., Wood, B.J., 1999. Crystal-chemical controls on trace element partitioning between garnet and anhydrous silicate melt. Am. Mineral. 84, 838–847] and crystal structure data for spessartine, andradite, and uvarovite, leads to the following equations for r₀(3+) and E_X(3+) as a function of garnet composition (X) and pressure (P):

r₀(3+) [Å]=0.930X_Py+0.993X_Gr+0.916X_Alm+0.946X_Spes+1.05(X_And+X_Uv)−0.005(P [GPa]−3.0)(±0.005 Å)

E_X(3+) [GPa]=3.5×10¹²(1.38+r₀(3+) [Å])^−26.7(±30 GPa)

Accuracy of these equations is shown by application to the existing garnet–melt partitioning database, covering a wide range of P and T conditions (1.8 GPa<P<5.0 GPa; 975°C<T<1640°C). D^Grt/Melt for all 3+ elements entering the X-site (REE, Sc and Y) are predicted to within 10–40% at given P, T, and X, when D^Grt/Melt for just one of these elements is known. In the absence of such knowledge, relative element fractionation (e.g. D_Sm^Grt/Melt/D_Nd^Grt/Melt) can be predicted. As an example, we predict that during partial melting of garnet peridotite, group A eclogite, and garnet pyroxenite, r₀(3+) for garnets ranges from 0.939±0.005 to 0.953±0.009 Å. These values are consistently smaller than the ionic radius of the heaviest REE, Lu. The above equations quantify the crystal-chemical controls on garnet–melt partitioning for the REE, Y and Sc. As such, they represent a major advance en route to predicting D^Grt/Melt for these elements as a function of P, T and X.     

High Precision Determination of 48Ca/42Ca Ratio by TIMS for Ca Isotope Fractionation Studies

For studies of mass-dependent fractionation of calcium isotopes in natural materials, the ⁴⁸Ca/⁴²Ca ratio is a superior choice to the conventionally measured ⁴⁴Ca/⁴⁰Ca ratio for two important reasons. These are (1) mass-dependent fractionation can be determined free from the effects of inherited or ingrown radiogenic ⁴⁰Ca and (2) this ratio increases the spread of measured isotopic masses by 50%, resulting in statistically better resolution of fractionation, assuming similar precision. A third, though strictly technical, advantage is the inherent ability of a mass spectrometer to measure ratios close to unity (⁴⁸Ca/⁴²Ca) more precisely than very small or large ratios (⁴⁴Ca/⁴⁰Ca). However, because of the very low natural abundance of both ⁴⁸Ca and ⁴²Ca, their ratio has been very difficult to measure, the only attempt so far being on a high mass resolution MC-ICP-MS with a precision of 0.33%. We report here determination of the ⁴⁸Ca/⁴²Ca ratio by the more commonly available and user-friendly multi-collector TIMS using a ⁴³Ca-⁴⁶Ca double-spike, with a significantly better precision of 0.18% (2s). The ⁴⁸Ca/⁴⁰Ca or ⁴⁴Ca/⁴⁰Ca ratio can also be measured in the same mass spectrometer run to provide complementary information on any radiogenic component.     

地下水硝酸盐污染源解析及氮同位素分馏效应研究进展

地下水硝酸盐污染已成为世界范围内最严重的环境地质问题之一。全面并准确识别硝酸盐污染源,对地下水的有效管理及污染防治具有重要的指导意义。从地下水硝酸盐来源、同位素检测方法、污染源同位素特征、定量解析模型构建、硝酸盐主要转化过程及同位素分馏效应等方面进行总结,比较不同解析方法在硝酸盐溯源中的应用与发展,建议采用多学科、多方法相结合的方式,提高对硝酸盐污染源的全面理解。同位素富集系数是定量解析硝酸盐污染源的重要参数,在源解析过程中探讨硝酸盐转化及同位素分馏机制,能够更好地诠释地下水硝酸盐来源和迁移转化过程,提高源解析的准确性,为地下水硝酸盐污染的准确溯源与有效防治提供参考。     

压力对淤泥中C-N-S-Fe-H2O体系的影响

C、N、S、Fe是地下水中控制氧化-还原反应的主要元素,淤泥是黏土的演化初期,淤泥演化为黏土过程中会影响含水层水量水质,可能会造成地下水污染;其中的水岩相互作用可以概化为C-N-S-Fe-H₂O体系的相互作用。淤泥演化过程的实质是淤泥在压力的作用下孔隙度不断变小,逐渐固结成岩;淤泥内部不断发生生物地球化学反应,C-N-S-Fe-H₂O体系驱动各种物质的形态结构不断发生改变,其中加压速率和加压模式会影响淤泥里的C、N、S、Fe重要组分固液相的转化。本研究运用自主研发设计的增压装置,探究在3种加压速率(0.04 MPa/12 h、0.04 MPa/24 h、0.04 MPa/36 h)和加压模式(0.040.02 MPa/12 h、0.04 MPa/12 h、0.040.06 MPa/12 h)的情况下,固体介质中C、N、S、Fe向孔隙水释放的规律。结果表明:(1)匀速加压速率越慢,加压初期溶解性有机碳(DOC)、 {\mathrm{SO}}_4^{2-}释放速率越快, {\mathrm{NO}}_3^{-}和Fe²⁺浓度变化增大;DOC、 {\mathrm{SO}}_4^{2-}、 {\mathrm{NO}}_3^{-}、Fe²⁺释放总量越多。(2)不同的加压模式,加速加压(0.040.06 MPa/12 h)下 {\mathrm{NO}}_3^{-}、Fe²⁺的浓度波动较大;DOC、 {\mathrm{NO}}_3^{-}、 {\mathrm{SO}}_4^{2-}和Fe²⁺的总释放量为加速加压(0.040.06 MPa/12 h)大于匀速加压(0.04 MPa/12 h)。(3)加压过程中,DOC和 {\mathrm{SO}}_4^{2-}呈显著正相关,改变加压速率会改变DOC, {\mathrm{NO}}_3^{-}、 {\mathrm{SO}}_4^{2-}和Fe²⁺的相关性。本研究表明改变加压速率和加压模式会对DOC、 {\mathrm{NO}}_3^{-}、 {\mathrm{SO}}_4^{2-}和Fe²⁺的释放速率、释放总量和C、N、S、Fe的转化造成影响,其本质为氧化-还原反应和水岩相互作用的强弱发生了变化;本研究为地质演化过程中压力导致的主要元素变化提供了新的认识,认识到了隔水层会影响含水层的水质和水量,为原生劣质地下水的成因和地下水污染防治提供了新思路。     

氧同位素示踪夏季北冰洋（62.3°~74.7° N）大气硝酸盐形成途径的研究

大气硝酸盐（包括颗粒态硝酸盐和气态硝酸）是一种重要的含氮物质,在北冰洋氮的生物地球化学循环中起着重要作用。然而,目前关于北冰洋上大气硝酸盐形成机制的研究较少,限制了对该地区氮氧化物（NO_X）到硝酸盐相关大气化学过程的理解。作为2012年夏季中国第五次北极科学考察的内容之一,本研究采集了科考航线上的大气气溶胶样品,并对北冰洋航段（62.3°~74.7° N）上样品中硝酸盐的氮氧同位素（δ¹⁵N,δ¹⁷O和δ¹⁸O）进行了分析以研究该区域大气硝酸盐的形成过程。观测到的Δ¹⁷O（NO{}_{\mathrm{3}}^{–}）变化范围为21.7‰~28.8‰,均值为（25.4±2.7）‰;δ¹⁵N（NO{}_{\mathrm{3}}^{–}）变化范为是-7.5‰~0.8‰,均值为（-4.2±3.0）‰。整体上,Δ¹⁷O（NO{}_{\mathrm{3}}^{–}）与采样纬度呈现相反的变化趋势,与夜间时长和O₃浓度呈现相似的变化趋势;δ¹⁵N（NO{}_{\mathrm{3}}^{–}）与气温呈现相反的变化趋势。基于化学动力学的分析表明,Δ¹⁷O（NO{}_{\mathrm{3}}^{–}）的变化可能主要反映的是NO₂+OH、N₂O₅+H₂O（aq）、NO₃+HC/DMS、NO₃+H₂O（aq）、XNO₃+H₂O（aq）（X=Br、Cl、I）等硝酸盐生成途径的变化。基于Δ¹⁷O（NO{}_{\mathrm{3}}^{–}）的计算表明：低Δ¹⁷O（NO{}_{\mathrm{3}}^{–}）样品［Δ¹⁷O（NO{}_{\mathrm{3}}^{–}）=21.7‰~24.5‰,66.2°~74.7° N］的主导反应为NO₂+OH,其对硝酸盐的可能平均贡献是68%~81%;对于高Δ¹⁷O（NO{}_{\mathrm{3}}^{–}）样品［Δ¹⁷O（NO{}_{\mathrm{3}}^{–}）=27.5‰~28.8‰,62.3°~69.9° N］,NO₃+HC/DMS、NO₃+H₂O（aq）和XNO₃+H₂O（aq）三者一起的贡献最高,可达35%~50%。结合BrO柱浓度的分析表明,XNO₃+H₂O（aq）反应对高Δ¹⁷O（NO{}_{\mathrm{3}}^{–}）样品的作用可能不可忽略,该作用有待结合大气化学模型进一步探索。     

秦岭主峰太白山北麓降水化学特征分析

利用太白山北麓2011年12月-2013年7月共39次降水样品数据资料, 定量分析了该区域降水化学的特征和时间变化规律. 结果表明: 太白山北麓地区降水中, 除常量离子Na⁺、NH₄⁺、K⁺、Mg²⁺、Ca²⁺、F^-、Cl^-、SO₄^2-、NO₃^-外, CO₃^2-、HCO₃^-、PO₄^3-及低分子有机酸也占有相当比例. 研究区降水常量离子浓度的顺序依次为: NH₄⁺ > SO₄^2- > Ca²⁺ > NO₃^- > Na⁺ > Cl^- > Mg²⁺ > K⁺ > F^-, 离子总浓度表现出明显的季节变化: 夏季(轻度污染) < 秋季(中等污染) < 春季(严重污染) < 冬季(极重污染). 利用因子分析法得出太白山北麓地区降水组分主要有三种来源; Na⁺、Cl^-、Mg²⁺、Ca²⁺主要来自地壳源, SO₄^2-、NO₃^-、NH₄⁺主要来自人为源, K⁺和F^-主要由海盐源和人为源共同贡献. 根据Hysplit 后向气流轨迹分析, 得出不同路径气团降水离子组分不同: 受地形等因素影响, 北方路径的气团比南方路径气团离子总浓度较高; 受土壤类型影响, 西北方向气团降水Na⁺、Mg²⁺、Ca²⁺浓度较高; 受人为活动影响, 东北方向SO₄^2-、NO₃^-、NH₄⁺浓度较高.     

Magnitude-frequency distribution in the European-Mediterranean earthquake regions

The European-Mediterranean earthquake catalogue from 1901 to 1985, which comprises uniformly determined magnitudes M_S and m_B(h ≥ 60 km) of 13300 events, was used in the study of cumulative magnitude-frequency relationships N_c(M) compiled for 75 earthquake regions and 25 larger provinces. In the whole magnitude range observed, the Gutenberg-Richter formula log N_c(M) = a − bM very rarely fits the cumulative (log N_c, M) distributions. The b-values of log-linear segments of N_c(M) vary regionally from b = 0.7 to b = 1.3; averaging of all values leads to (shallow events, M_S and ).

Most distributions pertain to the Mediterranean area (b = 0.86 from the graph for shallow events) and many of them indicate the existence of characteristic earthquakes in accordance with the theoretical single-fault model. Other observed shapes of N_c(M) can be explained by the superposition of populations of different M_max values or by the presence of swarm-type activity. The observed N_c(M) distributions depend very much on the delineation of earthquake regions i.e. on the number and dimension of seismoactive faults in the investigated region.

A premonitory enhancement of medium earthquake activity (M = 4.5–5.5) can be observed only very rarely.     

Marcasite precipitation from hydrothermal solutions

Pyrite and marcasite were precipitated by both slow addition of aqueous Fe²⁺ and SiO₃²⁻ to an H₂S solution and by mixing aqueous Fe²⁺ and Na₂S₄ solutions at 75°C. H₂S₂ or HS₂⁻ and H₂S₄ or HS₄⁻ were formed in the S₂O₃²⁻ and Na₂S₄ experiments, respectively. Marcasite formed at pH < pK₁ of the polysulfide species present (for H₂S₂, pK₁ = 5.0; for H₂S₄, pK₁ = 3.8 at 25°C). Marcasite forms when the neutral sulfane is the dominant polysulfide, whereas pyrite forms when mono-or divalent polysulfides are dominant. In natural solutions where H₂S₂ and HS₂ are likely to be the dominant polysulfides, marcasite will form only below pH 5 at all temperatures.

The pH-dependent precipitation of pyrite and marcasite may be caused by electrostatic interactions between polysulfide species and pyrite or marcasite growth surfaces: the protonated ends of H₂S₂ and HS₂ are repelled from pyrite growth sites but not from marcasite growth sites. The negative ions HS₂ and S₂²⁻ are strongly attracted to the positive pyrite growth sites. Masking of 1π_g^* electrons in the S₂ group by the protons makes HS₂ and H₂S₂ isoelectronic with AsS²⁻ and As₂²⁻, respectively ( et al., 1981). Thus, the loellingitederivative structure (marcasite) results when both ends of the polysulfide are protonated.

Marcasite occurs abundantly only for conditions below pH 5 and where H₂S₂ was formed near the site of deposition by either partial oxidation of aqueous H₂S by O₂ or by the reaction of higher oxidation state sulfur species that are reactive with H₂S at the conditions of formation e.g., S₂O₃²⁻ but not SO₄²⁻. The temperature of formation of natural marcasite may be as high as 240°C ( and , 1985), but preservation on a multimillion-year scale seems to require post-depositional temperatures of below about 160°C ( , 1973; and , 1985).     

天津平原区加油站地下水石油烃污染特征及其生物降解机理研究

加油站地下水中石油烃污染是较为普遍的现象,本文对研究区位于不同水文地质条件的加油站地下水进行取样分析,分析加油站地下水中石油烃的污染特征和地下水化学类型特征,并运用因子分析、相关性分析和多元回归分析揭示加油站地下水中石油烃潜在的生物降解机制。研究结果表明,地下水化学类型主要可划分为Cl-Na型、HCO₃-Na型、HCO₃-Ca型和SO₄-Na型4类。加油站地下水中石油烃的检出率为85.71%,检出浓度为0.020.35 mg/L。因子分析结果表明影响地下水化学组成的因素主要以水-岩相互作用和石油烃的生物降解为主。TPH与地下水化学指标间的相关关系表明:TPH与K⁺、Na⁺、Cl^-、Mn、Mg²⁺、 {\mathrm{SO}}_4^{2-}呈现负相关的关系,与pH值、 {\mathrm{HCO}}_3^{-}、 {\mathrm{NO}}_3^{-}、 {\mathrm{NO}}_2^{-}、Ca²⁺、Fe不存在显著的相关关系。加油站地下水环境中可能存在嗜盐或耐盐微生物,导致随着盐度的升高,总石油烃(total petroleum hydrocarbon,TPH)生物降解率加快,TPH浓度呈现出降低的趋势。微生物利用电子受体( {\mathrm{SO}}_4^{2-}、Mn、 {\mathrm{NO}}_3^{-}、Fe)降解TPH的过程中,电子受体的贡献率为:铁还原(64.88%)>锰还原(24.86%)>硫酸根还原(5.78%)>硝酸盐还原(4.46%),即加油站地下水中铁锰还原菌的石油烃生物降解为优势反应。