NaAlSi3O8熔体粒子扩散行为压力效应的分子动力学研究

为了研究压力对钠长石成分熔体粒子微观扩散行为的影响,本文用分子动力学方法,探讨了2001．5K温度下,压力由50MPa上升到19862MPa的过程中,熔体的微观结构、粒子自扩散系数随压力的变化规律。研究表明,在升压过程中,低次配位体Al和Si向5次和6次配位体转变,Al的含量在15GPa达到极大值,而Si含量的极大值在20GPa仍未出现。Na的自扩散系数随压力升高单调下降,Al、Si和O的自扩散系数随压力升高先增后减,在8～10GPa左右达到极大值。网架形成粒子自扩散系数的极大值与Al和Si含量的极大值对应的压力点不一致。所有粒子的自扩散系数与它们与O之间键的寿命呈线性负相关。     

钙长石成分熔体粘滞度和自扩散系数压力效应的分子动力学研究

用分子动力学方法,研究了1999 K下,压力由23 MPa上升到15183 MPa的过程中,CaAl_2Si_2O_8成分熔体的微观结构、剪切粘滞度和粒子自扩散系数的压力效应。在此基础上,探讨压力对剪切粘滞度与粒子自扩散系数之间关系的影响,并将它同微观结构的变化联系起来。结果表明,粒子自扩散系数的压力效应与熔体结构有很强的相关性;压力的挤压效应阻碍了粒子的扩散,而Si-O和Al-O 5次配位体的形成又加速了扩散过程,两种相反的作用相互抵消,造成的结果是在0～5 GPa范围内,Si~(4 ),O~(2-)和Al~(3 )等网架形成粒子的自扩散系数随压力变化不明显;当压力继续增大时,挤压效应占了主导,导致自扩散系数值快速减小。Ca~(2 )作为网架修饰粒子,自扩散系数随压力升高单调下降。压力小于5 GPa时,粒子自扩散系数的大小关系是:D_(Ca)>D_(Al)>D_O>D_(Si)。系统粘滞度随压力的变化与熔体中BO的含量密切相关:BO含量小于域值时,一定范围内BO含量的变化不会对粘滞度产生很大的影响,超过域值,BO含量的微小增加会导致粘滞度值迅速增大。有效应用Eyring方程的关键是方程中粒子跳跃距离的确定,本研究发现,Si~(4 )和O~(2-)的跳跃距离可以通过系统中非桥氧的百分含量来获得。这一发现使得我们能够利用系统中NBO的含量,结合Eyring方程有效进行不同压     

榴辉岩部分熔融过程中钒分配系数的实验测定

钒(V)是常见的变价元素,其在矿物-熔体间的分配行为主要受氧逸度控制。近年来, V的分配行为与氧逸度之间的关系常被用于揭示地幔的氧化还原状态。板块俯冲过程中, V能否迁移是理解俯冲带V地球化学行为的关键环节,也是探讨俯冲带地幔楔氧逸度的重要前提。本文使用活塞圆筒装置模拟含水榴辉岩部分熔融过程,测定石榴子石、单斜辉石和金红石与熔体之间V的分配系数。实验压力为2.5GPa、温度介于900～1125℃之间,实验产物计算的氧逸度ΔFMQ介于-5.24～+0.74之间,实验结果表明V在石榴子石、单斜辉石和金红石中为相容元素(矿物/熔体分配系数D>1.0),并且DV(金红石)>DV(单斜辉石)>DV(石榴子石); V的分配系数也是氧逸度、温度和熔体聚合度的函数,随氧逸度和温度的增加,石榴子石、单斜辉石和金红石的V分配系数都减小,而随着熔体聚合程度的增加, V分配系数增大。模拟结果表明在榴辉岩部分熔融过程中熔体将显著亏损V,因此, V在榴辉岩(俯冲带洋中脊玄武岩)部分熔融过程中是不运移的;而板块俯冲过程中,榴辉岩部分熔融产生的熔体交代地幔楔不能明显改变地幔的V含量, V在地幔矿物和...     

北部湾涠洲岛橄榄岩中熔体包裹体——大陆岩石圈地幔交代作用的新证据

根据北部湾涠洲岛晚更新世火山岩中尖晶石二辉橄榄岩的矿物化学和形成条件推测,它们是来自地下约40km-50km的大陆岩石圈地幔样品。涠洲岛地幔橄榄岩中同时出现高硅（64％～68％）和低硅（49％～57％）两种熔体成分,它们普遍富碱、Al2O3和H2O、CO2等挥发组分（2％-5％）。研究认为,两种熔体存在不同的成因机制。高硅熔体可能与软流圈上升的玄武质岩浆和斜方辉石反应或下地壳物质循环进入地幔后的部分熔融有关。低硅熔体直接提供了富硅熔体与橄榄石发生交代作用的证据。这可以用富SiO2熔体＋Ol→贫SiO2熔体＋Opx反应解释,其结果是消耗橄榄石生成斜方辉石。涠洲岛橄榄岩中两种熔体的发现,进一步提供了发生在大陆岩石圈地幔流（熔）体与橄榄岩交代作用的普遍性、复杂性,以及地幔熔体多样性的新证据。     

埃达克岩的Na亏损及其对地幔Na交代的指示意义

埃达克岩是玄武质洋壳部分熔融的产物。然而,与实验室玄武岩部分熔融产生的埃达克质熔体相比,天然埃达克岩明显地高Mg、Cr和Ni,这表明埃达克岩浆在上升过程中有地幔成分的加入。本文的观察结果表明,全球新生代埃达克岩的Na2O含量低于5.8%,大约95%的新生代埃达克岩样品Na2O含量小于5.0%。然而,在埃达克岩产生的压力范围(1.5～3.0GPa),实验的玄武岩部分熔体大多数Na2O含量超过5.0%,最高达到9.0%,显示埃达克岩具有明显的Na亏损现象。我们认为这是埃达克熔体在热的地幔楔中与地幔橄榄岩反应的结果。在俯冲带,大洋板片熔融产生的熔体(埃达克熔体)上升并与地幔橄榄岩发生反应,原始的埃达克熔体获得MgO、Cr及Ni等地幔组分,但其Na2O和SiO2等通过反应进入地幔,导致地幔交代作用。根据长英质熔体与橄榄岩反应体系的相关系,我们认为,地幔单斜辉石、橄榄石、尖晶石的混染作用以及钠质角闪石和斜方辉石的分离结晶作用,是改变埃达克熔体组成并导致其Na亏损的一个重要的过程。埃达克岩的Na亏损为地幔Na交代作用和一些富Na的弧岩浆成因提供了重要证据。     

大陆岩石圈地幔异剥橄榄岩化的证据和意义

异剥橄榄岩化是地幔橄榄岩与硅不饱和熔体发生强烈相互作用的地幔过程。这一过程通常伴随地幔物理-化学性质的显著改变,与克拉通岩石圈减薄和破坏密切相关。本文梳理了前人对异剥橄榄岩化的驱动机理、结构和成分特征及其对大陆稳定性影响等方面的定性认识,并在此基础上通过热力学模拟,刻画了不同属性地幔与熔体在不同温度压力条件下的相互作用过程,目标是为定量限定异剥橄榄岩化的发生条件、物理-化学效应及地球动力学意义。研究显示,异剥橄榄岩化通常会出现磷灰石、角闪石、金云母和碳酸盐等标志性交代矿物,并以斜方辉石被单斜辉石替换为典型特征,还可发育海绵边、熔体囊（已冷却结晶为单斜辉石、橄榄石等细粒矿物）和矿物环带等非平衡结构。热力学模拟表明,熔岩反应过程受原岩、熔体性质以及熔/岩比例的共同控制,不同属性地幔（难熔方辉橄榄岩、饱满二辉橄榄岩）与贫硅（如霞石岩）熔体反应都能生成富单斜辉石橄榄岩,且在较高压力（如2.5GPa和4.0GPa）条件下更容易形成异剥橄榄岩;相比之下,不同性质地幔与富硅（如MORB）熔体反应在任何压力条件下均不能产生异剥橄榄岩。此外,两类熔体参与的熔岩反应均能引起围岩密度逐渐增加,并在高压条件下能导致饱满岩石圈地幔密度超过地幔参考值、达到岩石圈失稳的条件。因此,本文从热力学的角度定量约束了异剥橄榄岩化的发生条件和对岩石圈地幔的影响,为前人提出的橄榄岩-熔体反应能够造成岩石圈地幔减薄和破坏这一概念模型提供了理论实证,对评估大陆稳定性具有重要意义。

     

磷在硅酸盐矿物与熔体之间分配系数的研究进展

硅酸盐矿物与熔体之间的磷分配系数对研究岩浆演化和结晶分异程度具有重要意义,也是了解地幔磷储库和建立地球各圈层间磷运移模式的基础。本文分析和总结了前人采用天然样品和合成实验样品研究不同硅酸盐矿物和熔体间的磷分配系数的成果,分析了不同物理化学参数对分配系数的影响,包括熔体组成(如Mg O、Al2O3含量)、矿物结构(分配系数与[Si O4]4-聚合度呈负相关关系)、温度、压力和氧逸度等,指出当前研究中有关更高压力条件(15 GPa)及有流体存在时分配系数的研究是不足的。     

俯冲带壳-幔相互作用的高温高压实验:对地幔不均一性成因的启示

使用活塞-圆筒式高温高压装置进行一系列榴辉岩部分熔融熔体与橄榄岩反应实验,可以为深入了解俯冲带壳-幔相互作用的影响因素及地幔不均一性的成因提供重要信息.实验使用反应偶的方法,并在0.8~3.0 GPa和1 200~1 425℃条件下进行.实验结果表明,榴辉岩部分熔融熔体-橄榄岩反应的动力学和结果受控于熔体主量元素成分、熔体中的H₂O、温度、压力和橄榄岩的物理状态等因素.大陆俯冲带地幔岩石中斜方辉石的富集是再循环陆壳熔体与上覆地幔反应的结果,地幔岩石中斜方辉石岩脉的形成与含水熔体交代有关,地幔岩石中的石榴辉石岩和石榴石岩可能形成于高压、低温条件下的熔体-橄榄岩反应.      

Ag在橄榄石、斜方辉石、单斜辉石和玄武质熔体间的分配

地幔部分熔融过程中亲S元素Ag的分配行为能够限定地幔中Ag含量,同时可以追踪地幔中S含量和去向。在地幔部分熔融过程中, Ag的分配行为与其在地幔硅酸盐矿物–玄武质熔体间的分配系数密切相关。因此准确地测定Ag在除硫化物之外地幔硅酸盐矿物和共存熔体之间的分配系数是预测Ag分配行为的必要条件之一。目前缺乏Ag在地幔矿物(橄榄石、辉石等)和玄武质熔体之间分配系数的报道,阻碍了对Ag在地幔部分熔融过程中分配行为的研究。本研究通过高温高压实验获得了在洋中脊玄武岩(MORB)产生的温度和压力条件下,Ag在橄榄石(ol)、斜方辉石(opx)、单斜辉石(cpx)与玄武质熔体(melt)之间的分配系数,分别为D_Ag^ol/melt=0.0005±0.0002、D_Ag^opx/melt=0.007±0.003和D_Ag^cpx/melt=0.046±0.009。根据实验获得的分配系数进行模拟的计算结果表明,太古代科马提岩和洋中脊苦橄岩源区的地幔Ag含量为(8±2)×10-9。如果这个值...     

陕西老牛山印支期高Ba-Sr花岗岩成因及其构造指示意义

老牛山复式花岗岩基位于华北克拉通南缘小秦岭地区,锆石LA-ICP-MS U-Pb 定年结果表明,该岩基早期花岗岩--
康坪岩体形成于晚三叠世［（207.9±0.72）］Ma,是早中生代岩浆作用的产物。该岩体具有高硅、富碱、准铝的地球化学特征,
铁镁比值较高,富集LILE（尤其是Sr 和Ba）和LREE,Eu 无明显异常,相对亏损HREE 和Y,可归属为高Ba-Sr 花岗岩。但
与典型埃达克岩相比,康坪岩体Cr,Ni 等相容元素含量较低,而K2O 含量明显偏高,属高钾钙碱性系列,重稀土元素分馏
不显著。在成岩过程中,康坪岩体的地球化学行为主要受角闪石（单斜辉石）、斜长石（钾长石）以及极少量石榴子石的分
离结晶控制。元素和同位素地球化学研究表明,老牛山复式花岗岩基康坪岩体成岩物质主要来自含远洋沉积物俯冲板片析
出流体/ 熔体交代的富集地幔以及古老太华群基底物质所组成的混合源区,是大陆碰撞造山晚期后碰撞“松弛”阶段,俯冲
板片断离后下地壳底部物质发生部分熔融形成的岩浆产物。     

Self-diffusion of Si and O in diopside-anorthite melt at high pressures

Self-diffusion coefficients for Si and O in Di₅₈An₄₂ liquid were measured from 1 to 4 GPa and temperatures from 1510 to 1764°C. Glass starting powders enriched in ¹⁸O and ²⁸Si were mated to isotopically normal glass powders to form simple diffusion couples, and self-diffusion experiments were conducted in the piston cylinder device (1 and 2 GPa) and in the multianvil apparatus (3.5 and 4 GPa). Profiles of ¹⁸O/¹⁶O and ^29,30Si/²⁸Si were measured using secondary ion mass spectrometry. Self-diffusion coefficients for O (D(O)) are slightly greater than self-diffusion coefficients for Si (D(Si)) and are often the same within error. For example, D(O) = 4.20 ± 0.42 × 10⁻¹¹ m²/s and D(Si) = 3.65 ± 0.37 × 10⁻¹¹ m²/s at 1 GPa and 1662°C. Activation energies for self-diffusion are 215 ± 13 kJ/mol for O and 227 ± 13 kJ/mol for Si. Activation volumes for self-diffusion are −2.1 ± 0.4 cm³/mol and −2.3 ± 0.4 cm³/mol for O and Si, respectively. The similar self-diffusion coefficients for Si and O, similar activation energies, and small, negative activation volumes are consistent with Si and O transport by a cooperative diffusion mechanism, most likely involving the formation and disassociation of a high-coordinated intermediate species. The small absolute magnitudes of the activation volumes imply that Di₅₈An₄₂ liquid is close to a transition from negative to positive activation volume, and Adam-Gibbs theory suggests that this transition is linked to the existence of a critical fraction (∼0.6) of bridging oxygen.     

Calculated diffusion coefficients and the growth rate of olivine in a basalt magma

Concentration gradients in glass adjacent to skeletal olivines in a DSDP basalt have been examined by electron probe. The glass is depleted in Mg, Fe, and Cr and enriched in Si, Al, Na, and Ca relative to that far from olivine. Ionic diffusion coefficients for the glass compositions are calculated from temperature, ionic radius and melt viscosity, using the Stokes-Einstein relation. At 1170°C, the diffusion coefficient of Mg²⁺ ions in the basalt is 4·5.10^?9 cm²/s. Comparison with measured diffusion coefficients in a mugearite suggests this value may be 16 times too small. The concentration gradient data and the diffusion coefficients are used to calculate instantaneous olivine growth rates of 2–6.10^?7 cm/s. This is too slow for olivine to have grown in situ during quenching. Growth necessarily preceded emplacement such that the composition of the crystals plus the enclosing glass need not be that of a melt. The computed olivine growth rates are compatible with the rate of crystallization deduced for the Skaegaard intrusion.     

Visualization-based analysis of structural and dynamical properties of simulated hydrous silicate melt

We have explored first-principles molecular dynamics simulation data for hydrous MgSiO₃ liquid (with 10 wt% water) to gain insight into its structural and dynamical behavior as a function of pressure (0–150 GPa) and temperature (2,000–6,000 K). By visualizing/analyzing a number of parameters associated with short- and mid-range orders, we have shown that the melt structure changes substantially on compression. The speciation of the water component at low pressures is dominated by the isolated structures (with over 90% hydrogen participated) consisting of hydroxyls, water molecules, O–H–O bridging and four-atom (O–H–O–H and H–O–H–O) groups, where every oxygen atom may be a part of polyhedron or free (i.e., bound to only magnesium atom). Hydroxyls favor polyhedral sites over magnesium sites whereas molecular water is almost entirely bound to magnesium sites, and also interpolyhedral bridging (Si–O–H–O–Si) dominates other types of bridging. Water content is shown to enhance and suppress, respectively, the proportions of hydroxyls and molecular water. As compression increases, these isolated structures increasingly combine with each other to form extended structures involving a total of five or more O and H atoms and also containing threefold coordination species, which together consume over 80% hydrogen at the highest compression studied. Our results show that water lowers the mean coordination numbers of different types including all cation–anion environments. The hydrous melt tends to be more tetrahedrally coordinated but with the Si–Si network being more disrupted compared to the anhydrous melt. Protons increase the content of non-bridging oxygen and decrease the contents of bridging oxygen as well as oxygen triclusters (present at pressures above 10 GPa). The calculated self-diffusion coefficients of all atomic species are enhanced in the presence of water compared to those of the anhydrous melt. This is consistent with the prediction that water depolymerizes the melt structure at all pressures. Our analysis also suggests that proton diffusion involves two processes—the transfer of H atoms (requiring the rupture and formation of O–H bonds) and the motion of hydroxyls as hydrogen carriers (requiring the rupture and formation of Si–O and/or Mg–O bonds). Both the processes are operative at low compression whereas only the first process is operative at high compression.     

A subsidiary fast-diffusing substitution mechanism of Al in forsterite investigated using diffusion experiments under controlled thermodynamic conditions

Diffusion of Al in synthetic forsterite was studied at atmospheric pressure from 1100 to 1500 °C in air along [100] with activities of SiO₂, MgO and Al₂O₃ (a_SiO2, a_MgO and a_Al2O3) buffered. At low a_SiO2, the buffer was forsterite + spinel + periclase (fo + sp + per) at all temperatures, while at high a_SiO2 and subsolidus conditions a variety of three-phase assemblages containing forsterite and two other phases from spinel, cordierite, protoenstatite or sapphirine were used at 1100–1350 °C. Experiments at high a_SiO2 and 1400 °C used forsterite + protoenstatite + melt (fo + en + melt), and at 1500 °C, fo + melt. The resulting diffusion profiles were analysed by LA–ICP–MS in scanning mode. Diffusion profiles in the high a_SiO2 experiments were generally several hundred microns in length, but diffusion at low a_SiO2 was three orders of magnitude slower than in high a_SiO2 experiments carried out at the same temperature, producing short profiles only a few microns in length and close to the spatial resolution of the analytical method. Interface concentrations of Al in the forsterite, obtained by extrapolating the diffusion profiles to the crystal/buffer interface, were only a fraction of those expected at equilibrium, and varied among the differing buffer assemblages according to (a_Al2O3)^1/2 and (a_SiO2)^3/4, pointing to the substitution of Al in forsterite by an octahedral-site, vacancy-coupled (OSVC) component with the stoichiometry Al _4/3 ³⁺ vac_2/3SiO₄, whereas the main substitution expected from previous equilibrium studies would be the coupled substitution of 2 Al for Mg + Si, giving the stoichiometry MgAl₂O₄. It is proposed that this latter substitution is not seen on the length scales of the present experiments because it requires replacement of Si by Al on tetrahedral sites, and is accordingly rate-limited by the slow diffusivity of Si. Instead, diffusion of Al by the OSVC mechanism is relatively fast, and at high a_SiO2, even faster than Fe–Mg interdiffusion.     

Partitioning of manganese between forsterite and silicate liquid

Partition coefficients for Mn between forsterite and liquid in the system MgO-CaO-Na₂O-Al₂O₃-SiO₂ (+ about 0.2% Mn) were measured by electron microprobe for a variety of melt compositions over the temperature range 1250–1450°C at one atm pressure. The forsterite-liquid partition coefficient of Mn (mole ratio, MnO in Fo/MnO in liquid, designated D_mn^fo?Liq) depends on liquid composition as well as temperature: at 1350°C, D_Mn^Fo?Liqranges from 0.60 (basic melt, SiO₂ = 47wt%) to 1.24 (acidic melt, SiO₂ = 65wt%). At lower temperatures, the partition coefficient is more strongly dependent on melt composition.The effects of melt composition and temperature on D_Mn^fo?Liq can be separately evaluated by use of the Si:O atomic ratio of the melts. A plot of D_mn^Fo?Liq measured at various temperatures vs melt Si:O for numerous liquid compositions reveals discrete, constant-temperature curves that are not well defined by plotting D_Mn^Fo?Liq against other melt composition parameters such as melt basicity or MgO content. For constant Si:O in the melt, In D_Mn^Fo?Liq vs reciprocal absolute temperature is linear; however, the slope of the plot becomes more positive for higher values of Si:O, indicating a higher energy state for Mn²⁺ ions in acidic melts than in basic melts.Comparison of Mn partitioning data for the iron-free system used in this study with data of other workers on iron-bearing compositions suggests that the effect of iron on Mn partitioning between olivine and melt is small over the range of basalt liquidus temperatures.     

Molecular dynamics simulations of interdiffusion in MgSiO3-Mg2SiO4 melts

Molecular dynamics simulations based on ab initio interatomic potentials have been performed to study the kinetics and mechanisms of interdiffusion in MgSiO₃ and Mg₂SiO₄ melts. Diffusion coefficients in the presence of a concentration gradient are lower than self-diffusion coefficients due to the requirements of local charge-balance within the system. Extrapolations of Mg²⁺ diffusion coefficients obtained at high temperatures (5000 to 3000 K) into geologically relevant temperatures (1500 to 2500 K) are reasonably accurate compared to experimental Mg²⁺ diffusion coefficients in a compositionally similar system. A significant system-size effect is also observed on the rates of diffusion obtained from the molecular dynamics simulations. Diffusion mechanisms involve movement of individual Mg²⁺ and O^2- ions and anionic [SiO_n]^(4–2n) complexes for both self-diffusion and interdiffusion.     

Diffusion and viscosity of Mg2SiO4 liquid at high pressure from first-principles simulations

We investigate two key transport properties, self-diffusion and viscosity, of Mg₂SiO₄ liquid as a function of temperature and pressure using density functional theory-based molecular dynamics method. Liquid dynamics in a 224-atom supercell was captured in equilibrium simulations of relatively long durations (50-300 ps) to obtain an acceptable convergence. Our results show that Mg and Si are, respectively, the most and least mobile species at most conditions studied and all diffusivities become similar at high pressure. With increasing temperature from 2200 to 6000 K at ambient pressure, the self-diffusivities increase by factors of 25 (Mg), 80 (Si) and 65 (O), and the viscosity decreases by a factor of 30. The predicted temperature variations of all transport coefficients closely follow the Arrhenian law. However, their pressure variations show a significant non-Arrhenian behavior and also are sensitive to temperature. At 3000 K, the diffusivity (viscosity) decreases (increases) by more than one order of magnitude between 0 and 50 GPa with their activation volumes increasing on compression. Over the entire mantle pressure range, the variations at 4000 K are of two orders of magnitude with nearly constant activation volumes whereas the variations at 6000 K are within one order of magnitude with decreasing activation volumes. The predicted complex dynamical behavior of Mg₂SiO₄ liquid can be associated with the structural changes occurring on compression. We also estimate the diffusivity and viscosity profiles along a magma ocean isentrope, which suggest that the melt transport properties vary modestly over the relevant magma ocean depth ranges.     

一种计算NaAlSi3O8熔体粘度的理论方法

硅酸岩熔体的结构特征是制约熔体粘度的主要因素,熔体结构的变异是其中粘流作用发生的原因,化学成分对熔体粘度的控制是通过改变熔体结构而实现的。ＳｉＯ２熔体中仅存在Ｓｉ－Ｏ键,而ＮａＡｌ－Ｓｉ３Ｏ８熔体中存在Ｓｉ－Ｏ键,Ａｌ－Ｏ键和Ｎａ－Ｏ键,Ｎａ－Ｏ键在熔体结构中通过Ｏ与Ｓｉ－Ｏ键相联结,并且使与之相联的Ｓｉ－Ｏ键的键强变弱。因此,熔体结构单元中与Ｎａ－Ｏ键相联结的Ｓｉ－Ｏ键最易断开,并因此导致流变作用的发生。文中计算了不同温度条件下ＮａＡｌＳｉ３Ｏ８熔体中Ｓｉ－Ｏ键的键强,以ＳｉＯ２熔体中的Ｓｉ－Ｏ键的键强和ＳｉＯ２熔体的粘度为标准,建立了计算了ＮａＡｌＳｉ３Ｏ８熔体粘度的理论模型,依此理论模型求得的熔体粘度在合理的地质温度范围内与实验结果完全吻合     

Surface chemistry and dissolution kinetics of glassy rocks at 25°C

The weathering rates and mechanisms of three types of glassy rocks were investigated experimentally at 25 °C, pH 1.0 to 6.2, and reaction times as much as to 3 months. Changes in major element chemistry were monitored concurrently as a function of time in the aqueous solution and within the near surface region of the glass. Leach profiles, obtained by a HF leaching technique, displayed near-surface zones depleted in major cations. These zones increased in depth with increasing time and decreasing pH of reactions. Release rates into the aqueous solution were parabolic for Na and K and linear for Si and Al. A coupled weathering model, involving surface dissolution with concurrent diffusion of Na, K, and Al, produced a mass balance between the aqueous and glass phases. Steady state conditions are reached at pH 1.0 after approximately 3 weeks of reaction. Steady-state is not reached even after 3 months at pH 6.2.An interdiffusion model describes observed changes in Na diffusion profiles for perlite at pH 1.0. The calculated Na self-diffusion coefficient of 5 × 10^?19 cm²·s^?1 at 25°C approximates coefficients extrapolated from previously reported high temperature data for obsidian. The self-diffusion coefficient for H₃O⁺, 1.2 × 10^?20 cm²·s^?1, is similar to measured rates of water diffusion during hydration of obsidian to form perlite.