Mapping the state of fracture around cavities

The state of stress around cavities is heterogeneous. Consequently, the state of fracture may also vary from point to point. Under compressive loading, cavity may be in one of four possible states: pre-fracture (pre-microfracture initiation), microfracture propagation (initiation to the onset of dilata dilatancy to failure) and post-failure. These four states are separated by the crack initiation stress, the crack damage stress and the failure stress. fracture events with confining pressure is examined with reference to three intact rocks: a brittle granite, a semi-brittle limestone and a ductile sal

The maximum principal stress (σ₁) at crack initiation, crack damage (onset of dilatancy), yielding and failure are established as a function stress (σ₃). For a single intact rock, all four fracture events can be represented using one function (the Rocker function) with a single fac various fracture states.

The proposed fracture criteria, based on the experimental data, are combined with the existing state of stress to prepare a fracture map around an elli intact Lac du Bonnet granite. The state of stability is expressed through a newly defined stability factor, the unconfined strength ratio (USR), wh to the traditional safety factor. In contrast to the conventional safety factor in rock mechanics (SFstrength/σ₁), which is σ₃ 3–σ₁, space of the stability diagram.     

A major geodynamic change revealed by Quaternary stress patterns in the southern Apennines (Italy)

In southern Italy, analysis of fault slip data sets, in particular from Quaternary formations, provides evidence for a recent change of the stress field. During the Early Pleistocene, the horizontal maximum stress axes were ENE-WSW trending. The deformation was ENE-WSW compression near the front of the chain, and NNW-SSE extension close to the back-arc basin. Some time after the Early Pleistocene, the direction of the largest horizontal stress axes changed to northwest-southeast. Only extensional deformation (σ₂, NW-SE trending; σ₃, NE-SW trending) is observed for this phase and focal mechanisms indicate that it is still active. This NE-SW extension invaded areas previously affected by compression or NNW-SSE extension and coincides with major uplift of Pleistocene marine sediments in the chain and the foredeep up to 700 m above sea level. This change in the stress regime corresponds to the end of accretion processes that had prevailed since the Middle-Late Miocene. As a consequence of this discovery of a recent regional stress and deformational style change, the present-day normal and strike-slip faulting earthquake focal mechanisms in the Southern Apennines should not be considered representative of Tyrrhenian Sea opening and Apennines accretion.     

Crack damage stress as a composite function of porosity and elastic matrix stiffness in dolomites and limestones

Twenty-five uniaxial compression tests were performed to determine stress at onset of dilation, referred to herein as “the crack damage stress,” in heterogeneous dolomites and limestones. A simplified model for crack damage stress (σ_cd) is developed here using porosity, elastic modulus, Poisson's ratio and three empirical coefficients. The model shows that when porosity decreases and elastic modulus increases, σ_cd rapidly increases and approaches its maximum value. On the other hand, when porosity increases and elastic modulus decreases, σ_cd rapidly decreases and approaches its minimum value. The proposed model is validated for six heterogeneous limestone and dolomite formations which are widely distributed in Israel.     

Burial-dominated cementation in non-tropical carbonates of the Oligocene Te Kuiti Group, New Zealand

Cementation of bryozoan-echinoid-benthic foraminiferal temperate shelf carbonates of the Oligocene Te Kuiti Group, North Island, New Zealand, occurred mainly during subsurface burial. The calcite cements in the limestones are dominated by equant and syntaxial rim spar which typically becomes ferroan (given an iron supply) and, compared to the skeletal material with normal marine δ¹⁸O values from +2 to −1‰, more depleted in ¹⁸O with depth of burial, the δ¹⁸O composition of bulk cement samples ranging from −1 to −7‰. These trends reflect the establishment in pore waters during sediment burial of reducing conditions and gradually increasing temperatures (20–50°C), respectively. The δ¹³C values (0 to +3‰) of the cements remain the same as the host marine shells, suggesting the source of carbon in the cements was simply redistributed marine carbonate derived from shell dissolution.

Two gradational burial diagenetic environments influenced by marine-derived porewaters are arbitrarily distinguished: shallow burial phase and moderate burial phase. During the shallow burial phase, down to 500–600 m sub-bottom depth, the carbonates lost at least 25% of their original porosity by mechanical compaction and were selectively cemented by non-ferroan or usually ferroan, variably luminescent, slightly ¹⁸O-depleted sparry calcite cement (δ¹⁸O −2 to −4‰), mainly as syntaxial rims about echinoid grains. These shallow-burial cements form less than about 10% of total cement in the majority of the limestones and their source was probably mainly mild intergranular dissolution of calcitic skeletal fragments accompanying the onset of chemical compaction. During the moderate burial phase, between about 600 and 1100 m sub-bottom depth, porosity loss continued (typically to about 70% of its original value) as a result of pressure-solution of calcitic bioclasts associated with more advanced stages of chemical compaction. This involved development of a wide variety of non-sutured and microstylolitic solution seams, including both single and composite, wispy or continuous, bedding-parallel types and non-parallel reticulate forms. The released carbonate was precipitated as ferroan (or non-ferroan where iron supply was negligible), dull luminescent, strongly ¹⁸O-depleted (δ¹⁸O −4 to −7‰), mainly equant calcite spar cement, occluding available pore space in the limestones.     

Palaeostress analysis of the northern Nijar and southern Vera basins: constraints for the Neogene displacement history of major strike-slip faults in the Betic Cordilleras, SE Spain

This paper presents the results of a detailed structural analysis of the northern Nijar and southern Vera basins with special emphasis on the evolution of the regional stress field and the associated timing of movement of the Serrata, Gafarillos and Palomares strike-slip fault zones. These major fault zones control the Neogene deformation of the SE Internal Betic Cordilleras in Spain. Detailed stress analysis on Neogene sediments of the Vera and Nijar basins shows a strike-slip regime with NW–SE-oriented subhorizontal maximum principal stress (σ₁) during Tortonian and earliest Messinian times. Under the influence of this stress field, dextral displacement along the N090E-trending Gafarillos fault zone resulted in deformation of the sediments of the southern Sorbas and northeastern Nijar basins. During the early Messinian a clock-wise rotation of the stress field occurred. Stress analysis in rocks with late–early Messinian up to Quaternary ages in the Nijar and Vera basins indicates a strike-slip regime with N–S-oriented subhorizontal maximum principal stress (σ₁). Under the influence of this stress field the main activity along the N010E-striking Palomares strike-slip fault zone took place, resulting in deformation of the Neogene sediments of the southeastern Vera basin and culminating in a maximum sinistral displacement of more than 20 km. At the same time the stress field was not suitably oriented to exert a large shear component on the Gafarillos fault zone, which activity ended after the earliest Messinian. Fault and outcrop patterns of syntectonic Neogene sediments in the Vera basin show that displacement along the Palomares fault zone decreased at the end of the Middle Miocene although minor displacement phases may still have occurred during the Late Miocene and possibly even Pliocene. From the Middle Miocene onward, deformation in the Nijar basin was controlled by sinistral displacement along the N040E-trending Serrata strike-slip fault zone.     

锦屏一级水电站左岸浅表大理岩的卸荷微裂隙特征

在高山峡谷区,浅层岩体的表生改造相当发育。在锦屏一级水电站坝区陡峭的岸坡浅表大理岩岩体中采集定向标本,制作定向薄片,利用偏光显微镜统计和分析了微破碎带及带中微裂隙的方向分布情况。结果表明,（1）垂直于最小主应力σ₃的薄片中微破碎带在整体上未见明显定向性,垂直于最大主应力σ₁或中间主应力σ₂的薄片中微破碎带在整体上存在明显定向性,基本与岸坡平行;（2）微裂隙往往沿低指数晶面（包括解理面）发生,故晶内裂隙表现出直线式或台阶状样式,这符合最小能量原理;（3）卸荷应力场诱导控制微观卸荷裂隙的方向并使之具有强定向性。     

结构面力学性质的定量鉴定

变形带力学性质的鉴定是地质力学研究中的先行基础步骤.近来出现一些新的概念和方法,可用以定量表征变形带的力学性质.天然变形带通常是一般剪切作用的产物,是纯剪切(共轴缩短或伸展)和简单剪切的组合.为了定量说明两者间的相对贡献,提出了运动学涡度(W_k)这一物理量,并简单地定义为cos υ.υ是主变形面内两特征方向间的夹角.纯剪切的υ=90°,W_k=0;简单剪切的υ=0°,W_k=1.一般剪切的υ介于0°和90°之间,W_k为0到1.运动学涡度符号的正负分别代表变形带的减薄和增厚.υ可通过极摩尔圆法求出.主压应力(σ₁)方向与W_k的关系为W_k=sin2ξ.ξ是σ₁与变形带法线间的夹角.因此,可用以确定变形带的W_k和力学性质.根据最大有效力矩准则,韧性变形带与主压应力(σ₁)方向间的夹角为55°,可用以确定古应力轴的方向,并可能确定变形时差应力的大小.      

Variability of the Denmark Strait Overflow during the Last Glacial Maximum

The Denmark Strait Overflow (DSO) today compensates for the northward flowing Norwegian and Irminger branches of the North Atlantic Current that drive the Nordic heat pump. During the Last Glacial Maximum (LGM), ice sheets constricted the Denmark Strait aperture in addition to ice eustatic/isostatic effects which reduced its depth (today ∼630 m) by ∼130 m. These factors, combined with a reduced north-south density gradient of the water-masses, are expected to have restricted or even reversed the LGM DSO intensity. To better constrain these boundary conditions, we present a first reconstruction of the glacial DSO, using four new and four published epibenthic and planktic stable-isotope records from sites to the north and south of the Denmark Strait. The spatial and temporal distribution of epibenthic δ¹⁸O and δ¹³C maxima reveals a north-south density gradient at intermediate water depths from σ₀ ∼28.7 to 28.4/28.1 and suggests that dense and highly ventilated water was convected in the Nordic Seas during the LGM. However, extremely high epibenthic δ¹³C values on top of the Mid-Atlantic Ridge document a further convection cell of Glacial North Atlantic Intermediate Water to the south of Iceland, which, however, was marked by much lower density (σ₀ ∼28.1). The north-south gradient of water density possibly implied that the glacial DSO was directed to the south like today and fed Glacial North Atlantic Deep Water that has underthrusted the Glacial North Atlantic Intermediate Water in the Irminger Basin.     

Petrology of the Hopen mangerite-charnockite intrusion, Lofoten, north Norway

The Hopen massif, intrusive age 1900 m.y., exposed area 15 km², in the Lofoten-Vesterålen granulite facies province has the mineral assemblages: (1) mesoperthite+plagioclase (An_7–20)+quartz+clinopyroxene (Di_20–25)+orthopyroxene En_15–25+opaques±minor amphibole±minor biotite; (2) mesoperthite+plagioclase (An <2)+quartz+clinopyroxene (Di <10)+olivine Fe lt;5)+opaques. By using mineral and whole rock analyses, the crystallization conditions were estimated to be 1000°C, 12 kb load pressure and an oxygen fugacity approximately corresponding to the WM buffer. Rocks with the assemblage of type (2) contain secondary orthoferrosilite (Fe_0.90–0.95Mn_0.04–0.07Mg_0.01Ca_0.01)₂Si₂O₆, generated by reactions involving fayalite, magnetite and quartz at 800°C, 10kb load pressure and at oxygen fugacities approaching QFM buffer conditions. Subsequent to a crustal thickening, the mangeritic rocks in Lofoten-Vesterålen were emplaced in a tensional environment comparable with modern continental rifts. A ‘gabbro pillow’ magma chamber at the crustal base is proposed as parental magma for the mangeritic rocks, of which the Hopen massif represents a late differentiation.     

Oxygen and carbon isotope composition of cold-water Berriedale Limestone (Lower Permian), Tasmania, Australia

The Berriedale Limestone formed at about 80°S paleolatitude and contains many glacial dropstones. It formed during a period of major Gondwana deglaciation.

The Berriedale Limestone contains mostly bryozoans, brachiopods and bivalves, with some intraclasts and rare pellets. The faunal diversity is low and the fauna are similar to the modern cold-water foramol faunal assemblage. Micrite, microspar and spar occur as equant to well developed rhombs of calcite. The coarse spar cements are bored and are ruptured by dropstones, indicating submarine origin of low-Mg calcite at water-temperatures of around 3°C. The mixing zone cementation was preceded by erosion of early formed crystals. The eroded crystals occur as inclusions in mixing zone cements.

The fauna are characterized by heavy δ¹³C and light δ¹⁸O. The whole-rock field of δ¹⁸O-δ¹³C falls at the edge of “Normal Marine Limestone” and deviates to lighter δ¹⁸O values (down to −16.7‰ PDB). Lightest δ¹⁸O values ( −22‰ PDB) of fresh-water sparry calcite cement are similar to those in the Early Permian continental tillites, suggesting that the Permian sea was diluted by isotopically light melt waters. Micrite δ¹⁸O values (−9.2 to −12.6‰ PDB) are within the range of whole-rock values. The δ¹⁸O values of calcite in shales are lighter than limestone values.

The δ¹⁸O values of the fauna give an unrealistic range of sea-water temperatures because the fauna have equilibrated with variable amounts of melt waters. However, calculated original δ¹⁸O values of the fauna indicate temperatures < 4°C. The heaviest δ¹⁸O of fauna gives cold temperatures of 9°C (with δ_w −2.8‰) and −3°C (with δ_w −6‰). The lightest values of sparry calcite cements (−22‰ PDB) indicate that the limestone reacted with cold melt waters.

The δ¹⁸O of Permian sea is estimated to be about +1.2‰ and was diluted by melt waters as light as −27‰ SMOW.     

Temperature independent thermal expansivities of sodium aluminosilicate melts between 713 and 1835 K

The thermal expansivities of eight sodium aluminosilicate liquids were derived from the slope of new volume data at low temperatures (713−1072 K) combined with the high temperature (1300−1835 K) volume measurements of Stein et al. (1986) on the same liquids. Melt compositions range from 47−71 wt% SiO₂, 0−31 wt% A1203, and 17−33 wt% Na₂O; the volume of albite supercooled liquid at 1092 K was also determined. The low temperature volumes were derived from measurements of the glass density of each sample at 298 K, followed by measurements of the glass thermal expansion coefficient from 298 K to the respective glass transition interval. This technique takes advantage of the fact that the volume of a glass is equal to the volume of the corresponding liquid at the limiting fictive temperature (T′_f), and that T′_f can be approximated as the onset of the rapid rise in thermal expansion at the glass transition in a heating curve (Moynihan, 1995). No assumptions were made regarding the equivalence of enthalpy and volume relaxation through the glass transition. The propagated error on the volume of each supercooled liquid at T′_f is 0.25%. Combination of these low temperature data with the high temperature measurements of Stein et al. (1986) allowed a constant thermal expansivity of each liquid to be derived over a wide temperature interval (763−1001 degrees) with a fitted 1σ error of 0.6–4.6%; in every case, no temperature dependence to dV/dT^liq could be resolved. Calibration of a linear model equation leads to fitted values ± 1σ (units of cm³/mole) for (26.91 ± .04), (37.49 ± .12), (26.48 ± .06) at 1373 K, and (7.64 ± .08 × 10^-3 cm³/mole-K). The results indicate that neither Si02 nor Al₂O₃ contribute to the thermal expansivity of the liquids, and that dV/dT^liq is independent of temperature between 713–1835 K over a wide range of liquid composition. Calculated volumes based on this model recover both low and high temperature measurements with a standard deviation <0.25%, whereas values of dV/dT^liq can be predicted within 5.6%.     

Stress fields about strike-slip faults inferred from stylolites and tension gashes

In general, the long axis of the tension gashes and stylolitic columns developed in limestones during a single phase of compressional deformation occur parallel to the direction of the maximum compressive stress (σ₁). This is the case in the Languedoc for structures developed in the Jurassic limestones during the N-S Pyrenean compression. Exceptionnally, however, these microstructures turn in direction and become oblique (even orthogonal) one to the other, probably as a consequence of a variation in intensity and direction of the stress field at the end of a microfault. This mechanism also occurs in a larger scale structure involving segments of pre-tectonic joints that act as “en échelon” microfaults in a brittle “kink-band” equivalent to a peculiar type of potential wrench-fault.     

含柯石英榴辉岩形成深度的构造校正测算

应用透射电子显微镜(TEM)对大别地区英山县含柯石英榴辉岩、石英榴辉岩及石榴角闪岩中石榴子石进行研究,结果表明在强塑性变形的三类岩石中,石榴子石的超微构造特征存在明显差异。在含柯石英榴辉岩中的石榴子石位错密度比角闪岩中的低。修正石榴子石材料系数α为0.25,用石榴子石位错密度估算了相对差异应力值,并讨论了在超高压榴辉岩形成和退变质过程中各阶段的变质条件。根据石榴子石位错密度测定的差异应力,结合石榴子石的变形测量,恢复构造三维主应力及构造附加静水压力值P_S,从柯石英相的转变压力P中减去构造附加静水压力值P_S后,利用单纯由重力引起的静水压力值P_G换算上覆岩石的重力和厚度,获得大别超高压变质带含柯石英榴辉岩形成深度仅为 ≥ 32.09~32.11km.因此提出,该含柯石英榴辉岩是在这一地壳深处(或稍深一些)受强烈构造作用形成的新认识。同位素资料分析表明,大别地区榴辉岩系地壳成因,这对于榴辉岩是壳内产物的认识提供了进一步证据。      

多轴压缩条件下层状硬质片岩的力学特性研究

在深部工程中经常会遇到层状岩体,由于高应力的影响,在工程活动中发生因层状结构面诱发的岩体灾害问题。这与深部工程中的真三向高应力环境及层状结构面产状密切相关。为此,基于一种取自某深部金属矿山的层状硬质片岩,开展了考虑片理方位的真三轴压缩试验研究,获取了该片岩在两种片理加载方位下,不同应力差条件时,试样的变形、强度及破裂数据。结果表明,该硬质片岩的力学特性受片理加载方位和应力条件影响较大。具体表现在,当中间主应力σ₂平行片理走向时,试样的脆性更强,且最小主应力σ₃ 越小脆性越强。当σ₂垂直片理走向时试样的强度更高,但强度随σ₃增加而增加的敏感性较弱。当σ₂平行片理走向时,试样的破坏均以沿片理的剪切为主;而当σ₂ 垂直片理走向时,试样在低σ₃ 时,主要发生穿片理的拉破坏,高σ₃ 时,则转变为沿片理的剪切破坏。试验结果对陡倾层状硬质岩体工程的稳定性评价有一定的启示意义,即当片理走向与洞轴线的夹角较小时,浅层围岩片理面的法向应力释放程度较高,易发生受片理结构控制的脆性破坏;反之,夹角较大时,岩体的稳定性较强。     

Reactions and textures in grossular–wollastonite–scapolite calc–silicate granulites from Maligawila, Sri Lanka: evidence for high-temperature isobaric cooling in the meta-sediments of the Highland Complex

Grossular–wollastonite–scapolite calc–silicate granulites from Maligawila in the Buttala klippe, which form part of the overthrusted rocks of the Highland Complex of Sri Lanka, preserve a number of spectacular coronas and replacement textures that could be effectively used to infer their P–T–fluid history. These textures include coronas of garnet, garnet–quartz, and garnet–quartz–calcite at the grain boundaries of wollastonite, scapolite, and calcite as well as calcite–plagioclase and calcite–quartz symplectites or finer grains after scapolite and wollastonite respectively. Other textures include a double rind of coronal scapolite and coronal garnet between matrix garnet and calcite. The reactions that produced these coronas and replacement textures, except those involving clinopyroxene, are modelled in the CaO–Al₂O₃–SiO₂–CO₂ system using the reduced activities. Calculated examples of T–X_CO2 and P–X_CO2 projections indicate that the peak metamorphic temperature of about 900–875 °C at a pressure of 9 kbar and the peak metamorphic fluid composition is constrained to be low in X_CO2 (0.1<X_CO2<0.30). Interpretation of the textural features on the basis of the partial grids revealed that the calc–silicate granulites underwent high-temperature isobaric cooling, from about 900–875 °C to a temperature below 675 °C, following the peak metamorphism. The late-stage cooling was accompanied by an influx of hydrous fluids. The calc–silicate granulites provide evidence for high-temperature isobaric cooling in the meta-sediments of the Highland Complex, earlier considered by some workers to be confined exclusively to the meta-igneous rocks. The coronal scapolite may have formed under open-system metasomatism.     

D–H evidence for the timing of kaolinization in Northeast Bavaria, Germany

The δD_SMOW values of sedimentary kaolins from the western border of the Bohemian Massif, northeast Bavaria, that did not suffer a deep burial (less than 1000 m) nor a hydrothermal overprint, change systematically from Late Triassic (−50‰) to Mid-Jurassic and Late Cretaceous (−56‰ to −66‰) to Upper Oligocene–Mid-Miocene (−77‰ to −90‰). All analyzed clays are far from hydrogen isotope equilibrium with present-day meteoric waters. Combined oxygen and hydrogen isotope data of selected samples indicate low temperatures of formation (<30°C) and no evidence for preferential D/H exchange with younger waters. The hydrogen isotopic evolution of kaolins is interpreted as reflecting a systematic isotopic change of paleo-meteoric waters in that region. This can be related mainly to the northward drift of stable Europe after the break-up of Gondwana. Increasing continentality, surface uplift and global cooling are additional factors responsible for decreasing δD_SMOW values since the Mid-Cretaceous.

Kaolinite hydrogen isotope ratios of two large residual economic deposits (Tirschenreuth: δD_SMOW=−80‰ to −76‰; Hirschau–Schaittenbach: δD_SMOW=−70‰ to −63‰) can be used in combination with additional geological evidence to constrain the timing of weathering in these areas. A late Early Cretaceous kaolinization age is suggested for the Early Triassic sandstone-hosted deposits near Hirschau–Schnaittenbach, whereas a Late Oligocene to Mid-Miocene age is indicated for the Carboniferous granite-hosted Tirschenreuth deposits.     

Status report on stability of K-rich phases at mantle conditions

Experimental research on K-rich phases and observations from diamond inclusions, UHP metamorphic rocks, and xenoliths provide insights about the hosts for potassium at mantle conditions. K-rich clinopyroxene (Kcpx–KM³⁺Si₂O₆) can be an important component in clinopyroxenes at P>4 GPa, dependent upon coexisting K-bearing phases (solid or liquid) but not, apparently, upon temperature. Maximum Kcpx content can reach 25 mol%, with 17 mol% the highest reported in nature. Partitioning ^(K)D_(cpx/liquid) above 7 GPa=0.1–0.2 require ultrapotassic liquids to form highly potassic cpx or critical solid reactions, e.g., between Kspar and Di. Phlogopite can be stable to about 8 GPa at 1250 °C where either amphibole or liquid forms. When fluorine is present, it generally increases in Phl upon increasing P (and probably T) to about 6 GPa, but reactions forming amphibole and/or KMgF₃ limit F content between 6 and 8 GPa. The perovskite KMgF₃ is stable up to 10 GPa and 1400 °C as subsolidus breakdown products of phlogopite upon increasing P. ^(M4)K-substituted potassic richterite (ideally K(KCa)Mg₅Si₈O₂₂(OH,F)₂) is produced in K-rich peridotites above 6 GPa and in Di+Phl from 6 to 13 GPa. K content of amphibole is positively correlated with P; Al and F content decrease with P. In the system 1Kspar+1H₂O K-cymrite (hydrous hexasanidine–KAlSi₃O₈·nH₂O–Kcym) is stable from 2.5 GPa at 400 to 1200 °C and 9 GPa; Kcym can be a supersolidus phase. Formation of Kcym is sensitive to water content, not forming within experiments with H₂O2O>Kspar. Phase X, a potassium di-magnesium acid disilicate ((K_1−x−n)₂(Mg_1−nM_n³⁺)₂Si₂O₇H_2x), forms in mafic compositions at T=1150–1400 °C and P=9–17 GPa and is a potential host for K and H₂O at mantle conditions with a low-T geotherm or in subducting slabs. The composition of phase-X is not fixed but actually represents a solid solution in the stoichiometries □₂Mg₂Si₂O₇H₂–(K□)Mg₂Si₂O₇H–K₂Mg₂Si₂O₇ (□=vacancy), apparently stable only near the central composition. K-hollandite, KAlSi₃O₈, is possibly the most important K-rich phase at very high pressure, as it appears to be stable to conditions near the core–mantle boundary, 95 GPa and 2300 °C. Other K-rich phases are considered.     

Evolution of the early Earth: Constraints from Nd---Nd isotopic systematics

Combined ¹⁴⁷Sm---¹⁴³Nd and the now extinct [τ(1/2)₁₄₆=103×10⁶ yr] ¹⁴⁶Sm---¹⁴²Nd isotopic systematics are reported for early Archean gneisses from Greenland (Amîtsoq and Akilia associations), and Canada (Acasta gneiss). Using both field relationships and high resolution U---Pb SHRIMP ion-probe ages, it has been possible to identify the most ancient rocks in these terrains for isotopic analyses. Preliminary ¹⁴²Nd analyses of a still limited number of samples have failed to identify terrestrial ¹⁴²Nd anomalies. Effects, if present, are limited to < 10 ppm and we have thus been unable to confirm the +33±4 ppm ε₁₄₂ value claimed by Harper and Jacobsen (1992a, b) for a single sample. From the lack of ¹⁴⁶Sm---¹⁴²Nd effects we infer that large-scale fractionation events that may have occurred in the first 200 Ma of Earth history did not leave a significant nor widespread imprint on the early Archean mantle or crust. If a terrestrial magma ocean, with associated LREE fractionation, formed as a result of planetary accretion, then it had a lifetime of at most 250 m.y. before being remixed into the Earth's mantle.

The samples analysed in this study have a range of ε₁₄₃ values including highly positive values of up to +4.2. This requires that the earliest known Archean crust was differentiated from a reservoir that was strongly depleted in the LREE as compared with chondritic compositions. In the early Archean it is proposed that the depletions in LREE are a consequence of extraction of a limited fraction of the Earth's continental crust ( < 10%) from the upper 200 km of the mantle. A three reservoir model, consisting of the continental crust, depleted mantle and a more primitive mantle reservoir can be extended to account for both the present-day, as well as the evolving Nd isotopic composition of the Earth's crust and mantle. In contrast to previous models, the rate of growth of the continental crust is used as an input parameter to constrain the concomitant growth and evolution of the depleted mantle reservoir. Recycling of large volumes of bulk continental crust into the mantle is not considered to be an important process, nor is the existence of an additional major enriched component in the early Archean mantle.     

Comparative study of the kinetics and mechanisms of dissolution of carbonate minerals

The influence of pH on the rate of dissolution of various carbonates (calcite, aragonite, witherite, magnesite and dolomite) has been investigated at 25°C using a continuous fluidized bed reactor. The general rate dependence on pH observed for the simple carbonates is very similar and is in agreement with the results observed for calcite and aragonite by L.N. Plummer and coworkers. However, the rate of dissolution of magnesite is approximately four orders of magnitude lower than calcite.

For simple carbonates, the elementary steps involved in the dissolution reaction are:

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where M represents the metal ion which can be Ca, Mg and Ba. According to the stoichiometry of the three reaction steps and the thermodynamic constraints, the total forward and backward rates can be expressed as:

R_f=k₁a_H+k₂a_H2CO3^*+K₃

r_b=k_-1^aM²+^aHCO₃^-+k_-2^aHCO3^-+k_{-3^aM²+^aCO3^2-}

The rate constants (k₁, k₂, k₃ and k₋₃) determined with our experimental results for calcite, aragonite and witherite show that the dissolution rates are similar for these three minerals and that the nature of the cations does not play a significant role. The good agreement between the K_sp calculated from the measured k₃/k₋₃ ratio and the theromodynamic value suggests that our dissolution mechanism is coherent.

The rate dependence on pH of the dissolution of dolomite obeys a fractional order at low pH's and confirms previously published observations therein. However, the two-step reaction mechanism proposed does not explain the fractional reaction order observed, which is likely due to a more complex surface reaction.     

黄土地层中的CaCO3与环境

本文根据大量观察分析,对黄土地层中的CaCO₃含量、存在形式、淀积深度进行了研究,并进行了分类。结果表明,不仅CaCO₃含量能够反映气候变化,而且其存在形式和淀积深度同样能反映气候变化;其淀积深度很少受时间影响,比含量更能可靠地用于气候研究。