The spatial extent of chemical equilibrium in some high-grade metamorphic rocks from the grenville of southeastern Ontario

Many of the recent studies of chemical equilibrium in metamorphic rocks may have been hampered by sampling which did not reflect single regions or domains of local equilibration. This paper records results of tests performed to determine the specific volume of rock in chemical equilibrium with respect to a certain phase, under a particular set of conditions. Two samples of high-grade metamorphic gneisses from the Grenville Series of southeastern Ontario were selected for intensive study. The garnets of one specimen, possessing a biotite-garnet-cordierite assemblage, underwent in situ laser microprobe spectrochemical determinations for Fe, Mg, Mn and Ca. Conclusions are thus possible as to the volumes over which free diffusion and chemical equilibrium took place. These volumes were found to be on the order of only a few cubic centimeters and their shapes are strongly controlled by rock structures such as foliation and lineation. A higher-grade pyroxene granulite was also investigated with respect to garnet and biotite equilibrium. Somewhat larger volumes of equilibration were noted in this rock.     

Pressure and equilibrium in deforming rocks

It is widely proposed that tectonic pressure (the difference between the mean stress and the pressure arising from a lithostatic load) is large, and has a significant influence on mineral phase equilibria in deforming metamorphic rocks. The implication/assertion is that the mean stress is equivalent to the thermodynamic pressure which characterizes mineral phase equilibria and is a measure of how the energy changes as the volume changes. We distinguish two useful thermodynamic pressures. The first is an equilibrium thermodynamic pressure, characteristic of non‐dissipative systems and related directly to equilibrium values of the chemical potentials that define stable, equilibrium phase assemblages. The second is a non‐equilibrium thermodynamic pressure characteristic of dissipative systems with zero net entropy production and related to non‐equilibrium chemical potentials that define stable non‐equilibrium phase assemblages. In many dissipative metamorphic systems discussed in the literature, the concepts of thermodynamic pressure and chemical potential are not usefully defined because the system is not at equilibrium and/or no volume change is involved in the deformation. The conclusion of this note is that the influence of tectonic pressure on phase equilibria is minor. The role of tectonic pressure is an important issue but is only relevant to phase equilibrium when an equilibrium thermodynamic pressure can be defined; in such cases, the influence of tectonic pressure is small compared to many proposals in the literature. Except for elastic deformations, the mean stress is not useful in discussing mineral phase equilibrium.     

Grain‐scale pressure variations and chemical equilibrium in high‐grade metamorphic rocks

In the classical view of metamorphic microstructures, fast viscous relaxation (and so constant pressure) is assumed, with diffusion being the limiting factor in equilibration. This contribution is focused on the only other possible scenario – fast diffusion and slow viscous relaxation – and brings an alternative interpretation of microstructures typical of high‐grade metamorphic rocks. In contrast to the pressure vessel mechanical model applied to pressure variation associated with coesite inclusions in various host minerals, a multi‐anvil mechanical model is proposed in which strong single crystals and weak grain boundaries can maintain pressure variation at geological time‐scales in a polycrystalline material. In such a mechanical context, exsolution lamellae in feldspar are used to show that feldspar can sustain large differential stresses (>10 kbar) at geological time‐scales. Furthermore, it is argued that the existence of grain‐scale pressure gradients combined with diffusional equilibrium may explain chemical zoning preserved in reaction rims. Assuming zero net flux across the microstructure, an equilibrium thermodynamic method is introduced for inferring pressure variation corresponding to the chemical zoning. This new barometric method is applied to plagioclase rims around kyanite in felsic granulite (Bohemian Massif, Czech Republic), yielding a grain‐scale pressure variation of 8 kbar. In this approach, kinetic factors are not invoked to account for mineral composition zoning preserved in rocks metamorphosed at high grade.     

Phase equilibria in the hornblende-bearing basic gneisses of the Uvete area, central Kenya

Abstract The hornblende-bearing basic gneisses in the Uvete area, central Kenya, were metamorphosed under a narrow range of P and T (6.5 ± 0.5kbar and 530 ± 40°C) of the staurolitekyanite zone in the Mozambique metamorphic belt. They show a wide variety of divariant and trivariant mineral assemblages consisting of hornblende, cumminatonite, gedrite, anthophyllite, chlorite, garnet, epidote, clinopyroxene, plagio-clase and quartz. The bulk and mineral chemistries and the graphical representation of phase relations show that each mineral assemblage approaches chemical equilibrium and defines a unique composition volume in the A'(Al + Fe³⁺− (13/7)Na)-F(Fe²⁺)-M'(Mg)-C'(Ca-(3/7)Na) tetrahedron. The composition volumes are distributed quite regularly and do not overlap each other.
The phase relations in the Uvete area are in contrast with those in the staurolite-kyanite zone amphibolites in the Mt. Cube quadrangle, Vermont. The amphibolites there contain low-variance mineral assemblages formed under different values of μ_H2O and μ_CO2. These assemblages define overlapping composition volumes in the A'-F'-M'-C'tetrahedron.
The mineral assemblages in the Uvete area are interpreted as having formed in equilibrium with fluid at a high and nearly constant μH₂O value. Such a fluid composition was externally controlled by the supply of H₂O-rich fluid expelled from the surrounding pelitic and psammitic rocks. The body size of the basic gneisses in the Uvete area (less than 400m in thickness) was small enough for the fluid to migrate completely.     

浙江大桥坞铀矿床深部流体作用的地质-地球化学证据

笔者通过流体包裹体的岩相学、显微测温学以及激光拉曼成分的对比研究,探明了大桥坞铀矿床成矿流体的基本性质（温度、盐度及成分）,结合该矿床的构造和地质-地球化学特征,对成矿流体的来源进行了探讨。研究结果表明,该矿床主成矿期成矿温度为200-250℃,属于中温热液矿床,其成矿流体为富含CO2、H2、CH4等气体组分的中高盐度流体,反映该矿床成矿过程以深部流体作用为主,成矿流体主要为来自地幔的流体。     

一种计算岩石中矿物组成的新方法

介绍根据显微下观察,应用岩石化学全分析结果和分子量计算法计算岩石中矿物组成的新方法。所得各种矿物的组成是整块岩石在三维立体体积中各种矿物的质量分数,比目前沿用的目测一个岩石切面上各种矿物的面积百分比法更准确,比CIPW标准矿物分子法更符合岩石样品组合的实际情况,而且可用于含云母族、绿泥石族和铀矿物等蚀变矿化的花岗岩及沉积岩、变质岩的矿物组成计算。     

Compositional homogeneity in low-temperature chlorites

Electron microprobe analyses of small chlorite grains (10–20 μm width) in diagenetically altered rocks from three deep wells and a series of outcrop samples ranging in maximum age from 4 to 1300 Ma show an increasingly smaller range in grain-to-grain composition as a function of the average age of the specimens in a series. The scatter of composition in a sample in each series changes little with depth despite present day, or estimated maximum temperature differences of 70° C to 100° C from top to bottom. Comparison of these chlorite compositions with those published for geothermal and metamorphic rocks formed under conditions of 300–450° C indicates that the homogeneity of chlorite composition is a function of both the temperature of equilibration and its duration. Apparently total homogenization of Fe/(Fe+Mg), Al/(Al+Mg+Fe) content will occur after 10¹⁰ years at low temperatures. Simple calculations indicate that a slow process such as solid state diffusion could be responsible for the eventual homogenization of mineral grain composition to reach chemical equilibrium after phase equilibrium has been reached.     

Retrieval of P–T information from shear zones: thermobarometric consequences of changes in plagioclase deformation mechanisms

Changes in deformation mechanism coupled with spatial and temporal variations in reaction rates can result in preservation of disequilibrium mineral compositions in rocks affected by synmetamorphic shearing. Thermobarometric calculations on such rocks may thus yield meaningless results. We use Garbenschiefer samples from a shear zone in the Eastern Alps to study the effects of different deformational processes on calculated pressures and temperatures in samples that experienced the same overall PTt history. We focus on plagioclase, which accommodates strain by a variety of deformation mechanisms and is a key mineral in many thermobarometers. Plagioclase that deformed largely via dislocation creep mechanisms shows concentric chemical zoning, whereas plagioclase that experienced dissolution-precipitation creep preserves complex zoning. Rim compositions in the latter domains are not necessarily the youngest compositions, nor did they typically equilibrate with other phases in the assemblage. The timing of hornblende breakdown reactions relative to changes in plagioclase deformation mechanism also affected chemical zoning. Samples that escaped shear strain while near the thermal maximum yield internally consistent thermobarometric results, whereas samples that experienced shearing near the thermal maximum yield scattered results. Some of the variability in the results likely represents real differences in the P–T conditions at which equilibration occurred during deformation. However, much of the variability represents spurious results obtained by pairing mineral compositions that were never in equilibrium with one another. Extraction of useful P–T information from samples that experienced synmetamorphic deformation requires careful documentation of the relationships between deformation mechanisms and chemical zoning in order to select appropriate mineral compositions for thermobarometric calculations.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

Chronology of the high-pressure metamorphism of Norwegian garnet peridotites/pyroxenites

Eclogite facies mineral assemblages are variably preserved in mafic and ultramafic rocks within the Western Gneiss Region (WGR) of Norway. Mineralogical and microstructural data indicate that some Mg–Cr-rich, Alpine-type peridotites have had a complex metamorphic history. The metamorphic evolution of these rocks has been described in terms of a seven-stage evolutionary model; each stage is characterized by a specific mineral assemblage. Stages II and III both comprise garnet-bearing mineral assemblages. Garnet-bearing assemblages are also present in Fe–Ti-rich peridotites which commonly occur as layers in mafic complexes. Sm–Nd isotopic results are reported for mineral and whole rock samples from both of these types of peridotites and related rocks. The partitioning of Sm and Nd between coexisting garnet and clinopyroxene is used to assess chemical equilibrium. One sample of Mg–Cr-type peridotite shows non-disturbed partitioning of Sm and Nd between Stage II garnet and clinopyroxene pairs and yields a garnet–clinopyroxene–whole-rock date of 1703 ± 29 Ma (I= 0.51069, MSWD = 0.04). This is the best estimate for the age of the Stage II high-P assemblage. Other Stage II garnet–clinopyroxene pairs reflect later disturbance of the Sm–Nd system and yield dates in the range 1303 to 1040 Ma. These dates may not have any geological significance. Stage III garnet–clinopyroxene pairs typically have equilibrated Sm–Nd partitioning and two samples yield dates of 437 ± 58 and 511 ± 18 Ma. This suggests that equilibration of the Stage III high-P assemblage is related to the Caledonian orogeny and is more or less contemporaneous with high-P metamorphism of ‘country-rock’eclogites in the surrounding gneisses. The Sm–Nd mineral data for the Fe–Ti-rich garnet peridotites and for a superferrian eclogite, which occurs as a dyke within the Gurskebotn Mg–Cr-type peridotite, are consistent with a Palaeozoic high-P metamorphism. Finally a synoptic P–T–t path is proposed for the Mg–Cr-type peridotites which is consistent with the petrological and geochronological data.     

渝东南渝页1井下志留统龙马溪组页岩孔隙特征及其主控因素

富有机质黑色页岩的孔隙结构控制了页岩气的赋存状态和储气量。中国南方地区下志留统是页岩气发育的最重要层位之一。为研究页岩的孔隙特征及其主控因素,对以下志留统龙马溪组页岩气为勘探目标的渝页1井的岩心进行系统的采样,并进行了比表面和孔径、有机质成熟度(Ro)、显微组分、总有机碳(TOC)含量、全岩X射线衍射和粘土矿物含量等一系列分析测试。结果显示,黑色页岩的孔径主要分布于2~5 nm,即以中孔隙为主;中孔体积占总体积的70%左右,微孔体积和宏孔体积分别占10%和20%左右。页岩孔隙结构(微孔体积、中孔体积和宏孔体积)和组成(碎屑矿物成分、粘土矿物成分、TOC和Ro)的相关关系分析表明：粘土矿物对微孔体积和中孔体积都具有控制作用,并且对中孔体积的控制作用更加显著;陆源碎屑含量的增加有利于宏孔体积的增加;有机质成熟度较高时和高成熟度有机碳含量都与宏孔隙体积呈正相关,这可能与高成熟有机质中nm级显微裂缝的发育导致宏孔体积增加有关。     

Blueschist and Eclogite transformations in Fe-Ti Gabbros: A Case from the Western Alps Ophiolites

The study of the alpine metamorphism of three suites of Fe-Timetagabbros occurring in the western Alps ophiolites has showna set of reactions governed by T, P, X_H2O, and diffusion. T-Pestimates point to 350?50?C at a minimum of 9–10 kb forthe Queyras blueschist rocks and to 450–500 ?C at a minimumof 12–13 kb for the Lanzo and Rocciavr` eclogitized rocks.These variations are the result of different T-P-time trajectoriesduring subduction/obduction events of alpine age. In the Fe-Timetagabbros, little-deformed volumes showing a crystallizationhistory controlled by local equilibrium are bounded by mylonites.Water-poor and water-rich volumes alternate during eclogitizationof the Rocciavr? suite. The persistence in the little-deformedrocks of prealpine metastable relics, of corona structures andof chemical gradients, demonstrates that a complete high pressureequilibration is inhibited by slow reaction kinetics and slowdiffusion. Only in the mylonites has the catalytic effect ofdeformation favoured an approach to bulk-rock metamorphic equilibration.In the eclogitized coronitic rocks the apparent O₂, releasefrom the alteration of the magmatic opaques plays an importantrole in reaction rates; increasing extent of eclogitizationmay be enhanced either by the release of free O₂ from the rocks,or by a process in which new H₂O formed by the combination ofoxygen with hydrogen introduced into the system.     

Role of chemical processes on shear zone formation: an example from the Grimsel metagranodiorite (Aar massif,Central Alps)

Alpine deformation in the Grimsel granodiorite (Aar massif, Central Alps) at greenschist facies conditions (6.5 ± 1 kbar for 450°C ± 25°C) is characterized by the development of a network of centimetre to decametre localized shear zones that surround lenses of undeformed granodiorite. Localization of deformation is assumed to be the result of a first stage of extreme localization on brittle precursors (nucleation stage) followed by a transition to ductile deformation and lateral propagation into the weakly deformed granodiorite (widening stage). A paradox of this model is that the development of the ductile shear zone is accompanied by the crystallization of large amounts of phyllosilicates (white mica and chlorite) that maintains a weak rheology in the localized shear zone relative to the host rock so that deformation is localized and prevents shear zone widening. We suggest that chemical processes, and more particularly, the metamorphic reactions and metasomatism occurring during re‐equilibration of the metastable magmatic assemblage induced shear zone widening at these P–T–X conditions. These processes (reactions and mass transfer) were driven by the chemical potential gradients that developed between the thermodynamically metastable magmatic assemblage at the edge of the shear zone and the stable white mica and chlorite rich ultramylonite formed during the first stage of shear zone due to localized fluid infiltration metasomatism. P–T and chemical potential projections and sections show that the process of equilibration of the wall rocks (μ–μ path) occurs via the reactions: kf + cz + ab + bio + MgO + H₂O = mu + q + CaO + Na₂O and cz + ab + bio + MgO + H₂O = chl + mu + q + CaO + Na₂O. Computed phase diagram and mass balance calculations predict that these reactions induce relative losses of CaO and Na₂O of ～100% and ～40% respectively, coupled with hydration and a gain of ～140% for MgO. Intermediate rocks within the strain gradient (ultramylonite, mylonite and orthogneiss) reflect various degrees of re‐equilibration and metasomatism. The softening reaction involved may have reduced the strength at the edge of the shear zone and therefore promoted shear zone widening. Chemical potential phase diagram sections also indicate that the re‐equilibration process has a strong influence on equilibrium mineral compositions. For instance, the decrease in Si‐content of phengite from 3.29 to 3.14 p.f.u, when white mica is in equilibrium with the chlorite‐bearing assemblage, may be misinterpreted as the result of decompression during shear zone development while it is due only to syn‐deformation metasomatism at the peak metamorphic condition. The results of this study suggest that it is critical to consider chemical processes in the formation of shear zones particularly when deformation affects metastable assemblages and mass transfer are involved.     

Contact metamorphism around the Stawell granite, Victoria, Australia

The contact metamorphosed metapelitic and metapsammitic rocks surrounding the Stawell granite, western Victoria, Australia, are divided into three zones: the low-grade zone, the medium-grade zone and the high-grade zone. Detailed petrological study shows consistency of element distributions, implying that equilibrium was widely attained in the rocks, although equilibrium volumes are generally small (millimetre scale) and considerable mineral chemical variations exist between adjacent domains. The metamorphic mineral assemblages are generally of high variance (KFMASH variance ≤ 2). Consequently, the chemical evolution of assemblages is controlled largely by bulk composition and metamorphic temperature, the former factor being more important in most rocks. The chemographic relations of mineral assemblages in low- and medium- to high-grade zones are presented in compatibility diagrams projected from biotite, quartz and H₂O, and biotite, K-feldspar and H₂O, respectively. These compatibility diagrams have the advantage of showing both quartz-bearing and quartz-absent assemblages. The metamorphic reactions are modelled successfully by a calculated petrogenetic grid that combines both KFASH and KMASH equilibria. Based on petrographic observations and with constraints from the calculated petrogenetic grid, the following KFMASH reactions, in the order of increasing metamorphic grade, are responsible for producing the various mineral assemblages in the Stawell rocks: chl + mu + q = bi + cd + V, chl + q + cd = g + V, mu + bi + q = ksp + cd + V, mu + q = ksp + and + cd + V (or KASH mu + q = ksp + and + V), mu + cd = ksp + and + bi + V, mu + bi + and = ksp + sp + V, and + bi = ksp + sp + cd + V, mu + bi = ksp + cor + sp + V, mu = ksp + cor + and + sp + V (or KASH mu = ksp + cor + V), bi + cd + q = g + ksp + V. The combined KFASH and KMASH grid provides constraints on reaction coefficients in the above sequence of reactions and on temperature and pressure of metamorphism.     

Evidence of a Temperature-dependent 'Blueschist' to 'Eclogite' Transformation in High-pressure Metamorphism of Metabasic Rocks

Textures in the blueschist metabasic rocks of the island ofSyros, Greece, indicate a reaction forming omphacite and garnetfrom earlier glaucophane and epidote. A balanced ‘wholerock’ reaction can be written using the phase compositionsand modal mineralogy of the products observed. This reactionis continuous in P-T space if Mg and Fe²⁺ are independent components.The available thermodynamic data suggest that the ‘eclogite’(garnet plus omphacite) assemblage is favoured by higher temperatures. It cannot, however, be conclusively shown that the rocks wentthrough an up-temperature interval of metamorphism. The reactionseen could be promoted by reduced silica, or water activity.The details of the reaction textures and mineral zonation patternsshow furthermore that chemical equilibrium was not maintainedthroughout the rock development. The reaction textures differin detail in different samples. In those samples in which thetextures are most consistent with maintained chemical equilibriumhowever, the mineral zonation patterns do imply up-temperaturemetamorphism.     

硅酸盐体系的化学平衡:(1)物质平衡原理

通过具体应用实例,系统介绍了在硅酸盐体系的化学平衡研究中,依据物质平衡原理,求解“相混合方程”(PME)而进行物相定量分析的“相混合计算”(PMC)方法。应用实例包括矿物原料和结晶岩物相的定量分析,复杂固溶体矿物的端员组分计算,多组分硅酸盐陶瓷的配料比例计算,以及硅酸盐陶瓷制品物相的定量分析。物相定量分析结果是结晶岩和工业岩石原料分类命名的基础,可以为改进矿物原料预处理工艺提供依据,也是研究硅酸盐体系的化学平衡、对材料制备过程进行热力学分析的基础。实际计算中必须合理估计各种分析数据的累积误差。优化计算结果的理论依据主要有矿物晶体化学原理、矿物共生组合规律和次要组分分配的固溶体矿物相优先原则。     

“Calcic amphibole equilibria and a new amphibole-plagioclase geothermometer”: Reply to the comments of Hammarstrom and Zen,and Rutherford and Johnson

Conclusions We reaffirm the barometric potential of our amphibole-plagioclase thermometer for rocks where (and only where) the final equilibration temperature is very well constrained. In the advantageous case of granitoids with simple thermal histories this temperature may be the wet granitoid solidus at the pressure of interest. We emphasise the need for careful petrographic assessment of equilibrium between plagioclase and amphibole before attempting total-Al barometry and recommend that a relatively large number of pairs are analysed for each sample. In rocks with complex post-consolidation or fluid-flow histories such barometry requires an independent means of determining amphibole equilibration temperature.     

郯庐断裂带南段桴槎山韧性剪切带糜棱岩的变形条件和组分迁移系

本文对郯庐断裂带南段主干断裂典型的韧性剪切带进行了系统的剖析。从糜棱岩塑性变形的亚颗粒化、动态重结晶和矿物成分特征及岩石组分迁移变化等入手进行系统的研究工作，计算了岩石形成的温度、压力和流动应力和流变速率参数；模拟计算了岩石在剪切变形作用下的体积亏损及组分迁移的量值，探讨了变形－变质及流体的相关关系     

Deep crustal carbonates as CO2 fluid sources: Evidence from metasomatic reaction zones

Metasomatic reaction zones which developed at marble-pelitic schist contacts in a granulite facies terrane in West Greenland contain a consistent sequence of five mineralogical zones. Outward from the carbonates the zones are characterized by the assemblages grossular-diopside-meionite (I), meionite-anorthite-diopside (II), anorthite-diopside-edenitic hornblende (III), anorthite-enstatite (IV), plagioclase-almandine-sillimanite (V). Sphene is superceded by ilmenite between zones (II) and (III); quartz is present in all zones except zone I. Scapolite, plagioclase, clinopyroxene and mica exhibit a small degree of compositional variation which correlates with distance from the carbonate. These small compositional variations are superimposed on a strong CaO chemical potential gradient. Compositional features, zone distributions and CaO activity calculations demonstrate that the zones developed in response to CaO diffusion along a chemical potential gradient of 2 kcal/m. The CaO source appears to be carbonate rocks which release calcium as decarbonation reactions proceed. The maximum volume of CO₂ released in this process, and that released during discontinuous reactions in the marbles, will contribute a total volume of CO₂ approximately equivalent to the volume of carbonate in the rock. Calculations demonstrate that a terrane consisting of as little as 8% carbonate will release sufficient CO₂ to result in complete dehydration of an amphibolite terrane, at deep crustal conditions. Dehydration through CO₂ release will be accomplished either through rapid burial, which would prevent both equilibration of mineral assemblages and CO₂ release at intermediate crustal levels, or through diffusion-driven metasomatic reactions which would lead to CO₂ release primarily at the high temperatures of deep crustal environments. The latter process would be the dominant CO₂ source at deep crustal levels if carbonate rocks occur predominately as relatively thin layers.     

Compositions, Proportions, and Equilibrium Temperature of Coexisting Two-feldspar in Crystalline Rocks

Compositions, proportions, and equilibrium temperature of coexisting two-feldspar in crystalline rocks are of great importance to classification in petrography and interpretation of petrogenesis. Crystalline rocks are usually composed of 4-6 minerals (phases), depending on their independent chemical components and the equilibrium temperature of crystallizations. In general, number of mineral phases can be determined by the “Phase Rule”. According to the mass balance principle, bulk composition of coexisting two-feldspar could be evaluated from the bulk chemistry of a rock, provided that the compositions of the coexisting mafic mineral phases containing calcium, sodium, and potassium oxides are determined, e.g., by microprobe analysis. The compositions, proportions, and temperature of two-feldspar in equilibrium can thus be simultaneously resolved numerically from bulk composition of the rock, by incorporating the activity/composition relations of the ternary feldspars with the mass balance constraints. Upon the numerical approximation method presented in this paper, better-quality, internally consistent data on feldspar group could usually be obtained, which would be expected more realistic and accurate in consideration of thermodynamic equilibria in the system of crystalline rocks, as well as bulk chemistry of a rock and the composing minerals.     

Shale basins,sulfur-deficient ore brines and the formation of exhalative base metal deposits

The massive sulfide deposits of the Iberian Pyrite Belt are interbedded with felsic volcanic rocks and shale, and underlain by several thousand meters of siliciclastic sedimentary rocks known as the PQ Group. Isotope geochemistry and regional geology are both consistent with equilibration of the ore-forming fluids with the PQ Group, prior to ore deposition near the former seafloor. The average Cu:Zn:Pb ratio of the PQ Group rocks (ca. 26:55:19) is similar to the weighted average of all the massive sulfide orebodies combined (ca. 25:52:23).The genetic relationship between massive sulfide deposits and a siliciclastic sedimentary metal source is explained here by a thermodynamic model, proposing that mildly reducing redox conditions imposed by equilibration with the sedimentary rocks are most critical for the formation of an effective ore-forming fluid. Relatively metal-rich but organic-poor pyrite-bearing shale undergoing dewatering of saline pore fluids is an effective source for the generation of sulfur-deficient but relatively iron and base metal-rich brines. Thus, we propose that the giant deposits of the Iberian Pyrite Belt owe their existence not to exceptionally metal-enriched (e.g., magmatic) fluids, but to the existence of a fairly ordinary but large metal source in reactive siliciclastic sediments, combined with an underlying igneous heat source and a particularly efficient mechanism of sulfide precipitation by mixing with H₂S-rich fluids at or near the seafloor.Essentially similar mineral equilibria are imposed when saline fluids are buffered by typical continental basement rocks. Leaching of retrograde minerals and possibly residual salts from their magmatic or metamorphic prehistory is expected to generate similar, variably metal-rich but relatively sulfide-deficient fluids. Thus, the existence of mildly reducing rocks can be the dominant chemical control in the source of fluids generating many volcanogenic, Irish-type or sedex deposits, many of which are known to precipitate their metal load in response to biogenic sulfide addition at the ore deposition site.