Precious metals in massive base metal sulfide deposits

Gold and silver are ubiquitous, sometimes minor but economically important metals in massive base metal sulfide ores. Their content, proportions and distribution in the ores depend on complex, interrelated factors of their source, mobilization, transport and deposition.Different types of these deposits are formed by similar seafloor hydrothermal systems operating, however, in widely differing tectono-stratigraphic environments which span a spectrum from ensimatic-oceanic, through continent-margin to ensialic-continental ones. Like those of the base metals, the proportions and distribution of the precious metals in the ores vary regionally with these changing depositional environments. This suggests that precious metal content of the sub-seafloor rocks in which the generative fluids circulate is one factor that governs the amounts and distribution in the ores. The lithology of these source-rocks is also important. Pillowed, tholeiitic basalts have high permeability, golddepleted crystalline pillow interiors and relatively gold-rich palagonitic rims, and are consequently particularly favorable sources.Mobilization of gold from the sub-seafloor rocks may require basalt-water, and/or carbonaceous sediment-water reactions to produce strongly reduced bisulfide, carbonyl or cyanide complexes that promote gold transport. Chloride complexing and transport are less important for gold but more so for silver and the base metals.Seafloor hydrothermal discharge at shallow depth is commonly accompanied by boiling, steamblast explosions in the vent and resulting deep penetration and mixing of cool, oxygenated seawater with rising hot, reduced metalliferous fluid. This results in deposition of both chloride- and isulfide-complexed gold at depth and centrally in the footwall stockwork or in copper ore in the base of the massive body. Chloride-complexed silver, stable to lower temperatures, is carried farther and deposited with higher-level and more distal, massive zinc-lead ores. Boiling in deep water, however, although possible, is rare. This fact minimizes deep fluid mixing and allows transport of lower temperaturestable, bisulfide-complexed gold to the seafloor and outward from the vent. Gold too, is then deposited with the shallower, distal, massive zinc-lead-silver ore. Late-stage changes in fluid Eh, salinity and activity of sulfur during evolution of the generative hydrothermal system, and by discharge through previously deposited, early stage sulfides around the vent also cause diagenetic remobilization of gold, moving it to shallower, more distal locations in the system. In combination, these relationships explain the three associations of gold in primary, in-situ massive sulfide deposits; in central, deep footwall stockwork mineralization with or without copper, in central copper ore in the base of the massive body and in shallow, peripheral pyritic zinclead-silver ore.Primary, in-situ ore near the vent is sometimes reworked by seafloor density flows which transport clasts of the primary sulfides down-slope, mix them with rock and sedimentary detritus and redeposit them to form secondary, transported ore. Gold, like iron and the base metals, is diluted during this clastic transport. But silver and barite may be enriched indicating transport in the density flows not only as clasts of primary ore but partly also m solution in the hydrothermal fluids that, in this case, must have lubricated the density flows.

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Zusammenfassung Gold- und Silbervorkommen in massiven Metallsulfid-Lagerstätten sind stets ökonomisch wichtige Metalle, auch wenn sie nur in geringen Konzentrationen vorliegen. Der Gehalt an diesen Metallen und ihre Verteilung innerhalb der Lagerstätte hängt von komplexen, sich gegenseitig beeinflussenden Faktoren wie Metallquelle, Art der Mobilisation, Transport und Fällung ab.Unterschiedliche Lagerstättentypen werden von ähnlichen hydrothermalen Systemen auf den Ozeanböden gebildet. Die tektonostratigraphischen Environments unterscheiden sich dabei allerdings beträchtlich; sie befinden sich in ensimatisch-ozeanischen, kontinentalrandlichen und ensialischkontinentalen Bereichen. Innerhalb dieser regional wechselnden Ablagerungsbedingungen variiert Konzentration und Verteilung der Edelmetalle in den Lagerstätten wie bei den einfachen Metallen. Dies bedeutet, daß der Gehalt an Edelmetallen der Gesteine, die den Meeresboden unterlagern und durch die die metallhaltigen Lösungen zirkulieren, ein Faktor ist, der Menge und Verteilung der Metalle in der Lagerstätte steuert. Ebenso ist die Lithologie dieser Gesteine von Bedeutung. Als besonders gut geeignete Quellen gelten kissenartige tholeitische Basalte mit hoher Permeabilität, goldarmen Kisseninneren und relativ goldreichem palagonitischem Rand.Um das Gold aus diesen Gesteinen mobilisieren zu können, bedarf es einer Reaktion zwischen Basalt und Wasser und/oder eines karbonatischen Sediments mit Wasser, um stark reduziertes Bisulfid, Carbonyl-oder Cyanidkomplexe zu bilden, die den Goldtransport ermöglichen. Chlorid-Komplexbildung und -Transport sind zwar wichtig für Silber und einfache Metalle, für Gold spielen sie nur eine untergeordnete Rolle.Der Austritt hydrothermaler Lösungen an Ozeanböden in geringer Tiefe wird in der Regel von Sieden und explosionsartigem Dampfaustritt begleitet und führt deshalb zu einem tiefen Eindringen und Durchmischen von kaltem, sauerstoffreichen Meereswasser mit den aufsteigenden heißen, reduzierten metallischen Lösungen. Daher kommt es zur Fällung von sowohl an Chloridkomplexe als auch an Bisulfidkomplexe gebundenem Gold. Diese Ausfällung findet in größerer Tiefe statt und zwar hauptsächlich im liegenden Stockwerk oder mit Kupfer zusammen an der Basis der massiven Lagerstätte. An Chloridkomplexe gebundenes Silber ist auch bei niedrigeren Temperaturen stabil, wird also weiter transportiert und in einem höheren Niveau in distal gelegenen Blei-Zink-Lagerstätten gefällt. In größeren Wassertiefen kommt es seltener zu dem beobachteten Sieden der austretenden Lösungen. Diese Tatsache reduziert das Durchmischen der Lösungen in größeren Tiefen und ermöglicht den Transport von Gold, das an Bisulfidkomplexe gebunden ist. In diesem Fall ist die Verbindung auch bei niedrigeren Temperaturen noch stabil also transportfähig und kann bis zum Meeresboden oder außerhalb des Schlotes in Lösung bleiben. Dabei kann das Gold zusammen mit Blei, Zink und Silber in mehr distalen Lagerstätten angereichert werden. Späte Änderungen in Eh, Salinität und Schwefelaktivität der Lösungen während der Entwicklung des hydrothermalen Systems, sowie der Austritt durch früher abgelagerte den Schlot umgebende Sulfide, können eine diagenetische Gold-Remobilisation auslösen. Auch dabei kann das Metall zu in geringer Tiefe liegenden, distalen Ablagerungsorten transportiert werden. Berücksichtigt man alle Faktoren, so erklären diese Verhältnisse die drei möglichen Goldvorkommen in primären, in-situ vorliegenden Sulfid-Lagerstätten: Mit Kupfer vergesellschaftet, allerdings nicht unbedingt, zentral im liegenden Stockwerk; an der Basis der Kupferlagerstätte und in geringer Tiefe in Verbindung mit peripheren Blei-Zink-Silber-Vorkommen.Primäre, in-situ neben Schloten vorkommende Lagerstätten werden in einigen Fällen von meeresbodennahen Masseströmen aufgearbeitet. Diese transportieren Sulfidkomponenten, die während des Transports mit Sediment und Gesteinsbruchstücken vermischt und schließlich als sekundäre sedimentäre Lagerstätte abgelagert werden. Durch diesen Transport und die Mischung der Klastika wird die Goldkonzentration in der späteren Lagerstätte stark reduziert. Silber und Barit können dagegen in Ausnahmefällen während des Transports angereichert werden, da diese Komponenten nicht nur als Sulfidbruchstücke transportiert werden, sondern auch in Lösung in den hydrothermalen Lösungen vorhanden sein können. Diese Lösungen dienen in solchen Fällen den Masseströmen als Gleithorizont.

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Résumé Dans les gisements de sulfures métalliques massifs, l'or et l'argent sont des métaux ubiquistes, parfois mineurs, mais toujours d'importance économique. Leur teneur et leur distribution dans les corps minéralisés dépendent de facteurs complexes, en relation les uns avec les autres, tels que: leur source, leur mobilité, leurs modalités de transport et de dépôt.A partir des mêmes systèmes hydrothermaux en action sur le fond de la mer, divers types de gisements peuvent être engendrés, selon leur environnement tectono-stratigraphique: océanique ensimatique, de marge continentale ou continental ensialique. Les teneurs et la répartition des métaux précieux, comme celle des autres métaux varient régionalement selon ces divers milieux. Ceci suggère que le contenu en métaux précieux dans les roches sous-jacentes au fond marin à travers lesquelles circulent les solutions minéralisantes est un facteur qui détermine leurs teneurs et leurs répartitions dans les minerais. La lithologie de ces roches-sources est également importante. Une source particulièrement significative est représentée par les coussins des basaltes tholéiitiques, très perméables, avec leur coeur pauvre en or et leur couronne palagonitique relativement riche.Le lessivage de l'or dans les roches situées sous le fond marin peut impliquer des réactions eau-basalte et/ou eausédiments carbonatés, réactions susceptibles d'engendrer les bisulfures très réduits et les complexes carbonés ou cyanurés qui permettent le transport de l'or. Le transport par complexes chlorurés joue un rôle subordoné dans le cas de l'or, mais important dans le cas de l'argent et des autres métaux.L'arrivée de solutions hydrothermales sur les fonds marins peu profonds est d'ordinaire accompagnée d'ébullitons et d'émissions explosives de vapeur, ce qui provoque la pénétration profonde d'eau de mer froide et oxygénée et son mélange avec les fluides métallifères chauds et réducteurs ascendants. Il en résulte le dépôt de complexes aurifères bisulfurés et chlorurés. Cette précipitation s'opère en profondeur, particulièrement dans les roches sous-jacentes ou dans le minerai de cuivre, à la base des corps minéralisés massifs. L'argent des complexes chlorurés, stables à plus basse température, est transporté plus loin et se dépose, en situation plus distale, dans les minerals massifs de Pb-Zn. Dans les mers profondes, l'ébullition, sans être impossible, est néanmoins un phénomène rare; cette circonstance minimise le mélange des fluides en profondeur et permet le transport de l'or jusqu'à la surface du fond et même loin des évents sous la forme de complexes bisulfurés stables à basse température. L'or est alors déposé en situation distale peu profonde avec les minerals massifs de Zn-Pb-Ag. Des modifications tardives d'Eh, de salinité et d'activité du soufre dans les solutions au cours de l'évolution du système hydrothermal, de même que le lessivage des sulfures déjà accumulés autour des évents entraînent une remobilisation diagénétique de l'or vers des situations distales d'eau peu profonde. La combinaison de ces divers facteurs permet d'expliquer les trois occurrences de l'or dans les dépôts in situ de sulfures massifs primaires: dans les parties centrales des masses sous-jacentes en association ou non avec le Cu, à la base des corps minéralisés en Cu, et à faible profondeur, en liaison avec les gisements périphériques de Pb-Zn-Ag.Les gisements primaires, formés in situ près des évents sont parfois remaniés par des courants de densité, qui emportent des clastes de sulfures, les mélangent aux débris sédimentaires et les redéposent sous forme de minerais secondaires. De tels transports provoquent la dilution de l'or, en même temps que celle du fer et des autres métaux. Par contre, l'argent et la barite peuvent subir un enrichissement car leur transport dans les courants de densité ne s'effectue pas seulement sous forme de clastes, mais également en solution dans des fludies hydrothermaux, lesquels, dans ce cas, contribuent à lubrifier le courant de densité.

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Comparative compressibilities of majorite-type garnets

Relative compressibilities of five silicate garnets were determined by single-crystal x-ray diffraction on crystals grouped in the same high-pressure mount. The specimens include a natural pyrope [(Mg_2.84Fe_0.10Ca_0,06) Al₂Si₃O₁₂], and four synthetic specimens with octahedrally-coordinated silicon: majorite [Mg₃(MgSi)Si₃O₁₂], calcium-bearing majorite [(Ca_0.49Mg_2.51)(MgSi)Si₃0₁₂], sodium majorite [(Na_1.88Mgp_0.12)(Mg_0.06Si_1.94)Si₃O₁₂], and an intermediate composition [(Na_0.37Mg_2.48)(Mg_0.13Al_1.07 Si₀₈₀) Si₃O₁₂]. Small differences in the compressibilities of these crystals are revealed because they are subjected simultaneously to the same pressure. Bulk-moduli of the garnets range from 164.8 ± 2.3 GPa for calcium majorite to 191.5 ± 2.5 GPa for sodium majorite, assuming K′=4. Two factors, molar volume and octahedral cation valence, appear to control garnet compression.     

Microfacies and diagenesis of older Pleistocene (pre‐last glacial maximum) reef deposits,Great Barrier Reef,Australia (IODP Expedition 325): A quantitative approach

During Integrated Ocean Drilling Program Expedition 325, 34 holes were drilled along five transects in front of the Great Barrier Reef of Australia, penetrating some 700 m of late Pleistocene reef deposits (post‐glacial; largely 20 to 10 kyr bp ) in water depths of 42 to 127 m. In seven holes, drilled in water depths of 42 to 92 m on three transects, older Pleistocene (older than last glacial maximum, >20 kyr bp ) reef deposits were recovered from lower core sections. In this study, facies, diagenetic features, mineralogy and stable isotope geochemistry of 100 samples from six of the latter holes were investigated and quantified. Lithologies are dominated by grain‐supported textures, and were to a large part deposited in high‐energy, reef or reef slope environments. Quantitative analyses allow 11 microfacies to be defined, including mixed skeletal packstone and grainstone, mudstone‐wackestone, coral packstone, coral grainstone, coralline algal grainstone, coral‐algal packstone, coralline algal packstone, Halimeda grainstone, microbialite and caliche. Microbialites, that are common in cavities of younger, post‐glacial deposits, are rare in pre‐last glacial maximum core sections, possibly due to a lack of open framework suitable for colonization by microbes. In pre‐last glacial maximum deposits of holes M0032A and M0033A (>20 kyr bp ), marine diagenetic features are dominant; samples consist largely of aragonite and high‐magnesium calcite. Holes M0042A and M0057A, which contain the oldest rocks (>169 kyr bp ), are characterized by meteoric diagenesis and samples mostly consist of low‐magnesium calcite. Holes M0042A, M0055A and M0056A (>30 kyr bp ), and a horizon in the upper part of hole M0057A, contain both marine and meteoric diagenetic features. However, only one change from marine to meteoric pore water is recorded in contrast with the changes in diagenetic environment that might be inferred from the sea‐level history. Values of stable isotopes of oxygen and carbon are consistent with these findings. Samples from holes M0032A and M0033A reflect largely positive values (δ¹⁸O: ?1 to +1‰ and δ¹³C: +1 to +4‰), whereas those from holes M0042A and M0057A are negative (δ¹⁸O: ?4 to +2‰ and δ¹³C: ?8 to +2‰). Holes M0055A and M0056A provide intermediate values, with slightly positive δ¹³C, and negative δ¹⁸O values. The type and intensity of meteroric diagenesis appears to have been controlled both by age and depth, i.e. the time available for diagenetic alteration, and reflects the relation between reef deposition and sea‐level change.     

通过第一性原理预测内地核的成分与结构

内地核成分与结构的确定一直是地球深部研究的重要课题。目前地核的公认成分是铁和少量的镍。但由于地核密度低于纯粹的铁镍合金(固态内核2%～3%,液态外核6%～7%),其中必定掺杂有一定量的轻元素,其种类与浓度有待确定。除成分外,地核条件下铁的晶体结构也存在争议。根据地震学观测,声波沿地轴方向的传播速度比赤道平面方向快大约3%～4%。这意味着内地核是各向异性的;但在极端高压下,晶体结构中的原子应该按致密的密排六方结构(h.c.p)排列,而h.c.p结构对声波传输是高度各向同性的,这就需要确定地核条件下铁的晶体结构。根据第一性原理计算得到的高压下体系能量以及爱因斯坦谐振子模型,本项研究估算了给定结构的自由能以及掺杂轻元素后的影响。根据计算结果可以定性的分析得出,在高压OK下致密的h.c.p结构显然比疏松的体心立方(b.c.c)更稳定;而随着温度的升高,原子核的振动造成b.c.c结构的自由能比h.c.p结构下降得更快,因此在高温下b.c.c结构更稳定;掺杂轻元素后,这种优势变得更加明显,而3.6at.%的Si则恰好同时解释了2%～3%的密度缺失和b.c.c结构在内地核条件下的稳定性。因此我们建议内地核的基本结构与成分应为以体心立方结构存在的铁,掺杂约3.6at.%的硅元素,内地核温度至少在5500K以上。这一结论与其它更复杂的方法得到的结果一致。     

The mineralogical composition of precursor sediments of calcareous rhythmites: a new approach

Previous studies in Silurian carbonates from Gotland (Sweden) have led to a model for the development of limestone-marl alternations. This model postulates that early diagenesis of precursor sediments without strong primary differences can result in a differentiation by selective dissolution of aragonite in marl beds and reprecipitation of calcite cement in limestone beds. This model is described as a set of mathematical equations that quantify the diagenetic processes (aragonite dissolution and calcite reprecipitation) that occur during the formation of limestone-marl interbeds from a hypothetical homogeneous precursor sediment. The calculations demonstrate that resulting hypothetical limestone-marl alternations show characteristic mathematical relationships between the ratios of the bed thicknesses of limestones and marls on one side, and the carbonate contents, on the other. By reversing this model, the original mineralogical composition of the precursor sediment of real-world rhythmic successions can be determined. In this study, alternations from the Silurian of Gotland, the Cambrian, Devonian, and Mississippian of North America, the Jurassic of France and Germany, and the Cretaceous of France are shown to exhibit mathematical relationships similar to those calculated for hypothetical precursor sediments without primary differences. Therefore, the mineralogical composition of their precursor sediments can be estimated. In contrast, the clear mismatch shown by the Lower Jurassic Belemnite Marls from Dorset indicates that these rhythms did not suffer an early diagenetic overprint. Our model helps to differentiate between rhythmites with strong depositional variations and those without; however, it cannot indicate whether a given alternation is the product of rhythmic diagenesis of a homogeneous precursor sediment or the result of diagenetic enhancement of subtle underlying sedimentary rhythms. For horizontally correlated patterns, such as laterally extensive beds and layers of nodules, an a priori unknown external signal has to be assumed.     

Formation and Modification of the Shallow Sub-continental Lithospheric Mantle: a Review of Geochemical Evidence from Ultramafic Xenolith Suites and Tectonically Emplaced Ultramafic Massifs of Western and Central Europe

The petrology and geochemistry of shallow continental lithosphericmantle (SCLM) can be studied via (1) tectonically emplaced ultramaficmassifs and (2) mantle xenoliths entrained in alkaline magmas.Data from these two separate sources are used to identify processesthat have formed and modified the SCLM. In western and centralEurope where the continental crust consolidated in Phanerozoictimes, both sources of information are available for study.Rock types found in ultramafic massifs in Europe are generallysimilar to those found in ultramafic xenolith suites. The mostfrequent lithology is anhydrous spinel lherzolite, grading towardsharzburgite. Massifs reveal pyroxenite layering, harzburgitebands and cross-cutting mafic and ultramafic dykes. The PhanerozoicEuropean SCLM xenoliths and massifs show broad mineralogicaland chemical similarities to Phanerozoic continental spinelperidotites world-wide. The main process that controls the geochemistryof the SCLM is depletion by removal of basaltic melt. Differencesfrom this norm reflect significantly different processes inthe SCLM, such as interaction with melts and fluids. Such processesprobably gave rise to hornblendite veins and pyroxenite layers,although the latter have also been interpreted as recycled oceaniccrust. Rare earth element data for whole-rock peridotites andtheir constituent clinopyroxenes show a variety of patterns,including light rare earth element (LREE) depletion as a resultof removal of basaltic melt, LREE enrichment caused by metasomatism,and U-shaped REE patterns that are probably due to interactionwith carbonatite melts. Extended mantle-normalized incompatibletrace element patterns for whole rocks show enrichment in Rband Ba in peridotites considered to have been subduction-metasomatized,whereas those considered to be carbonate-metasomatized havestrong negative anomalies in Zr, Nb and Hf. Mantle amphibolesare strongly enriched in LREE when found in veins, but can beLREE depleted if they are interstitial. Radiogenic isotope ratiosfor xenoliths and massifs largely overlap, although the xenolithsshow a significant clustering around a ‘plume-component’identical to the Neogene alkaline magmatism of Europe. Thiscomponent is lacking in the massifs, most of which were emplacedinto the crust before the onset of Neogene plume activity. Infiltrationof carbonatite melts is observed petrographically in some xenolithsand evidenced by low Ti/Eu ratios in bulk rocks, but is veryrare. The effect of passage of hydrous fluids from subductingslabs is also seen in some suites and massifs, being exhibitedmainly as unusual Sr and Pb isotope ratios, although enrichmentin K, Rb and Ba, and the presence of modal phlogopite, may alsopoint to subduction-metasomatism. KEY WORDS: peridotites; xenoliths; orogenic massifs; Europe     

Magmatic Evolution of the La Pacana Caldera System, Central Andes, Chile: Compositional Variation of Two Cogenetic, Large-Volume Felsic Ignimbrites

La Pacana is one of the largest known calderas on Earth, andis the source of at least two major ignimbrite eruptions witha combined volume of some 2700 km³. These ignimbrites have stronglycontrasting compositions, raising the question of whether theyare genetically related. The Toconao ignimbrite is crystal poor,and contains rhyolitic (76–77 wt % SiO₂) tube pumices.The overlying Atana ignimbrite is a homogeneous tuff whose pumiceis dacitic (66–70 wt % SiO₂), dense (40–60% vesicularity)and crystal rich (30–40 % crystals). Phase equilibriaindicate that the Atana magma equilibrated at temperatures of770–790°C with melt water contents of 3·1–4·4wt %. The pre-eruptive Toconao magma was cooler (730–750°C)and its melt more water rich (6·3–6·8 wt% H₂O). A pressure of 200 MPa is inferred from mineral barometryfor the Atana magma chamber. Isotope compositions are variablebut overlapping for both units (⁸⁷Sr/⁸⁶Sr_i 0·7094–0·7131;¹⁴³Nd/¹⁴⁴Nd 0·51222–0·51230) and are consistentwith a dominantly crustal origin. Glass analyses from Atanapumices are similar in composition to those in Toconao tubepumices, demonstrating that the Toconao magma could representa differentiated melt of the Atana magma. Fractional crystallizationmodelling suggests that the Toconao magma can be produced by30% crystallization of the observed Atana mineral phases. Toconaomelt characteristics and intensive parameters are consistentwith a volatile oversaturation-driven eruption. However, thelow H₂O content, high viscosity and high crystal content ofthe Atana magma imply an external eruption trigger. KEY WORDS: Central Andes; crystal-rich dacite; eruption trigger; high-silica rhyolite; zoned magma chamber     

Kulkeite,a new metamorphic phyllosilicate mineral: Ordered 1∶1 chlorite/talc mixed-layer

Kulkeite occurs as platy, colorless, porphyroblastic, single crystals up to 2 mm in size in a low-grade dolomite rock associated with a Triassic meta-evaporite series at Derrag, Tell Atlas, Algeria, It is associated with sodian aluminian talc, unusual chlorite polytypes, and both K and Na phlogopite. Kulkeite is optically biaxial, negative, n _x=1.552, n _y=1.5605, n _z=1.5610, 2V_z=24° (obs.). Based on microprobe analysis the empirical formula is (Na_0.38K_0.01Ca_0.01)(Mg_8.02Al_0.99)[Al_1.43Si_6.57O₂₀](OH)₁₀ with some variation in Na, Si, and tetrahedral Al. The crystals are monoclinic with a=5.319(1), b=9.195(2), c=23.897(10) Å, β=97° 1(3)′; Z=2; the calculated density is 2.70 g cm^?3. The four strongest lines in the X-ray powder pattern are (d, I, hkl): 7.90, 100, 003; 1.533, 100, 060; 7.42, 80, 002; 3.38, 80, 007; the 001 reflection with 23.7 Å has intensity 10. Transmission electron microscopy confirms the nature of a regular 1∶1 mixed-layer, which consists of 14 Å chlorite (clinochlore) sheets alternating with sheets of one-layer (9.5 Å) talc characterized by the lattice substitution NaAl→Si just as in the talc occurring as a discrete mineral co-existing with kulkeite. Kulkeite is intergrown with lamellae of clinochlore that represent two-layer and five-layer (70 Å) polytypes with optical birefringence exceeding the normal value for clinochlore by a factor of 3. The origin of kulkeite is due to low-grade metamorphism with temperatures probably not exceeding 400° C. As the clinochlore lamellae and sodian aluminian talc are found in mutual contact, kulkeite seems to represent a metastable mineral at least during the latest phase of metamorphism. However, at an earlier stage, prior to clinochlore formation, kulkeite might have been stable, and the incorporation of Na and Al into its talc component could indeed be the decisive factor for the formation of the mixed-layer.