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.     

Generalized ‘dependencies’ and parameter variance

The autodependence, (a special case of the — now quite obsolete — dependences, which had been introduced for very specialized astrometric purposes) is proportional to the parameter variance which is the expectation of the variance of the systematic error of a function evaluated with estimated parameters.     

Chemical exchange during hydrothermal alteration of basalt by seawater—I. Experimental results for major and minor components of seawater

Fresh mid-ocean ridge basalt of varying crystallinity has been powdered and reacted with seawater and an artificial Na-K-Ca-Cl solution at 200–500°C and 500–1000 bar in sealed gold capsules. Water/rock mass ratios of 1–3 were used and durations ranged from 2 to 20 months.These time periods were sufficient for most elements to approach a steady-state concentration in solution which was determined by equilibrium with alteration minerals (Mg, SiO₂, SO₄), by rate of formation of these minerals (Na, Ca), or by depletion from the rock (K, B, Ba). The resulting solutions closely resemble the brines from the basalt-seawater geothermal system at Reykjanes, Iceland. Mg was almost completely removed from seawater into the alteration products smectite, tremolite-actinolite, or talc. Sulfate also was removed to low concentrations, both by precipitation of anyhydrite and by reduction to sulfide. Net transfer of Na from seawater into solids occurred in most experiments by formation of sodic feldspar and possibly analcime. Sr was removed from seawater in some experiments but showed no change or a small gain in others. SiO₂, Ca, K, Ba, B and CO₂ were leached from basalt and enriched in solution. SiO₂ concentrations were controlled by saturation with quartz at 300°C and above. The principal Ca-bearing phases which formed were anhydrite, the hydrated Ca-silicate truscottite, tremolite-actinolite, and possibly wairakite. No K-rich phases formed. For some minerals the crystallinity of the starting basalt affected the amount which formed.Removal of Mg from seawater into solid alteration products occurred rapidly and was balanced largely by leaching of Ca from basalt. Net transfer of Na from seawater into solids occurred more slowly and was balanced mainly by leaching of additional Ca from basalt. Thus, reaction between seawater and basalt at low water/rock ratios can be considered to consist of two exchanges: Mg for Ca, and Na for Ca.     

α-Emitting mineral inclusions in apatite, their effect on (U-Th)/He ages, and how to reduce it

U-Th rich mineral inclusions in apatite are often held responsible for erroneously old (U-Th)/He ages, because they produce “parentless” He. Three aspects associated with this problem are discussed here. First, simple dimensional considerations indicate that for small mineral inclusions, the parentless helium problem might not be as serious as generally thought. For example, a mineral inclusion that is 10% the length, width and height of its host apatite needs to be a thousand times more concentrated in U and Th to produce an equal amount of He. Therefore, single isolated inclusions smaller than a few μm are unlikely to contribute significant helium. For larger or more abundant inclusions, the parentless helium problem can be solved by dissolution of the apatite and its inclusions in hot HF. Second, besides creating parentless helium, inclusions also complicate α-ejection corrections. Mathematical exploration of this latter problem for spherical geometries reveals that for randomly distributed inclusions, the probability distribution of single-grain ages is predicted to have a sharp mode at the mean age, with tails towards younger and older ages. Multiple-grain measurements will yield accurate and precise age estimates if 10 or more randomly distributed α-emitting mineral inclusions are present in a sample. Third, thermal modeling indicates that mineral inclusions have a non-trivial but minor (<5 °C) effect on the closure temperature. These predictions were tested on apatites from rapidly cooled migmatites of Naxos (Greece) which contain abundant U-rich zircon inclusions. Thirty-seven samples were subjected to two kinds of treatment. The “pooled” age (i.e., the synthetic multi-grain age computed from a number of single-grain analyses) of four inclusion-free samples (13 apatites), prepared in HNO₃ is 10.9 Ma, close to apatite and zircon fission-track ages from the same rock. (U-Th)/He ages of 14 inclusion-bearing samples dissolved in HNO₃ range between 9 and 45 Ma, with a pooled age of 22.6 Ma. The ages of 19 HF-treated samples range between 5 and 16 Ma, with 10 of 14 single-grain samples between 9 and 13 Ma and a pooled age of 10.9 Ma. These observations agree with the theoretical predictions and support the addition of HF-treated apatite (U-Th)/He dating to the thermochronological toolbox.     

Über Verformung von Klüften bei der Schichtenfaltung am Beispiel des Salzgitterer Sattels

Zusammenfassung Bei kleintektonischen Messungen am Salzgitterer Sattel wurden an der Zerstückelung von Klüften die in gefalteten Schichten üblichen Vorschiebungen festgestellt, bei denen die muldenwärtigen Gesteinsbänke an den sattelwärtigen emporbewegt sind. Daneben wurden in überkippten Schichten entgegengesetzte Bewegungen, gleichsam Überschiebungen an Schichtfugen, beobachtet.Weiter wurde in normal einfallenden Schichten eine gesetzmäßige Schrägstellung von Klüften zur Schichtung erkannt, die in ihrer Wirkung und in ihrer Abhängigkeit vom Grade der Schichtaufrichtung den makroskopischen Vorschiebungen entspricht und deshalb durch gleiche Vorgänge kleinster Größenordnung gedeutet wurde. Ebenso treten in überkippten Schichten Verdrehungen der Klüfte auf, die in ihrer Wirkung den Überschiebungen an Schichtfugen entsprechen.Sichtbare Verschiebungen und Verdrehungen gehen nebeneinander her. Die Verdrehungen erfordern eine gewisse Plastizität des Gesteins bei der Faltung. Welcher Vorgang überwiegt, dürfte daher im wesentlichen von der Art des beanspruchten Materials abhängen; Untersuchungen hierüber müßten sich über ein größeres Gebiet erstrecken.Erweiterter Ausschnitt aus der Anfang 1938 in Berlin eingereichten, unveröffentlichten Dissertation Kimmerische und subherzynische Gebirgsbildung im Salzgitterer Erzgebiet.     

Synthesis of monticellite–forsterite and merwinite–forsterite symplectites in the CaO–MgO–SiO<Subscript>2</Subscript> model system: influence of temperature and water content on microstructure evolution

Homogeneous single crystals of synthetic monticellite with the composition \({\text{Ca}}_{0.88}{\text{Mg}}_{1.12}{\text{SiO}}_4\) (Mtc I) were annealed in a piston-cylinder apparatus at temperatures between 1000 and \(1200\,^{\circ }\hbox {C}\), pressures of 1.0–1.4 GPa, for run durations from 10 min to 24 h and applying bulk water contents ranging from 0.0 to 0.5 wt% of the total charge. At these conditions, Mtc I breaks down to a fine-grained, symplectic intergrowth. Thereby, two types of symplectites are produced: a first symplectite type (Sy I) is represented by an aggregate of rod-shaped forsterite immersed in a matrix of monticellite with end-member composition (Mtc II), and a second symplectite type (Sy II) takes the form of a lamellar merwinite–forsterite intergrowth. Both symplectites may form simultaneously, where the formation of Sy I is favoured by the presence of water. Sy I is metastable with respect to Sy II and is successively replaced by the latter. For both symplectite types, the characteristic spacing of the symplectite phases is independent of run duration and is only weeakly influenced by the water content, but it is strongly temperature dependent. It varies from about 400 nm at \(1000\,^{\circ }\hbox {C}\) to 1200 nm at \(1100\,^{\circ }\hbox {C}\) in Sy I, and from 300 nm at \(1000\,^{\circ }\hbox {C}\) to 700 nm at \(1200\,^{\circ }\hbox {C}\) in Sy II. A thermodynamic analysis reveals that the temperature dependence of the characteristic spacing of the symplectite phases is due to a relatively high activation energy for chemical segregation by diffusion within the reaction front as compared to the activation energy for interface reactions at the reaction front. The temperature dependence of the characteristic lamellar spacing and the temperature-time dependence of overall reaction progress have potential for applications in geo-thermometry and geo-speedometry.