Submarine metalliferous carbonate mounds in the Cambrian of the Baltoscandian Basin induced by vent networks and water column stratification.

Two massive precipitation events of polymetallic ore deposits, encrusted by a mixture of authigenic carbonates, are documented from the Cambrian of the semi-enclosed Baltoscandian Basin. δ34S (‒9.33 to ‒2.08‰) and δ33S (‒4.75 to ‒1.06‰) values from the basal sulphide breccias, sourced from contemporaneous Pb-Zn-Fe-bearing vein stockworks, reflect sulphide derived from both microbial and abiotic sulphate reduction. Submarine metalliferous deposits were triggered by non-buoyant hydrothermal plumes: plumes of buoyant fluid were trapped by water column stratification because their buoyancy with respect to the environment reversed, fluids became heavier than their surroundings and gravitational forces brought them to a halt, spreading out laterally from originating vents and resulting in the lateral dispersion of effluents and sulphide particle settling. Subsequently, polymetallic exhalites were sealed by carbonate crusts displaying three generations of ikaite-to-aragonite palisade crystals, now recrystallized to calcite and subsidiary vaterite. Th of fluid inclusions in early calcite crystals, ranging from 65 to 78 ºC, provide minimum entrapment temperatures for carbonate precipitation and early recrystallization. δ13Ccarb (‒1.1 to + 1.6‰) and δ18Ocarb (‒7.6 to ‒6.5‰) values are higher than those preserved in contemporaneous glendonite concretions (‒8.5 to ‒4.7‰ and ‒12.4 to ‒9.1‰, respectively) embedded in kerogenous shales, the latter related to thermal degradation of organic matter. Hydrothermal discharges graded from highly reduced, acidic, metalliferous, and hot (~ 150 ºC) to slightly alkaline, calcium-rich and warm (< 100 ºC), controlling the precipitation of authigenic carbonates.

Glendonite occurrences in the Tremadocian of Baltica: first Early Palaeozoic evidence of massive ikaite precipitation at temperate latitudes.

The Tremadocian (Early Ordovician) is currently considered a time span of greenhouse conditions with tropical water surface temperature estimates, interpolated from oxygen isotopes, approaching 40 °C. In the mid-latitude Baltoscandian Basin, conodonts displaying low δ18O values, which suggest high temperatures (>40 °C) in the water column, are in contrast with the discovery of contemporaneous glendonite clusters, a pseudomorph of ikaite (CaCO3·6H2O) traditionally considered as indicator of near-freezing bottom-water conditions. The massive precipitation of this temperature sensitive mineral is associated with transgressive conditions and high organic productivity. As a result, the lower Tremadocian sediments of Baltoscandia apparently contain both "greenhouse" pelagic signals and near-freezing substrate indicators. This paradox points to other primary controlling mechanisms for ikaite precipitation in kerogenous substrates, such as carbonate alkalinity, pH and Mg/Ca ratios, as recently constrained by laboratory experiments. Preservation of "hot" conodonts embedded in kerogenous shales rich in δ18O-depleted glendonites suggests both the onset of sharp thermal stratification patterns in a semi-closed basin and the assumed influence of isotopically depleted freshwater yielded by fluvial systems.