Organic chemical signatures of New Zealand carbonate concretions and calcite fracture fills as potential fluid migration indicators

Abstract

Macroscopic calcite crystals are common in sedimenta¬ry strata, occurring both as tectonic veins and also filling one or more generations of septarian rupture or later brittle fractures in calcareous concretions. Traces of hydrocarbons are frequently present in calcite crystals, especially near active petroleum systems, and are routinely the object of fluid inclusion studies linking source and migration pathway. Such calcites are shown here also to contain fatty acids in widely varying amounts ranging from 0.2 to more than 5 μg/g. Vein calcites examined are typically near the lower figure, close to analytical blank levels, and this is also true of some concretionary fracture fill calcites, notably those from the Palaeocene Moeraki ‘boulders’. Other concretionary fracture fill calcites (Jurassic, Scotland; Eocene, Waikato Coal Measures and associated marine strata) have much higher fatty acid contents, especially those filling later brittle style fractures. Although usually less abundant than the fatty acids in the concretions themselves, they lack the long chain n-acids derived from terrestrial vegetation and are commonly dominated by dioic acids. Exceptionally, in the calcitic septarian fill of a sideritic Coal Measures concretion, their abundance far exceeds that of concretion body fatty acids. They appear to be fluid transported, probably in aqueous solution, and have molecular signatures potentially distinctive of maturing organic matter sources from which the fluids derived.