Regional geochemical variations in a metamorphosed black shale: a reconnaissance study of the Silurian Smalls Falls Formation, Maine, USA

Abstract

A reconnaissance geochemical study of 21 samples of sulphidic black phyllite and schist from the Silurian Smalls Falls Formation in Maine was undertaken in order to evaluate compositional changes during regional metamorphism. These samples represent variably metamorphosed black shale. Analyzed samples come from the chlorite zone in northern Maine and the biotite, garnet, and staurolite-andalusite zones in west-central Maine. Strata of the Smalls Falls Formation are distinctive in containing abundant pyrite and/or pyrrhotite (total S = 1.2–9.7 wt%), but only minor organic matter or graphite (TOC = 0.43–1.85 wt%); TOC/S ratios are uniformly low (average = 0.37 ± 0.22). Median enrichment factors were calculated for each element by normalizing the concentration to Ti in each sample to the Ti-normalized median composition of global black shale. In the chlorite zone, moderate to large decreases in enrichment factors (-23.1 to -49.8%) are evident for V, Cr, Cu, Ni, Zn, Pb, Sb, and U, attributed here to various factors during sedimentation plus variable element mobility during diagenesis. With increasing metamorphic grade (biotite through staurolite-andalusite zones), systematic small to extreme decreases (-14.5 to -99.0%) were found for Ba, Sb, Au, and U, together with less-systematic moderate to large decreases (-35.4 to -61.1%) for V and As. Molybdenum shows an extreme decrease (-94.7%) from the garnet to staurolite-andalusite zones. Excluding Ba, these results are interpreted to mainly reflect mobility of trace elements during pyrite recrystallization, and during the metamorphic transformations of organic matter to graphite and of pyrite to pyrrhotite. Moderate to large increases for Rb (+28.1 to +61.5%) and Th (+39.1 to +47.3%) from the biotite to staurolite-andalusite zones likely record the introduction of alkalis and mass loss, respectively, during metamorphism. Three samples from one site in the garnet zone differ in having anomalously high Fe/Al and low La/Yb ratios, attributed here to epigenetic formation of pyrite and related leaching of light rare earth elements during syn-metamorphic, channelized fluid flow.
Geologic and geochemical data indicate that strata of the Smalls Falls Formation were deposited during an interval of anoxia on the northwestern flank of the Central Maine Basin, for which detrital sources included an evolved continental arc. Onset of anoxia coincided with deposition of the Mayflower Hill Formation of the Vassalboro Group, on the basin’s southeastern flank, related to emergence of the Brunswick subduction complex. We suggest that this emergence played a role in promoting both lateral and vertical circulation changes, nutrient loading, and deoxygenation through subsequent basin closure that culminated with Acadian deformation and metamorphism. Based on the relatively high contents of total sulphur present in our Smalls Falls samples, sediments in the Black Sea represent the only known plausible candidate among those in modern suboxic to euxinic basins.