M. Cusack et A. Williams, CHEMICO-STRUCTURAL DEGRADATION OF CARBONIFEROUS LINGULID SHELLS, Philosophical transactions-Royal Society of London. Biological sciences, 351(1335), 1996, pp. 33-49
Shells of Lingula squamiformis from argillaceous sediments at three ho
rizons within the Dinantian Series, exposed at three localities in Sco
tland, have been studied to determine chemico-structural changes resul
ting from fossilization. Biomineral structures are essentially the sam
e as those of living Lingula anatina with apatitic granules aggregatin
g into spherules, up to 60 nm in size, and larger spheroidal bodies as
well as rods and rarer lath-like plates. These aggregates and the ori
ginal organic constituents were secreted as stratiform successions in
two distinct layers, as in Recent L. anatina. The outer, lithified par
t of the primary layer bears microstructural moulds of a totally degra
ded periostracum and was probably composed mainly of acidic glycosamin
oglycans (GAGs); the inner part evidently contained a higher proportio
n of spherular apatite within the GAGs than in living species. The sec
ondary layer consists of variably complete rhythmic sets of compact, r
od and plate (virgose), and membranous laminae. Compact laminae are no
rmally cleaved along degraded walls of GAGs whereas the original GAGs-
filled spaces of virgose laminae are partly occupied by recrystallized
apatitic sheets with kaolinite. The phosphatized membranous laminae p
robably contained more spherular apatite in life than present day Ling
ula. The shell is canaliculate with chambers and galleries well develo
ped in the virgose laminae. There is a decrease in concentration of am
ino acids from the posterior to the anterior of the valves of living L
ingula anatina and Glottidia pyramidata resulting from the proteinaceo
us coat of the apatitic spherules. A similar distribution of hydroxypr
oline occurs, indicative of collagen in the body platform of living li
ngulids. Nearly all organic constituents have been degraded in the Car
boniferous valves but threads, about 50 nm thick, occasionally travers
e spaces in virgose laminae and even form a network coated with spheru
lar apatite, which resembles webs of collagens or actin found in livin
g lingulids. Acidic and aliphatic amino acids were extracted from L. s
quamiformis valves from Calderwood and Kinghorn whereas the narrower r
ange of amino acids from the heavily pyritized valves from Ardross con
firmed differential degradation of organic material during the fossili
zation of penecontemporaneous samples. The fossilization of complete s
hells of L. squamiformis is not due exclusively to catastrophic burial
as has been deemed necessary to preserve Recent Lingula intact. The l
iving shells of Carboniferous species were more apatitic than those of
Recent Lingula, especially in the anteriomedian sectors of the second
ary layers.