ORIGIN OF BITUMEN

The origin of bitumen excavated from archaeological sites in Hokkaido, the northernmost
island in Japan, was sought by means of field-ionization mass spectrometry (FI-MS) and
gas chromatography - mass spectrometry (GC-MS) of the hydrocarbon components. The
field-ionization mass spectra were decomposed by Z-numbers into several components,
where the Z-number refers to z in the formula CnH2n+z. This is equivalent to the deficit
number of H atoms, when compared to the corresponding saturated hydrocarbon, which
is related to the number of saturated hydrocarbon rings in alkanes. By use of the spectral
intensities of the seven alkane components in each sample, multiple discriminant analysis
was employed for the data of raw bitumen samples and excavated samples from
archaeological sites. Based on this method and the gas chromatogram type, the following
bitumen trade in the prehistoric age of Japan was elucidated: bitumen from Niigata, one
of the main sources on the main island of Japan, spread to the north in 2000 BC, probably
via the coastal zone, and reached a small island near the north end of Hokkaido. Bitumen
from Sakhalin reached the central lowland in Hokkaido, but it went no further. Bitumen
from Akita, another main source on the main island, spread over northern Honshu much
earlier and reached the Oshima peninsula, the southwestern part of Hokkaido. The Akita
bitumen scattered into the central lowland after the Niigata and Sakhalin bitumen. This
area is believed to be the place where people from the south and the north met in those
perTwo ring-like artefacts from the aceramic Neolithic site of Demirköy Höyük in
southeastern Turkey were analysed using geochemical techniques in order to determine
whether they were prepared using a bitumen amalgam or not. The artefacts, dated 8100
BC, are early evidence of the innovative use of a petroleum-based material to prepare
pieces of ornaments (beads, rings, etc.) for the elite of a Neolithic settlement. In order to
trace the source of the presumed bitumen, two oil seeps, Boğazköy and Yeşilli, were
sampled. To complete the genetic references, geochemical data on crude oils from the
main oil fields from the area were compiled.Basic geochemical data show that bitumen is
present in the artefacts. Sterane and terpane patterns, as well as carbon isotopic data on
C15+ saturated and C15+ aromatic hydrocarbons, allowed us to conclude that the Demirköy
Höyük bitumen and the Boğazköy oil seep were generated from a Silurian source rock.
The detailed geochemical characteristics show,