K. Marumo et al., STABLE-ISOTOPE GEOCHEMISTRY OF CLAY-MINERALS FROM FOSSIL AND ACTIVE HYDROTHERMAL SYSTEMS, SOUTHWESTERN HOKKAIDO, JAPAN, Geochimica et cosmochimica acta, 59(12), 1995, pp. 2545-2559
Miocene submarine to Quaternary terrestrial volcanism in southwestern
Hokkaido, Japan, is associated with hydrothermal clay alteration and m
ineralization, including Kuroko-type deposits at Kagenosawa (14.2 Ma,
Cu > Zn, Pb > Au) and Minamishiraoi (12.5 Ma, Ba > Zn, Pb, Cu), vein-s
tyle mineralization at Date (5.2 Ma, Au-Ag-Cu-Pb-Zn) and Chitose (3.6
Ma, Au-Ag), and geothermal activity at Noboribetsu (less than or equal
to 1.8 Ma). The delta D and delta(18)O values of mica (sericite), mic
a-smectite, chlorite, chlorite-smectite, nacrite, dickite, kaolinite,
and smectite were used to deduce the type(s) of hydrothermal fluid at
each locality. Calculated compositions for Minamishiraoi and Kagenosaw
a fluids suggest that seawater was dominant, but some mixing with magm
atic water is also indicated, particularly for the polymetallic Kageno
sawa deposit. Hydrothermal fluids at Date, Chitose, and the Noboribets
u geothermal area were dominated by meteoric water. Minor involvement
of magmatic water during mineralization at Date cannot be ruled out, b
ut evolution of local meteoric water along an evaporation trend and/or
an O-18-shift due to hydrothermal rock-meteoric water interaction als
o could have produced appropriate fluid compositions. The delta D and
delta(18)O values of modern hot-spring waters at Noboribetsu closely p
arallel fluid compositions calculated for the clay alteration at Date,
Chitose, and Noboribetsu. Because relatively poor reproducibility was
obtained for the delta S values of the swelling clays, additional tes
ts were conducted. Stepwise heating showed that, for some smectitic cl
ays, water evolved between 200 and 300 degrees C had anomalously high
delta D values because of residual interlayer water. This error can be
minimized by sufficiently long preheating (in vacuo) at less than or
equal to 200 degrees C. In vacuo TG patterns of other smectitic clays
suggested gradual loss of hydroxyl-groups beginning near 200 degrees C
, rather than the more typical distinct separation between interlayer
water at <200 degrees C and hydroxyl-groups at >400 degrees C. This be
haviour constrains the maximum temperature that can be used for in vac
uo preheating. Furthermore, shifts to lower delta D values (by as much
as 19 parts per thousand) were obtained when this smectite was disper
sed in low-D water for three weeks, perhaps indicating isotopic exchan
ge. However, with appropriate care, delta D values obtained by convent
ional procedures (including preheating to less than or equal to 200 de
grees C) normally reproduced natural compositions of the smectitic cla
ys with acceptable accuracy and precision.