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TRANSCRIPT
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HIG 79 9
CHLORIDE MAGNESIUM
RATIO
OF SHALLOW GROUNDWATERS
AS A
REGIONAL GEOTHERMAL INDICATOR
IN HAWAII
MALCOLM E COX
nd
DONALD
M.
THOMAS
Assessment
of Geothermal
Resources
in Hawaii:
Number 3
1
f
NOVEMBER 1979
Prepared for
WESTERN
STATES
COOPERATIVE
DIRECT
HEAT
RESOURCES ASSESSMENT
under rant no
DO
E I 1 713 4
H W II
INSTITUTE
OF
GEOPHYSICS
UNIVERSITY OF HAWAII
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HIG 79 9
CHLORIDE MAGNESIUM RATIO
OF SH LLOW
GROUNDW TERS
S A REGIONAL GEOTHERM L INDICATOR
IN
HAWAII
Malcolm
E Cox
and
Donald M
Thomas
Assessment
o f
Geot he rma l Re sou rc es
in
Hawai i :
Number
November
1979
Prepared fo r
Western
S ta t e s
ooperat ive
Direc t
Heat Resou rc e A ss es smen t
under
gran t
no
DOE/ID/017l3 4
har les
E Hels ley
Di rec to r
Hawaii I n s t i t u t e of
Geophysics
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STR CT
Because of
th e
complex
geo log i c a l and hyd ro log i c a l
cond i t ions
and
th e
v i r t u a l
l ack
of
t h e rma l
s p r i ng s r e g i on a l
geothe rmal
i nve s t i g a t i on s in Hawai i r equ i r e th e
use
o f
t echn iques
s u b s t an t ia l l y d i ff er en t from
those conven t iona l ly
app l i ed in
o the r
g eo th e rma l e n vi ro nment s. The l a r ge number
of
h y dr ol og ic al w e lls
in th e
s t a t e prov ides an app re c i ab l e
sou rce of gro undw ater ch em ica l da t a .
However
l a rge ly
because
of
th e i s l and
env i ronment i n t e r p r e t a t i o n
of
much of
th e se d a ta
as
geo thermal i nd i ca t o r s becomes ambiguous .
I n i t i a l l y Si02 and
t empera tu re
o f g ro un dw ate rs were used
to i d en t i fy
t h e rma l l y
anomalous zones bu t on
a
r eg iona l
ba s i s
has been found
t h a t t h e se
c r i t e r i a
a re
no t a lways
s u c c e s s f u l .
s a f u r t h e r c r i t e r i o n fo r as ses smen t th e Cl/Mg
r a t i o
of
th e
groundwate r
has been
used .
On a
s t a t e -w ide
ba s i s t h i s
r a t i o
has been succes s fu l
in
f u r t h e r
s c reen ing
th e
Si02 - t empera tu re
s e l ec t ed
s i t e s and
in
de f i n i ng more
s pe c i f i c a rea s
which
war ran t fu r t he r
i n v e s t i g a t i o n .
Tempera tu re
Si02
and Cl/Mg va lues
fo r
nea r ly 400 groundwate r
samples a re
i nc luded .
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TABLE OF CONTENTS
ABSTRACT
LIST OF TABLES
LIST OF FIGURES
INTRODUCTION
OCCURRENCE
OF
GROUNDW TER
IN
HAWAII
Dike impounded
Sedimenta ry and a l l u v i a l
asa l
SILICA TEMPERATURE CRITERIA
S i l i c a
Tempera ture
CHLORIDE/MAGNESIUM RATIOS
Genera l
Theory
hlor ide
Magnesium
COMPARISONS
OF
Cl Mg
RATIOS
IN
OTHER
THERM L W TERS
APPLICATION OF
Cl Mg IN
HAWAII
Kauai
Molokai
Oahu
Maui
Hawai i
CONCLUSIONS
KNOWLEDGMENTS
REFERENCES
APPENDIX
v i i
ix
1
2
2
2
3
5
8
8
9
9
11
12
16
18
18
23
23
23
30
30
31
35
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LIST TABLES
Table
Comparison of d i f f e r e n t
a n a l y s e s
2 Averaged va lues of
known
thermal
and o the r
waters
6
1
3
Chemical da ta of va r ious geo thermal waters 13
Appendix
Table
Kauai
37
Mo1okai
39
Oahu 4
Maui
44
Hawaii
48
v i i
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LIST O
FIGUR S
Figure
1
Log log p lo t of
Cl versus g fo r
a va r i e t y
of
geothe rmal
wate r s from d i f f e r e n t
envi ronments
15
2 Charac t e r i s t i c s
of
I Mg
r a t i o s
fo r d i f f e r e n t
wa
t
e r types in Hawai i
17
3
Tr i ang l e diagram
of
Cl
and g
concen t r a tons
from Kauai 19
4 Locat ion
of
groundwater wel l s on Kauai 20
5
Tr i ang l e
diagram
of
Cl
and
g
concen t r a t i on s
from
Molokai 21
6 Locat ion o f gro und water wel l s on
Molokai 22
7 Tr i ang l e diagram
of
Cl
and
g concen t r a t i on s
from
Oahu
24
8 Locat ion of g ro und water wel l s on Oahu 25
9 Tr i ang l e
diagram of
Cl
and g concen t r a t i on s
from
Maui
26
1 Locat ion of
groundwate r
wel l s on Maui
27
11 Tr i ang l e
diagram
of Cl
and
g concen t ra t ions
from Hawai i 28
12 Locat ion of groundwater wel l s
on Hawai i 29
ix
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INTRODU TION
Geothermal i nve s t i g a t i on s conducted dur ing
th e 1973-
1977
Hawai i
Geothermal Pro j e c t ,
which
led
to the
succes s fu l
d r i l l i ng
s i t e
of geo therm al
wel l
HGP-A,
were
l a rge ly
r e s t r i c t ed to
s eve r a l
spec i f i c
a r ea s .
To gain a more comple te
unders tand ing
of
th e
geo thermal po t en t i a l
in
Hawai i ,
the
cu r r en t
geo thermal
i nve s t i g a t i on Hawaii Geo th erma l Resource
Assessment Program
i s
conduct ing
a sys t ema t i c s tudy
of th e
Hawaiian I s l ands on a s t a t e -w ide ba s i s .
The i n i t i a l phase of the r eg iona l
survey
has been th e
compi la t ion and assessment of a l l ava i l ab le groundwater
chemis t ry
wi th in th e
s t a t e .
T his app ro ach to
geo thermal
exp lo ra t ion in Haw aii has
l a rgeLy
been o f nece s s i t y . Thermal
sp r ings
occur only in
a
sma l l
number
o f
c oa sta l lo ca tio ns
because
of
th e b a sa lt ic t e rr a in and the
complex
hyd ro log i c a l
cond i t ions
in t h i s i s l and env i ronment . Consequent ly many of
th e r ec on na is sa nc e
i nve s t i g a t i on
t echn iques
employed
in
con t i nen t a l , or o lde r env i ronments ,
a re
u nsu ita ble in Hawai i .
The use
o f ex i s t i ng
groundwater chemis t ry da ta has
prov ided
an
exce l l en t
f i r s t s t age reconnai s sance too l
because
o f th e
l a rge
number
of groundwater wel l s
d r i l l ed
in
Hawai i . Most
chemica l ana lyses used in t h i s
r epo r t
a re
from
th e
f i l e s of
the
Honolulu of f i c e of th e
U
S.
Geolog ica l
Survey.
w
bas ic
c r i t e r i a
were i n i t i a l l y es t ab l i s hed to asse ss
the
water
chemis t ry
da ta :
t empera tu re
and Si02 concen t r a t i on s .
Tempera tures of g rea t e r than 26C o r Si02 concen t r a t i on s
g rea t e r than 55
ppm
fo r Oahu and 30
ppm
fo r th e o the r i s l ands
H .G.R.A.P ., 1978; Thomas e t
al
1979 were
cons idered
to
be an om alo us.
S tud ies in the
Puna
a rea
on th e
i s l and
of
Hawai i
McMurtry
e t al
1977 showed t h a t th e Si02 con t en t
o f g rou nd water in t h i s ac t ive
area
was i nd i ca t i v e o f zones of
high subsu rface tem pera tu re . F ur the r app l i ca t ion of t he se
c r i t e r i a fo r use on a r eg iona l bas i s has shown
t h a t many
va r i ab l e s
ex i s t
which
lead to ambigu i t i e s
in
i n t e rp r e t a t i on ,
t h e r e fo r e ano ther geochemica l parameter was sought in
an
a t t empt
to c l a r i f y o r r e i n fo rce
the
S i02 - t empera tu re
c r i t e r i a .
Examinat ion
of
th e chemical
ana lyses
ava i l ab le showed
t ha t
under
Hawaiian
cond i t i on s ,
d i f f i c u l t i e s
a r i s e
in
using
the major i ty
of
e l emen t s ,
o r
r a t i o s of e lements , as
geo thermal
i nd i c a to r s .
The Cl/Mg
r a t i o
appeared
to
be
the
most success fu l
i nd i ca t o r fo r the
type of water being
s tud ied shal low ground
wate r . It d i s t i ngu i she s between th os e S i0 2- temp er at ur e
anomal ies most
l i ke ly to
be
caused by
anomalous geo thermal
hea t from those
due to
o the r cond i t i on s .
This r epo r t
di scusse s
some
of the
problems
in
us ing
the
Si02- tempera tu re
c r i t e r i a fo r
sha l low groundwater assessment
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and
the
app l i c a t i on s of th e Cl/Mg r a t i o .
Also pre sen ted
a re
those areas
with in
th e
s t a t e
t h a t
a re cons idered to possess
po t en t i a l on the
bas i s of t h e i r Cl/Mg r a t i o .
O URREN E OF
GROUNDW TER IN HAWAII
Any
r eg iona l
assessment
of th e chemica l p rope r t i e s of
groundwater from a
l a rge number of
environments
i s d i f f i c u l t
due to th e va r i a t i on in such
parameters
as dep th of
wel l
and
ca s i ng ) ,
topograph ic
and
geographic
l o ca t i on and
the
type / s
of
aqu i f e r which
each wel l
pene t r a t e s .
These va r i a t i on s
a re majo r prob lems in
u t i l i z i ng
th e
Si02 concen t r a t i on s
and
t empera tu re
va lues o f
groundwate r
and
make r e l a t i v e comparisons
d i f f i c u l t .
One
of
the
most
impor tan t
f a c to r s
def in ing
th e
cha rac t e r
of
the
groundwate r in a given l o ca l e
i s th e
type of aqu i f e r
from which
th e
water
i s
drawn. G enera lly , th ree bas ic
groundwater types can
be cons idered in
Hawaii :
i )
i i )
dike- impounded occurs
with in
basa l t s
from
nea r
s ea - l eve l to
high
e l eva t ions , but i s most
o f t en
as soc i a t ed
with rift zones; usua l ly of l o c a l
recha rge . Where t h i s aqu i f e r type occurs near
s e a - l eve l , and
th e
dikes
a re pa r a l l e l to
the
coas t ,
en cro achmen t o f
s a l i ne wate r i s r e s t r i c t e d ,
and th e f r esh groundwater
wi l l not
nece s sa r i l y
be
cont inuous
to
th e deeper
under ly ing
s a l i ne
wate r
S tea rns e t
al
1940) .
Numerous
dike
format ions
can
form success ive
r e se rvo i r s
of
t h i s
type
to highe r e l eva t i on s r e s u l t i ng in a
s t epped groundwate r g rad i en t .
sedimentary
and a l l uv i a l occur a t lower
e l eva t ions ,
u su ally w ith in
the l a rge r
va l l ey s and
in
co a s t a l
a r ea s . The sed imentary mate r i a l i s
usua l ly
of l imi t ed th ickness
and
low
pe rmeab i l i t y ;
however in la rg e v al le ys the
sed iments can be
s eve r a l
hundreds of meters t h i ck and
of bo th
marine
and
t e r r e s t r i a l
o r i g i n .
These
sed imentary
a rea s are of ten
highly
popula ted
and
con ta in many
groundwater wel l s ,
and
consequen t ly i n f i l t r a t i on
of s a l i ne water in to a l l u v i a l aqu i fe rs has
in
many
places
been enhanc ed by
cont inuous
pumping.
Most of the
groundwater i s of l o c a l r echarge ,
but
i s
of ten
a l t e r ed
chemica l ly because
of
i r r i g a t i on
and the
consequen t
recyc l ing .
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i i i bas a l non-a r t e s i an groundwater ;
unde r l i e s
a l l
of
the major i s l ands
in the
Hawaiian cha in , and
can
extend
to
g rea t
depth .
It i s
usua l ly
t r a n s i t i ona r y
through
a zone
of
mixing to deep
s a l i ne
water
in
permeable
a rea s
with
deep
l avas
S tea rns e t
al 1940 .
This wate r p ro bab ly
extends
to 5
to
6
m below the l a r g e s t
i s l ands and
i s th e major
source of groundwater in
Hawai i .
Cumulat ive
pumping
of wel l s
with in
t h i s
aqu i f e r
type
has
a lso
produced
some
l oca l
upwel l ing of
th e u nd erly in g s a l i ne water
Swain,
1973 . In
much
of the s t a t e , and e spec i a l l y southern Oahu,
the Ghyben-Herzberg f r e shwa t e r - s a l i n e water
i n t e r f a ce i s replaced by a t r an s i t i on zone
of
mixing due
to th e
a r t i f i c i a l
and na t u r a l
dynamic
s t r e s s e s
a r i s ing from
heavy withdrawal
and
the
seasona l na tu re
of
th e rech arg e
imposed
on
t h i s
deep
groundwater Mink, 1961 . n
the
o lde s t
i s l ands e . g . Maui, Oahu , th e
bas a l
aqu i f e r in
th e co a s t a l
regions
i s capped by marine sedimentary
depos i t s
which l a rge l y re ta rd inward or outward
groundwate r migra t ion
in
the sha llow
pa r t s of
these r e s e rvo i r s Mink,
1964 .
Div i s ions
among
th e d i f f e r en t
aqu i f e r s
a re
no t always
wel l def ined , and
aqu i fe rs with
in te rmed ia te cha r ac t e r i s t i c s
a lso ex i s t .
In
some a rea s of
h ighe r
e l eva t i on , groundwate r
can be perched on impermeable ash beds . Areas with a low
dens i ty
of
dikes
and s t r u c t u r a l
permeab i l i ty
wi l l
al low
more
e x te n si ve s ub su rf ac e movement of wate r . In a rea s where
s i gn i f i c an t s ub su rf ac e h ea t
ex i s t s ,
the equ i l ib r ium
of
the
Ghyben-Herzberg
zone
may
be
des t royed by a
lower ing
of the
dens i ty
of the
s a l i ne wate r
thus
induc ing l o ca l i z ed
upwel l ing
of s a l i ne wate r i n to
th e fre sh w ate r
l en s . The chemis t ry
and
volume
of
su r face waters and groundwaters
in Hawaii i s
also
a f fec ted by th e preva i l ing t r ade wind pa t t e r n s . The
i s l and
topography produces d i s t i n c t windward and leeward c l ima t i c
cond i t ions which a f f e c t r echa rge r a t e s and c rea t e
l a rge
va r i a t i ons
in
e ro s i on , wea the r ing , and
s o i l t ypes ,
in
some
cases wi th in r e l a t i v e l y
l o ca l i z ed
a rea s ; thus
any r eg iona l
survey of groundwaters
in Hawaii must be able
to d i s t i ngu i sh
between chem ic al a nomal ie s due to mixing
o f g eo th erm ally
a l t e r ed
groundwate r and those
caused
by o the r phenomena
a r i s ing from the l o ca l i z ed na tu re of the hydrogeo logy .
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4
SILICA TEMPERATURE CRITERIA
S i l i c a
The
s i l i c a
concen t r a t i on in
thermal
waters
i s
widely
used
as bo th
a qua l i t a t i v e and q u a nt i ta tiv e in d ic ato r of subsur face
hea t Mahon, 1966; Fourn ie r and Rowe, 1966; E l l i s 1970;
Fournie r and Truesde l l 1970 .
On
the i s l and of Hawaii the
concen t ra t ipn
of Si02 was
also succe s s fu l l y
app l i ed to sha llow
the rmal groundwater McMurtry e t
al 1977 .
While
Si02
concen t ra t ion
i s reasonably success fu l as
a broad
qua l i t a t i v e
i nd i c a to r of
anomalous
subsur face
t empera tu re cond i t ions
when
appl ied to a l l
groundwaters
in
Hawaii ,
it i s a f f ec t ed
by
many
fac to rs which
render
the i n t e rp r e t a t i on of
th e
da t a
ambiguous .
Two
areas of uncer t a in ty ex i s t with th e use of th e repor ted
Si02
concen t ra t ions .
One
i s th a t
a
va r i a t i on
of
from
20
to
85 ppm
Si02 can occur
among
d i f f e r en t
aqu i f e r s in
the same
re gio n; seco nd ly
va r i a t i on s of up
to 5
have
been
noted in
d i f f e r en t ana lyses
from th e
same w ell w ate rs
Table 1 . The
l a t t e r
appears to
be
due to both
ana l y t i c a l
procedure
used and
cond i t ions of co l l e c t i on and s t o rage .
The ranges of Si02 with in waters from d i f f e r en t aqu i fe rs
has been summari zed by Davis 1969 .
He
notes
t ha t
to
3 ppm
Si02 wi l l
a lmo st immedia te ly
m inutes go in to
so lu t i on
as ra in
comes in
con tac t
with
the ground
su r f ace . During
su r face
and
subsur face movement of t h i s wate r
it wi l l reach a Si02
con ten t
of
5
to
20
ppm
be fore
en te r ing
high
l eve l
aqu i f e r s .
During
re s idence t he r e the Si02
i n c r ea s e s
to a pp ro xim ate ly 15 to 45
ppm
and i s ty p i f ied by high l eve l w a ter supply
tu nn el w ate r .
Water
l eaking from t he se aqu i fe rs and from
s o i l
to the
basa l
aqu i fe rs
d i s so lve s
more s i l i c a r e su l t i ng in Si02 concen t ra t ions of 30
to 60
ppm. Higher
l e ve l water which di scha rges as
streamflow
has a
Si02 con ten t of 15
to 30 ppm. One f e a t u re noted
by Davis
1969 i s t ha t th e Si02 con ten t
of
f lood
or ephemera l
s t ream-
flow
from heavy r a i n f a l l
i s
not apprec iab ly
lower
than
t ha t
in
more con t inuous ly
f lowing s t reams .
Water
en te r ing
sedimentary aqu i f e r s commonly has a Si02
con ten t of 5 to
5
ppm,
which i n c r ea s e s
to 60
ppm
whi le
in
the
aqu i f e r . This
water
i s e s pe c ia ll y s u sc e pt ib le to
fu r the r
inc reases
in
Si02 due
to r ec i r cu l a t i on
by i r r i g a t i on and
r e in j e c t i on
of
i ndu s t r i a l
wate r .
These
l a t t e r
occur rences can
inc rease the range of Si02
va lues up
to 50 to 85 ppm. Visher
and Mink 1964 cons ide r
t ha t
the Si02 concen t ra t ion of 40 to
75 ppm in re tu rn i r r i g a t i on water
i s der ived
from acce le ra t ed
l eaching
of s o i l and
rock be cau se
of th e cumula t ive
e f f e c t
of
a g rea t e r volume of water
plus the
s lower
movement of
ground-
water with in t he se low permeab i l i ty mate r i a l s .
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f u r t h e r
va r i ab l e in
Si02
concen t r a t i on i s th e
re s idence
t ime of wate r in aqu i f e r s ; groundwater appears
to
con t inuous ly
d i s so l ve
av a i l a b l e
Si02 from
th e
rocks
t h rough
which it
pe r co l a t e s .
The
high r a i n f a l l
on
th e
windward
s ide of
the
i s l ands
removes
s i l i c a
more
r ap id ly
from s o i l
and
rock ,
r e su l t i ng
in a r e l a t i v e l y
g r e a t e r
av a i l a b i l i t y
o f s i l i c a
fo r
d i s so lu t i on t han
in th e
l e s s weathe red rocks of
th e
leeward
s i de s . Other f a c t o r s caus ing i n c r e a s e s
in d is so lv ed
Si02
a re
ag r i c u l t u r a l phosphates Fox e t al 1 96 7 , bu rn in g
of
ag r i c u l t u r a l wastes
and reduc t ion
o f
s o i l Davis ,
1969 .
f u r t he r cause
of
Si02
va r i a t i o n s i s th e na t u r a l
d i f f e r ence
in the
chemica l
compos i t ion of th e
rock types between
d i f f e r e n t
a r e a s .
Table
compares
ana l y t i c a l r e su l t s from
e l even
wel l s in
va r i ous l o c a l i t i e s un t i l th e p re s en t . S ix of the se
we l l s
have
average
t empera tu re s
of
30C
or
g r e a t e r
and
t h e i r
comple te
ana ly ses
a re inc luded
in
Table
2.
Without engaging
in
a
d e ta ile d d is cu ss io n ,
th e
va r i a t i o n s
in rep or ted
s i l i c a
concen t ra t ions
can
be a t t r i bu t e d
to bo th d i f f e r ences
in
an a l y t i c a l t echn ique
as we l l
as
in
th e methods of co l l e c t i on
and
s to r age .
The
e a r l i e s t
ana lyses
by S ta t e
and Fede ra l
agencies a re
more
con s i s t e n t over
t ime ,
but the
more recen t
ana ly ses i n d i v i du a l s
o r
depar tments of th e
Unive rs i ty
of
Hawai i show g re ate r v a ri at io n
due
to
th e d i f f e r e n t
s to rage
and
an a l y t i c a l
t e chn iques app l i e d .
Probab ly
th e major cause
of the se v ar i a tio ns i s th e form
o f
s to r age . I d e a l l y , ana lyses
fo r
s i l i c a shou ld
be conduc ted wi th in
s eve r a l days , bu t
it i s
l i ke ly
t h a t
fo r most
o f
th e o lde r an aly se s th e samples
were
not
ana lyzed
fo r many weeks. This i n c r e a s e s
th e l i k e l i hood
of
polymer iza t ion and many of
th e e a r l i e r
repor t ed ana ly ses a re
lower than more
r e c en t ones .
Cu r ren t
work
by HIG,
however,
sugges t s
t h a t t empora l va r i a t i on s
in
th e Si02
concen t ra t ion
do occu r .
Tempera ture
The t empera tu re measurement
o f g ro und water i s
probab ly
a more
r e l i ab le id e n ti fi ca t io n
c r i t e r i o n fo r a
t h e rma l
anomaly
than i s Si02 ; however , its use i s cu r r en t l y l im i t ed because of
th e
r e l a t i v e l y sma l l
number o f m ea su re men ts and some que s t i on s
c on ce rn in g th e
accuracy
o f th e
repor t ed
da t a .
On
th e ex t i n c t
vo l c an i c i s l ands groundwater t empera tu re s
27C
and over a re
cons ide red
s i gn i f i c an t ;
those
g r e a t e r
than 29C, high ly
anomalous.
The
t empera tu re o f
groundwater wi th in th e aqu i f e r s
above
s e a - l e v e l
i s r e la te d to bo th t empera tu re o f
p r e c i p i t a t i on and
t empera tu re of
su r f a c e
wate r as it en t e r s the
aqu i f e r .
Mink
1964 cons ide r s t h a t th e o r i g i n a l wate r en t e r i ng
an
aqu i f e r
can ga in hea t
from
i vo l c an i c a c t i v i t y ; i i f r i c t i o n a l f low;
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Table
1 Comparison of different analyses
Well
Temp. C1
5i02
Number Location Date
OC
ppm ppm ppm
C1/Mg
HAWAII
2982-01
Geoth Test 3
7/75 3410 59
57 80
1/75 93 0
3274 52
96 6
62 96
12/74
86 0
4200 184
12/74
88 0 3850
187
Average 89 0 3684
55 5
156 60 38
2783-01 Ma1ama-Ki
1/75 52 2
3811 210
100 7
18 15
1/74 54 0 11000
90
9/62
5850
324 59
18 06
Average 53 1
6887
267 83 2
18 11
3081-01
Kaphoho Test
7/75
33 5 316
27 2
11 62
1/75 36 8 303.5
28
71 3
10 84
12/74
34 0
750
53
1/74 38 0
560
56
1961
320 17 1
70 5
18 71
Average
35 6 450
24 1
62 7
13 72
2881-01
Allison
Well
1/75
37 8
281 15
24 1 18 73
1/74
38 1400
53
Average
37 9
840 5
15 38 6
18 73
6147-01
Kawaihae 3
2/74
31 0
300
8
1974
31 0
253
32
84 7 91
6/63
255 31
78 8 23
6/63
35 8
250 33
89
7 58
Average
32 60
264 5
32
64 8
7 91
3758-01
Kailua/Kona
1974
25 0 459
27
43
17 0
6/74
25 0
800
40
12/58
440 37
26
11 89
3/55
485
35 33
13 86
11/49
450 9 7
46
46 39
9/49
460
28 68
16 43
Average
25 0
515 7
27 3 42 7
21 11
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Table. 1. Comparison of different
analyses cont.
Well
Temp. C1
Mg
Si02
NlD Iber
Location
Date
OC
ppm)
ppm)
ppm)
C1/Mg
MAUl
4835-01
Ukumehame
10/78
33.1
459
26 115
17
.65
9/74 32 660 66
2/70 400
29
60
13.79
10/69 33.0 354 15
59
23.60
8/69 373 17 58 21.
94
4/69
34.0 432 21 71 20.57
1/69 33.0 400 24 71 16.67
7/68
420 23 68
18.26
Average
33.0
437.3
22.1 71.0
18.93
O U
2508-02
Waianae
8/78 27.0
260
80
32
3.25
8/75
28.0
520 101
10/71 29.0
292
102 92 2.86
10/71
29.0
382
108 89 3.54
2/54
520 127
84
4.09
2/39
250 111
87
2.25
8/39
360 130
88
2.77
Average
28.3
369.1
109.7 81.9 3.13
2808-01
Lua1ua1ei
8/78 26.5
138
7
38
5.11
7/75
27.0
430
74
2/72 26.7
160 28 63
5.71
9/57
26.6
165
12/56
164
34
Average
26.7 211.4 27.5
52.3
5.41
2812-01
Makaha
8/78 26.0 92
34
40
2.71
3/71
82
6/70 95
1969
26.5
93 4.9
66 18.98
2/62
100 33
71 3.03
Average
26.3
93.6
24.0
66.4
8.24
2808-02
Lua1ua1ei
8/78
19.0
23 6.5
27
3.54
2/72
18.5
26
7. 4 49
3.51
2/72
26
7.3
49
3.56
6/67
32
6.0
56
5.33
1966
30
8.2
62 3.66
Average
18.8
27.4
7.1 48.6
3.92
7
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i i i ) r e tu rn i r r i ga t i on water and
r e l a t i v e l y
l imi t ed recharge
from r a in
in
i r r i ga t ed a reas ;
i v )
t e r r e s t r i a l hea t
f low.
The t emperature of sa l ine
water
in deep basa l
aqu i f e r s i s
inc reased by approximate ly 14C by t e r r e s t r i a l hea t
flow
to
t emperatures
of
approximate ly
23.3C, as
the
water
migra t es
from the ocean bottom to the aqui fe r
Mink, 1964) .
In regard
to
the supply
of hea t
to
groundwaters
fo r
geothermal cons ide r -
a t i on , the r e s idua l hea t
with in
i n t r u s i v e
mate r i a l i s
co ns id ere d to be the
most s i gn i f i c an t .
Groundwater
t emperatures in
areas
where sur face
mani fe s t a t ions
of vo lcan ic
or g eo th erm al
ac t i v i t y
occur
such
as on the
lower
eas t
r t
of
Kilauea) have
b ee n mea su red from
30C
to
approximate ly
90C
in sha l low hydro log ica l d r i l l ho l e s .
In o the r
a r eas , and espec i a l l y on the
i s l ands
where
t he r e a re
no
sur face express ions of cu r r en t a c t i v i t y ,
t emperatures
a re
lower ,
ranging
from
l8 .5C
as high as
33C
Appendix
I ) .
Observed groundwater
t emperatures
can be
r e l a t ed
to d i f f e r en t
aqu i f e r types . High l eve l usua l ly d ik e- impounded ) g roundwa te r
ranges from 18
to
21C; basa l groundwater from 20 to 24c
and sed imenta ry groundwater from
to
26C. Anomalous
t emperatures of 27C and above do no t ,
however,
neces s a r i l y
denote
the
exi s t ence of a s i gn i f i c an t the rmal anomaly. I t
appears t ha t in some a re as , lo ca liz ed and r e l a t i v e l y sha l low
low
magni tude the rmal
anomal ies
may
ex i s t
which i nc rease
groundwater
t emperatures by
or 3C.
CHLORIDE MAGNESIUM RATIOS
Genera l
Because
of
the numerous f ac to r s
in Hawaii
which a f f e c t
the
chemis t ry of
groundwater ,
t
i s d i f f i c u l t
to
apply
a
chemica l geothermal
i nd i ca to r without
making a
complex
and
i nd i v i dua l
assessment
of the
da ta
from each wel l .
Fu r t he r ,
the
ch em i ca l g eo th ermome te rs
S i02 , Na/K/Ca, Na/K) commonly
u t i l i z ed fo r the rmal
waters
a re no t appl i cab le
to
low
t emperature
shal low g rou ndw aters of H aw aii.
Limited
appl ica t ion
of
the
Cl/Mg
r a t i o
to
low
t emperature
groundwaters in New Zealand
Schof i e ld ,
1956) was to some
degree succe s s fu l in
d i s t i ngu i sh ing between sa l ine
groundwater
of marine or ig in and high chlor ide groundwater o f g eo th erm al
or ig in .
Appl ica t ion of
t h i s
r a t i o to
those
groundwaters
in Hawaii
t ha t
have been
se lec ted as
anomalous by
Si02-
tempe ra tu re ) p ro vid es
a f u r t h e r , more cont ro l l ed
c r i t e r i on
fo r
s e l ec t i ng anomalous l o c a l i t i e s . Of
the
397
se t s of Si02-
temperature
ana lyses s t ud i ed , 53
se t s
have a s ign i f i c an t ly
anomalous Cl/Mg
r a t i o
~ 1 5
and
30 se t s have
a
marg ina l ly
anomalous
r a t i o 12.0
to 14 .9 ) . The
Cl/Mg
r a t i o s of
an
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9
add i t i ona l
50 ana ly s e s , which
were
or ig ina l l y
r e j e c t ed by
the
Si02- tempera ture
c r i t e r i a ,
were
a l so ca l cu l a t ed n ot inc luded
in t h i s r epo r t ) ; excep t fo r
6 s l i gh t l y
anomalous ca se s , a l l
were
found to be
cons i s t en t ly
very low.
Theory
The
assumpt ion
in using the CI/Mg r a t i o as a
geo thermal
i nd i ca t o r
i s
t h a t
th e
ch lo r ide
con ten t of
seawater and
g ro undwa te r r ema in s
l a rge ly
una f fec t ed
by
thermal processe s
or ion exchange when seawater
i n f i l t r a t e s
the i s l and
aqu i f e r s ,
or during subsur face
groundwater
migra t i on . The
magnesium i on ,
however , i s s t r ong ly dep le t ed
in
concen t r a t i on where
ground-
waters have been a f f ec t ed by thermal
p roces s e s ,
thus producing
a h ighe r Cl/Mg r a t i o . A ssess ing the
chemica l
da ta ava i l ab l e
sugges t s t h a t r a t i o s
of g r e a t e r
than
t h a t of seawater ~ 1 5
i nd i ca t e t ha t
anomalous
thermal
cond i t ions
have
a f f ec t ed
aqu i f e r rock chemis t ry by
hydro thermal
a l t e r a t i on
o r
have
caused an i nc rea sed
degree of
r e ac t i on
between groundwater
and
rock inc lud ing sed imentary mate r i a l and c l a y s ) . Heat ing
of
s a l i ne
wate r
in th e deep
basa l
aqu i f e r s
a l so enhances
dep le t ion .
Chlor ide
Chlor ide i s the major
ion
in a l l
forms of
water wi th in
an
i s l and
env ironm ent such as Hawaii.
This
i nc ludes r a i n , s t reams
and high l eve l groundwater as wel l as w ate rs of l ower e leva t ion
aqu i fe rs
Tab le
2 ) .
The
ch lo r ide
i s
a lmos t
en t i r e l y
of
marine
o r i g i n from a i rborne s a l t s
o r
s a l i n e wate r i n f i l t r a t i o n . The
highe r
concen t r a t i on s of ch lo r ide
in
groundwaters
can be
r e l a t ed to th e amount of
seawate r
i n f i l t r a t i on by th e
approx imat ion
Seawater
= 100 Cl groundwater Cl
s t reamwater )
Cl
seawater
The
s u i t a b i l i t y of ch lo r ide
as
a
s tandard in
asses s ing
the amount of seawater
mixing
i s t h a t the
ch lo r ide ion
i s
highly
s t ab l e in th e groundwater
in
both ba sa l t i c and
sed imentary
rocks m arine
and
t e r r e s t r i a l ) . I t
does
no t
en t e r
in to chemical r e ac t i on
with
o the r ion s o r an ion ic
exchange
wi th in
sed iments Scho f i e ld ,
1956;
Mink,
1961; Swain ,
1973) .
Fur the r ,
the Cl con ten t o f seawater i s una f fec t ed
even
a t
t empera tu res of up to
350C Bischoff
and Sey f r i ed , 1978) .
Sources of c hlo rid e o th er
than
sea s a l t s to
groundwaters
in Hawaii are c on side re d to
be minimal .
The
ch lo r ide
con ten t
of Hawaiian
l avas
i s low,
in
th e
range
of
0 .01
to 0.2
Macdonald e t
al
1973) .
Some
con t r i bu t i on of ch lo r ide from
rocks to deep , h igh
t empera tu re
groundwaters
in a rea s
of
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0
Tab le 2 .
Averaged value s o f
known
thermal and other
waters
Well
Temp.
Na
K
Ca
Mg
Cl Si02 HCO SO.
F
NO
Cu
Pb Zn
As Fe
Mn
Number
Name
OC)
pH
ppm) ppm) ppm)
ppm) ppm) ppm)
ppm)
ppm) ppm) ppm)
p pm ) p pm )
ppm ) pp m) ppm) ppm)
HAWAII
HGP-A
300
4 4 800 149
96
1. 0
1150
501 =45
=176
--
0.13
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11
ac t i v e volcanism may occur , however . E l l i s 1966
exper imen
t a l l y
obta ined aqueous so lu t i on s wi th
60
and 250 ppm Cl
from
r eac t i on s
with
d i s t i l l e d wate r and
ba s a l t a t 200C and
300C
r e spec t i v e l y . Exper iments by El l i s and
Mahon 1964
showed
th a t b a s a l t e a s i ly
l o s t
about
75 of
its
t o t a l
ch lo r ide
to
wa te r
a t t empera tu re s
of 300 to
350C.
The
conc lus ion of
El l i s and
Mahon 1964 was t h a t ch lo r ide i s ea s i l y
l o s t
from
ba s a l t because
much
of the
l eached ch lo r ide
i s
held on su r faces
wi th in
th e rocks r a t h e r than in s o l id s o lu tio n .
This
may mean
t h a t minor
amounts
of ch lo r ide
cou ld be
gained by
groundwate rs
th rough
low t empera tu re wate r - rock i n t e r a c t i on and a long
re s idence
t ime
which
would enhance
the
use
of Cl/Mg
r a t i o
as
a geo thermal i nd i c a t o r .
Magnesium
Magnesium
ion
concen t r a t i on s
can
be
s u b st an t i a l ly a lt er ed
by
high t empera tu re
r e a c t i o n s . Labora to ry s tud i e s
of wate r
rock equ i l i b r i a have
shown t h a t
magnesium can
be e f f e c t i v e l y
removed
from
so lu t i on by the
fo rmat ion
of
high
t empera tu re
rock a l t e r a t i on s produc t s E l l i s
and
Mahon, 1964; Mahon, 1967 .
The two pr imary
removal
mechanisms a re t h rough fo rmat ion
of
ch l o r i t e
[Mg3 Si4010
OH 2Mg3 OH 6]
u nd er extrem e
cond i t i on s
and
illite [ AlMgFe 4 SiAl a02o OH 4] a t lower
t empera tu re s .
Another
high
t empera tu re
r eac t i on
i s t h a t of seawa te r with
ba s a l t s , which
produces
p r e c i p i t a t e s of magnesium oxysu l f a t e s
B ischof f and
Sey f r i ed ,
1978 and hydroxy la ted magnesium
s i l i c a t e s
Mackenzie e t
al.
1967 .
Fie ld s t ud i e s in
Hawai i
have i d en t i f i e d th e h igh e r
tempera ture
magnesium s i l i c a t e s c h l o r i t e
and
illite
in
both
ex t i n c t hydro thermal systems
Fu j i sh ima
and Fan, 1977 and
in
drill core from HGP A geo thermal wel l
S tone ,
1977;
Stone
and
Fan, 1978 In t e rmed ia t e t empera tu re 70 to 150C
r eac t i on s
can a lso d ep le te magnesium th rough the fo rm ation o f smec t i t e
c lay s S ey fr ied and Bi scho f f ,
1979 .
The
sequence of low t empera tu re
r eac t i on s
undergone by
magnesium in a
ba sa l t i c
env i ronment can be qu i te
complex.
Ra in fa ll , e sp ec ia lly on windward s ide s
of
th e i s l a nd s ,
gene ra l l y c a r r i e s sma l l concen t r a t i on s o f sea s a l t and has a
Cl/Mg ion
r a t i o of
app rox ima te ly
7. This wate r
pe r co l a t e s
down
t h rough
th e
i s la nd a qu ife rs
and very r ap id ly d is so lv es
enough m agnesium from
the
f e r romagnes i an
minera l s in th e
ba s a l t
to lower
the Cl/Mg r a t i o
to a pp ro xim a te ly
2
to 3 .
I n f i l t r a t i o n
of
s a l i n e wate r i n to
the
ba sa l aqu i f e r s invo lves a
somewhat
d if f e re n t s er ie s of r e a c t i o n s . The most
impor tan t
of
t he se
i s
the
ca t ion -an ion e xc ha ng e b etwee n th e in t rud ing
seawa te r
and
th e
ca lca reous
marine s ed im ents th ro ug h
which
it
must
pass .
Obse rva t ions
on
Oahu
Mink,
1961 sugges t t h a t th e
i n t r ud ing
wate r ga ins and Ca and l o s e s Na and K to th e s ed im en ts .
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12
Mink 1961)
exp res ses t h i s
r e a c t i o n by
th e
fo l low ing
gene ra l i zed
equa t i on :
Ca, Mg c lay 2Na+, K 2Na, K c l ay ca++, Mg
The s a l i n e wa t e r ,
a f t e r
en t e r i ng the ba s a l t i c aqu i f e r ,
undergoes l ttl f u r t h e r exchange and , as a consequence , ba s a l
wate r s
t h a t
have
been
mixed w ith sm all amounts o f i n t r ud ing
seawa te r commonly have
Cl/Mg
r a t i o s r ang ing from
2
to as
high
as
6.
Rat io s of
5 to 8 a re
common in sed imen ta ry
aqu i f e r s
in
a reas of low topography l a rge
va l l ey s ;
coa s t a l
s t r i p s
where
some
Mg l o s s to c l ays
produced by
wea the r ing
occu r s . Some
sa l i n e water i n f i l t r a t i o n
i s a lso common wi th in
t h e se aqu i f e r s ,
o f t en having been enhanced by con t inuous pumping of a l a r ge
number of wel l s .
Thus
th e
o v er al l in d ic a t io n
and
assumpt ion
app l i ed
i s
t h a t
lower
t empera tu re r eac t i on s
undergone by magnesium main t a in
a
Cl/Mg r a t i o
in th e
range o f to 8
fo r
most Hawai i groundwaters ;
however ,
as
groundwate r
t empera tu re s
i n c r e a s e ,
magnesium
concen t r a t i on s
a re
seve re ly
dep l e t ed , r e su l t i n g
in
a s ub s t a n t i a l
i n c r e a s e in th e obse rved Cl/Mg r a t i o s . The dep l e t i on of
magnesium and
consequent
h ighe r Cl Mg
r a t i o s
appear to
con t inue
to be r e f l e c t e d
even
a f t e r th e h ea te d w ate rs have been
cooled
to
nea r -amb ien t t empera tu res
t h rough
conduct ion
or mixing
with
coo l e r n o n- sa lin e w a te rs .
COMPARISONS
OF
Cl/Mg
RATIOS
IN
OTHER
THERM L W TERS
In o rde r to fu r t he r a s s e s s th e app l i c ab i l i t y of
th e
Cl/Mg
r a t i o
as
a t r a c e r fo r the rm al g roundw ate rs , the
r a t i o s
have
been ca l cu l a t ed fo r a number of
geo the rma l
system s T ab le 3)
in
a va r i e t y of
t e r r a i n s . Inc luded in t h i s
t a bu l a t i o n
a re
thermal
wa te r s
from o the r i s l and
env i ronmen t s ,
many of
which
a l so have app re c i ab l e
seawa te r mix ing , as
wel l
as t ho se
t y p i c a l con t i n en t a l geothe rmal sy s t ems .
The
Cl
and Mg va lues
fo r these
wate r s have been p lo tte d lo g ar ith m i ca lly F ig .
1)
r e l a t i v e
to
th e average pa ram ete rs
of
t h e se
i ons
in
Hawai ian
wa t e r s .
Three
gene ra l
group ings emerge: wate r s from vapo r
dominated
sys tems , low ch lo r i de thermal wa t e r s , and high
ch lo r i de wate r s as soc i a t ed
wi th
a rea
of a c t i v e
volcan ism.
True vapor -domina ted
sys tems a re gene ra l l y cha r ac t e r i z ed
by
low
ch l o r i d e , high S ~
and low pH .
Water
discharged
from
s t eam-domina ted
sys tems
p l o t
in th e upper
l e f t - hand quad ran t
of Figu re I because of th e r e l a t i v e l y low CI/Mg r a t i o
due
to
h ighe r magnesium
concen t r a t i on s . This i s n ot u ne xp ec te d,
in
t h a t l Mg r a t i o s r e f l e c t t empera tu re dependent wate r - rock
e qu i l i b r i a ; wate r d i scha rged
from
t h e se sys tems
i s
gene ra l l y
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Tab le 3.
Chemical
data
of var ious
geothermal
waters
Quartz
Loc. No.
Estim.
on
Water Temp.
S04
Cl Mg
Fig. 1 Ref*
Locality
Type
OC
pH ppm
ppm ppm
C1/Mg
VAPOR SYSTEM
OR STEAM
HEATED
1
A
White Island,
N.Z.
surface
in 163 acid
10500
61840
7310
8. 5
crater
2 I
Rabaul, New Britain, P. N.G.
shoreline
158 7. 9 1420 9264 550 16.8
thermal spring
3 F
Tatun, Taiwan Hole
El02
deep thermal
180
3. 5
825
149
6.1
24.4
4 D
Carboli
A
Italy
deep thermal
--
--
137
42.6
5. 0
8. 5
5
D
Matsukawa, Japan Well MR-l
deep thermal
244
4.9
1780 12 8.7 1. 4
6
D
Yellowstone Mud Vole , Wyo.
thermal
spring
173 7. 0
65.3
13.5 16.4
0.8
7 D The Geysers, Calif. thermal
spring
115 neutral 766 1. 5 108
0.01
HIGH
I ~ O R I E W TER SYSTEMS
8 A
Wairakei, N.Z. Hole 20
deep thermal 239
8.4
35 2215
0.04
55375
9 B
Waiotapu, N.Z. Hole 6 deep thermal 222
8.9
52 1450
0.06
26167
10
D Yellowstone Norris Bas. ,
Wyo.
thermal spring 230
7.5
38
744
0.2
3720
11
A
Rotorua,
N.Z. Hole 137 deep thermal
196 9. 4 30
632
0.2
3160
12
D
Steamboat
Springs,
Nev.
thermal
spring
191
7.9
100 865
0. 8
1081
K
HGP-A Hawaii deep thermal
218 4. 4
1150
:1...0
1150
14
A
Ngawha, N.Z.
Jubilee Bath
thermal
spring
163 6.4
347 1250 2. 5
500
15 A
Wairakei,
N.Z. thermal
spring
178 6. 8 72
1110 4. 2
264
16
J
Pt.
Resolution, Tanna, New Heb.
thermal
spring
156
8.5
365 1775
4
444
17
L
Nakama,
Savusavu,
j
thermal spring
156
7. 8
236
4762
3
1587
18
C
Akrane, Iceland deep thermal
111 7.1
60 3017
12
251
19
C
Reykjanes, Iceland
deep thermal
219 6. 6
94
23250 25
930
20
E
Wilbur Spring,
California
thermal spring
169
6.9
9
9700 38
255
21
J
W Takara, Efate, New Heb. thermal spring 125
7. 5
140
8670
47
185
22
E
Oilf ield brine, Wilbur, Calif.
deep brine cold 8. 6
72
11400
124
I
w
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T ab le 3 .
Chemical
data of various geothermal waters cont.
I
Loc. No.
on
Fig. 1 Ref*
Locality
Water
Type
Quartz
Estim.
Temp.
OC
pH
S04
ppm
C1
ppm
Hg
ppm
C1/Mg
WATER SYSTEMS WITH GROUNDWATER MIXING
23 L
Waingge1e,
Fi j
i
thermal
spring
24 G
Gran it e Mt ., Alaska
thermal
spring
25
C
Hengi11,
Iceland Well G-3 deep thermal
26 A
Hanmer Spring, S. N.Z.
thermal spring
27
H Paraso, Vel la Lave11a, Solomon
thermal spring
28 L
Emperor Gold Mine, iji deep thermal
groundwater
29 A Lytte1ton, S. NZ thermal spring
A Ellis and Mahon, 1964
B. ~ l l s 1966
C.
Arnason
and Tomasson, 1970
D vfuite
et
a1.,
1971
E. White
et
a1.,
1973
F.
MRSO
1974
G
Miller
e t a1., 1975
H
Taylor,
1975
I Green
et
a1. , 1976
J MacFarlan, 1977
K Kroopnick e t a 1., 1978
L.
Cox
and
Hulston,
in
press
110
6.0
514
138 0.02
6900
121
10.1
62
9. 3
0.04 233
212
6. 8 89
153 0.24
638
100
8.0 43
451 0.2 2255
126
7. 0
224 149 6. 1
24
100
7.25
667
404
23 18
130
7. 1
110 513
163 3.2
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15
0
0
0
0 0
0 0
0 0
0
0
0
0
0
N
0
0
N
CHLORIDE
ppm
DEEP SURFACE
A
STEAM
AFFECTED
WATER
SYSTEM
3
1
5
1
5
E
10
Q
5
w
1.0
z
5
0.1
5
0.01
5
1
Fig. 1. Log-log
plot
of chloride versus magnesium
concent ra tion for
geo
thermal waters Table 3 from various world environments. The
t r i ngle
shows the Cl and parameters
for
dif ferent water
types
in
Hawaii.
The solid p r l le l diagonal l ines represent Cl Mg r t ios
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6
s team hea ted ,
nea r - su r f a ce water
which o f t en has no t come i n to
con tac t wi th r e s e r vo i r
rocks .
Another
category
of the s team
dominated
sys tems or systems
wi th a s team phase , i s found in
i s l and or coa s t a l envi ronments where s a l i n e
water
o f
marine
or ig in
i s
being
steam
hea t ed .
These
systems
have
high
ch lo r ide
and o the r ocean
s a l t s concen t r a t ions
and because
of
g en era lly s ho rt
r e s idence t imes ,
have
no t
ach ieved
equ i l i b
rium with the hea ted
aqu i f e r
rocks . Under these c i r cums tances
the
Cl/Mg
r a t i o
i s
even lower because of
the
apprec iab le
c h lo ri de c o nc en tr at io n .
Low ch lo r ide
the rmal sys tems
u su al ly a lso show e leva ted
CI/Mg r a t i o s . In some i n s t a nc e s , however , pa r t i cu l a r y in low
t empe ra tu r e
systems
and
in
thermal waters t ha t
are
apprec i ab ly
d i l u t ed
by f r e sh groundwate rs ,
th e
r a t i o s obse rved
do
no t
conform to
the
CI/Mg r a t i o s cha r a c t e r i s t i c of high
ch lo r i d e
wate r s ystem s.
These
lower
r a t i o s
can
probably
be
a t t r i bu t ed
to non- equ i l i b r a t i on between the l i qu id and mine ra l phases
of the
co un try ro ck .
Thermal
groundwate rs in Hawaii
t yp i ca l l y
f a l l in the
ca tegory of high ch lo r ide thermal
sys tems.
The CI/Mg
r a t i o s
in
these
systems
~ n r l l y inc rease
with
inc reas ing t emper
a tu r e ; however , quan t i t a t i v e e s t ima t e s of t empe ra tu r e based
on CI/Mg r a t i o s are
genera l ly
prec luded due to the
va r i ab l e
amounts
of d i l u t i on and mixing of thermal ly equ i l i b r a t ed
f lu id s
with
non- thermal f l u i d s . The
deep thermal
wate r from
the
Hawaii geo thermal
wel l HGP-A
i s a high ch lo r i d e
type and
has
a Cl/Mg r a t i o
of over
1000. CI/Mg
r a t i o s
t end ing toward
the upper r i gh t s i d e of
the
diagram
F ig .
1 i nd i c a t e
degrees
of mixing betw ee n
th erm al w a te rs
and
s a l i ne waters
see
Fig .
2 . The
su r f a ce d i scharges of
these
wate r s a l l have
Cl/Mg r a t i o s we l l over
15 ,
and the deep waters of t h i s type
have
a r a t i o of
grea t e r
than 400.
These comparisons
show
t h a t
high Cl/Mg
r a t i o s
occur
in
o the r
high
t empe ra tu r e
thermal
wa te r s t ha t have
s imi l a r
chemica l ch a r a c t e r i s t i c s to those in Hawai i . More impor tan t ly ,
e spec i a l ly to
t h i s
app l i c a t i on
in
Hawa i i ,
h igh Cl/Mg
r a t i o s
occur in high
ch lo r i d e thermal
sp r ing waters
which
a re
known
to have both s a l i ne
wate r
and cool groundwater mixing ,
c i r cums tances
under
th i ch
ne i t h e r
s i l i c a nor
Na-K-Ca
geothermometers can always
be
r e l i a b ly
app l i ed .
APPLICATION Cl/Mg
IN
HAWAII
Figure presen t s th e CI/Mg paramete rs
of d i f f e r en t
types
of
wate r in Hawaii .
The
common grouping t r ends of non
thermal ly a l t e r ed groundwaters of d i f f e r e n t types are shown to
th e l e f t of the
t r i a ng l e
boundary. High l e v e l waters
c lose
to
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17
GROUNDWATER TYPES
A. Unconfined lower elevation
B.
High
elevation and
dike impounded
C. More direct precipitation
D. Sedimentary. alluvial
.....
,.
:::>
.
V
w
A
--
..............
C>
,.
I
\
\
:E
Y
r
1 1 ,
C>
.
. .
0
....
=[
....
v.p
/
STREAM \
/ --
; e- 1
\
I
I
I
I
I
\
GRE TER FRESH
- GROUNDWATER
LOG CHLORIDE
Fig.
2. Character is t ics
of
Cl/Mg
ra t ios of
dif ferent
w ater ty pes and of
groundwaters
in
Hawaii.
The t r iangle
out l ines
the
broad
parameters
for
Hawaii
conditions. The common groupings
of
non-thermal
water to
the l e f t
of the t r iangle are denoted
by A B C
and
A lower
elevat ion
uncon
fined groundwater and basal
groundwater;
B
high
elevat ion,
largely
dike-impounded groundwater; C shallow groundwater, usually
character
ized
by high recharge, and commonly occurring
on
windward sides of is -
lands;
D
groundwater in sedimentary aquifers
usually
shallow and
basal groundwater
with
sa l ine
water mixing.
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18
t h e i r
p r e c i p i t a t i on
source
tend
to f a l l a long , or above , th e
l i ne between th e Cl/Mg r a t i o s of seawa te r and
stream
wate r .
Sedimentary aqu i f e r waters have r a t i o s t h a t f a l l between t h i s
upper
l i ne
and th e Cl/Mg r a t i o l i ne of
seawate r ;
t h i s r e l a t i v e
disp lacem ent to the
r i gh t
i nd i ca t e s
a
n on- the rma l )
l o s s
of
to c lay mine r a l s . Waters with
Cl/Mg r a tio s f a ll in g
to
the
r i gh t of th e seaw ater
r a t i o
l i ne
i.e. Cl/Mg
15
a re
co nsid ered to
be
anomalous.
In gene r a l ,
the h igh e r the r a t i o ,
the
g r e a t e r
i s
th e
thermal
e f f e c t i nd i ca t ed . The degree of
disp lacement towards seawater
approx imates th e amount of
seawater mixing
based
on
ch lo r ide con t en t ) .
The
degree of
disp lacement
to
th e l e f t of the t r i ang l e
i.e.
dec rea s ing
ch lo r ide )
i nd i ca t e s
r e l a t i v e amounts of f r e sh groundwater
m ixing . H igh ly anomalous r a t i o s in low t empera tu re ground
wate r s t h a t p lo t near the ex trem e b ottom
of
th e t r i a ng l e
or po in t s
t h a t p lo t
to th e
r i gh t
of
th e t r i ang l e have
been
found
to
i nd i c a t e
er roneous
da t a .
Erroneous
concen t ra
t i ons were
found
in
some
of th e o ld er a na ly se s; in some of
t he se cases the wel l s
were
resampled and rea na ly ze d fo r
Mg
The
r e ca l cu l a t ed Cl/Mg r a t i o
fo l lows
th e
t yp i c a l
pa t t e rn and
p lo t s
wi th in
th e
t r i ang l e .
In
cons ide r ing the d i s t r i bu t i on and th e number of po in t s
in th e se
t r i ang l e
diagram s, th e d i s t r i bu t i on of
the
l o ca t i on
of groundwater wel l s
F ig .
4, 6 , 8 , and 10 ) , and th e
ava i l ab i l i t y of chemica l da ta must be
cons ide red .
Kauai F igure s
and 4
Kauai , th e o lde s t
major
i s l and
in
the
Hawaiian cha in ,
i s
a
low t empera tu re env i ronment .
The
Cl/Mg r a t i o of ground
water
l a rge l y approx imates t h a t of
s t ream wate r ,
i nd i ca t i ng
tha t
it i s l a rge ly
unconfined or
dike- impounded
groundwater
con ta in ing an apprec iab le amount of wate r
from
sedimentary
and bas a l aqu i f e r s . Both of t he se
groundwaters
have va ry ing
degrees of seawa te r mixing .
Many
of
the Si02-anomalous
groundwaters
on the i s l and
a re
found
with in
sed iments and probab ly show some
r e c i r cu l a t i on
concen t r a t i on
of d i s so lved s i l i c a . The
one
Cl/Mg
anomaly i s
cons ide red
due
to
a
spur ious ly
low
ana ly s i s .
Molokai
F igure s
5 and
6
Few Si02- t empera tu re
anomal ies
occur
on
Molokai
and
of
t he se only two have Cl/Mg anomal ies .
Both
a re of low order .
Most wel l s pene t r a t e sedimentary or
b asa l a qu ife rs
and
some
show s a l i ne
wate r
mixing . Well
1011-01
in
the
w es t , w ith a
r epor ted
water
tempera ture of 33 .9C, has a low Cl/Mg r a t i o
7 . 3 ) .
This
wel l
i s
a pp ar en tly w i th in an a rea
as soc i a t ed with
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2000
I
/
1000
KAUAI
500
/ ;1;
/
/
/
I Mg
15 0
l M g
S 11.
1
E
50
)
w
Z
)
1
TtU::A
IC
5 0
/
/
/
?
1
J
_
0 5
0 0
0
0
0
0 0
0
0
00
v
V )
0
0
0 0
0
00
V )
0
0
0
00
V )
0
00
N M
CHLORIDE ppm
Fig
3 Log log
t r iangle
diagram
of
chloride and
magnesium
concentrations
of
groundwater for the island
of
Kauai
A suspect
rat io i s denoted by ? ; there
are
no Cl/Mg
anomalies in
these
data
I-
1 0
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2
---
o
o
---
- - - ~ - - ~ - - - - -
0
/ \
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0 0
0 0
00
00
N M
o 0
o 0
o 0
U ) 0
o
0
o 0
U )
0
MOLOKAI
o 0
U ) 0
A
//
/
/
/
/
/
/ 0
/
, / /
/
/
/.
/
/
/
o
vi
A C l/Mg 1 2.0
14 9
Cl/Mg
1.0
50
05
1/ /
I
I I I I I I I I I
o
5.0
500
1000
2000 I
I I I I I I I
I
V
W
Z
E
CHLORIDE
ppm)
N
I
Fig
5
Log log t r iangle diagram of
chloride and
magnesium concentrations of ground-
water for the island of Molokai
Solid
tr iangles indicate low order
Cl/Mg anomalies
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N
N
- \ -
.
\
/
...-
_ :
-
-
4
I
1
o
I
.
\ ~ ~
V _
_ : ~ : : - - - : . : - , r - -
_- - - - -
CfJ2 ~ ~
33 9
21
10
20
60
N
Well location (no chemistry)
o
Si0
2
or temperature anomalous
+
Low order
CI/Mg
anomaly
12 -14.
9)
- \ Generalised
outline
of
coastal lowland
- :::: Approximate trend of
rift
zones
15720 W
15710
15660
15650
Fig
6
Location
of
groundwater wells on th e
island
of Molokai i nc lud ing those having anomalous chemis-
try and
temperatures 30C
wo
low
magnitude anomalous areas
are enclosed in boxes
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an anc i en t rift zone .
The i s l a nd
i s i nd i c a t ed
to be
gene ra l ly
a low t empera tu re envi ronment
which
con t a in s l o c a l i z ed ,
pos s ib ly
sha l l ow ,
low magni tude th erm al zo nes .
Oahu
F igu res
and
8
A l a rge
number
of wel l s on
Oahu
a re w ith in , or
pass
t h rough ,
th e
sed imentary aqu i f e r . Many of
th e se a re wi th -
drawing
wate r from th e
ba s a l
aqu i f e r
u nd er ly in g th e i s l a nd .
Of th e w el ls wi th
anomalous
Cl/Mg, 1749-18
and 2054-03 a re
co ns id ere d to
have
su spec t Mg va lue s . The o the r
anomalous
r a t i o s a re c on sid ere d r e a l
and
worthy o f
f u r t h e r
i nve s t i g a t i on .
Wells
2409-07 and 2409-23
in th e
Lua lua l e i
Val ley
a re i nd i c a t ed
by wate r chem is try to be s i gn i f i c a n t l y
anomalous .
A
de t a i l e d
i nv e s t i g a t i o n of
t h i s
a r e a ,
wi th in
which
i s th e ca l de r a of
th e
anc i en t Waianae vo lcano ,
was
completed in
1978
Cox e t al
1979 .
These
da t a
s t rong ly
sugges t
the
p resence
of
anomalous
subsu r face
hea t in
the wes t , c en t r a l no r t h , sou th and
pos s ib ly
sou t h ea s t of Oahu. S ign i f i c an t l y e l eva t ed 30C+ groundwate r
t empera tu res occur in
s e v e r a l l o c a l i t i e s ,
bu t
do no t
always
co r r e l a t e wi th Cl/Mg r a t i o s .
Maui F igu res and 10
The d i s t r i bu t i on
of Maui
wel l s
sugges t s t h a t
a l a rge
number a re wi th in th e sed imenta ry aqu i f e r . Some s a l i n e wate r
i n f i l t r a t i o n i s a l so
i n d i c a t ed . There
a re
very few wel l s
p lo t t ed
nea r
th e r a t i o of
s t ream
w a te r, su gg es t in g
t h a t
only
a
l imi t ed
amount
of h igh
e l eva t i on
wate r
i s
p re s en t ,
probab ly
because most of
th e
w ells a re
l oca t ed
on
th e
leeward
low
r a i n f a l l
s i de of th e
i s l a nd .
The high number of
Si02
anomal ies
in
the a l l u v i a l i s thmus between west and
e a s t
Maui
i s due to r e c i r c u l a t i on and r e s i dence t ime e f f e c t s caused by
ex t ens ive a g r i c u l t u r a l i r r i g a t i on in t h i s
district Based on
th e data a va il a b le , th is i s l a nd i s i nd i c a t ed to
be
a
medium
to
low
t empera tu re env i ronmen t , however , s e v e r a l
r eg ions
show
de f i n i t e
i nd i ca t i on s of anomalous
subsu r face t h e rma l
cond i t i on s .
These a r e a s
of i n t e r e s t
a re in th e no r th ,
no r t h -
wes t ,
and
sou thwes t
F igu re
10 .
Hawai i
F igu res 11 and 12
The p l o t of th e da t a shows a cons ide rab l e
spread
demon
s t r a t i ng th e r ange of groundwate r
env i ronmen t s .
The l a rge
number
of
wel l s p lo t t ed between s t ream
and
r a i nwa t e r r a t i o s
most ly
l oca t ed on
th e
windward
s i d e ; both
dike - impounded
groundwaters
and
tho se w ith more d i r e c t p r e c i p i t a t i o n
a re
i nd i ca t ed .
Sedimenta ry aqu i f e r s a re
much
more l im i t ed
on
Hawai i than on th e o th er i s la nd s
and
th e trend towards th e
seawa te r
r a t i o
l i n e
i s
commonly
due to
t he rmal d i s rup t i on
o f
th e
Ghyben-Henzberg
l en s caused by anomalous ly high subsu r face
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N
-l>-
00
00
00
60
NM
o
o
o
6
o
o
o
\I )
o
o
o
o
o
\I )
OAHU
o
o
\I )
SEAWATER
/ I
/ I
,
I
/
/
/
/
.
/
/
. I
I
.. .
I
.
,
A
)
I
I
\A
I
I
I
I
I
o
U
-
Cl Ma 15 0
A
Cl Ma
12.0 - 1
9
Cl Ma 11.9
2000
i I I > I I j
500
0 5
q
1000
5 0
1
50
V
w
Z
1
1
Q.
CHLORIDE (ppm)
Fig.
7.
Log log
t r i ngl
diagram
of
chloride and magnesium concentrat ions of
groundwaters for
the
is land of Oahu A suspect
r t io
is denoted
by ? ;
s ol id t ri an g le s show
low order
Cl/Mg anomalies and sol id squares indicate
h igh o rd er anoma li es .
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15740
5750
Well
location no
chemistry)
o Si0
2
or temperature anomalous
w order CI/Mg anomaly 12-14.9)
High order CI/Mg anomaly 15.0)
/
Generalised outline
of
coastal lowland
::::: Approximate
trend of
rift
zones
15760
5810
5820 W
21
20
0
-
J
}
o
0
21
~
~ ~ I
0
e
08
0
o.
21
4
N
Fig
8
Location
of g roundwater
wells on
th e
i s land of
Oahu including
those
having anomalous
chemistry
and temperatures
> 30C Si x l Mg anomalous
areas enclosed
in
boxes are
shown
in order of
impor-
tance to
geothermal studies
The area
denot ed 1
covers t he c al de ra of
th e
Waianae volcano
N
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N
o
o
o
o
o
o
o
II
o
o
o
o
o
II
o
2
o
II
.
o
ii i
MAUl
- < 9 > / _ _
RAIN
/
Cl Mg
15.0
Cl Mg 12.0 - 1 .9
Cl Mg
SI1 9
Q
2000 I , J
0 5
5 0
1
500
1000
[
Q.
50
c.I
w
Z
CHLORIDE ppm
Fig. 9.
Log log
t r i a n g l e
diagram
of th e chlor ide
an d
magnesium c o n c e n t ra t i o n s
fo r th e is land of Maui.
So l i d
t ri a ng l es i n di c at e lo w order
Cl/Mg
anomalies
s o l i d
s q u ar es show high
o rd e r
anomalies.
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I
~ /
o
\
\
\
\
\
\
\
\
\
\
/
11//
/ /
/
o
/
/
3
Well location no chemistry)
o Si 0
2
or temperature anomalous, ,
+ oworder C1/Mg anomaly
12-14.9)
High order
CI Mg
anomaly
~ 1 5 . 0
/ -
Generalised outline of
coastal lowland
=Approximate trend of rift
zones
2
20
40
20
50
20
60
N
15640 15630
15620
15610
15560 W
Fig 1
Location
of groundwater
wells
on th e
island
of Maui i n clud ing tho se having anomalous chemistry
and temperatures 3 C Five Cl/Mg anomalous
areas
enclosed in boxes
are
in order o f i mp or ta nc e to
geothermal
studies
N
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N
00
HAWAII
SEAWATER
/ .
/
,,
/
,,/
,I
,, . .
Cl/Mg 15
CI/Mg12.0-14.9
Cl/Mg 11 9
1
0 5
Q
0
0
0
0
0
0 0 0
vi
\I
0
0
0
0
0
\I 0
0
0
\I
0
0 -
0 -
CHLORIDE
ppm)
2000 I
I
I I I I . :::l
500
1000
5
1
Q.
:E 50
::>
Vl
w
Z
( )
:E 10
Fig. 11. Log-log t r iangle
of
th e chloride and magnesium
concentrat ions
for
th e
is land of
Hawaii.
A suspect ra t io
is denoted by ? . Solid t r iangles
show
low order Cl Mg
anomalies and solid
squares
indicate
high order anomalies.
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20
20
N
__I
-
\
\\
2
/
,/
~ / /
. /
I I
I I
I I
Well location no chemistry)
o
Si0
2
or temperature anomalous
+ low order CI/Mg anomaly 12-14.9)
* High order CI/Mg
anomaly 15)
...
-
, Generalised outline
of
coostal lowland
-
:::: Approximate trend
of
rift
lones
Fig 12 Location of groundwater wells on the is land of Hawaii
including
those having anomalous chemistry and temperatures 3 C
Seven
Cl/Mg
anomalous areas enclosed in boxes are in order of importance to geo-
thermal studies
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3
hea t on t h i s
v o lc a ni ca ll y a c tiv e
i s l a nd . The
major i ty
o f
we l l s on Hawai i pene t r a t e ba sa l and low
e l eva t i on
d ike
impounded
aqu i f e r s .
Seve r a l of t h e se aqu i f e r s show seawa te r
mixing , which
i s
e s p e c i a l l y
most s i g n i f i c a n t in those we l l s
w i th in a reas
of
known
high
subsu r f a c e
t empera tu res
such
as
th e
lower eas t ri t of
Kilauea . The
ove r a l l a i s t r i b u t i o n
of po in t s
i n d i c a t e s th e
high
t empera tu re
envi ronment
of
the Big I s l and .
CONCLUSIONS
The Cl/Mg
r a t i o
o f g ro un dw ate rs i s a su i t ab l e geochemical
i n d i c a t o r
fo r
r eg i ona l r econna i s sance
assessment
of a l a r ge
volume
of
da ta in an envi ronment
where
much of the o the r
wate r
chemis t ry can be ambiguous We be l i e ve t h a t use of
t h i s
i nd i ca t o r has succes s fu l l y l oca t ed a rea s in which fo l low-up
surveys
a re w arra nte d.
t
f u r t h e r
appears
t h a t
t h i s
r a t i o
can a lso be
app l i ed
in
a s im i l a r
way
in
o the r
env i ronment s
which
posses s cha r a c t e r i s t i c s
s im i l a r
to
Hawai i and which
may
have geo the rmal po t en t i a l
bu t
l im i t ed
s ur fa ce m a n if es ta tio n s
and a l a r ge
volume
o f g ro un dw ater
chemis t ry .
The use o f Cl/Mg
on
p r ev ious ly ex i s t i ng da ta s e t s , h o w v ~ r i s obvious ly
no t
i n f a l l i b l e and shou ld be r e l a t ed to
o the r
c r i t e r i a such as
Si0
concen t r a t i on
and t empera tu re .
Areas
of
appa ren t anomalous
t h e rma l
cond i t i on s
have
been
de te rmined and a re i nd i c a t ed wi th in
boxes
in F igu res 4 , 6 ,
8 ,
l a , and
12 and
numbered
in
o rde r of p r i o r i t y fo r
each
i s l and . A
more comprehensive
a s se s smen t of the
po t en t i a l
of
the se and o the r a reas on a s t a t e -w ide ba s i s i s presen ted in
Thomas e t a la 1979 .
An obvious f ea tu r e in t h i s type of
a s se s smen t
i s th e
l im i t a t i o n placed
upon it
by
the
l o ca t i on
of wel l s and th e
ava i l ab i l i t y
of chem ical da t a . t i s
high ly
l i k e ly th a t
o the r
anomalous a reas ex i s t in the
s t a t e , which
were
no t
r e f l e c t e d
by
t h i s s tudy
because
o f
th e l a ck
of we l l s
in those a r e a s .
KNOWLEDGMENTS
We
acknowledge
th e a s s i s t a n c e of
Dale
Er landson
and
Les l i e Kaj iwara
in
th e
compi la t ion
and
s t o r age
o f
th e wate r
chemis t ry da t a . The coope ra t ion of th e
s t a f f
a t th e U.S .G.S .
Honolulu Of f i c e i s
app re c i a t ed .
The work was ca r r i ed out
under
th e Depar tment o f Energy
g r an t number
DOE/ID/017l3 4
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3
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