Applied Geochemistry, Vol. 6. pp. 1-15, 1991 0883-2927/91 $3.0(1+ .

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Organic acids and inorganic ions in waters from petroleum

reservoirs, Norwegian continental shelf: a multivariate statistical
analysis and comparison with American reservoir formation waters

TANJA BARTH
Department of Chemistry, University of Bergen, Allegt. 41, N-5007 Bergen, Norway

(Received 15 May 1989; accepted in revised form 15 March 1990)

A b s t r a c t - - A data base consisting of organic acid anion composition, reservoir depth, temperature and
pressure, and inorganic ion composition of 22 samples of produced formation waters from different wells
on the Norwegian continental shelf is presented. Correlation between the different properties of the
samples was explored by multivariate statistical analysis, with special emphasis on the organic acid
concentrations. Organic acid concentrations, pH and alkalinity are positively correlated with each other
and in general negatively correlated with the inorganic ion concentrations. No significantcorrelation was
found between organic acid levels and reservoir temperature. Alkalinity values can be predicted from the
remaining ionic composition of the samples with reasonable accuracy, while surface-measured pH cannot
be accurately predicted.
A comparable statistical analysis was performed on an American formation water data set. These
waters separate into statistically different classes based on reservoir types. Strong similarities are found for
the oil reservoir watcrs in the two data sets.

INTRODUCTION ficient number of good data sets from real waters,

SINCE C A R O T H E R S a n d K H A R A K A (1978) published
their paper on organic acids in produced formation
waters from oil reservoirs there has been a steadily
increasing interest in mapping the occurrence of
these compounds and discussing their possible influ-
ence on the reservoir water chemistry. Several
studies, both regional (e.g. MORTONand LAND, 1987;
HANOR and WORKMAN, 1986; MEANS and HUBBARD,
1987) and general (e.g. FISHER, 1987; SCHOCK, 1988)
have been published. The generation of organic acids
together with petroleum from many different source
rock types has been demonstrated in the laboratory
by simulated maturation experiments (e.g. BARTHet
al., 1988: LUNDEGARD and SENTFLE, 1987; KAWA-
MURA et al. 1986). The distribution of the acids
generated by the artificial maturing of kerogen or
source rock samples has been shown to be similar to
that in formation waters, with acetic acid as the major
component.
The organic acids are typically weak acids that exist
mostly as anions in the formation water at pH > 5.
They can influence the buffering capacity, pH and
oxidation potential of the waters (KHARAKAet al.,
1985). Their significance [or diagenetic processes in
reservoir rocks has been discussed by several authors
(e.g. SURDAM and MAcGOWAN, 1987; MAcGOWAN
and SURDAM, 1988; MASTand DREVER, 1987; BENNET
et al., 1988) but no general agreement on the import-
ance of these compounds in normal diagenesis has
been reached (e.g. GAUTIER,19861. The ability of the
organic acid anions in brines to function as ligands for
organic cations is of special interest with regard to
dissolution and transport processes. Lack of a suf-
AG6-1~A
where both organic acid anions levels and the corre-
sponding concentrations of the cations of interest
have been reliably measured, and as yet limited
results from controlled experimental investigations,
have made this discussion very speculative.
In this work the levels and composition of ionic
compounds in reservoir waters from Norwegian off-
shore oilfields are evaluated for possible correlations
between organic acid levels, measured pH and alka-
linity, and the concentrations of the major inorganic
constituents. The concentration and component dis-
tribution of organic acids in the waters have been
determined by isotachophoresis in this laboratory.
The inorganic ion composition is provided from rou-
tine analysis for oil companies operating on the
Norwegian continental shelf, and consists of surface-
measured pH and alkalinity and the concentrations
of CI, SO4, Na, Ca, Mg, Ba, Fe, Sr and K ions. The
reservoir conditions are specified by temperature,
pressure and depth.
The possible correlations between the organic acid
concentrations, the concentrations of inorganic
species and the reservoir parameters have been
investigated by multivariate data analysis. The multi-
variate approach is based on the possibility that
several (>2) different properties (variables) may
influence each other in a systematic manner which is
not easily determined when investigating only pairs
of variables at a time in a two-dimensional space, e.g.
dependence of acid concentration on temperature.
To discover multiple correspondences, all the vari-
ables are investigated simultaneously by multivariate
techniques.
Though multivariate analysis is well established as
2 T. Barth
a m e t h o d in s o m e areas of chemistry and geology it is
not yet generally applied in investigations o f the type
o f geochemical p r o b l e m a d d r e s s e d here. To enable
c o m p a r i s o n of this work with previous work in the
same field, an equivalent statistical analysis o f the
data p r e s e n t e d by FISHER (1987) has b e e n p e r f o r m e d
and is also included.
W h e n evaluating the results of the statistical ana-
lyses, the differences b e t w e e n the statistical m o d e l
g e n e r a t e d from the data analysis and a chemical
m o d e l for formation water c o m p o s i t i o n must be kept
in mind. In this application, the statistical t r e a t m e n t
is mainly used for data exploration, to point at
correlated and u n c o r r e l a t e d p r o p e r t i e s , and to deter-
mine such relations. The chemical relations that
underlie these correlations are not necessarily clear,
and must be evaluated and i n t e r p r e t e d on the basis of
chemical knowledge. The statistical analysis gives
pointers for constructing a chemical m o d e l , or con-
tradicts the implications of existing m o d e l s if they are
incorrect or applied to situations outside their scope.
It is not, h o w e v e r , in itself a chemical m o d e l of the
investigated system.
EXPERIMENTAL
Samples
Produced formation water samples from oil reservoirs
were provided by some of the oil companies operating on
the Norwegian continental shelf: Statoil, Saga Petroleum
a.s.; Phillips Petroleum Company Norway; and Norsk
Hydro A.S, The samples were collected offshore at well-
head or test separators, and transported onshore before
analysis. Samples were conserved by addition of HCI or
HNO 3, by refrigeration or freezing or by addition of
HgeCI2. The samples were stored at 5°C after arrival and
analysed for organic acids as soon as possible, normally
within a week. Re-analysis of samples after longer storage
periods (several months) indicated no deterioration of
sample quality with respect to organic acid content.
Information on reservoir conditions and the inorganic
composition data was provided by the oil companies where
the samples originated. For many samples more specific
information on the source was not publicly available. The
spread of sample types used in this analysis is limited by
what is available. The data set as presented here has been
chosen from >60 analysed samples to provide the best
possible spread of data from different reservoirs, but some
duplicates have bccn included (nos 4 and 5, nos 8 and 9, and
nos 19 and 20). Only samples where all or nearly all of the
properties of interest had been measured were included in
the data set used in the multivariate analysis.
Analytical methods
Organic acids were analysed by isotachophoresis, an
electrophoretic technique that separates ionic compounds
by their acid strength. Inorganic ions were removed in a
preseparation compartment, and the weaker organic acids
determined within a range o f p K A values determined by the
electrolyte system. The piocedure does not require any
pretreatment of the sample for the acid concentration levels
normally found in formation waters (I-20 mM), and has
been shown to be suitable for reservoir water analysis
(BARTH, 1987a). The di- or poly-functional acids that are
considered of special interest (e.g. malonic acid and hyd-
roxy acids) are determined with the same reliability as the
more common mono-funetional acids because their pKA
values are well within the range of the analytical window (1
< pK A < 5).
The surface pH-values of the samples were measured at
the collection site at room temperature and pressure. In the
data set used for the multivariate analysis the concentration
of H ion is used instead of the logarithmic pH value to
provide similarly scaled data. Alkalinity was determined by
titration by standard procedures. Inorganic ion concen-
trations are determined by ICP, with the exception of SO4
which was in some cases determined by ion chromatogra-
phy.
Da~ ana~s~
Multivariate data exploration consists of a search for
systematic covarianee in the ionic compositions and reser-
voir conditions by methods ~that look at all the sample
properties simultaneously. Th~set of n variable values for
each sample is registered as a po]Et in n-dimensional space,
and using a statistical prograng for data analysis, axes
through the resulting n-dimensional object "cloud" arc
calculated. The axes (or principal components, PCs) arc
chosen so that each describes the maximum amount of the
unexplained systematic variation in the data set, and each
axis is orthogonal to all the others. This procedure is called
principal component analysis (PCA) (WOLt) et al., 1984).
Each axis is checked for statistical significance by cross-
validation (WoLo, 1978), where groups of samples arc
removed and the components recalculated and compared.
The PCA model reduces the dimensions of the data set to
managable proportions in a way that gives emphasis to the
main trends in the systematic variation of sample proper-
ties. The result is a quantitative description of any linear (or
approximately linear) correspondence between any of the
variables.
If one or more of the properties or variables are expected
to be a function of other variables, this can be modeled
specifically by choosing axes in the system so that they
describe the maximum amount of variance for the chosen
variable(s). The values of the chosen variable arc modeled
as a linear function of the other variables in the data set, and
the contribution from each variable is determined. The
ensuing model can be evaluated by the amount of variance
that is explained for the target variable, and the validity of
the prediction ability of the model can be tested by predict-
ing values for samples not included in the modeling set. This
modeling is done by a partial least squares regression (PLS)
technique (GELAD1and KOWALSK1,1986).
The analysis of the formation water data sets were done
using the SIRIUS program (KVALHE1M and KARSTAN(~,
1987), one of several commercially available data programs
for PCA and PLS modeling. This system permits samples
with 10-20% missing data to be included in the data set
without affecting the calculations. Both univariate and
multivariate analyses were carried out. The preferred
method for this data set consisted of an initial principal
component analysis (PCA) to find the major systematic
relations between the samples and their properties, and a
subsequent partial least squares (PLS) modeling of the
relation between selected variables to evaluate their quanti-
tative significance. The data was autosealed (scaled to
variance = 1) before analysis. This was necessary because
the units of measurement are very different for different
variable types, e.g. depth in kilometers and millimolars of
CI ions. Both raw data and logarithmic data have been
analysed to ensure observation of correlations that become
 Organic acids in Norwegian formation waters
linear if the logarithmic form of the data set is used. The
results of the analysis on the logarithmic data set were in
general so similar to the untreated case that it has not been
considered necessary to present both versions. A possible
cause of spurious correlation exists in that the ionic data are
constrained by the requirement of charge balance, i.e. the
total charge on anions and cations must be equal. This part
of the data is a "closed" set, and extra caution in interpret-
ation of the results is required (AITCHlSON,1984).
Interpretation
The results of the data analysis are given as principal
components, specifying for each component the explained
variance (% of total variance) and whether the PC is found
to be statistically significant by cross-validation. The loca-
tion of the samples in the resulting coordinate systems is
given in score plots, showing the projection of the samples
from n-dimensional space onto the two-dimensional plane
defined by the principal components. The score plots make
it possible to evaluate how the samples interrelate in the
sample space and whether separate classes of samples exist.
Outlying samples that do not fit the modeled relations are
also identified by their location outside the statistical
classes. The Ioadings, or contributions from each variable to
the component, are shown in the complementary loading
plots, high values (positive or negative) showing that the
variable contributes strongly to the component. The posi-
tively correlated variables plot together, negatively corre-
lated variables plot opposite through the origin, and uncor-
related variables plot orthogonally to each other. Properties
with unsystematic variations that do not contribute to the
model plot near the origin. The sum of explained variance,
both for the whole data set and for each variable is also given
as a measure of how much of the variance in the data set is
found to be systematic and explained by the model gener-
ated.
Both general presentations of the data-analytical
approach and several applications to geochemical systems
are given in a themc issue of Chemolab (KVALHEIM,1987).
RESULTS, NORTH SEA PRODUCED
FORMATION WATERS
Determination of organic acid concentrations
The composition of the organic acid in 22 samples
of reservoir waters is given in Table 1. The samples
were taken from well tests or produced water from
reservoirs in the North Sea and Haltenbanken area.
Multiple samples were analysed for many of the
reservoirs, but in most cases only one representative
sample is used in the data base. The exceptions are
samples 4 and 5, 8 and 9, and 19 and 20, which c o m e
from the same reservoirs at different sampling times
or sampling locations, and are included here for
internal comparison. The concentrations of organic
acids vary considerably, from <1 m M to 17 m M of
acetic acid (60-1000 mg/l). Acetic acid is the quanti-
tatively dominant c o m p o u n d , and the concentration
of the higher acids systematically decrease with in-
creasing chain length. These compositional trends
are similar to that observed in other sedimentary
basins. Formic acid is tentatively determined in two
3
samples, but this may be an effect of contamination
by breakthrough of formaldehyde-treated injection
water. Small amounts of benzoic acid were identified
in some samples, but the concentrations are close to
the m i n i m u m detection level for the analytical
method. Di- or poly-functional acids are possibly
present in trace amounts, but do not reach the mini-
m u m level for precise identification and quantitative
determination in any sample. The reported values for
total acid concentration is determined in the ITP run
independently of the single components, and in-
cludes all compounds in the sample that have pKA
values within the analytical limits. The identified
components generally sum up to > 9 0 % of the total
concentration in uncontaminated, non-biodegraded
samples. The levels and composition of the organic
acids in the waters are generally comparable to those
reported for other areas, although the North Sea
waters are found mostly in the lower concentration
ranges.
Data analysis
Table 1 shows the reservoir and inorganic ion
composition for the samples used in the data analysis.
It was found to be sufficient to use only the concen-
trations of acetic and propanoic acid and the total
acid concentration as measures of organic acid com-
position. A wide range of reservoir conditions, salini-
ties and ionic compositions is covered by this data set.
The aim of the analysis is to discover the inherent
relations between the sample properties. These can
be found by inspection of the loading plots for contri-
butions from each variable and the correlations be-
tween them. The inter-relations between the samples
are shown in the score plots, where possible group-
ings of samples of similar type can be observed and
outlying samples that may distort the model may be
recognised.
Exploratory principal component analysis
The principal c o m p o n e n t analysis ( P C A ) of the
autoscaled data set gives three statistically significant
components, PC1 to PC3, that model the data set in
three-dimensional space. The score plot for the
samples in the PC1/PC2 plane is shown in Fig. 1.
Visual inspection suggests that samples 15 and 16 and
samples 19 and 20 might be outliers on each side of
the model, in which ease they would influence the
model structure unduly. To determine whether this is
the case the P C A was repeated With these samples
excluded. The ensuing model was not basically
changed, but it showed that the high salinity and low
p H in samples 19 and 20 (cf. Table 1) dominate the
relations where they are included and obscure the
details in the correlations of inorganic species. To
avoid this, these two samples are omitted in further
4 T. Barth

Table 1. Concentrations of organic acids in formation water samples and concentrations of inorganic ions and reservoir
conditions, given in millimolars (mg/I in brackets)

Sample Formic Acetic Propanoic Butanoic Pentanoic Hexanoic Benzoic Total

number acid acid acid acid acid acid acid acids

1 0,56 (34) 0.13 (10) tr 0.96

2 1.70 (102) 0.16 (12) tr 2.03
3 tr 1.25 (75) 0.05 (4) 1.80
4 0.32 (19) 0.17 (13) 0.75
5 0.39 (23) 0.33 (24) 0.51
6 4.19 1251) 0.32 (24) 0.16(141 4.87
7 0.94 (56) 0.15 (11) 1.49
8 5.60 (336) 0.64 (47) 0.16(14) 0.05 (5) 0.09(10) 6.07
9 7.60 (456) 0.92 (68) 0.23(20) 11.05 (5) 11.12(14) 9.63
10 7.05 (423) 0.59 (44) 0.20 1181 0.1)5 (6) 8.27
11 2.40 (144) 0.24 (18) 2.73
12 1.48 (89) 0.28 (21) 0.12 (11) 2.05
13 7.94 (476) 0.76 (56) 0.29 (26) 0.16 (16) 9,20
14 4.03 (2411 0.48 (36) tr 5.56
15 16.21 (972) 1.53 (113) 0.50 (44) 0.16 (16) 11.16 (19) 20.90
16 16.87 (1014) 1.47 (109) 0.82 (72) tr 0.03 (4) 18.56
17 4.32 (259) 0.54 (40) 0.19 1171 11.16 (16) 5.90
18 0.18 (8) 4.95 (297) 0.60 (44) 0.20(18) 0.36(37) 6.43
19 1.25 (58) 1.43 (86) 0.09 (7) tr tr 2.89
20 1.64 (98) 0.20 (15) 0.04 (4) tr 1.80
21 3.62 (217) 0.42 (31) tr tr 4.10
tr = trace.

Sample
number pH CI Alkalinity S04 Na Ca

1 6.7 52 (1843) 6.3 (384) 0.4 (38) -- --

2 6.3 823 (29175) 10.0 (610) 0.1 (10) 720(16698) 37.3 (1492)
3 6.1 918 (32543) 8.5 (519) 0.2 (19) 793(18239) 21.8 (872)
4 7.1 659 (23361) 8.2 (5011) 6.3 (604) 565 (12995) 55.0 (2200)
5 6.6 690 (24460) 9.0 (549) 9.6 (922) 600 (13800) 59.0 (2360)
6 7.9 621 (220•4) 10.5 (641) -- 561 (12903) 19.5 (7811)
7 6.5 567 (20100) 7.8 (476) 1,7 1163) 495 (11385) 52.4 (2096)
8 7.11 363 (12868) 12.7 (775) 0 305 (7015) 59.0 (2360)
9 7.3 376 (13329) 18.7(11411 0 382 (8687) 13.8 (552)
10 6.7 291 (10315) -- 0.1 (10) 298 (6854) 3.2 (128)
11 6.5 745 (26410) 8.4 (512) 0 666(15318) 59.9 (2396)
12 7.2 1031 (36549) 8.1) (488) 0 926 (21298) 71.11 (28411)
13 7.5 525 (18611) 12.11 (732) 0.1 (10) 486(11178) 33.9 (1356)
14 -- 676 (23964) 4,5 (275) 0.7 (67) 513(11799) 60.0 (240(I)
15 7.7 408 (14463) 19.8(1208) 0.1 (I0) 400 (9200) 17.1 (684)
16 6.3 620 (21979) 17.5 (1068) 0.5 (48) 565 (12995) 24.5 (980)
17 6.1 758 (26871) 6.6 (403) 1,2 (115) 726 (16698) 38.1 (1524)
18 6.3 618 (21908) 6.4 (390) -- 557(12811) 38.7 (1548)
19 4,8 4820 (170869) 0.3 118) 0.1 (10) 117/) (26910) 2970.0 (11880111
211 5.9 2530 (89689) 2.0 (122) 0.3 (29) 1420132660) 910.0 (36400)
21 6.5 1240 (43958) 4.2 (256) 1.1 (106) 1030123690) 134.0 (5360)
22 7.5 721 (25600) 8.3 (506) 5.7 (272) 618 (14200) 61,4 (1230)

(C'ontinued opposite)

modeling. Samples 15 and 16, however, are well
within the model and are still included, see Fig. 2.
The variables Ba, SO4 and total Fe were r e m o v e d ,
because they showed little systematic variation out-
side a negative correlation between Ba and SO 4.
Their levels are probably determined more by con-
tamination of the water during production than by
the initial in situ composition.
R e m o d e l i n g without samples 19 and 20 and vari-
ables Ba, Fe and SO4 gave eight statistically signifi-
cant PCs. Of these, only PC1-4 are quantitatively
important. Score plots on PC2/PC1 and PC3/PCI are
shown in Figs 2a and b. The samples are well spread
out and there are no outliers. No grouping into
separate water types is observed. The duplicate
samples do not plot at identical scores (dashed lines,
Fig. 2), implying that even minor variations in sam-
pling locations or times influence the sample compo-
sition sufficiently to give significant differences in the
scores in this model.
The four PCs account for 80.0% of the total vari-
ance in the data set as follows: PCI = 39.7%; PC2 =
 Organic acids in Norwegian formation waters

Table I. Continued

Sample Total
number Mg Ba Fe Sr K

l -- 0 0.81 (45) -- --
2 5.1 (124) 2.6 (357) -- 2.5 (219) 12.1 (473)
3 3.7 (9111 2.6 (357) 1.88(1115) 1.5 (131) 13.6 (532)
4 22.9 (556) 11.2 (27) 0 5.3 (464) 9.7 (379)
5 24.6 (598) 0.2 (25) 0.80 (43) 5.8 (508) 9.9 (387)
6 3.6 (87) 2.7 (371) 0.05 (3) 1.4 (123) 5.5 (215)
7 21t.9 (5118) 0.1 (14) 0 6.0 (526) 7.2 (218)
8 2.9 (711) (1.7 (96) 0 11.8 (70) 16.3 (637)
9 3.6 (87) 0.8 (11(I) 0 1.0 (88) 4.1 (16(I)
10 0.8 (19) 0.2 (27) (/.03 (2) 0.2 (18) 2.6 (1112)
11 5.2 (126) 4.4 (604) -- 4.6 (403) 12.3 (481)
12 14.11 (340) 14.11(1923) 0 7.0 (613) 15.11 (587)
13 8.6 (209) 11.6 (82) 11 2.3 (201) 4.6 (180)
14 8.1 (197) (I 0.02 (1) 3.2 (2811) 8.8 (344)
15 5.6 (136) (/.8 (110) 11 1.2 11115) 2.8 11119)
16 6.2 (151) 0.8 (108) -- 1.8 (158) 6.5 (254)
17 9.7 (236) 11.2 (27) 11.211 (11) 3.8 (333) 3.0 (117)
18 27.8 (676) 0 0 1.5 (131) 4.5 (176)
19 482.1/ (I 1713) 6.4 (879) -- 30.8 (2698) I511.11 (5865)
211 122.11 (2965) 11.7 (96) 11.211 ( 1 1 1 1 36.8(3224) 12.1 (473)
21 27.4 (666) 0.5 (69) 0 16.8 (1472) 5.3 (2117)
22 34.2 (416) 0.2 (14) 11 5.6 (244) 11.2 (438)

Sample Temperature Pressure Depth

number (°C) (kPa) (km)

I 154 437011 4.3

2 134 379(X1 4.0
3 142 188110 4.0
4 711 -- 1.9
5 70 -- 1.9
6 130 48900 3.5
7 -- -- 2.(1
8 99 4(I 10(I 2.7
9 99 4111(t0 2.7
10 114 312011 2.8
11 -- 350110 3.3
12 178 415110 4.3
13 85 34800 2.3
14 102 38900 2.1
15 90 344011 2.5
16 105 31111111t 2.6
17 120 26600 --
18 129 25800 3.0
19 121 158011 3.0
211 121 22000 3.0
21 129 2581111 3.0
22 74 2611011 2.0

16.7% ; PC3 = 14.7% a n d PC4 = 8 . 9 % . Cross plots
of the PC2/PC1 and PC3/PC1 loadings are s h o w n in
Figs 2c and d. T h e PCs are not d o m i n a t e d by any
single property. O n PC1, which describes the m a j o r
systematic variations, the acid c o n c e n t r a t i o n s have a
strong positive correlation with alkalinity a n d a w e a k
positive c o r r e l a t i o n with pressure, a n d the m a j o r
inorganic ions (Na, Ca, Sr a n d CI) are strongly
negatively c o r r e l a t e d with the acid c o n c e n t r a t i o n s .
O n PC2 the g r o u p of acid c o n c e n t r a t i o n s are nega-
tively c o r r e l a t e d to the reservoir conditions (tem-
p e r a t u r e , pressure and d e p t h ) , and with the excep-
tion of Na and K the inorganic ions are positively
c o r r e l a t e d to the acids. Principal c o m p o n e n t 3 shows
a positive c o r r e l a t i o n b e t w e e n the organic acids,
d e p t h , t e m p e r a t u r e , Na, H and CI c o n c e n t r a t i o n s .
Principal c o m p o n e n t 4 shows a m a r k e d negative
c o r r e l a t i o n b e t w e e n H c o n c e n t r a t i o n and pressure
a n d w e a k e r negative c o r r e l a t i o n of H to Ca and Sr.
T h e f o u r - c o m p o n e n t m o d e l accounts for the main
6 T. Barth

lated. P r o p a n o i c acid is slightly r e m o v e d f r o m the

others, but a l t o g e t h e r t h e i r relative c o n c e n t r a t i o n s
7.00
m
do n o t carry any significance for this data set. T h e
o organic acid c o n c e n t r a t i o n s are positively c o r r e l a t e d
o
with the m e a s u r e d alkalinity o n all PCs. B e c a u s e the
¢4
alkalinity is m e a s u r e d by p o t e n t i o m e t r i c titration,
~o 1.00
. 3+ '
a n d so includes the organic acid c o n c e n t r a t i o n
o~ t o g e t h e r with c a r b o n a t e ions in the total alkalinity,
such positive c o r r e l a t i o n is expected.

-5.00
0.00 5.00
Component i, Scores Interpretation
Fl(~. 1. Score plot from PCA of the complete North Sea T h e r e is no indication in this s a m p l e set t h a t the
formation water data set, showing the relative scores of the
22 samplcs on PC1 and PC2. m o n o - f u n c t i o n a l organic acid a n i o n s that are f o u n d
in these waters are sufficiently effective as ligands for
any of the m e a s u r e d cations to increase their concen-
part ( > 7 0 % ) of the variance in the data for most trations by increasing t h e i r solubilities or rate of
variables. T h e exceptions are the c o n c e n t r a t i o n s of K dissolution from m i n e r a l phases. Such processes
( 4 5 % ) and to a smaller degree alkalinity ( 6 9 % ) and would be e x p e c t e d to give positive correlations be-
pressure ( 6 8 % ) . t w e e n the organic a n i o n c o m p o s i t i o n a n d the concen-
T h e t h r e e values for the organic acids (concen- tration of the c o m p l e x e d cations. R a t h e r , the tend-
tration of acetic acid, p r o p a n o i c acid a n d total sum of ency in the data is the opposite, the correlations of
c o n c e n t r a t i o n s are very strongly positively corre- cations to organic acids b e i n g strongly negative o n

a
b
3.00
3.00.
o
o

0.00 * +, **
0.00
t *
*~
o • t
m t
~ -3.0o o° -3.o0

-3.00 0.00 3.00 -3.00 0.00 3.00

Component i, Scores Component 1, Scores

% C d
"r
op
0.30 m 0.30
op oR
"149
o
"~ 0.00 "Na 0.00
eklk
o#~C. a ~r
• ot.a me1
o -0.30
~r.a
;? o -0.30
k Tot.a
c.aeetPr.a
"%T "cq~
g "~q
"II

-0~30 OJO0 0130 -0.30 0.00 0.30

Component I, Loadinqs Component I, Loadings

FI(~. 2. Score plots and loading plots from PCA of the Norwegian formation water data set, samples 19 and
20 excluded. Variable symbols: Ac.a. = acetic acid; Pr.a. = propionic acid; Tot.a. = total organic acids; T
= tcmpcrturc; P = pressure; D = depth; AIk = alkalinity; H =hydrogcn ion concentration; Na = sodium;
K = potassium; Ca = calcium; Mg = magnesium; Sr = strontium; C1 = chloride. Duplicatc samples
conncctcd by dashed linc. a. Rclativc scores of samples in thc PC1/PC2 planc, b. Relativc scores of
samplcs in the PC1/PC3 planc, c. Loading plot showing thc contribution from each variable to PC2 and
PCI. d. Loading plot showing the contribution from each variable to PC3 and PC1.
 Organic acids in Norwegian formation waters 7

PC1 and weakly negative or uncorrelated on several "K "D

of the remaining PCs. Especially K shows a conse- sT
quently negative correlation with the organic acids, 0.30 Alk~Ac.a
but here the low level of explained variance should be g, sp Tot.a
~ r .a
kept in mind. Overall, there is a dominant trend of °Ca
"st
higher concentrations of the organic acid anions ~ 0.00 ÷

corresponding to lower concentrations of the ,v

measured cations. On PC2 there is some positive
R -o.3o
correlation between the organic acid concentrations
and the concentration of Ca, Mg, Sr and C1 ions, and "M 9

on PC3 for H, Na and Cl, but the importance of these I _ _

relations are not easily assessed. -0.20 0.I0 o14o

Component i, Loadings

Modeling interdependence of specific properties

The literature includes hypotheses for-the interde- / b

20.00
pendence of different properties of the samples that
are included in this data set, e.g. the dependence of /
acid concentration on temperature (CAROTHERSand *
, /
KnARAKA, 1978). In Fig. 2c there is a weak negative u >J
correlation on PC1 and a stronger negative corre- 10.00
lation on PC2 that can be taken as an indication of
such a relation. To investigate this more specifically, ,/
PLS modeling of the dependence of the acid concen- /
trations on the remaining properties was performed. 0.0C -/--. . . . . . . . . . . . . . . . .
This gave loading plots that were quite similar to the 0.00 5.00 10.00 15.00 20.00

PC analysis, with no increase in the significance of Measured Alk

temperature to the model. Removing the other vari-
ables and modeling only the organic acid concen-
trations and the temperature gave no statistically
significant components, indicating that there is no
measurable systematic correlation between these
properties. This is in agreement with the results
reported previously on a more limited set of samples
(BAR'rH, 1987b) and a general discussion of available
data (ScHoCK, 1988).
The data set includes two measured properties that
are known to be a function of the composition of
several of the dissolved compounds in the sample: the
pH and the alkalinity. To investigate such relations,
PLS was also used to model the dependence of pH
and alkalinity on the remaining variables.
Using the same data set as for the PCA analysis
(i.e. samples 19 and 2(1 deleted) for modeling alka-
linity as dependent on organic and inorganic ion
composition, one significant PLS component was
obtained, which explained 68.9% of the variance in
the data. The PLS2 is of uncertain significance, and
only explains 6.9% of the variance. The PLS2/PLS1
loading plot is shown in Fig. 3a. The PLS1 shows that
the organic acids contribute significantly to the
measured alkalinity and that pressure is also weakly
positively correlated, while the inorganic ionic com-
ponents, depth and temperature are negatively cor-
related to the alkalinity. The PLS2 mainly gives a
positive correlation with depth, K and CI, and nega-
tive with Mg and weakly negative with H. The pre-
dicted alkalinities, when each sample in turn is
excluded from the model used to predict its value,
FIG. 3. PLS prediction of alkalinity as a function of the
remaining variables for the North Sea formation watcrs.
Symbols as in Fig. 2. Dependent variable markcd with a
star. a. Loading plot showing the contributions of the
variables to the axes PLSI and PLS2. b. Plot of measured vs
predicted alkalinity.
gives a quite reasonable reproduction of the
measured values as shown in Fig. 3b. Only samples 9
and 14 differ significantly in predicted and measured
values. Altogether, the alkalinity is clcarly a function
of the overall ionic composition of the water.
Similarly, the pH values for the samples should be
a function of the levels of buffering ions. To investi-
gate this, the modeling of pH (the concentration of H
ion is used for calculations) as a function of the
remaining parameters was also attempted, again ex-
cluding samples 19 and 20 which have very much
lower pH values (4.8 and 5.9) than the rest of the
samples. This results in a three component model
explaining 32.5, 23.0 and 4.5% of the total variance
(total 60%). The score- and loading plots are quite
similar to the initial PCA decomposition, but tem-
perature, depth, Mg and K do not contribute to any
significant degree (<50% variance explained), and
pressure increases in importance and is found to be
strongly negatively correlated to H concentrations.
Figure 4a, the PLS2/PLS1 loading plot, shows the
most important variable contributions. The predic-
tions, again with each sample excluded from its own
prediction model, are compared to the measured
values in Fig. 4b. The predictions do not correspond
8 T. Barth

well with the measured values, indicating that factors
not covered by this model influence the surface-
measured pH. This may be related to the increased
importance of reservoir pressure, because uncon-
trolled degassing of dissolved gaseous species, espe-
cially CO 2, during sampling and measuring pro-
cedures will unsystematically influence the measured
values.
If the waters are mainly carbonate buffered, the
ambient buffer pH is 6.37 and increased alkalinity
should drive the pH toward this vahle. For an acetate
buffer, the buffer pH is 4.75, and an increase in the
organic concentration should give decreasing pH
values over the whole observed pH range. Inspection
of the H ion concentrations plotted against alkalinity
(Fig. 4c) and against total organic acid concentration
(Fig. 4d) show no clear concentration dependence,
and the majority of the samples have pH values >6.4,
irrespective of alkalinity and organic acid concen-
trations. This may be caused by the differences be-
tween the in situ pH values at reservoir temperature
and pressure as opposed to surface conditions. KHAR-
AKAet al. (1986) calculated that in situ pH values may
be as much as 3 pH units less than the surface
measured values, and the buffer pK values also
change over a range of 0.54).7 pH units over a
temperature range of 20-200°C. This means that
equilibrium relations at surface conditions cannot be
used to evaluate water compositions reflecting in situ
reservoir conditions.
AMERICAN FORMATION WATERS
FROM FISHER (1987)
Data set
From the data included in FISHER (1987), only the
samples containing measurable amounts of acetic or
propanoic acid anions were included for comparison
with the Norwegian waters. This resulted in a data set
of 108 samples, with nine variables: concentrations of
acetate (Ac) and propionate (Pr), temperature (T),
depth (D), alkalinity (Alk), total dissolved solids
(TDS), dissolved organic carbon (DOC), dissolved
inorganic carbon (DIC) and oxygen isotopic compo-
sition (61So). Exploratory analyses were performed
on this data set. Because it included many samples
with missing data for alkalinity, DOC and DIC, the
significance limits in the statistical treatment could be
negatively influenced. A reduced data set was de-
fined, excluding the samples containing more than
one missing value. This resulted in a data set of 87
samples, as specified in Table 2, which covers the

Ac.a
a
Tot.a ~ epr.a

0.30 eAlk

~ O, O0
°¢l~Na Z t
J ,
I
"p t
,~ -0.30 ~r 7 *
"ca B + *
t *

-0.30 0.00 0.30 2.00 6.00 10.00 14.00 18,00

Component i, Loadings Variable Tot.a

6.1 > b d
/
,f T~
/
i
, t

J, ,

~/v, 7
8 +

0 7 6.1 2,00 6.00 I0.00 14.00 18.00

Measured pH Variable AIW

FIG.4. Prediction of surface measured pH by PLS. Symbols as in Fig. 2. Dependent variable marked with a
star. a. Loading plot showing the contributions of the variables to the axes of PLSI and PLS2; b. Plot of
measured vs predicted alkalinity; c. Cross plot of pH to total organic acid anion concentration (raM); d.
Cross plot of pH to alkalinity (mM).
 Organic acids in Norwegian formation waters 9

Table 2. Identification of samples from the American data set from FISHER (1987) by score plot n u m b e r s

Basin Field Sample n u m b e r and well

Eastern Poui 1:A-8 2:A-2 3:B-12 4:A-14

Venezuelan 5:A-13 6:A-10 7:A-6 8: A-I
9:A-4

Saman 10:C-12 l l : B-12 12:B-10 13:C-7

14:B-5 15:A-2 16:B-3 17:A-14
18:B-2 19: A-I 2(1:C-3 21:C-14
22: C5X 23: B-I 24:B-15

Teak 25: C-I 26 C-12 27:C-6 28:C-11

29:A-6 30:C-14 31: C-5XX 32:E-14
33:E-8 34:A-9 35:E-12 36: C-7X
37:A-12 38:C-4 39: E-4X 40:A-13
41: E - ) I X 42:D-2 43:E-7 44:D-1
45:D-3 46:D-5 47:D-10 48:E-13
49:B-10 50:D-7

Gulf Coast McAIlen Ranch 51: #1l) 52:#14 53:#15 54:#22

Raton Wildcats 55: St.CO AS #1 56: St.CO A T #1 57: St.CO AS # 2

(Coal degasification 58: St.CO Au #1
wells)
Lorencito 59: M G P Ent. A) 611: M G P Ent. A2 61: M G P Ent. B1
Canyon

San-Juan Cedar Hill 62: Leeper #1 63: Ealum ' C " #1 64: Cahn #1
(Coal degasification 65: State BX #1 66: Keys "G" #1 67: Schneid.B #1
wells)
lgnacio D o m e 68: So.Ute B#1 69: So.Ute B # 3 70: So.Utc C#1
71: F.W.Beut. #1

Piceancc Wildcats 72: Pow. Fed #1 73: Somerset #1 74: Hotchk. R. #1

(Coal degasification
wells)

Denver Spindle 75: Teets #1 76: Miller # I 77: McCannon #1

78: Brown #1 79: Nordcn #1

Red Desert Sweetwater 80: Champ. 451A-1 81: Siberia R. # 6

W a m s u t t e r Arch Carbon 82: Champ. 242A-1 83: Champ. 276E-1 84: Champ. 276-B-I

Sweetwater 85: Champ. 345A-1

Washakie Carbon 86: Coal Gulch B 87: Champ. 226D 88: Champ. 242C
89: Champ. 226G 90: Champ. 261F

Sweetwatcr 91: Champ. 292B 92: Champ. 221(" 93: Tipton II # I

94: Champ. 449A

Western Overthrust Anschutz Ranch 95:WI6-ll6 96:W16-12 97:W19-16

98:W30-14 99:E35-05

Painter Cr. 100: 13-18A 101: 22-18A

Clear Creek 1[12:11-3B 103: 24-9B

Ryckman Cr. 104:#11 105:#27

Chicken Cr. 106: A m o c o - C h a m p . 3 6 3 - B I

Glassc. Hol. 107: Millis W) Unit 1

Pineview 1(18: Bingh. 2~4

l(i T. Barth

a b
4.00 4.00

o
o / * li* * rail*
<,,Z
0.00 /II tl (~,,~, ' ~ 0.00 /ll(D~)l'l;'i" *~
o #
e** ///
-4.00. -4.oo

-4.00 0.00 4.00 -4.00 0.00 4.00

Component i~ Scores Component i, Scores

C
0.40 0.40
%OC
eTDS~ eAc.a
,DIC 0.00 +
0.00 eD
+4 ePr.a
CA1 k edi80 eD

o -0.40
Alk~ DIC •T
~- - 0 . 4 o . ePr.a
~180 eTDS
"DOC'Ac.a

-0.40 0.00 0.40 -0.40 0.00 0.40

Component i, Loadings Component I, Loadings

FI(;. 5. Score plot and loading plots from PCA of the whole American formation water data set after
FiS,ER (1987). Variable symbols: Ac.a. = acetic acid; Pr.a. = propionic acid; T = temperature; D =
depth: A[k - alkalinity; DIC = dissolved inorganic carbon; DOC = dissolved organic carbon; TDS =
total dissolved solids; dlS0 = O~sO isotope in water, a. Relative scores of samples in the PC2/PCI plane; b.
Relative scores of samples in the PC3/PC1 plane; e. Loading plot showing the contribution from each
variable to PC2 and PCI; d. Loading plot showing the contribution from each variable to PC3 and PC[.

whole range of source types and Variations in the
measured properties. Comparison of analysis of the
initial data set and the reduced set showed similar
patterns. The results presented here are therefore
confined to the reduced set.
North Sea waters. H o w e v e r , the inclusion of waters
from low-temperature reservoirs and the clear indi-
cations of several water types in the sample set should
be noted. A more detailed data analysis was per-
formed to give a better understanding of the structure
in the data set.

Data analysis
Data analysis was pcrfl)rmed on the autoscalcd but
otherwise untreated data set. as discussed for the
Norwegian data set. The initial principal c o m p o n e n t
decomposition gave three significant PCs explaining
39.4, 18.7 and 17.4% of the total variance. The score
and loading plots are given in Figs 5aT-d. Inspection of
the score plot shows clear groupings of Samples, and
comparison with the loading plots shows that the low
temperature, high propionate samples, and the high
temperature, high T D S samples give a maximum
separation. Propionate, D1C and alkalinity are.posi-
tively correlated on all PCs, and they are largely
negatively or uncorrelated to temperature, depth' and
TDS. Acetate, D O C and a l s o are positively corre-
lated on PCI and PC2, and uncorrelated to the other
wlriables. This is a different situation than for the
In vestigation of c/ass separation
Inspection of the group of samples that plot at the
left the PCI/PC2 score plot (Fig. 5a) showed that it
was made up of waters from coal beds (sample nos
55-74). Defining these samples as a separate sub-
group, a new P C A was performed on this chlss (20
samples, 9 variables). This gave two significant PCs
explaining 54.6 and 18.8% of the variance. Score and
loading plots are shown in Figs 6a and b. The samples
are reasonably well spread out, though some basin-
related grouping is observed. All variables except
acetate are positively correlated on PC 1, while PC2 is
mainly depth and temperature negatively correlated
to oxygen isotope composition. The variance of acet-
ate and D I C are not well explained (26 and 52%,
respectively) indicating a largely unsystematic wlri-
 Organic acids in Norwegian formation waters 11

ation. Altogether, this pattern fits well with the

general description of waters from coal beds as hav-
ing a high propionate concentration, while acetate is
3.00
found in low and unsystematically varying amounts. i,t
This class model may be used for a quantitative
investigation as to whether there is a statistical differ- ~; 0.00

ence between the composition of the coal-bed waters

I
and the remaining samples, defined here as oil reser-
~ -3.00
voir waters (gas/condensate reservoirs are also in- i

cluded in this term). For this, a model of this latter

class is also required. A P e A of the remaining
samples (63 samples, 9 variables) gave two significant -3.00 0.00 3.00
components that explain 40.7 and 21.2% of the Component I, Scores

variance after three outliers (sample nos 19, 33 and

34) were removed. These samples were classified as
outliers in either class, which indicates that either the
conditions in these two reservoirs are atypical, or that b
mistakes have been made in some of the measure-
0.30
ments of the sample properties. The score and load-
ing plots are similar to the T > 55°C class modeled *DIC
o
below and shown in Figs 7a and b. Again, the samples 0.00
retain some basinal grouping, but otherwise span the
PC plane quite well. The loading plots show that
-0.30
acetate and propionate are now positively correlated,
o
~°e~c. a
~o
c~
and also positively correlated with alkalinity. The
ed180

-0.30 0.00 0.30

Component i, Loadings
a
//
. 2.00
/i
C
/
/
/ t+ 0.30
"~ 0,00 "p
i/h i eK
m / "Mg
/
m+ i I 0.00, ICa +
-2.oo I ,-,C (~Alk
eSr

=* Tot.a
o -0.30. Pr . ~ . ~ c . ~
o~
-2.00 0.00 2.00
"H
Component I, Scores

0.30 0+00 -0.30

Component I, Loadings

"T b! FIG. 7. Score plots and loading plots from PeA of the
American formation waters in the dam sct with T > 55°C,
and comparison with PC3/PCI readings for the Norwegian
0.30 data set. Symbols as in Figs 2 and 5+ Equivalent variables in
b and c marked with the same geometric symbols, a.
i Relative scores of samples in the PC2/PC1 phmc; b. Load-
- 0.00 klk + ~Ac . a ing plot showing the contribution from each variablc to PC2
TDS':~o~DIC and PCI: c. Loading plot of PC3 to PC1 (negative scale) for
o Pr.a the Norwegian data set for comparison (from Fig. 2.)
~+ -o.3o

relation of the organic acids with temperature, depth

-0.30 0.00
Component i, Boadings
FIe,. 6. Scoreplot and loading plot from PeA ()[the coal bed
waters subset of the American formation water data set+
Symbols as in Fig. 5. a. Relative scores of samples in the
PC2/PC1 plane; b. Loading plot showing the contribution
from each variable to PC2 and PC1.
0.30
and T D S is more complex, correlating negatively on
PC1 and positively on PC2. Evaluating the corre-
lations for D I e , D e c and 6tSO is difficult because
their variance is not well cxphiincd by the model
(28%, 48'>/o and 46%, respectively), but the alSO
seems associated with the organic acids, as also noted
12 T. Barth
for other waters (HANOR and WORKMAN, 1986). The
position of alkalinity intermediate between the acids
and DIC is reasonable because they both contribute
to the measured alkalinity value.
Separate modeling of the two classes, coal bed-
waters and non-coal waters, gave a class separation of
5.6 which is good (>>3; WOLD, 1976), and the model
places all samples as clearly in their own class. This
demonstrates that the two groups are statistically
different. Different chemical relations pertain, and
the two classes should be investigated separately.
Because the purpose here is a comparison with oil
reservoir formation waters, the analysis was con-
tinued only for the non-coal waters.
Investigation of temperature domains
If we again look at the relations between the
temperature and the acetate and propionate concen-
trations for the oil reservoir waters in Fig. 7b, the
quantitatively most important correlation is along the
PC1 axis (Fig. 7b), and shows reduction of concen-
trations with increasing temperatures, but a second-
ary positive correlation exists along PC2. These
opposing trends may reflect the opposite tempera-
ture dependence of the two processes that are con-
sidered to remove organic acid anions from the
waters, namely, maximum biodegradation at low
temperatures and increasing rate of chemical decar-
boxylation at higher temperatures. If these processes
together determine the acid concentrations, a maxi-
mum level should be found at some intermediate
temperature (80°C suggested by CAROTHERS and
KHARAKA(1978); 90°C indicated by FiShER (1987)).
To investigate this two new classes were defined,
dividing the non-coal waters into two temperature
classes, T < 65°C and T > 85°C, cf. Table 2 and
FISHER (1987). In the low-temperature set (Fig. 8a,b)
the correlation of organic acid concentrations to
temperature is negligible (very weakly positive),
while the PCA for the high-temperature class shows a
dominant negative correlation along PC1, as in the
T > 55°C model described above (Fig. 7). The low-
temperature class is still clearly different from the
coal waters considered above (class separation of 5,
all samples placed within their own class). But if we
seek class separation between the two temperature
domains, we find that these two classes are not
separate statistically, and class membership for the
individual samples is not clear. If we inspect the data
as a plot of acetic acid against temperature this lack of
separation is understandable, because the plot re-
sembles a normal distribution more than two linear
domains, see Fig. 9. The only class separation poss-
ible is for the small set of high temperature samples
(nos 51-54) plotting to the extreme left in Fig. 7a.
This class is, however, probably separate only be-
cause there are no samples in the data set from
reservoirs with intermediate temperatures.
Because of these temperature relations, a compari-
son between the Norwegian and American data sets
will be most reliable if performed over the same
temperature range. For this purpose a class of Ameri-
can waters was defined which covers the same tem-
perature range as the Norwegian waters. It includes
all oil reservoir samples with a temperature of 55°C or
higher (46 objects, 9 variables). A PCA decomposi-
tion was performed, giving two significant PCs
explaining 51.0 and 19.4% of the total variance.
Score and loading plots are shown in Figs 7a and b.
The basinal groupings are still observable in the score
plot, but the sample space is adequately spanned.
The loadings on PC1, describing the main variance,
shows a negative correlation between depth, tem-
perature and TDS, and the remaining variables. On
PC2, however, all variables are positively correlated,
except for DIC which does not contribute. With
minor variations the PC1/PC2 plot is similar to the
whole non-coal set discussed above.
The main relations found in the model places the
organic acid concentrations as clearly contributing to
the measured alkalinity, as does DIC (Fig. 7b), and
the organic acids also contribute significantly to the
DOC. The main relation with temperature and depth
a
3.00
8
0.00, ,÷
e •
-3.0
-3.00 0.00 3100
Component I, Scores
"D "T b
~, 0.30
=
"DIC "Alk
0.00 "dIBo
,i
-O.JO "DOC
"TDS
-0.30 0.00 0.30
Component I, Loadinga
FIG. 8. Score plots and loading plots from PCA of the oil
reservoir waters subset of the American formation water
data set with T < 65°C. Symbols as in Fig. 5. a. Relative
scores of samples in the PC2/PCI plane, b. Loading plol
showing the contribution from each variable to PC2 and
PC1.
 Organic acids in Norwegian formation waters 13

class of warm waters (T > 55°C) as shown in Fig. 7b,

40.00
we find that the loadings on PC1 are essentially
similar for the common variables. Concentrations of
organic acid anions are positively correlated with
each other and alkalinity, and negatively with depth,
• 4
temperature and TDS or inorganic ions. The arith-
ii •
metic sign of the loadings is changed, but this is a
20.00 calculation artefact and does not change the overall
@1 • • relative correlations indicated in the models. Further
comparison shows that PC3 for the North Sea waters
• mllll m
• T, o and PC2 for the American waters also are essentially

'i !7c:::i:
similar with a positive correlation of the common
" variables in both sets. Figure 7c shows the PC3/PC1
loading with the arithmetic sign on the PC1 scale
0.00
changed for simpler comparison. The remaining Nor-
wegian PC2 and (not significant) American PC3 also
40.00 60.00 80.00 i00.00 120.00 140.00 160.00
show some similarities, but do not completely corre-
Variable T
spond.
In all, the two significant PCs in the American
FIG. 9. Plot of concentration of acetic acid (in millimolars) to
model that explain 70.4% of the variance of the
reservoir temperature (°C) for the American data set.
whole data set correspond quite closely to two signifi-
cant PCs in the North Sea data set that explain 54.4%
is negative, as is the correlation with the bulk of the of the variance of the whole data set (which contains
dissolved ionic material as expressed by TDS. No more variables). This supports the basic assumption
increase in the levels of inorganic constituents, that PCA modeling can be used for showing general
measured as TDS, with increasing concentration of
organic acids is indicated; in fact, the negative corre-
lation is quite dominant, cf. Fig. 7b. T "TDS a
"D "Ac
0.301
Modeling interdependenceof properties %0~ *~l~
o "DIC
"~ 0.00'
As shown for the Norwegian data set, the alkalinity r,/

levels can be modeled as a function of the ionic

composition of the water. It is of interest to see o -0.3"0 •
o~
whether the smaller number of variables in this data
set still gives possibilities for predicting alkalinity.
Using PLS to model alkalinity as a function of the -0.30 0.O0 0.30
other variables in the T > 55°C class gave two Component 1, L0adings
statistically significant components explaining 84.4
and 4.3% of the variance, as shown in Fig. 10a. This
gives a model that covers most of the alkalinity
variations and shows the expected dependence on 60.00.
organic anion concentrations and DIC. The PLS
model gives quite good predictions of alkalinity from
sample composition, as shown in the plot of predicted ** ' t//,,,
vs measured alkalinity (Fig. 10b).
30.00 ,t ,
/
/
COMPARISON OF THE TWO SAMPLE SETS
/

A complete comparison of the statistical models of 0.0

the two sets of formation water data is difficult
because the measured variables are different, but a
comparison of the separately PCA decomposed data
sets can be attempted. This is preferable to modeling
based only on the common variables, which would
remove too much information from the data sets.
Comparing the loading plots from the PCA of the
North Sea data set (Figs 2c and d or Fig. 7c) and the
0.0 30.00 60.00
Measured ALIK
FIG. |0. PLS prediction of alkalinity as a function of the
remaining variables for the T > 55°C American formation
water data set. Symbols as in Fig. 5. Dependent variable
marked with a star. a. Loading plot showing the contri-
butions of the variables to the axes PLSI and PLS2. b. Plot
of measured vs predicted alkalinity.
14 T. Barth
trends in the complex multispecies relations that
determine reservoir water composition, and encour-
ages the use of these trends in constructing chemical
models for formation water composition relations.
While the approach as used here is mainly directed at
general trends found in all areas, a similar modeling
of specific basins may be even m o r e useful in the
investigation of effects of selected specific properties
in otherwise similar waters.
CONCLUSIONS
Multivariate statistical analysis of the two sets of
produced formation water samples, groups the or-
ganic acid concentration and titrated alkalinity as
strongly positively correlated properties, while the
inorganic ion concentrations are mainly negatively
correlated to this group. Thus, the levels of organic
acid ions in the formation waters do not seem to
influence the concentration of the cations to any
significant degree. The correlation of acid concen-
trations to reservoir properties shows no statistically
significant d e p e n d e n c e on temperature. The ionic
composition of the water as described by the
measured properties determines the alkalinity of the
waters to a large degree, and can be used to model it
with reasonable precision. Values of p H cannot be
m o d e l e d precisely, but the increase in importance of
P when the modeling is attempted suggests a contri-
bution from CO2 to this property.
A P C A analysis of the A m e r i c a n formation water
data set from FISHER (1987) shows that the waters
from coal beds have a clearly different composition
from waters from oil reservoirs. If the data set is
restricted to the oil reservoir samples, the relations
between the water composition and reservoir proper-
ties is found to be very similar in Norwegian and
A m e r i c a n waters.
The data base from the Norwegian continental
shelf is continually being expanded as new water
samples b e c o m e available. H o w e v e r , analysis of the
present data set already illustrates the complex
nature of the interdependences of water ionic compo-
sition and reservoir conditions, and should caution
against developing simple univariate models of the
relations between pairs of properties.
Acknowledgements--The oil companies Statoil, Saga Pet-
roleum a.s., Phillips Petroleum Company Norway and
Norsk Hydro A.S. are thanked for providing samples and
information. Olav Kvalheim and Terje Karstang, Depart-
ment of Chemistry, University of Bergen, Bergen, Norway,
and Kim Esbensen, Norwegian Computing Center, Oslo,
Norway, are thanked for helpful discussions about the data
analysis and interpretation. I am grateful to J. B. Fisher for
permitting the use of his data set and for well-informed
refereeing.
Editorial handling: Brian Hitchon.
REFERENCES
AITCHISONJ. (1984) The statistical analysis of geochemical
compositions. Math. Geol. 16, 531-564.
BARTH T. (1987a) Quantitative determination of volatile
carboxylic acids in formation waters by isotachophoresis.
Anal. Chem. 59, 2232-2237.
BARTHT. (1987b) Multivariate analysis of aqueous organic
acid concentrations and geological properties of North
Sea reservoirs. Chemolab. 2,155-160.
BARTHT., BORGUNDA. E., HOPLANDA. L. and GRAUEA.
(1988) Volatile organic acids produced during kerogen
maturation--amounts, composition and role in migration
of oil. In Advances in Organic Geochemistry 1987, (eds U
MA'ITAVELLIand L. NOVELLI), Org. Geochem. 13,461-
465.
BENNETP. C., MELCERM. E., SIEGELD. 1. and HASSETJ. P.
(1988) The dissolution of quartz in dilute aqueous sol-
utions of organic acids at 25°C. Geochim. Cosmochim.
Acta 52, 1521-1530.
CAROTHERSW. W. and KHARAKAY. K. (1978) Aliphatic
acid anions in oilfield waters. Am. Assoc. Petrol. Geol.
Bull. 62, 2441-2453.
FISHER J. B. F, (1987) Distribution and occurrence of
aliphatic acid anions in deep subsurface waters. Geochim.
Cosmochim. Acta 5, 2459-2468.
GAUTIER,D. L. (Ed.) (1986) Relationship of Organic Mat-
ter and Mineral Diagenesis, S.E.P.M. Short Course
Notes 17, 231 pp.
GELADIP. and KOWALSK1B. R. (1986) Partial least squares
regression (PLS): a tutorial. Anal. Chim. Acta 185, 1-17.
HANOR 1. S. and WORKMANA. L. (1986) Distribution of
volatile fatty acids in some Louisiana oil field brines.
Appl. Geochem. 1, 37--46.
KAWAMURAK., TANNENBAUME., HUIZINGAB. J. and KAP-
LAN I. R. (1986) Volatile organic acids generated from
kerogen during laboratory heating. Geochemistry 20, 51-
59.
KHARAKAY. K., HULL R. W. and CABOTHERSW. W. (1985)
Water-rock interactions in sedimentary basins. In Re-
lationship of Organic Matter and Mineral Diagenesis,
S.E.P.M. Short Course Notes 17, 79-174.
KHARAKA Y. K., LAW L. M., CAROTHERSW. W. and
GOERLITZD. F. (1986) Role of organic species dissolved
in formation waters from sedimentary basins in mineral
diagenesis. In Roles of Organic Matter in Sediment Diage-
nesis (ed. D. L. GAUTIER),S.E.P.M. Spec. Publ. No. 38.
KVALHEIMO. M. (Ed.) (1987) Proceedings of the multivar-
iate statistical workshop for geologists and geochemists,
Ulvik, Norway, 2-5 June 1986. Chemolab. 2, 13-243.
KVALHEIMO. M. and KARSTANGT. V. (1987) A general-
purpose program for multivariate data analysis, Chemo-
lab. 2,235-239.
LUNDEGARDP. D. and SENFTLEJ. (1987) Hydrous pyrolysis:
a tool for the study of organic acid synthesis. Appl.
Geochem. 2, 605-612.
MAcGOWAN D. B. and SURDAMR. C. (1988) Difunctional
carboxylic acid anions in oilfield waters. Org. Geochem.
12,245-259.
MASTM. A. and DREVERJ. 1. (1987) The effect of oxalate on
the dissolution rates of oligoclase and tremolite. Geo-
chim. Cosmochim. Acta 51, 2559-2568.
MEANS J. I. and HUBBARDN. (1987) Short-chain aliphatic
anions in deep subsurface brines. Org. Geochem. 11,
177-191.
MORTONR. A, and LANDL. S. (1987) Regional variation in
formation water chemistry, Frio Formation (Oligocene),
Texas Gulf Coast. Am. Assoc. Petrol. Geol. Bull. 71,
191-206.
SCHOCKE. L. (1988) Organic acid metastability in sedimen-
tary basins. Geology 16, 886-890.
SURDAMR. C. and MAcGOWAND. B. (1987) Oilfield waters
and sandstone diagenesis. Appl. Geochem. 2,613-619.
 Organic acids in Norwegian formation waters 15

WOLD S. (1976) Pattern recognition by means of disjoint
principal component models. Pattern Recognition 8, 127-
139.
WOLD S. (1978) Cross validitory estimation of the number
of components in factor and principal component models.
Technometrics 20, 397-405.
WOLD S., ALBANOW., DUNN W., EDLUNDU., ESBENSEN
K., GELADI P., HELLBERGS., JOHANSSONE., LINDaERG
W. and SJOSTROMM. (1984) Multivariate data analysis in
chemistry. In Chemometrics: Mathematics and Statistics
in Chemistry (ed. B. R. KOWALSKI),pp. 17-95, Reidel.