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Arkansas Water Resources Center
TRACE METAL AND MAJOR ELEMENTS IN WATER-SOLUBLE ROCKS OF NORTHWEST ARKANSAS
PREPARED BY:
George H. Wagner, Kenneth F. Steele and Doy L. Zachry, Jr.
PUB-036
October 1975
ARKANSAS WATER RESOURCES UNIVERSITY OF ARKANSAS
112 OZARK HALL FAYETTEVILLE, ARKANSAS 72701
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I TRACE METALS AND MAJOR ELEMENTS
INWATER-SOLUBLE ROCKS OF NORTHWEST ARKANSAS
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I by
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.1 George H. Wagner, Kenneth F. Steele and Doy L. Zachry, Jr.
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IARKANSAS WATER RESOURCES RESEARCH CENTER
I Publication No. 36
I1 October, 1975
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11 Table of Contents
Trace Metals and Major Elements inII Water-Soluble Rocks of Northwest Arkansas
~I I. Introduction 1
II. Experimental. 5
1 III. Discussion 8
IV. Tables. 17
1 Table 1 Comparison of Analyses on StandardsTable 2 Comparison of Hydrochloric and Acetic Acids
as Solvents for St. Joe Limestone. 1 Table 3 Comparison of N20-A?etylene and Air-Acetylene
Flames for Ana1ys1s of Ca and Mg'f Table 4 Kessler Limestone Analyses
1 Table 5 Brentwood Limestone Analyses
.Table 6 Pitkin Limestone Analyses
Table 7 St. Joe Limestone Analyses1 Table 8 Summary, Average Analyses for Kessler, Brentwood,
Pitkin and St. Joe LimestonesTable 9 Peaks in Areal Distribution of Fe, Mg, Mn and Sr
for Various Limestones
1 V. Figures.1 Figure 1 A Generalized Stratigraphic Column for Northwest
ArkansasFigure 2 Sampling LocationsFigure 3 E-W and N-S Variation of Fe Content of Limestones
1 Figure 4 E-W and N-S Variation of Mg Content of LimestonesFigure 5 E-W and N-S Variation of Mn Content of LimestonesFigure 6 E-W and N-S Variation of Sr Content of Limestones1 Figure 7 Na/Ca Ratio versus Mg/Ca Ratio of LimestonesFigure 8 Sr/Ca Ratio versus Mg/Ca Ratio of LimestonesFigure 9 Sr/Ca Ratio versus Na/Ca Ratio of LimestonesFigure 10 Zn/Ca Ratio versus Mg/Ca Ratio of Limestones
1 Figure 11 Mn/Ca Ratio versus Fe/Ca Ratio of LimestonesFigure 12 Co, Cr and Ni Content versus Mn Content for Kessler,
Brentwood, Pitkin and St. Joe Limestones1 Figure 13 Co, Cr and Ni Content versus Fe Content for Kessler,Brentwood, Pitkin and St. Joe Limestones
Figure 14 Co, Cr and Ni Content versus (Fe/Ca + Mn/Ca) for1 Kessler, Brentwood, Pitkin and St. Joe Limestones
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1 Trace Metals and Major Elements inWater-Soluble Rocks of Northwest Arkansas
1 George H. Wagner, Kenneth F. Steele and Doy L. Zachry Jr.,Department of Geology, University of Arkansas, Fayetteville, 72701
1 ABSTRACT
1 Trace metals in limestone are potential water contaminants be-
cause they can enter the ground water when the limestone is dissolved
1 by carbonic acid and other naturally occurring acids. Four local
1 limestones, the St. Joe and Pitkin Formations (Mississippian) and
the Brentwood and Kessler Members of the Bloyd Formation (Pennsylvanian)
.1 were sampled in a five county area in Northwest Arkansas. Atomic
absorption analyses were made for Na, K, Mg, Ca, Zh, Cu, Ba, Fe, Co,
1 Cr, Ni, Mn, Li and Sr on the acid soluble material of the samples.
1 All the limestones are relatively pure CaCO3 with Pitkin the purest,
93.4%. Calcium and acid soluble material values varied only 3-5%
1 from the average among the limestones whereas 71-108% variation
occurred for Fe, Mn, K and Cr. Other elements showed intermediate
1 variations. Only Fe and Mn are present on the average in the 1ime-
1 stones at concentration levels which might lead to contamination of
ground water to undesirably high levels. Analyses compare well with
1 the reported "average'! limestone except for acid insoluble elements
which were not dissolved in our scheme and lithium (1.5 ppm average
1 vs 20 in reference). Ratios of Sr/Ca and Mg/Ca were similar to
II reported values for limestones of comparable geologic age. Maxima
in the areal variation of these ratios occurred at about the same
1 latitude for three of the formations. The areal variation of Fe/Ca
and Mn/Ca was also determined for the four limestone formations.
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IInterelement correlations in the limestones showed: Na, Sr, Li, I
Fe and Zn contents increased with Mg content; Mn and Cr increased
with Fe content. Indications were obtained that detrital and other I
materials not in the calcite structure can be determined by their
relative insolubility in acetic acid compared to hydrochloric acid. I
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I Trace Metals and Major Elements inWater-Soluble Rocks of Northwest Arkansas
I George H. Wagner, Kenneth F. Steele and Doy L. Zachry Jr.,Department of Geology, University of Arkansas, Fayetteville, AR 72701
I Introduction
I In previous reports (Wagner and Holloway, 1974; Wagner, 1975)
I the elemental content of local rain water, including trace metals
was given. The present report is concerned with another potential
I source of trace metals, the local water-soluble rocks. Data from
both sources, rain water and limestones, are being used in a report
-II now in progress to explain the elemental composition of local ground
II water.
Potential sources of trace metals in ground water must include
I the water soluble rocks such as limestone and dolomite. These two
are the principal water-soluble rocks for Northwest Arkansas because
I other candidates such as evaporites, gypsum and halite, are missing
and the silicates such as chert are less soluble. Both limestone
I and dolomite are rather insoluble in water by themselves.* However,
I as illustrated below for limestone (ls), the rocks are dissolved by
the CO2 of the air which dissolves in water to make carbonic acid
I (H2C03) , a weak acid.
I *Comparative water solubility data are given below.
Solubilit6 ppm of Ca++ at Saturation(25OC)I Rock Mineral Formula Product(25 C) no CO2 added atmospheric CO2
limestone calcite CaC03 10=~735 5.4 20I dolomite dolomite CaMg(C03) 2 10_4 62 «5.4 ~20
gypsum gypsum CaS04.2H20 10. 600 600
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CO2 + H2O = H2CO3 (1) I
H2CO3 = H+ + HCO3 (2)
CaCO3(ls) + H+ = Ca++ + HCO3 (3) I
The air contain~ only.c3% CO2 and in.sPite of gO~d equilibration with I
water atmospher~c CO2 would only br~ng the calc1um content to about
20 ppm in water. Ground water frequently contains 40 ppm or more of I
calcium. This is attributed to plant respiration and decay of or-
ganic matter which can cause soil air to contain many times as much I
CO2 as the air above ground (see p. 136 of Hem, 1970). The soil
also contains organic acids which can dissolve limestone. Magnesium, I
.either from dolomite, or as a substitute ion for calcium in limestone I
dissolves by similar mechanisms. Calcium and magnesium which toge-
ther make up almost all the hardness of water, originate in the I
water-soluble rocks and find their way'into water as illustrated above.
The same pathway should be followed by trace metals and other ions I
which substitute for calcium or magnesium in limestone or dolomite. I
Magnesium, up to about 5 mol percent, can substitute for calcium
in calcite, the limestone mineral. It is expected that heavy metals I
in trace amounts, less than 1%, can do the same. Strontium, iron,
barium, zinc, and other divalent ions which form carbonate minerals I
should form solid solutions in calcite of 1% or less. See pages 7-9 I
of Graf (1960) for a more detailed discussion. Monovalent ions such
as sodium and potassium may do the same. Furthermore, any of the I
trace elements could occur as interstitial or occluded minerals in
limestone. Many minerals such as pyrite, clays, etc. can form in I
the limestone by authigenic and diagenetic processes or occur as II
detrital material. All the trace elements listed above and others
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I have been found in carbonate rock (Wolf, et. al., 1967). .
Dissolution of limestone by carbon dioxide as illustrated by
I equations (1) to (3), and by natural organic acids or by a strong
acid such as sulfuric acid from oxidation of pyrite, would be
I expected to librate the trace elements. By such dissolution the
I trace elements become potential pollutants for ground water. The
extent to which the elements actually dissolve in the water is a
I function of the acidity (pH) and oxidation potential (Eh) of the
I solution and the solubility product of the chemical species involved.
The trace element content of the water-soluble rocks thus measures
-I potential water pollution.
A generalized stratigraphic column for the Pennsylvanian and
I Mississippian age rocks of Northwest Arkansas is shown in Figure 1.
There are five limestone formations which, proceeding from youngest
I to oldest are: Kessler, Brentwood, Pitkin, Hindsville*and St. Joe.
I This report is concerned with the elemental analyses of all of
these except the Hindsville. Dolomite rocks are much older (Ordovi-
I cian), are at much greater depths in Northwest Arkansas and become
exposed only in northcentral Arkansas. In addition to the limestone
I formations mentioned above the Prairie Grove and Boone Formations
I shown in Figure 1 can be highly calcareous. The Boone Formation is
the aquifer most used for wells in the rural areas of Northwest
I Arkansas.
Figure 2 shows the sampling locations for the limestones used
I in this report. As shown in the following summary, 65 samples from
I 25 locations were analyzed.
I* Member of Batesvi11e Formation
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Number of Total Number ofLimestone Locations Sampled Samples Analyzed I
Kessler 4 8Brentwood 10 18 IPitkin 4 18St. Joe 7 21
Grand Total E 65 I
Analyses were made by dissolving the samples in acid and analyzing
the acid soluble portion by atomic absorption for the following 14 I
elements: Na, K, Mg, Ca, Zn, Cu, Ba, Fe, Co, Cr, Ni, Mn, Li and
Sr. Calcium is the most concentrated element and because of the I
high calcite (CaCO3) content most of the samples approach the theore- I
tical maximum of 40% calcium. Magnesium and iron are usually the
.next most abundant elements, occurring up to a few percent, followed I
by manganese which is in the tenths of a percent range in several
samples. Other elements are in the O.OX% (XOO ppm) range or less. I
As pointed out earlier, trace metals can originate from sub-
stitution in the calcite structure or from diagenetically formed I
minerals outside the structure. The analyses do not differentiate I
as to which of these is the source of the trace metals. However,
by comparing the metals dissolved by a weak acid (acetic) with those I
dissolved by hydrochloric acid, indications were obtained that iron
Iand other trace heavy metals, except manganese, are predominantly
from interstitial sources. Magnesium can come from both sources I
and Mn, Na, K, Li, Sr and Ba come primarily from the structure.
Whether the interstitial material was formed by remobilizing of the I
limestone or from foreign sources is not known.
Interrelationship of the various elements in the limestones are I
examined in this report. Correlation of the atomic ratios with age I
of the rocks and with determinations by other workers on other lime-
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I stones is also examined. The areal variation of the concentration
of various elements in the limestones is depicted and discussed
I with relation to their depositional setting. Implications of the
I results to the water chemistry of the area are given.
Experimental
I All Kessler samples were supplied by Mr. John G. Williams and
I the samples are further described in his M.S. thesis (Williams, 1975).
Brentwood samples were collected by one of us (Zachry). Eight of
I the Pitkin limestone samples correspond to those in Bennett (1965),
while the remaining 10 were field collected by the authors from
-II known Pitkin localities. Samples of St. Joe limestone were supplied
II by Mr. John D. Mc.Farland III and correspond to samples in McFarland
(1975).
'II Field samples were crushed with a hammer and 25-50 grams, free
of surface weathering and large fossils, were selected for further
II crushing in a mortar and pestle to about minus 325 mesh. Five grams
of the 325 mesh material were treated with 10 ml of concentrated
II hydrochloric acid for 13-19 hours in a 250 ml Erlenmeyer flask, then
II diluted with 20 ml of deionized distilled water and filtered through
a weighed 0.45 ~m Millipore filter. The weight of the undissolved
II residue was determined and all results were calculated on the amount
of material dissolved. The filtrate was diluted to 100 ml with
II deionized distilled water and analyzed by atomic absorption (A.A)
II spectrophotometry. Because of the large amount of calcium there was
appreciable molecular absorption at the standard A.A. analytical
II lines and adjacent lines were used to make corrections for this
molecular absorption. A summary of the analytical and correction
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lines is given below. .IAnalytical Line for Measuring
E!e~e~~~ Line (A ) Molecular Absorption (A )
Zn 2139 2100 ICu 3247 2961Co 2407 2331 INi 2320 2326
No suitable lines for making corrections for molecular absorption
for Pb and Cd could be found and analyses for these elements were I
abandoned. In the case of nickel where the 2326 A line is not non- I
absorbing the following relationship was used to find the molecular
absorption (m): I
B-m S-= -= constant Ib-m s.where B = % absorption of unknown at 2320 A
b = % absorption of unknown at 2326 AIs = % absorption of Ni standard at 2320 A
s = % absorption of Ni standard at 2326 A
Values of B should be kept, by dilution, to 20 and below for greatest I
accuracy, because the assumption made here is that the absorptions
are proportional when in reality it is the absorbances. At low I
values of B this assumption is approximately true. I
Atomic absorption measurements were made with a Perkin Elmer
Model 303 spectrophotometer. Recommendations and methods of the I
Perkin Elmer Handbook (Anonymous, 1973) were followed. Detection
limits and sensitivities for the various elements are given in the I
Handbook. Results in this study are reported to the number of figures I
considered significant by the author based on noise level and size
and reproducability of blanks. II
To measure the accuracy of the analytical scheme used here, two
standard rock samples were analyzed along with the unknowns. The II
rock standards, No. 401 and No. 402, are limestone samples from G. II
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1 Frederick Smith Company of Columbus, Ohio. Results of our work and
1 that of the supplier are compared in Table 1. Agreement is excellent
except in the case of Ba and Fe. In our scheme BaSO4 would not be
1 dissolved. Thus Ba would be low in those samples containing sulfate.
In the case of iron there is apparently an appreciable amount in the
1 acid insoluble material which would not be measured in our scheme.
In one set of experiments using St. Joe limestone samples, the
II relative solvent effects of acetic acid and hydrochloric acid were
1 measured. Acetic acid would not be expected to dissolve, at least
in the time intervals employed, iron oxide, pyrite and other expected
.1 interstitial compounds. However, because acetic acid does. dissolve
calcite those atoms substituted for Ca++ in the lattice should also
II be dissolved as well as fluid inclusions. Fluid inclusions have
II been reported in calcite (p 27 of Wolf, .et. al., 1967). These should
be dissolved by either of these acids as the calcite is dissolved.
1 Table 2 compares the relative dissolving power of acetic and
hydrochloric acid for 14 elements on 6 samples of St. Joe limestone.
II Those elements generally showing little or no difference between the
II two acids are Ca, K, Mn and Sr. Thus it is concluded that these
elements are solely in the structure. The elements Na, Ba and 1i
II show an increase of approximately 20% for acetic over hydrochloric
acid, which is the same amount that acetic exceeded hydrochloric in
II acid insoluble material. In other words, calculated on initial
II weight of sample basis rather than on the basis of "% dissolved",
the values for the Na, Ba and 1i are the same for the two samples.
II This indicates that about 20% of these three elements come from
easily dissolved structure sources, probably fluid inclusions.
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Of the remaining elements, 32% of the magnesium is indicated as I
coming from non-lattice sources, 45% for Zn, 74% for Fe, 73% for Ni
and similarly large amounts for copper and cobalt. Chromium was I
below detection limit in the case of both acids. I
In the above cited experiments with acetic and hydrochloric
acids, magnesium was determined by the use of A.A. employing an I
air-acetylene flame. Calcium results were with a N20-acetylene
flame and were higher than with air-acetylene for the acetic acid I
samples. Calcium was the same for both flames on HCl dissolved I
samples. Apparently there is an acetate complex with calcium which
.requires the hotter N20-acetylene flame to break it. Because of I
the similarity of Ca and Mg in chemical properties, magnesium was
also determined using both flames. The results for calcium and I
magnesium on acetic acid and HCl dissolved samples using air-acety- I
lene and N20-acetylene flames are compared in Table 3. It will be
noted that for acetic acid dissolved samples, the results for cal- I
cium, on the average, are 29% greater using the N20-acetylene flame
and only 5% greater for magnesium. Because the higher calcium results I
agree more closely with the hydrochloric acid values which in turn
agreed with the standards, the higher values for calcium are assumed I
to be the correct ones. The magnesium values are, within experimental I
error, the same for the two flames.
D o 0 I1.SCUSS1.on
Analyses for Kesslert Brentwood, Pitkin and St. Joe Limestone I
are summarized respectively in Tables 4,5,6 and 7. Locations for
the collection dates are also given in the tables. Sample numbers in I
many cases correspond to those in cited M.S. theses where the lithology, I
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petrography and environment of the samples are given. Average .
analyses for the four limestones are compared in Table 8. Important questions are the amount of compositional variation ..,
at a given location, from location to location, and for the various
limestone formations. The last part of this question is answered
in Table 8 by the "per cent of maximum deviation from the average"
for the various analyses. These maximum deviations from the average
are: 3-5% for Ca and acid insoluble material; 17 to 34% for Co, Li,
Cu, Zn, and Ba; 45-56% for Mg, Sr, Na, Ni; 71-108% for Cr, Mn, K,
and Fe. These variations are considered small in view of the several
million years difference in geologic age and an areal extent of
several counties which are represented
All the limestones are relatively pure CaC03 with Pitkin having
the most acid soluble material, 9'7.4%, and of this 96.4% was CaC03
for an overall CaCO3 content of 93.4% (0.974 X 96.4). The remainder
is probably moisture (samples were air dried), sulfates, phosphates,
aluminates, silicates and organics, materials for which no analyses
were made. While having the highest CaCO3 content, the Pitkin was
lowest in Mg, Zn, Co, Mn and Li, again indicative of its higher
purity. The Kessler limestone was highest in Mg, Cu, Fe, Cr and Mn
and lowest in Ca and K. The Brentwood limestone had the lowest
average acid soluble material, 90.8%, a relatively high level of Mg,
Fe and Mg, but below Kessler and the highest Zn, Li and Sr. St. Joe
limestone was about tied with Brentwood for lowest acid soluble
material, 90.9%, but had as high a Ca content as Pitkin based on
soluble material, 38.6%, the highest K and lowest Fe, Cr, Na and Sr
contents, indicative of the high purity of the soluble material.
10 I
The last line of Table 8 gives the composition of an average I
limestone from Wolf, et. al., (1967). The average of the four North-
west Arkansas limestones agree well with this "world" average in the I
case of Zn, Co, Cr, and Ni and agree with the higher value of 1400 I
ppm for Mn given by Wolf. Agreement is fair in the cases of Sr
(333 ppm vs 475 of reference) and Fe (0.84 wt. % vs 1.13 of reference). I
Agreement is poorest in the cases of K (44 ppm vs 1600 of reference),
Na (156 ppm vs 700 of reference), Cu (2.2 ppm vs 14 of reference), I
Ba (41 ppm vs 150 of reference) and Li (1.54 ppm vs 20 in reference). I
We have no explanation for Li but the other differences are believed
.to be due to the reference using a total analyses, which of cou~se I
includes acid insoluble material, whereas we have an analysis of
only acid soluble material. The much higher Na and K is probably I
due to the presence of clays in the "world" average samples which I
were commonly analyzed by emission spectrograph.
Sr/Ca and Mg/Ca average ratios are shoWn in Table 8 for the I
four limestones. Kessler and Brentwood are Pennsylvanian age lime-
stones. A Sr/Ca ratio of 0.05 atom % was obtained for these two I
limestones which compares to 0.072 obtained by Kulp, et. al. (1952) I
for Indiana limestones of Pennsylvanian age and a range of 0.043-0.13
for various other Pennsylvanian age limestones. The same investi- I
gators obtained 0.046 atom % Sr/Ca for Indiana limestones of Mississip-
pian age and a range of 0.014-0.173 for various other Mississippian I
age limestones. Our two Mississippian age limestones have Sr/Ca atom I
% ratios of 0.04 (Pitkin) and 0.02 (St. Joe), reasonably close to
the Indiana limestone values. I
The tabulated analyses for the various limestones in Tables 4
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-to 7 should be consulted for an appraisal of the vertical variation -.of the elements from location to location. At a given site the
.samples differ only in the level of the section from which they
were taken. It is difficult to make a general statement for so
many locations and for 14 elements.
Three pink limestone samples were selected from St. Joe lime-
stone samples and analyzed in order to determine if their pink
color is due to a unique concentration of some element. Manganese
was suspected because MnCO3 is pink. However, there is nothing
unusual about the Mn concentration nor of other elements. In sam-
ples 7 and 8 the pink was concentrated in the acid insoluble material.
Because of this the acid insolubles were analyzed and are shown in
Table 10. The acid insoluble material are high in Na and K (both
colorless ions), and in Fe, Ti and Ni. The latter are probably in
ilmenite, a dark mineral. It is suggested that the pink color is
due to organic material because the analysis of the inorganic
material does not suggest a likely candidate.
The areal variation of Fe, Mg, Mn and Sr for the four limestone
formations are shown in Figures 3 to 6. In these figures the North-
South distance, using 950 longitude as a base line, and the East-West
dist~nce, using 370 latitude as a base line, for a given sampling
site have been plotted against the average elemental concentrations
for that site. Pitkin limestone shows the least areal variation in
the concentration of Fe, Mg and Mn. St. Joe has the least areal
variation in Sr concentration. The distances corresponding to the
peak concentrations in Figure 3 to 6 have been summarized in Table 9.
Neglecting diagenetic effects and considering only the initialII
.12II
environment of formation, the higher Mg/Ca and Sr/Ca ratio might
be expected near shore in lagoons where the life of calcareous
secreting organisms fluorished and the ratio of biogenic to inor-
ganic calcite is high. Using this as a criteria, shorelines are
indicated for: Kessler Formation at N-S distance of 75 miles and
E-W distance of 46 miles; Brentwood Formation at N-S distance of
73 to 79 miles and E-W distance of 36 and 61 miles, Pitkin Forma-
tion at N-S distance of 79-80 miles and E-W distance of 39 miles,
St. Joe Formation at N-S distances of 36 and 60 miles and E-W dis-
tance of 28 and 43 miles. It is interesting that the N-S distance
indicative of a shoreline is about the same, 73-80 miles, for the
Kessler, Brentwood and Pitkin Formations.
Interrelationships of the metals in limestone are shown in
Figures 7-14. In these figures average analyses for a given site
are plotted if more than one sample was analyzed from the site.
The data are given as atomic % of calcium in many cases. Sr and
Na contents of all four limestones correlate well and increase
smoothly with Mg content (Figures 7,8 and 9). In a less precise
way, Li, Fe and Zn increase with Mg content. This latter relation-
ship is exemplified by Figure 10 for Mg/Ca versus Zn/Ca. Potassium
showed rlO similar correlation with Mg. Fe and Mn correlate reasona-
bly well, incr~asing together as shown in Figure 11. Cr tends to
increase with Fe while Co and Ni correlate poorly with Fe (Figure
13). Co correlates better with Mn whereas Cr and Ni correlate poorly
(Figure 12). Cr correlates better with the SU!'1 of the atomic per-
cent of Fe + Mn (Figure 14). Determining the ,duses of these
correlations is very difficult because of many variables and processes
1 13
II involved. Limestone may be formed by inorganic or biogenitic pro- .
cess. Each involves environmental factors. Biogenitic process
II involve phylogenic factors since different organisms synthesize
II skeletal material of unique trace element composition.
Implications of these results to the water chemistry of North-
II west Arkansas are listed below.
1) Limestones in Northwest Arkansas have normal compositions
II and are comparable to those of similar geologic ages in
II other areas. Thus no unusual contributions to the chemistry
of the local water is to be expected above the normal
.1 contribution to hardness.
2) Of the four limestone formations studied, Kessler has the
II greatest potential for contributing to the hardness and the
1 heavy metal content of ground water. This is because it
has the highest magnesium and heavy metal contents of the
II various limestones. However, it occurs highest in the
stratigraphic column and is least likely to be an aquifer.
II 3) The following metals in all samples analyzed were at such
II low concentrations as to pose no problem of water pollution
via the route of dissolving limestones: Zn, Cu, Ba and Cr.
1 This statement is based on the following type of calculations.
As an upper limit Northwest Arkansas waters contain 50-100
II ppm of Ca (Steele et a1, 1975). Assuming 100 ppm Ca in the
water, that all the calcium comes from a limestone and that
II the Ca/metal ratios in the limestone persist into the water,
II then the four limestones would yield water of the following
metal contents, using the average analyses for these 1ime-
II
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14 I
stones from Table 8. I
Ippb
limestone ~ ~ ~ ~ ~ .fE ~ ~ g ~ I
Kessler 9 1 12 4781 2 3 3 568 0.5 108
Brentwood 11 0.5 <5 3074 2 2 2 401 0.5 113 I
Pitkin 6 0.6 14 671 1 2 2 84 0.3 88
St. Joe 6 0.5 14 486 2 <0.5 4 448 0.3 44 I
Limits* 5000 1000 1000 300 -50 -50 --I
Co, Ni. Li and Sr based on the above table would also
.yield very low concentrations in water from dissolving I
limestones. However, no safe upper 1imits.are available I
for comparison. It will be noted that Fe and Mn could
easily exceed their recommended upper limits. I
4) It should be emphasized that the above statements are
based on averages. A unique composition of any of the I
limestones might be encountered at a given site. For
example, the St. Joe limestone which is the basal member II
of Boone Formation, a favorite aquifer in Northwest Arkansas, II
exhibited unusually high Mn and Ni contents at site GCG.
Several samples of St. Joe contained pyrite (FeS2) and I
could be a source of H2S in ground water.
III
* U.S. Public Health Service, 1962. II
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II Acknowledgements ~
II We wish to acknowledge the help in sample preparation and in
II the analyses given by Mr. Robert Tehan and Mr. S. J. Borengasser II.
Financial assistance was provided in part by the Office of Water
II Resources Research Act of 1964, Public Law 88-379 and administered
through the Water Resources Research Institute of Arkansas, and
II the Research Reserve Fund of the University of Arkansas, Fayetteville.
II
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I " ," ~
II
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Literature Cited .I
Anonymous, 1973, Analytical Methods for Atomic Absorption Spectropho- Itometry, Perkin Elmer Corp., Norwalk, Conn. U.S.A.
Bennett, Robert L., 1965, A petrographic study of a Pitkin reef com-plex located near Wesley, Arkansas, M.S. Thesis, University of IArkansas.
Graf, D.L., 1960, Geochemistry of carbonate sediments and sedimentary Icarbonate rocks. Illinois State Geol. Surv. Circ. No. 297,39 pp.
Hem, John D., 1970, Study and interpretation of the chemi"cal charac-Iteristics of natural water: U.S. Geol. Survey Water-Supply
Paper 1473, 2nd ed., 363 p.
Kulp, J.L., 1961, Geologic time scale, Science, 11l (No. 3459), 1105- I1114.
, Turekian, K.K. and Boyd, D.W., 1952, Sr content of lime- I.stones and fossils. Bull. Geol. Soc. Am., 63: 701-716.
McFarland, John D. III, 1975, Lithostratigraphy and conodont biostrati-Igraphy of Lower Mississippian strata, Northw~st Arkansas, M.S.
thesis, University of Arkansas.
Shaji, R. and Folk, R.L., 1964, Surface morphology of some limestoneItypes as revealed by electron microscope. J. Sediment. Petrol.,
34: 144-155.
Steele, K.F., MacDonald, H.C. and Grubbs, R.S., 1975, Composition of Iground water in Northwest Arkansas, Arkansas Farm Research,January-February, p 15.
U.S. Public Health Service, 1962, Drinking water standards, 1962: IU.S. Public Health Service Pub. 956, 61 p.
Wagner, G.H., and Holloway, R.W., 1974, Sodium, potassium, calcium Iand magnesium content of Northwest Arkansas rain water in 1973and trace metal analyses of 1974 rains, Arkansas Water Resources IResearch Center, Publication No. 25.
Wagner, G.H., 1975, Sodium, potassium, calcium and magnesium contentof Northwest Arkansas rain water in 1974, Arkansas Water Resources IResearch Center, Publication No. 29.
Williams, John G., 1975, Sedimentary petrology of the Kessler lime-Istone, Washington and Crawford counties, Arkansas, M.S. thesis,
University of Arkansas.
Wolf, K.H., Chilingar, G.V., and Beales, F.W., 1967, Elemental com- Iposition of carbonate skeletons, minerals, and sediments, inDevelopments in Sedimentology 9 B, Carbonate Rocks, Physicaland Chemical Aspects (Chilingar, Bissel and Fairbridge editors), IElsevier, New York, N.Y., 413 p.
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119
ITable 3
I Comparison of N20-Acety1ene and Air-Acetylene Flames
for Analysis of Ca and Mg
1 Wt. % of Acid Solub1es Wt. % of Acid Solub1es
Flame Calcium % Dev!ation(N20/air)for: Magnesium % Devi.ation(N2.2L~!:2ii.1 Sample No. Oxidant HC1* HOAc* HC1 HOAc HOAc* HOAc
BV-1 air 38.6 29.8 0.187N20 38.8 39.2 + 0.52 + 31.5 0.197 + 5.3
1 BV-2 air 38.0 31.0 0.230N20 39.0 39.6 + 2.6 + 27.7 0.249 + 8.3
1 BV-3 air 37.5 --N20 36.5 --2.7 -
.1 BV-4 air 39.7 --N20 39.9 -+ 0.50 -
BV-5 air 36.1 --1 N20 37.2 -+ 3.0 -
WEP-1 air 39.6 32.0 0.1941 N20 39.8 39.9 + 0.50 + 24.7 0.203 + 4.6
WEP-2 air 38.4 30.2 0.162N20 38.5 39.1 + 0.26 + 30.1 0.165 + 1.9
1 WEP-3 air 39.6 --N20 38.9 --1.8 --
1 WEP-4 air 37.4 --N20 37.3 --0.27 -
I WEP-5 air 40.0 --N20 39.7 --0.76 -
BF-1 air 40.0 --1 N20 39.8 --0.50 -
BF-2 air .40.1 31.8 0.2151 N20 39.1 40.1 -2.5 + 26.1 0.233 + 8.4
BF-3 air 39.3 29.5 0.150N20 39.2 39.8 -0.25 + 34.9 0.155 + 3.3
1 BF-4 air 39.3 --N20 39.4 -+ 0.25 -
1 401** air 36.1 --N20 36.5 -+ 1.1 -
1I
I20 I
Table 3 (continued) II
Wt. % of Acid Solubles Wt. % of Acid SolublesFlame Calci\nn % Deviation (N20/air) for: Magnesi\nn % Deviation(N20/air)for:
ISample No. Oxidant HCl* HOAc* HCI HOAc HOAc* HOAc
402** air 32.6 --N20 34.0 -+ 4.3 ---I
GCG-U3B6 air 37.2 --N20 38.8 -+ 4.3 ---
GCG-U3T air 38.6 --IN20 38.9 -+ 0.78 ---
GCG-U5A air 37.7 -- IN20 38.2 -+ 1.3 ---
GCG-U5C air 38.1 -- I.N20 39.0 -+ 2.4 '- --
GCG-U6T4 air 37.5 --N20 43.1 -+14.9 ---I
Average deviation % --+ 1.3 + 29.2 -+ 5.3 I
* Solvent for limestone, HOAc = acitic acid (50%); HCI = conc. hydrochloric acid. I** Analyses on dry wt. basis, all others on amount dissolved.
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II
I
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I
II
.1
IFigure 1.
I A Generalized Stratigraphic Column for Northwest Arkansas
I
IIIIIIII
I
II ~ z CI)
~ 0 t-
~ j:: COLUMNAR ~~ c:I C/) ~ MEMBER SECTION ~LL. DESCRIPTION '
>- (!: ~z0 :r-C/) LA.. t-
I TRACE ---Si 1 tstone, c1aystone, gray to~ CREEK b1ack, lenses of limestone.~ () KESSLER g Reddish-brown to gray limestone.
I Z b DYE SHALE (\J Siltstone, c1aystone, gray tooCt ~ I black, shaly."::i CD WOOLSEY g Si1tstone, sandstone, and coal.
I t> BRENTWOOD A1ternating 1 imestone-sandstone.
Z PRAIRIE 0 Limestone and sandstone, bedsI ~ ~ GROVE CD and unit vary latera1ly from
CL oCt Ii 1 imestone to ca1careous 1ime-:I: CANE HILL 0 stone.
U) Si1tstone and sandstone.
.1 I g Limestone, pure, medium-toPITKIN -1ight-gray, commonly oolitic
I lIJ .~ Gray to brown sandstone, In<t:r WEDINGTON part ca1careous.
I CI)
lIJ 0 f .. 1~ U) Black, carbonaceous, ISSI eI ~ ~ sha1e with clay ironstone, ~ ~ ~ concretions.« ~ -
-wI a.. >-a.. it
I ~ BATESVILL I ~ Gray to bro~n c~lcareo~s sand--stone and bituminous limestone.U)U)I -Massive, gray, crystal1ine,~ fossiliferous limestone with
much nodular and bedded chert.
I ~0 I
I ~
I Thin-bedded, non-cherty, grayST. JOE to reddish-brown crinoida1 lime-
stone.I 1
I
I
II .I .
I
II
I
.1
IFigure 2
I Sampling Locations
I
II
I
II
I
I
I
~,~
IIc
I0
() It:
0Z
~
~LLJ
lLJ-J
1-0 Z
cnz-, -
I(.!)
cnw
~lLJ
W
Ix: I-"
t:-J
~
CD
cn
a..
[J >
c 0 .
II ~
I
I
I 0)
0-~
~
I2
~
~
~.0..-
W-C
D
3: ~
(\J W
0
I z
9: g
f()
I :
C\J
I ~w
I C
\J
I ~
[J
0)
I; ~
~-
0
I ;;;(\J~
I f()It)
-
I N
C\J ---
II
II
I'I
I
I
I
.1
I Figure 3
I E-W and N-S Variation of Fe Content of Limestones
II
II
III
II
II .t 0 KESSLER
.BRENTWOODI 6 PITKIN
4. .ST. JOEI I
I ';3~EI ~ .0I "iC,.) 2
I I ..1 6~::=:::::~-.:~:::=:~=======:::~:::: --6~--
I 0 30 40 50 60 70 80
E-W DISTANCE (MILES FROM 950 LONGITUDE)
1 tI 4 A
1 3-I ~
0-1 ~o2
,C,.)1 ~
I I .6 ~ ~ 6
I0 30 40 70 80 90
1 N- S DISTANCE (MILES FROM 370 LATITUDE)
18\
II
II
I ~
I
I
.1
IFigure 4
I E-W and N-S Variation of Mg Content of Limestones
II
I
I
-I
I
I
I
I
: 0 KESSLER .I.BRENTWOOD I
Ii 6 PITKIN6, ST. JOE
1
1 60
1 5
1 --; 40'E0 3-
.1 202,U
1 ~ I
1 0 30 40 50 60 70 80 90
E-W DISTANCE (MILES FROM 950 LONGITUDE)
11 6
5
1 ~0 4
E
1 .; 3-0
1 ;;;U 2~
1 I -6
1 .0 30 40 50 60 70 80 90
N-S DISTANCE (MILES FROM 370 LATITUDE)
1
1.
II
I
II
I
I
.1
IFigure 5
I E-W and N-S Variation of Mn Content of Limestones
I
II
I
II
II
I
I 1.0 0 KESSLERI 6, .BRENTWOOD
0.9 6 PITKIN
6, ST. JOE
I 0.8
I 0.7
I 0.6
""0 0.5I ~
~ 0.40-
I ~0.3~ "0 ~-~~~~ -I 0 .2 --; ~'~~'~--- .
I 0 .I ~ ,,:=====~:::::::::;-.-;A. ~
61 0 30 40 50 60 70 80 90
E-W DISTANCE (MILES FROM 950 LONGITUDE)1.0
I0.9
I o.
I o.-("'\ p1 0 ~ /~ 0.5 I " /E I "
/0 I ,-I " /I 2 0.4 " /
0 I~ I
c: 0.3 II ~ 6, 60.2
1 0 .1 6 [ 6
1 030 40 50 60 70 80 90N-S DISTANCE (MILES FROM 370 LATITUDE)
I
I
I I
I .
I
I
II
I c,c .
.1
IF o . 6Igure
I E-W and N-S Variation of Sr Content of limestones
I
I
I
I
I
I
I
I
I
I .
0 KESSLER
I. 0.09 8 BRENTWOOD..ST. JOE
1 0.08 6 PITKIN
0.07 0
10.061 -
0 .0
~ 0.051 0
2. 0.04 if c -,U 6
1 ~ 0.03
.1 0 .0 2 "' ~.:.- A
0.01
10
30 40 50 60 70 80 901 E-W DISTANCE (MILES FROM 950 LONGITUDE)0.09 8t
II1 II0.08 II
I I8 I 1
1 0.07 I I,8; , I II I I
-/ 18 I1 ~ 0.06 /, I I IE I- I ( t ..0 I 6 /C 0.05 II r I
1 -II ~T'""",8 0.04 I' ~I~ /11 8I (/) 6""'".
0.03
1 0 .0 2 ~ /'~
1 0.01
.0I 30 40 50 60 70 80 90N-S DISTANCE (MILES FROM 370 LATITUDE)
1
I
II
II
I
I
I
.1
IFigure 7
I Na/Ca Ratio versus Mg/Ca Ratio' of Limestones
I
II
II
I
I
II
I
I 0 KESSLER.BRENTWOOD
I ~ PITKIN
..ST. JOE
I0.22
I0.20
I 0.18 .I -0.16
~01 g 0.14-
c-.1 c 0.12
~c1 Z 0.10 ..
0.08
.10.06
I 0.040 I 2 3 4 5 6 7 8 9 10
1 M9/Ca (atom %)
10.10
6
1 0.08-01 ~E 0.060-1 c-..c 0.04,u ..c
I Z 0.02
I 00 I 2 3 4 5 6 7 8 9 10
M9/ca (atom %)
1
1I
111 ~
11
.1
1Figure 8
1 Sr/Ca Ratio versus Mg/Ca Ratio of Limestones
I
111-I -,
I
1I
1
I 0 KESSLER
.BRENTWOOD6 PITKINI 0.12. .ST. JOE .
I 0.11
I 0.10
I 0.09-I ~ 0.08E 00 0.07 .
I ~00.06
I ,U 0.c/5 0.05
I 0.04 0
I 0.03 o.
I 0.020 I 2 3 4 5 6 7 8 9 10
I Mg/ca (atom %)
I 0.06
I 0.05-I ~ 0.04
0-,I 0 -0.03
0U
I ~" 0.02
0.01I .0 I 2 3 4 5 6 7 8 9 10
Mg/Ca (atom %)
I
II
IIIII
-I
IFigure 9
II Sr/Ca Ratio versus Na/Ca Ratio of Limestones
II
II
III
II
II
II
I
I
I 0 KESSLER
.BRENTWOODI 6 PITKIN
A ST. JOE
I 0.07
I 0.06 6
I -6~ 0.05E
I ] 0.04 6 6
cuI ~ 0.03 --""
(/) 6 6 6 ~A"""""
I 0.02 ~ A.A/A A
I 0.01
0I 0 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 .8 0.20 0.22 0.24No /Co (atom %)
./I .t /' .0.07 ./"
./'
I 0.06 /./'
../"I _/'~ 0.05 /'..,/" E /'I ~ 0.04 /4-/" .
cI (..) 0.03'-'
(/)
I 0.02
I 0.01
0I 0 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20 0.22 0.24
No/Co (atom %)
I
I I
I ,I I
I
I
I
I
-I
IFigure 10
I Zn/Ca Ratio versus Mg/Ca Ratio of Limestones
I
II
I
I
I
I
I
I.
I 0 KESSLER
.BRENTWOODI 6 PITKIN
.ST. JOEI
I ...:..
"'.'... ..., ,I 0.013 ...: .:. : .: :. .
' .':'... ::.::.: : : '.:I 0012 : .:: ..::...: .:.. .:: .:: .::.
0 0 11I ...::..::..: :..:::..::::..:..
:: :.. :.. :: :0010 , ..
I .:.. :..: : :..: :..: : :::::
9 0.00 :.:. :.I ~ 0008 ...: : ..: :: : ..
0 : :: ..: :: ,'.. :..:: ..
I E. ...: .: " 0 : .: : .: .: -0 .: :.:
c 0.0 : ...: oCt : .
I c : : .: .: U 0006 .:. ... '.&_.. 'eo. c .: .: : ~ ..: .:I u. ...
N 0.005 ~.:.:..~.:9.:.:::.:::.:::.:::.:.: 0
..'. ..."...I 0 004 :,6 ...:.. ..: ..: : :..:.:.. :.. ~. :.. ..: ..:::..
..A. ~ I 0.003. ::::~:::::::::::::::::::::::. ::::.~:::.
a.I 0.002 :.:.: : :..:.:
: :... :::...:...:...0 00I '. ...'I ' ...: ""...:
5 6 ~ 4 0 .2 0 I
I Mg/Ca (atom %)
I
I.
II .
IIII
I.1
IFigure 11
I Mn/Ca Ratio versus Fe/Ca Ratio of Limestones
IIIII
\1
II
I
I
I
I0 KESSLER
I .e BRENTWOOD6 PITKIN
I 0.9 .ST. JOE
I0.8
II 0.7 .
eA . .....I ..:.:::::::
I 0.6 ,
,,I .0 ,
,"0 ' '0' E 05 ..:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:..0I tJ tJ ~I " c
04 ...e ~I . 0'I 03I e
..:.:.:.:.:.:.:.:.:.:6.:.:.:.:.. e
02I ::::::::::::::::::::::::..~. .a ':I ...A: ..
0 I :.: :.~:..', 00I :.::::::::..
.....,'..~.......I .. 0 ..
0 I 2 3 4 5 6
Fe /Ca (atom %)
I.~-
II
I
I
I
I
I
.1
I Figure 12
Co, Cr and Ni Content versus Mn Content forI Kessler, Brentwood, Pitkin and S.t. Joe Limestones
I
II
I
I
I
I
I
I
1 0 KESSLER I.BRENTWOOD
1 6 PITKIN
.ST. JOE II
11
30
1 25 .
1 20-1 ~ 0~ 15 ...-..1 z 10 .0 0
&6 :0. .1 5.. 66.. .1 0
1 20 .15 0-
1 ~ 6 .0 0Q. 10 .l Eg 6.~ .
5 ...1 O' 6
1 1561 ~ 10 ..
a.. ..0 O'Q. ..01 -5 B. 6 .~~ ..66 6
0 61 0 1,000 2,000 3,000 4,000 5.000 6,000
Mn(PPM)
1
I
I I
I ~
I
I
I
I
I
.1
I Figure 13Co, Cr and Ni Content versus Fe Content for
I Kessler, Brentwood, Pitkin and St. Joe Limestones
II
I
II
I
I
I
I
I
,
I 0 KESSLER.BRENTWOOD
I 6 PITKIN ..ST. JOE
I .I 25
20
I ~ 0a. 15. .a. ..I ~IO 6 00 ...0I 5 ~ .6 6 .
6 ..1 0
I 25
20
I ~ 0 .a. 15a.I -6 ~ 0 0U 10 6 ../(\66 .I 6 6 0 ..
5 .....I o'
I ~20a.-15
I 8 .10 6 .
6 .I 6 0 0 0
.6 05 6. ...I 0 ~ 6
0 0.2 0.4 0.6 08 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8
I Fe (Wt.%)
I
.
II
I
II
I
I
-I
I Figure 14
Co, Cr and Ni Content versus (Fe/Ca + Mn/Ca) forI Kessler, Brentwood, Pitkin and St. Joe Limestones
I
II.I
I
I
I
II
I
I 0 KESSLER
.BRENTWOOD
I 6 PITKIN
6 ST. JOE
II 30 6
25
I_20 0
I ~ 0~ 15. .
I z 6 .10 6
.0I 6 0 ...5 Cf6 .6 6. .I 0 .I 20
O'I ~ 15Q. 6 0 0a.. 10 ..
I -f!;'- 6 0 I I .<..> 5 ..I 6 .
0
I 15
I -6~ 10. .~ 6. ..00 0
I 0 6~ 0 .<..> 5 l5. ..6c;t.I 0 ..
0 I 2 3 4 5 6
I (Fe/ca + Mn/ca) Mol %
I
