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Possible use of strontium in sedimentary carbonate rocks as a paleoenvironmental indicator
Sedimentary Geology- Elsevier Publishing Company, Amsterdam- Printed in The Netherlands
POSSIBLE USE OF S T R O N T I U M IN S E D I M E N T A R Y C A R B O N A T E ROCKS AS A P A L E O E N V I R O N M E N T A L I N D I C A T O R * J. VEIZER 1, R. DEMOVIC1 AND J. TURAN2
1 Geological Institute of the Slovak Academy o f Sciences, Bratislava (Czechoslovakia) 2 Department of Economic Geology and Geochemistry, Comenius University, Bratislava (Czechoslovakia) (Received August 15, 1969)
SUMMARY
The differences in present-day Sr concentrations in pure limestones (average insoluble residue < 5~) of the Western Carpathians region are interpreted as being due mainly to their original mineralogy. It is proposed that Sr content in conjunction with other observations may be used to distinguish between physicochemical and organodetrital carbonate sediments. INTRODUCTION
It is known (GRAF, 1960; WOLF et al., 1967) that Sr in sedimentary carbonate rocks occurs mainly in the carbonate portion and particularly in CaCO3. This observation has been confirmed by analyses carried out on sedimentary carbonate facies of the Western Carpathians (VEIZER, 1968b; DEMOVI~, 1968). The correlation coefficient for 228 samples, calculated according to the formula: 1 rsr,Ca ~
/7
(XSr--XSr ~
O'Sr
"
XCa--Xca'} ~Ca I
where rsr,Ca--- correlation coefficient of Sr and Ca; /7 ~ number of analyses; x ~ absolute value of each sample; ~ =: arithmetical average; a = standard deviation, gave a significant correlation of Sr to CaO ( + 0.37). Correlation coefficients of the other minor and trace elements are negative or not significant (Ba, Mn, Ti, Cr, B, V, Y, Cu, Pb, Ag, Ni) because of the low sensitivity of the method used (10 p.p.m.). Thus it might be suggested that rocks of similar major component composition (CaO, MgO, insoluble residue = 1.R.) should have similar Sr concentrations. However, initial studies in the West-Carpathian region (VEIZER and DEMOVlC, * Present address: Department of Geophysics and Geochemistry, Australian National University, Canberra, A.C.T., Australia
Sediment. Geol., 5 (1971) 5-22
6
J, \EtZER [!1 A I
1970a) showed that the Sr concentrations of the rocks with similar major component compositions are signilicantly different (see Table I). These observations suggest that Sr concentration of carbonate rocks is nt~ only dependent on the CaCO3 content but on some other factors as welt. TABLE 1 THE AVERAGE MACROCHEMICAI. (?OMPOStIIONS AND Sr C'ONCENFRA]IONSOF THE I)IS('USSI~I)[A(|,\L I'YPES
Carbonate hwie.~
High Tatra Mantle Series region Lower Anisian Upper Anisian Bajocian-Bathonian Malmian-Neocomian U r g o n i a n (Barremian-Aptian) Slovak Karst-algal limestones U p p e r Anisian
Ladinian
("aO
MgO
I.R.
Sr
, ",)
~ ~'.
(",>/
(p.p,m.,
~,'r, ( a . 1( !
5 I, 16 53.54 53.39 53,55 5404
2.00 0.99 1.21 0.47 0.28
4.22 2.33 1.95 3.55 2.96
653 797 137 159 167
I, 79 2.09 t).3f~ 0.42 [).43
5423 53.44
0.75 I. 16
1.70 1.93
140 97
(1.3~5 0.25
SEDIMENTARY AND IF('TONIC EVOI,UTION OF THE CENIRAL WESTERN CARPATHIANS
The evolution of this area (Fig.I) is described briefly as a background to the mineralogical and geochemical studies. This description follows the scheme for preorogenic development or" the Central Carpathian Mesozoic given by VEIZEI{ (1968a,b). For details of stratigraphy and geology see MAHEL and Bur)AY (19681,
.J
~,
(.~,
) <
~.~.
C" P~A6ut
%.~,..j%.~ --~
Z
1 I
HtGH ~'i J~"~ TATRA
~ CN
\.
S
0
Z 0
.F'L'"~.~. k..j.~.
l'J
A '~ e~'~e~ %, ~ F'..,%~
/ 0
V
100kin
K
"~
#Car~,athlQ~s ~;~
/
~.~.
(,)
OETVA
C e~'~°\ "%
SLOVAK KARST ~t.~.~ r
Fig.1. Map or the localities. (1) First sedimentation cycle (Werfenian-Norian)-unstable shelf stage. The area in this period may be described as unstable shelf with hot arid climate. Because of the tectonic and climatic factors mainly carbonate facies art: Sedinlenl.
(':co/,. > (1971) " ~.:
SR IN CARBONATE ROCKS AS A PALEOENVIRONMENTAL INDICATOR
7
developed in which one can see lateral changes (from N to S) from nearshore facies of partly evaporitic origin (High Tatra Mantle Series) through mainly dolomitic types of intermediate character to the developments of the open (?) shelf in the form of algal limestones (banks, reefs) in the most southern part of Slovakia (Slovak Karst). Younger sediments in the last mentioned area are developed only locally. (2) Second sedimentation cycle (Rhaetian-Liassic)-stage of individualisation of the orthogeosynclinal evolution. Increasing tectonic activity has caused division of this area into a system of individualised ridges and troughs. The climate was warm and probably humid. This paleogeography involved the development of basins with partly restricted circulation of the water body thus forming mostly detrital and reducing character of the sedimentary facies, especially in the northern (external) parts of the Western Carpathian geosyncline. (3) Third sedimentation cycle (Doggerian-Aptian)-development stage; preflysch period of the orthogeosynclinal evolution. With continuing subsidence of particular ridges and troughs the paleogeographical features established in the previous period became more apparent. The climate was most probably warm but humidity and aridity cannot be determined because of open marine sedimentation. The sedimentation of this period was mainly pelagic with pelagic carbonates on the ridges of Briangon type (MalmianNeocomian of the High Tatra Mantle Series) and radiolarites in the troughs. The sedimentation of this cycle was finished with development of the detrital reef facies in Barremian-Aptian on the external ridges of the Western Carpathian geosyncline (Urgonian of the High Tatra Mantle Series). (4) Fourth sedimentation cycle (Albian-Lower Turonian)--development stage; flysch period of the orthogeosynclinal evolution. Mainly flysch-like sediments developed, which were followed by the main orogenetic movement of the Central Western Carpathians which formed the present tectonic style of the area. ANALYTICAL TECHNIQUE
The major components (CaO, MgO, I.R.) were determined using the manometrical method described by TURAN 0965). The Sr determinations were made using a PGS-2 optical spectrograph. Details of the method are given elsewhere (MEDVED 1967; DEMOVl~, 1968). Reproducibility of the method expressed as percent standard deviation was ± 9~. Sr DISTRIBUTION
For details of Sr distribution see Fig.2,3,4,5. The Sr concentration of nearly Sediment. Geol., 5 (1971) 5-22
8
J. VEIZER ET A|..
Sr ppm 1500F i
•
H~GH TATRA Lower Anisian
• Upper Anlsian
•.
.°" o. ,,"
lO0Or •o
i
5oo!
I
UD
i 200 L
i 46
48
50
52
54
56
ZCaO
Fig.2. Sr distribution in the Anisian limestones of the High Tatra Mantle Series region Sr
ppm
HIGH TATRA • Malmian~ Neocorma 3
1500'
I • Urgonan
1000"
500
200[
• ,o
•
i
.,~.
oe
""
Fig.3. Sr distribution in the Malmian-Neocomian and Urgonian limestones o[ the High Tatra Mantle Series region.
each single sample from the Anisian of the Mantle Series of the High Tatra region is 3-4 times higher than in the Malmian-Neocomian and Urgonian limestones o | the same region and about 4-9 times higher than in the limestones of" the Anisian and Ladinian age of the Slovak Karst region, and in the limestones of the BajocianBathonian age of tile High Tatra Mantle Series region. Because the limestones of late Anisian and Ladinian age of the Slovak Karst region are supposed to be of similar origin they are combined into one c o m m o n group. For the same reason the Lower and Upper Anisian limestones of the High 5"ediment. G c o t .
~ i 1971) i~, ! '
SR IN CARBONATE ROCKS AS A PALEOENVIRONMENTAL INDICATOR
9
Sr ppm. 150C HIGH T A T R A eBajocian- Bathonian . .
I00C .
50(
200
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
....
~
e e
46
48
50
52
54
56
"/.CaO
Fig.4. Sr distribution in the Bajocian-Bathonian limestones of the High Tatra Mantle Series region. Sr pprn
1500
IOOC
SLOVAK_KARST
.
.
.
.
.
.
.
.
• Upper Ani~ian • Ladinian
500
•
vA
200 •A
A.
46
48
50
52
•A
54
•
56 %CaO
Fig.5. Sr distribution in the Upper Anisian and Ladinian limestones of the Slovak Karst region. Tatra Mantle Series region are also combined. Thus we shall discuss only five populations of limestones: Upper Anisian and Ladinian limestones of the Slovak Karst region; Anisian limestones of the High Tatra Mantle Series region; BajocianBathonian limestones of the High Tatra Mantle Series region; Malmian-Neocomian limestones of the High Tatra Mantle Series region; Urgonian (BarremianAptian) limestones of the High Tatra Mantle Series region. Sediment. Geol., 5 (1971) 5-22
lO
J. \ E I Z E R
t;1 AI_
F o l l o w i n g the test for n o r m a l d i s t r i b u t i o n (density) given by KRUMBEIN and GRAYBILL (1965, p.94) it was l~und that the Sr distributions of all five p o p u l a t i o n s are o f n o r m a l character. The positive correlation of Sr to C a O is confirmed within each separalc p o p u l a t i o n . An exception from this basic pattern are the U r g o n i a n limestones i~; which a slight negative correlation was observed (see Fig.3). We do not know an~ sufficient e x p l a n a t i o n o f this observation. The most likely speculations explaining this feature are: (/) The negative correlation might reflect changes within the assemblage o l organic skeletons building the CaCO~ portion o f the samples. (2) This correlation might be caused by an increased p r o p o r t i o n o f the secondary sparry calcite, the Sr content of which is lower than that of the originai rock. Statistical constants o f all five p o p u l a t i o n s are given in Table 11.
TABLE 11 STATISTICAL PARAMETERS OI IHE DISCUSSED CARBONAIE FA('IES
Number o f sample.~
Arithmetical Standard average o f Sr deviation (p.p.m.
b tlriation coefficieni ' ",,
High Tatra Mantle Series region Anisian Urgonian Malmian-Neocomian Bajocian-Bathonian
39 19 30 II
760 167 137
314 71 82 72
41.3 I 42.38 51.51 52.43
Slovak Karst-algal limestones Upper Anisian and Ladinian
25
116
65
56,37
I G
=:
159
yN
"V/N I i :
1
(.v~
/2):
V = c;-_ . I00 ,u where a :-- standard deviation: N : number of samples; xi ...... absolute value of each sample: /2 = mean (arithmetic average): V ~ variation coefficient.
The lowest variation coefficient r e p o r t e d for the Anisian limestones of the H i g h T a t r a M a n t l e Series is e x t r a o r d i n a r y because the changes in m a c r o c h e m i c a l c o m p o s i t i o n o f these limestones are the highest from all five p o p u l a t i o n s (Fig.2). Using the t-test (MILLS, 1956) to test the mean (:-: arithmetical average) differences, it was f o u n d that the between m e a n differences for the 0.01 confidence level are significant only in plotting the High T a t r a Anisian limestones against the Sediment. Geo/, 5 I I~)71 ) ~ _%
SR IN CARBONATEROCKS AS A PALEOENVIRONMENTALINDICATOR
11
four others (6.44; 8.06; 10.04; 10.10). The other between mean differences (2.51; 2.05; 1.12; 0.84; 0.78; 0.34) are not significant. Thus this conclusion indicates that Sr may be used as a paleoenvironmental indicator only in the case of the High Tatra Anisian limestones against the four others. The use of Sr within the last mentioned group of populations (Bajocian-Bathonian, Malmiam-Neocomian, Urgonian and Slovak Karst) is questionable. PROPOSED ORIGINAL MINERALOGYOF FACIES Compaling the facies in Table II the following suggestions may be drawn regarding their original carbonate mineralogy: (1) Limestones of the Malmian-Neocomian age (High Tatra Mantle Series): The limestones are formed in substantial part from debris of the carbonate skeletons of pelagic organisms (mainly "protoglobigerinoidal" Foraminifera). Skeletons of recent pelagic Foraminifera are known containing mainly low-Mg calcite (BLACKMONand TODD, 1959). The Sr concentrations of recent pelagic foraminiferal tests are~ 1200 p.p.m. (TUREKIAN, 1964). (2) Limestones of the Urgonian age (High Tatra Mantle Series): The limestones are described as proximal reef detrital facies formed from skeleton debris of different organisms, mainly mollusca. Original mineralogical composition of the sediments reflected the mineralogy of skeletons, i.e., intercalations of lowMg calcite and aragonite (THOMPSONand CHOW, 1955). The average Sr concentration of recent molluscs is~ 1,500 p.p.m. (TUREKIAN, 1964). Thompson and Chow reported 1,540 p.p.m, of Sr as the average content for 64 pelecypods and 1,390 p.p.m, for 53 gastropods (Prosobranchia). Studying recent pelecypod skeletons we found 1939 p.p.m, as an average Sr content for 60 samples. (3) Limestones of the Bajocian-Bathonian age (High Tatra Mantle Series): The limestones are composed from crinoidal calcitic monocrystals (crinoidal biosparite). These are known to be high-Mg calcite in recent Crinoidea (GRAF, 1960). The Sr concentrations of recent Crinoidea are ~ 1,450 p.p.m. (GRAE, 1960). (4) Limestones of the Upper Anisian and Ladinian age (Slovak Karst region): They are formed mainly from debris of algal skeletons (Dasycladaceae) which are known to be mainly high-Mg calcite in recent genera and species (CHAVE, 1954). The Sr concentrations of recent Dasycladaceae are not available. There are only few data of Sr concentrations in green algal calcitic skeletons (LOWENSTAM,1963) with about I-1.5 tool ~ of Sr. However these concentrations are very high in comparison with Sr concentrations of other classes and do not agree very well with the known concentration factors of Sr for both high- and low-Mg calcites. (5) Limestones of the Anisian age (High Tatra Mantle Series): By analyzing physicochemical conditions of the first sedimentation cycle in the High Tatra Mantle Series region (VEIZER, 1968b) it was found that sedimentation of this area was partly of hypersaline character because of evaporation in the back-reef (backSediment. Geol., 5 (1971) 5--22
12
J. VIEIZER ET tsl,
bank) area. This conclusion is indicated by: (a) the development of red beds (with gypsum and anhydrite in the southern parts of the West-Carpathian geosyncline) at the beginning and the end of this sedimentation cycle; (b) intercalation oi limestones (especially in Lower Anisian) with sheet dolomites of early diagenetic or primary origin; (c) existence of cavernous "dolomites" with pseudomorphs after gypsum; (d) existence of pseudomorphs after gypsum and NaCI in this limestone described by MIgiK (1968). The evidence is supported by extremely fine texture of the limestones and lack or sporadic occurrence of organisms. The hypersaline conditions are characterized by higher pH as well as Mg/Ca and Sr/Ca ratios which shifts the equilibrium towards physicochemical or biochemical? (bacterial) precipitation of aragonite (ZELLERand WRAY, 1956: WRAY and DANIELS, 1957; GOTO, 1961 ; TAFT, 1962). According to BATHURST(1964), aragonitc is the only physicochemica[ carbonate mineral precipitating IYom sea water. KINSMAN and HOLLAND (1969) found experimentally that aragonite is the o n b mineral precipitating from sea water at temperature above 30 ':C. The Sr concentrations of similar recent facies are ,- 9,000 p.p.m. (KINSMAN, 1969). In agreement with this interpretation are the very fine textures as well as the extremely high Sr concentrations (ODUM, 1957). The conclusions of supposed original mineralogy of the above-discussed populations are summarized in Table Ill. TABLE I11 SUPPOSED ORIGINAL MINERALOGY AND AVERAGE sr CONCENTRATIONS
O F T H E D I S C U S S E D FACIES
Supposed original mineralogy
Sr' Ca. l 0 Sr (p.p.m,)
High Tatra Mantle Series region
Malmian-Neocomian Bajocian-Bathonian
physico-chemical (biochemical?) aragonite mixture of organic low-Mg calcite and organic aragonite organic low-Mg calcite organic high-Mg calcite
Slovak Karst-algal limestones Upper Anisian and Ladinian
organic high-Mg calcite
Anisian Urgonian
760
2.02
167 159 137
0.43 0.42 0.36
116
0.31
DISCUSSION
Sr in recent carbonate sediments occurs mainly in the aragonitic lattice (THoMPSON and CHOW, 1955; ODUM, 1957). KINSMANand HOLLAND (1969) lkmnd that the concentration factor of Sr for aragonite is 1,17 :~: 0.04 (16°C) and (i).88 : 0.03 Sediment. Geol.. ~ II971 )5 22.
SR IN CARBONATE ROCKS AS A PALEOENVIRONMENTAL INDICATOR
13
(80 °C) whereas for calcite it is only 0.11 :~: 0.02 (30°C) and 0.07 :J: 0.004 (95°C) according to OXBURGHet al. (1959). Also St/Ca ratio of inorganic aragonites is higher than that of most organic aragonites (GOLDBERG, 1957). This short review suggests that different mineralogical composition caused by different conditions in sedimentary environments might explain the differences in Sr distribution as given in Tables I-IlI. Comparison of the assumptions regarding original carbonate mineralogy with the average Sr concentrations and the average Sr/Ca ratios (Table I11) shows that both are decreasing in sediments expected to be aragonitic, through mixture of organic aragonite and organic low-Mg calcite, organic low-Mg calcite to organic high-Mg calcite (Fig.6). Sr R.p.m.
1500
1000
--
--
--
4
-
-
Q------
. . . . •
-
ARITHMETIC AVERAGE OF Sr CONCENTRATIONS
STANDARD DEVIATION - VARIATION
--.
COEFFICIENT
._g g "5
"~
-og 500
-o g
~9 -100 °/, '~
300 \
lo~
.....
_o
o
>Y--\~ "
. . . . _......... - . . . . . . . . .
_._
.=
o
2OOlooLs° °~°
g
~
.~o
~
"~
-
N
.o_=
~ o
o
o
a
Fig.6. AverageSr concentrations and supposed original mineralogy of the limestonefacies. Also in limestones of Early Anisian age (Slovak Karst and Gemeridy Unit), which by the senior author (J.V.) are supposed to be of bacterial origin, three analyses showed very high Sr content (740, 832 and 1,110 p.p.m.). Carbonate mineral precipitated by marine bacteria is aragonite (GREENFIELD, 1963). It is very difficult to prove directly the character of the original mineralogy of Sediment. Geol., 5 (1971) 5-22
14
J. VEIZER [-:[ \ i
these sediments because of diagenetic changes, but it is interesting to note that the decreasing Sr content is in agreement with the known concentration factors l~,r these minerals. This indicates that the original mineralogy should be an important factor controlling the present-day Sr concentration of fossil carbonate sediment~. Interesting restalts were obtained using the electron microscope to study the above-mentioned facies. In the limestones of the High Tatra Anisian (aragonite~ grain relicts of elongated shape were tbund (Fig.7), whereas in the M a l m h m Neocomian limestones (low-Mg calcite) the relicts were only of polygonal shape (Fig.8). This mighl be related to the differences in original mineralogy as well.
Fig.7. Electron-microscope photograph of the Anisian limestone (High Tatra Manth: Series region). Note the elongated shape and straight boundaries of the grain in the left centre ~ the picture. (Photo M. Harman: replica technique.)
The assumption that Sr differences are caused by original mineralogy J~ supported by results of FC0GEL and FLOGEL-KAHLI~R(1962) who have found that there are differences in Sr concentrations of the fore-reef and back-reef samples oi the Rhaetian age in the eastern Alps. They concluded that differences were caused S'edinlent,
(,'~,,
~ i l~-i
i "
'
SR IN C A R B O N A T E R O C K S AS A P A L E O E N V I R O N M E N T A L I N D I C A T O R
15
Fig.8. Electron-microscope photograph of the Malmian limestone (High Tatra Mantle Series region). Note the polygonal shape of the grains. (Photo M. Harman; replica technique.) by different assemblages of the organisms in both environments and thus by different original mineralogy of these sediments. Studying Sr concentrations in recent pelecypods (VEIZER and DEMOVI~', 1970b), we found that Sr concentrations of inner layers of the shells are in average two times higher than Sr concentrations of the whole shells (35 exemplars). The inner layer of pelecypod shells is mainly aragonitic (P~vETEAU, 1952). Using Feigel solution to test the mineralogy it was established that the majority of aragonite was already converted to calcite. This indicates that certain partition of Sr in carbonate fraction is possible in spite of conversion of unstable minerals (aragonite, high-Mg calcite) into stable ones (low-Mg calcite and dolomite). However, although the original mineralogy might be the most important factor controlling the present-day Sr concentrations of the above-mentioned facies, it is inevitable to discuss a possible diagenetic influence. During the initial stage of syndiagenesis (FAIRBRIDGE, 1967), which is characterized by squeezing out of the trapped interstitial waters, no substantial Sediment. Geol., 5 (1971) 5 22
16
J. VEIZI-R E l A L
changes should occur, because the composition of the interstitial water is similar to the composition of the water body above the sediment surface. The carbonate minerals are thus in equilibrium with the surrounding media. This conclusion is supported by results of BErNER (1966), who has found that the original mineralogy, is relatively very stable in contact with sea water. A similar feature may be expected also in the areas of hypersaline solutions. According to Berner, the conversion ol unstable minerals into stable ones was observed only in the areas exposed to the influence of brackish or fresh waters. This might be to a certain extent the case of the Urgonian limestones, which were exposed above the sea level during the Lower Albian period. The behaviour of Sr during the later stages of diagenesis (early burial stage, anadiagenesis and epidiagenesis) is not well documented, however it is reasonable to conclude that under higher P and T conditions the unstable carbonate minerals which are converted into stable ones, release part of their Sr into pore solutions. The increased Sr/CI ratio and higher Sr content of these solutions in comparison to sea water has been observed by several authors (CARPENTER and MILLer, 1969: COLLINS, 1969; RITTENHOUSEet al., 1969; and others). At this stage of diagenesis permeability (K.K. Turekian, personal communication, 1969) might be the controlling factor of the Sr movement. Apparently, the more compressible and les.~ permeable fine-grained carbonate sediments may retain higher Sr concentrations, although not necessarily being incorporated into the calcite or dolomite crystal lattice, than the organodetrital ones. Arranging the above-mentioned facies according to this criterion, Ihc succession is as follows: Bajocian-Bathonian (137 p.p.m.) : Urgonian (167) > Slovak Karst (I 16) > > > Malmian-Neocomian (159) ~- Anisian (760). l h e Sr content of the highly permeable and possibly partly recrystallized (fresh-water influence) Urgonian is higher than the Sr content of the less permeable MalmianNeocomian. Also it is very difficult to explain the remarkably different Sr con~ centrations in the two last mentioned facies in spite of their similar permeability Considering the positive correlation between supposed original mineralogy, assumed original Sr concentrations (Fig.8,9) and present-day Sr concentrations ol the facies discussed, one may see that there is approximately a tenfold decrease m the average Sr concentrations regardless of their permeability. The problem to resolve is the nature of this transition. There are two general schools of thought about the transition of unstable carbonate minerals into stable ones. These are the solid-solid transition and the solution-precipitation process. In the light of recent data (FLOGEL and WEDEPOHL, 1967: WEDF~POHL, 1969: KINSMAN,1969; and others) the latter is generally favoured. These authors have developed models in which the Sr concentration of the final phase would depend on the original Sr content, original mineralogy and the nature and character of circulating solutions. Since, during later stages of anadiagenesis compaction of sediments is high Sediment. Gco!
5 (1971~ ~ ?:
SR IN CARBONATE ROCKS AS A PALEOENVIRONMENTAL INDICATOR I~pm. Sr 10000
"..L~ . ~ / / L ' . , ' / ' / . / //',,
1
/ /
f
/
,/,-
///
/,
/.
17
o,ogon~,e ~n
" " " ,
/with sea
.... water
Ii assumed original Sr concentration 5000
opte~ent - day Sr content rahon
]
......
,,, f ,i/, 1000
" +
,
,
.
.
,1 ..... 1
,,
/+/
. ca,. . . . . .
equilibrium 4~ . wlth //. sea waler ,
,
500
I00
Fig.9. A s s u m e d original a n d present-day Sr concentrations of the limestone facies. T h e succession of facies is as in Fig.6.
and porosity low (cf., FAIRBRIDGE, 1967), it is reasonable to suppose that the system acted more or less as a closed system and that the major transitions occurred prior to this period. There should be no substantial changes during the initial stage of syndiagenesis as discussed previously. The stages during which these transitions probably occurred are thus early burial stage of syndiagenesis and early stage of anadiagenesis. These processes during the early burial stage are controlled by entrapped connate waters, which are chemically modified by bacteria and organisms, usually lowering pH values. This might be a period of major transitions within the inorganic and biochemical facies, whereas the organodetrital facies were probably altered during an early stage of anadiagenesis, which is characterized by compaction and maturation of sediments. The very fine-grained texture of the first group would also support an earlier conversion. FLUGEL and WEDEPOHL(1967) developed six models of diagenetic processes, which are in general agreement with KINSMAN'S (1969) data. The closed system model may produce a final phase (low-Mg calcite) with Sr concentrations ~ 700 p.p.m, or more from original aragonites and with ~ 150 p.p.m, or more from original calcites. This would be in excellent agreement with our results. In an open system under the influence of sea water the precipitated calcites should contain ~ 1,000 p.p.m, of Sr, regardless of their original mineralogy. However, the Sr contents of the organodetrital facies are too low to be compatible with this hypothesis. Sediment. Geol., 5 (1971) 5--22
18
J. VEIZER E l AL,
In an open system, which was dominated by fresh waters, the precipitated calcites should have ~ 150-300 p.p.m, of Sr. The original mineralogy does have some influence, but it is generally not very significant. This explanation is incompatible with the high Sr contents observed in the inorganic or biochemical sedi. ments. The role of possible fresh-water influence has already been stressed in the case of the Urgonian facies. With more or less difficulty it would be possible h~ suppose a fresh-water influence for the Bajocian-Bathonian and Stovak Kars~ facies, although no geological evidence is yet available to support this view. This explanation, however, is unlikely for the Malmian-Neocomian sediments, since they were deposited in a pelagic ridge area. They were not exposed above sea level until at least Albian and most probably much later. Thus the minimal period l'oJ lithification of the top part of this suite was ~ 18 million years and of the bottom 51 million years. It is probable that these sediments were already compact and mature before they were exposed to fresh-water influence. A fresh-water influ>~ through seaward-dipping permeable sediments might also be excluded, since the High Tatra Mantle Series ridge was separated from land by the Pieniny trough with radiolarite sedimentation. It would be possible to assume a closed-system model for the "'aragonitic" and Malmian-Neocomian facies and a fresh-water open system for the Urgtmian, Bajocian-Bathonian and Slovak Karst facies (which is a reasonable probability) or to introduce a separate model for each facies. However, the generally equal decrease in Sr concentrations of all facies and the satisfactory agreement with the closed-system model indicates that the facies acted more or less as closed systems (at least within the first group) during their diagenetic history, A closed system of diagenesis might be reasonably assumed for fine-grained carbonate sediments. Since the entrapped water of these s~,diments was very high, the process of diagenesis might cause greater squeezing out of entrapped water and decrease in permeability than an "open"-system circulation of solutions. Such unidirectional movement of connate solutions is also required to explain the pattern of doiomitisation within the Western Carpathians (VEIZER, 1968b) and is in agreement with isotopic data observed by the senior author. The problem is more complicated in the presence of porous sediments with complicated mineralogy in such environments as reefs, banks, etc., which may easily be exposed to fresh-water influence. Nevertheless, the results obtained by the senior author on Australian Precambrian and Palezoic carbonates are very encouraging. As inorganic and biochemical carbonate facies are usually very fine-grained sediments of semirestricted basins with high ionic concentrations (i.e., Sr) and aragonitic mineralogy, they would act as more or less closed systems during the early burial and early anadiagenetic alterations. The chance of retaining Sr concentrations > 700 p.p.m, is thus high and the chance of fresh-water alteration is low, since they are mainly sediments of arid regions and the usually high alkaline Sediment. Geol.. 5 ( 1971 ) 5 22
SR IN CARBONATEROCKS AS A PALEOENVIRONMENTALINDICATOR
19
reaction of ground waters of such regions would not support their solution. This assumption in conjunction with other observations may serve to distinguish such sediments from organodetrital ones, which have a tendency (unless well preserved) to retain lower Sr values. However, the conclusions discussed above need further detailed studies of similar facies and studies of Sr behaviour during diagenetic history. There are two other factors, which might substantially influence the Sr concentration of the carbonate facies. These are the I.R. (insoluble residue) content and composition as well as the degree of recrystallization. It could be argued that there is a substantial partition of Sr in the I.R. which might cause the above-mentioned differences of the whole rock Sr analyses. We did not carry out chemical analyses of the I.R., but we do not think that this interpretation is correct for the following reasons: (1) The average I.R. content and composition of all facies is similar (see Table I). (2) As mentioned earlier there is negative correlation of Sr with I.R. (- 0.29) and MgO (- 0.27) and a positive correlation with CaO ( + 0.37). This indicates that the major part of Sr occurs in CaCO3. (3) The |.R. is composed mainly of a detrital fraction <2]~. The mineralogy of this fraction is uniform in all facies (VEIZER, 1968b). The most abundant mineral is illite, with only sporadic chlorite, montmorillonite and kaolinite. The less abundant fraction > 2/L is composed mainly of quartz with very small amounts of mica and feldspar. (4) The highest value of the Sr concentration in deep-sea clays reported by DASCH (1969) was 452 p.p.m, and less in clays with a higher proportion of illite. The highest Sr concentration in illitic clays analyzed by W. Compston (personal communication, 1969) was 125 p.p.m. The "average" shale of TUREKIAN and KULP (1956) contains ~ 300 p.p.m, of Sr. The average Sr concentration of the Atlantic shales given by WEDEPOHL (19601) is 120 p.p.m. The value reported by TUREKIAN (1964) is 130 p.p.m. This review indicates that the Sr content of shales is lower than that of carbonates. Even a concentration of 500 p.p.m. Sr in the I.R. cannot influence the whole rock Sr concentrations (~ 4 ~ of I.R.) by more than 20 p.p.m. The following reasons support our view that the differences in Sr concentrations are not caused by different degrees of recrystallization: (1) There was no notable difference in the degree of recrystallization in the majority of thin-sections (contact of grains, sparry calcite, shape of grains, etc.). (2) The older sediments of the same area contain higher Sr concentrations than the younger ones and the Sr concentrations of the organodetrital limestones are of the same order in both areas in spite of the different ages. (3) Sediments from the tectonically more disturbed area (High Tatra) contain higher Sr concentrations than the sediments from the less deformed area (Slovak Karst plateau). Sediment. Geol., 5 (1971) 5-22
20
J. VEIZER ET AL.
(4) Any type of recrystallization effects more the fine-grained micritic muds than the coarser remains of organic skeletons. However, the Sr content of the micritic facies is higher or similar to the Sr content of the organodetrital sparitic facies. CONCLUSI()NS
The average Sr concentrations of the supposed original aragonite facies are significantly higher than those of the calcite facies. This succession is in agreemem with known Sr concentration factors for these minerals and thus original mineralogy might be an important factor influencing the present-day Sr distribution of the sedimentary carbonate rocks, although the diagenetic changes may significantly alter this pattern. The Sr concentration, in conjunction with other observations, might serve as ~ valuable tool to distinguish physicochemical (biochemical?) aragonitic carbonate sediments from the organodetrital ones. The Sr concentrations within the organodetrital carbonate facies group are dependent on a great number of t'actor~ and thus are less favourable for diagnostic purposes. ACKNOWLEDGEMENTS
We would like to acknowledge a great debt of gratitude to Drs, S.R. Iaylor, K.A.W. Crook, E, J. Dasch, H. H. Veeh and W. Compston for criticism and specific suggestions. REFERENCES BATHURSr, R. G. C., 1964. Diagenesis and paleoecology: a survey. In: J. IMBRIEand N. Ntz~w~tA IEditors), Approaches to Paleoeeology. Wiley, New York, N.Y., pp.31%-344. BERNER, R. A., 1966. Chemical diagenesis of some modern carbonate sediments. Am. J. Sci.~ 264:1-36. BLACrCMON, P. D. and TODD, R., 1959. Mineralogy of some Foraminifera as related to their classification and ecology. J. Paleontol., 33:1 15. CARPENTER, A. B. and MILLER, J. C., 1969. Geochemistry of saline subsurface water, Saline County (Missouri). Chem. Geol., 4:135-167. CHAVE, K., 1954. Aspects of the biochemistry of magnesium, 1. Calcareous marine organism~;. J. Geol., 62:266-283. COLLINS, G. A., 1969. Chemistry of some Anadarko Basin brines containing high concentration~ of iodide. Chem. Geol., 4:169-187. DASCH, E. J., 1969. Strontium Isotopes in Weathering Profiles, Deep-sea Sediments, and Sedimentary Rocks. Thesis Yale Univ,, New Haven, Conn., 94 pp. DEMOVI~, R., 1968. Geochemistry of Sedimentary Carbonate Rocks and of Some Recent Pelecypoa Skeletons. Thesis Geol. Inst. Slovak Acad. Sci., Bratislava, 203 pp. (in Slovak). FAIRBRIDGE, R. W., 1967. Phases of din.genesis and authigenesis. In: G. LARSEN and G. '~ CHmINGAR(Editors), Diagenesis in Sediments (Developments in Sedimentology, 8). Elsevier. Amsterdam, pp. 19-90.
Sediment. Geol.. 5 (1971) 5 22
SR 1N CARBONATE ROCKS AS A PALEOENV1RONMENTAL INDICATOR
21
FL/.)GEL, E. und FLOGEL-KAHLER, E., 1962. Mikrofazielle und geochemische Gliederung eines obertriadischen Rifles der nordlichen Kalkalpen. Mitt. Bergbau, Geol. Tech., Landesmuseum Joanneum, 24:1-128. FL/SGEL, H. W. und WEDEPOHL, K. H., 1967. Die Verteilung des Strontiums in oberjurassischen Karbonatgesteinen der N6rdlichen Kalkalpen. Beitr. Mineral. Petrog., 14:229-249. GRAE, D. L., 1960. Geochemistry of carbonate sediments and sedimentary carbonate rocks, l ~ . Illinois State Geol. Surv., Circ., 297, 298, 301, 308:250 pp. GOLDBERG, E. O., 1957. Biogeochemistry of trace metals. In: J. W. HEDGPETH (Editor), Treatise on Marine Ecology and Paleoecology, 1. Ecology--Geol. Soc. Am., Mere., 67:345-358. GoTo, M., 1961. Some mineralo-chemical problems concerning calcite and aragonite with special reference to the genesis of aragonite. J. Fae. Sci. Hokkaido Univ., Set. IV, 1(4):571-640. GREENFIELD, L. J., 1963. Aragonite formation by marine bacteria. Bull. Am. Assoc. Petrol. Geologists, 47:p.358 (abstr.). KINSMAN, D. J. J., 1969. Interpretation of Sr 2+ concentrations in carbonate minerals and rocks. J. Sediment. Petrol., 39:486-508. KINSMAN, D. J.J. and HOLLAND, H. D., 1969. The co-precipitation of cations with CaCO3, 4. The co-precipitation of Sr 2~ with aragonite between 16-96 °C. Geochim. Cosmochim. Acta. 33:1-18. KRUMBEIN, W. C. and GRAYBILL, F. A., 1965. An Introduction to Statistical Models in Geology. McGraw-Hill, New York, N.Y., 475 pp. LOWENSTAM, H. A., 1963. Biologic problems relating to the composition and diagenesis of sediments. In: W. DONELLY (Editor), The Earth Sciences--Problems and Progress in Current Research. Univ. Chicago Press, pp.137 195. MAHEI~, M. and BUDAY, T., 1968. Regional Geology o f Czechoslovakia, 2. T/re West Carpathians. 1].I_).G., Prague, 723 pp. MEDVEI~, J., 1967. Quantitative Spectral Analytical MethodJbr Determination o f Mieroelements in Carbonates. Thesis Dept. Econ. Geol. Gecchem., Comenius Univ., Bratislava, 107 pp. (in Slovak). MILLS, F. C., 1956. Introduction to Statistics. Henry Holt, New York, N.Y., 673 pp. MI~iK, M., 1968. Traces of Submarine Slumping and Evidences of Hypersaline Environment in the Middle Triassic of the West Carpathian Core Mountains. Geol. Sb. (Bratislava), 19(l) :205-224. ODUM, H. T., 1957. Biochemical deposition of strontium. Texas Univ., Inst. Marine Sci., 4:39-114. OXBURGH, U. M., SEGNIT, R. E. and HOLLAND, H. O., 1959. Co-precipitation of Sr with calcium carbonate from aqueous solutions. Geol. Soc. Am., Abstr., 60:1653-1654. PIVETEAU, J., 1952. l~tude microseopique et p6trographique de la coquille des lamellibranches. In: J. PIVETEAU, (R6dacteur), Traitd de Paldontologie, 2. Masson, Paris, pp.246 261. R1TTENHOUSE, G., FULTON lit, R. B. GRABOWSKI, R. J. and BERNARD, J. L., 1969. Minor elements in oil-field waters. Chem. Geol., 4:189 209. TAFT, W. H., 1962. Influence of magnesium on the stability of aragonite, high-Mg calcite and vaterite and its control on the precipitation of aragonite. Trans. Am. Geophys. Union, 43:p.477 (abstr.). THOMPSON, Z. G. and CHOW, T. J., 1955. The St/Ca ratio in carbonate secreting marine organisms. Deep-Sea Res., 3:20-30. TURAN, J., 1965. Quantitative manometrische Bestimmung yon Karbonaten des Typs KalkDolomit. Geol. Sb. (Bratislava), 16(1):231-240. TUREKIAN, K. K., 1964. The marine geochemistry of strontium. Geochim. Cosmochim. Acta, 28:1479-1496. TUREKIAN, K. K. and KULP, J. L., 1956. The geochemistry of strontium. Geochim. Cosmoehim. Acta, 10:245-296. VElZER, J., 1968a. High Tatra Mantle Series (Slovak Part)--Stratigraphy and Geology. Thesis Dept. Geology, Comenius Univ., Bratislava, 64 pp. (in Slovak). VE1ZER, J., 1968b. High Tatra Mantle Series ( Slovak Part)--Sedimentary Petrology, Geochemistry, Synsedimentary Tectonic and Facial Development, Tectonogenesis and Orogenesis. Thesis Geol. inst. Slovak Acad. Sci., Bratislava, 244 pp. (in Slovak).
Sediment. Geol., 5 (1971) 5-22
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J. VEIZER ET AL.
VEIZER,J. and D~MOW~, R., 1970a. Geochemistry of the sedimentary carbonate rocks of the Western Carpathians region (Slovak Karst and High Tatra Mantle Series). 1. Systematical description. Geol. Sb. ( Bratislava) , in press. VEIZER, J. and DEMOVI~, R., 1970b. Strontium concentrations of some Recent pelecypod shells. Geol. Sb. (Bratislava), in press. WEDEPOHL, K. H., 1960. Spurenanalytische Untersuchungen an Tiefseetonen aus dem Atlantik. Geochim. Cosmochim. Acta, 18:200-231. WEDEPOHL, K. H., 1969. Prim~ire und diagenetische Strontiumgehalte von Karbonatgesteinen. Ber. Geol. Ges. Deut. Demokrat. Rep. Gesamtgebiet Geol. Wiss., 14(1):17 23. WOLF, K. H., CHIUNGAR, G. V. and BEALES, F. W., 1967. Elemental composition of carbonate skeletons, minerals and sediments. In: G. V. CHILINGAR,H. J. BtSSEL and R. W. F air~BRIDGE, (Editors), Carbonate Rocks, B. Elsevier, Amsterdam, pp.23-50. WRAY, J. L. and DANIELS, F., 1957. Precipitation of calcite and aragonite. J. Am. Chem. Soc. 79:2031-2034. ZELLER, E. J. and WRAY, J. L., 1956. Factors influencing precipitation of calcium carbonate Bull. Am. Assoc. Petrol. Geologists, 40:140 152.
Sediment. Geol., 5 (1971)5 22
POSSIBLE USE OF S T R O N T I U M IN S E D I M E N T A R Y C A R B O N A T E ROCKS AS A P A L E O E N V I R O N M E N T A L I N D I C A T O R * J. VEIZER 1, R. DEMOVIC1 AND J. TURAN2
1 Geological Institute of the Slovak Academy o f Sciences, Bratislava (Czechoslovakia) 2 Department of Economic Geology and Geochemistry, Comenius University, Bratislava (Czechoslovakia) (Received August 15, 1969)
SUMMARY
The differences in present-day Sr concentrations in pure limestones (average insoluble residue < 5~) of the Western Carpathians region are interpreted as being due mainly to their original mineralogy. It is proposed that Sr content in conjunction with other observations may be used to distinguish between physicochemical and organodetrital carbonate sediments. INTRODUCTION
It is known (GRAF, 1960; WOLF et al., 1967) that Sr in sedimentary carbonate rocks occurs mainly in the carbonate portion and particularly in CaCO3. This observation has been confirmed by analyses carried out on sedimentary carbonate facies of the Western Carpathians (VEIZER, 1968b; DEMOVI~, 1968). The correlation coefficient for 228 samples, calculated according to the formula: 1 rsr,Ca ~
/7
(XSr--XSr ~
O'Sr
"
XCa--Xca'} ~Ca I
where rsr,Ca--- correlation coefficient of Sr and Ca; /7 ~ number of analyses; x ~ absolute value of each sample; ~ =: arithmetical average; a = standard deviation, gave a significant correlation of Sr to CaO ( + 0.37). Correlation coefficients of the other minor and trace elements are negative or not significant (Ba, Mn, Ti, Cr, B, V, Y, Cu, Pb, Ag, Ni) because of the low sensitivity of the method used (10 p.p.m.). Thus it might be suggested that rocks of similar major component composition (CaO, MgO, insoluble residue = 1.R.) should have similar Sr concentrations. However, initial studies in the West-Carpathian region (VEIZER and DEMOVlC, * Present address: Department of Geophysics and Geochemistry, Australian National University, Canberra, A.C.T., Australia
Sediment. Geol., 5 (1971) 5-22
6
J, \EtZER [!1 A I
1970a) showed that the Sr concentrations of the rocks with similar major component compositions are signilicantly different (see Table I). These observations suggest that Sr concentration of carbonate rocks is nt~ only dependent on the CaCO3 content but on some other factors as welt. TABLE 1 THE AVERAGE MACROCHEMICAI. (?OMPOStIIONS AND Sr C'ONCENFRA]IONSOF THE I)IS('USSI~I)[A(|,\L I'YPES
Carbonate hwie.~
High Tatra Mantle Series region Lower Anisian Upper Anisian Bajocian-Bathonian Malmian-Neocomian U r g o n i a n (Barremian-Aptian) Slovak Karst-algal limestones U p p e r Anisian
Ladinian
("aO
MgO
I.R.
Sr
, ",)
~ ~'.
(",>/
(p.p,m.,
~,'r, ( a . 1( !
5 I, 16 53.54 53.39 53,55 5404
2.00 0.99 1.21 0.47 0.28
4.22 2.33 1.95 3.55 2.96
653 797 137 159 167
I, 79 2.09 t).3f~ 0.42 [).43
5423 53.44
0.75 I. 16
1.70 1.93
140 97
(1.3~5 0.25
SEDIMENTARY AND IF('TONIC EVOI,UTION OF THE CENIRAL WESTERN CARPATHIANS
The evolution of this area (Fig.I) is described briefly as a background to the mineralogical and geochemical studies. This description follows the scheme for preorogenic development or" the Central Carpathian Mesozoic given by VEIZEI{ (1968a,b). For details of stratigraphy and geology see MAHEL and Bur)AY (19681,
.J
~,
(.~,
) <
~.~.
C" P~A6ut
%.~,..j%.~ --~
Z
1 I
HtGH ~'i J~"~ TATRA
~ CN
\.
S
0
Z 0
.F'L'"~.~. k..j.~.
l'J
A '~ e~'~e~ %, ~ F'..,%~
/ 0
V
100kin
K
"~
#Car~,athlQ~s ~;~
/
~.~.
(,)
OETVA
C e~'~°\ "%
SLOVAK KARST ~t.~.~ r
Fig.1. Map or the localities. (1) First sedimentation cycle (Werfenian-Norian)-unstable shelf stage. The area in this period may be described as unstable shelf with hot arid climate. Because of the tectonic and climatic factors mainly carbonate facies art: Sedinlenl.
(':co/,. > (1971) " ~.:
SR IN CARBONATE ROCKS AS A PALEOENVIRONMENTAL INDICATOR
7
developed in which one can see lateral changes (from N to S) from nearshore facies of partly evaporitic origin (High Tatra Mantle Series) through mainly dolomitic types of intermediate character to the developments of the open (?) shelf in the form of algal limestones (banks, reefs) in the most southern part of Slovakia (Slovak Karst). Younger sediments in the last mentioned area are developed only locally. (2) Second sedimentation cycle (Rhaetian-Liassic)-stage of individualisation of the orthogeosynclinal evolution. Increasing tectonic activity has caused division of this area into a system of individualised ridges and troughs. The climate was warm and probably humid. This paleogeography involved the development of basins with partly restricted circulation of the water body thus forming mostly detrital and reducing character of the sedimentary facies, especially in the northern (external) parts of the Western Carpathian geosyncline. (3) Third sedimentation cycle (Doggerian-Aptian)-development stage; preflysch period of the orthogeosynclinal evolution. With continuing subsidence of particular ridges and troughs the paleogeographical features established in the previous period became more apparent. The climate was most probably warm but humidity and aridity cannot be determined because of open marine sedimentation. The sedimentation of this period was mainly pelagic with pelagic carbonates on the ridges of Briangon type (MalmianNeocomian of the High Tatra Mantle Series) and radiolarites in the troughs. The sedimentation of this cycle was finished with development of the detrital reef facies in Barremian-Aptian on the external ridges of the Western Carpathian geosyncline (Urgonian of the High Tatra Mantle Series). (4) Fourth sedimentation cycle (Albian-Lower Turonian)--development stage; flysch period of the orthogeosynclinal evolution. Mainly flysch-like sediments developed, which were followed by the main orogenetic movement of the Central Western Carpathians which formed the present tectonic style of the area. ANALYTICAL TECHNIQUE
The major components (CaO, MgO, I.R.) were determined using the manometrical method described by TURAN 0965). The Sr determinations were made using a PGS-2 optical spectrograph. Details of the method are given elsewhere (MEDVED 1967; DEMOVl~, 1968). Reproducibility of the method expressed as percent standard deviation was ± 9~. Sr DISTRIBUTION
For details of Sr distribution see Fig.2,3,4,5. The Sr concentration of nearly Sediment. Geol., 5 (1971) 5-22
8
J. VEIZER ET A|..
Sr ppm 1500F i
•
H~GH TATRA Lower Anisian
• Upper Anlsian
•.
.°" o. ,,"
lO0Or •o
i
5oo!
I
UD
i 200 L
i 46
48
50
52
54
56
ZCaO
Fig.2. Sr distribution in the Anisian limestones of the High Tatra Mantle Series region Sr
ppm
HIGH TATRA • Malmian~ Neocorma 3
1500'
I • Urgonan
1000"
500
200[
• ,o
•
i
.,~.
oe
""
Fig.3. Sr distribution in the Malmian-Neocomian and Urgonian limestones o[ the High Tatra Mantle Series region.
each single sample from the Anisian of the Mantle Series of the High Tatra region is 3-4 times higher than in the Malmian-Neocomian and Urgonian limestones o | the same region and about 4-9 times higher than in the limestones of" the Anisian and Ladinian age of the Slovak Karst region, and in the limestones of the BajocianBathonian age of tile High Tatra Mantle Series region. Because the limestones of late Anisian and Ladinian age of the Slovak Karst region are supposed to be of similar origin they are combined into one c o m m o n group. For the same reason the Lower and Upper Anisian limestones of the High 5"ediment. G c o t .
~ i 1971) i~, ! '
SR IN CARBONATE ROCKS AS A PALEOENVIRONMENTAL INDICATOR
9
Sr ppm. 150C HIGH T A T R A eBajocian- Bathonian . .
I00C .
50(
200
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
....
~
e e
46
48
50
52
54
56
"/.CaO
Fig.4. Sr distribution in the Bajocian-Bathonian limestones of the High Tatra Mantle Series region. Sr pprn
1500
IOOC
SLOVAK_KARST
.
.
.
.
.
.
.
.
• Upper Ani~ian • Ladinian
500
•
vA
200 •A
A.
46
48
50
52
•A
54
•
56 %CaO
Fig.5. Sr distribution in the Upper Anisian and Ladinian limestones of the Slovak Karst region. Tatra Mantle Series region are also combined. Thus we shall discuss only five populations of limestones: Upper Anisian and Ladinian limestones of the Slovak Karst region; Anisian limestones of the High Tatra Mantle Series region; BajocianBathonian limestones of the High Tatra Mantle Series region; Malmian-Neocomian limestones of the High Tatra Mantle Series region; Urgonian (BarremianAptian) limestones of the High Tatra Mantle Series region. Sediment. Geol., 5 (1971) 5-22
lO
J. \ E I Z E R
t;1 AI_
F o l l o w i n g the test for n o r m a l d i s t r i b u t i o n (density) given by KRUMBEIN and GRAYBILL (1965, p.94) it was l~und that the Sr distributions of all five p o p u l a t i o n s are o f n o r m a l character. The positive correlation of Sr to C a O is confirmed within each separalc p o p u l a t i o n . An exception from this basic pattern are the U r g o n i a n limestones i~; which a slight negative correlation was observed (see Fig.3). We do not know an~ sufficient e x p l a n a t i o n o f this observation. The most likely speculations explaining this feature are: (/) The negative correlation might reflect changes within the assemblage o l organic skeletons building the CaCO~ portion o f the samples. (2) This correlation might be caused by an increased p r o p o r t i o n o f the secondary sparry calcite, the Sr content of which is lower than that of the originai rock. Statistical constants o f all five p o p u l a t i o n s are given in Table 11.
TABLE 11 STATISTICAL PARAMETERS OI IHE DISCUSSED CARBONAIE FA('IES
Number o f sample.~
Arithmetical Standard average o f Sr deviation (p.p.m.
b tlriation coefficieni ' ",,
High Tatra Mantle Series region Anisian Urgonian Malmian-Neocomian Bajocian-Bathonian
39 19 30 II
760 167 137
314 71 82 72
41.3 I 42.38 51.51 52.43
Slovak Karst-algal limestones Upper Anisian and Ladinian
25
116
65
56,37
I G
=:
159
yN
"V/N I i :
1
(.v~
/2):
V = c;-_ . I00 ,u where a :-- standard deviation: N : number of samples; xi ...... absolute value of each sample: /2 = mean (arithmetic average): V ~ variation coefficient.
The lowest variation coefficient r e p o r t e d for the Anisian limestones of the H i g h T a t r a M a n t l e Series is e x t r a o r d i n a r y because the changes in m a c r o c h e m i c a l c o m p o s i t i o n o f these limestones are the highest from all five p o p u l a t i o n s (Fig.2). Using the t-test (MILLS, 1956) to test the mean (:-: arithmetical average) differences, it was f o u n d that the between m e a n differences for the 0.01 confidence level are significant only in plotting the High T a t r a Anisian limestones against the Sediment. Geo/, 5 I I~)71 ) ~ _%
SR IN CARBONATEROCKS AS A PALEOENVIRONMENTALINDICATOR
11
four others (6.44; 8.06; 10.04; 10.10). The other between mean differences (2.51; 2.05; 1.12; 0.84; 0.78; 0.34) are not significant. Thus this conclusion indicates that Sr may be used as a paleoenvironmental indicator only in the case of the High Tatra Anisian limestones against the four others. The use of Sr within the last mentioned group of populations (Bajocian-Bathonian, Malmiam-Neocomian, Urgonian and Slovak Karst) is questionable. PROPOSED ORIGINAL MINERALOGYOF FACIES Compaling the facies in Table II the following suggestions may be drawn regarding their original carbonate mineralogy: (1) Limestones of the Malmian-Neocomian age (High Tatra Mantle Series): The limestones are formed in substantial part from debris of the carbonate skeletons of pelagic organisms (mainly "protoglobigerinoidal" Foraminifera). Skeletons of recent pelagic Foraminifera are known containing mainly low-Mg calcite (BLACKMONand TODD, 1959). The Sr concentrations of recent pelagic foraminiferal tests are~ 1200 p.p.m. (TUREKIAN, 1964). (2) Limestones of the Urgonian age (High Tatra Mantle Series): The limestones are described as proximal reef detrital facies formed from skeleton debris of different organisms, mainly mollusca. Original mineralogical composition of the sediments reflected the mineralogy of skeletons, i.e., intercalations of lowMg calcite and aragonite (THOMPSONand CHOW, 1955). The average Sr concentration of recent molluscs is~ 1,500 p.p.m. (TUREKIAN, 1964). Thompson and Chow reported 1,540 p.p.m, of Sr as the average content for 64 pelecypods and 1,390 p.p.m, for 53 gastropods (Prosobranchia). Studying recent pelecypod skeletons we found 1939 p.p.m, as an average Sr content for 60 samples. (3) Limestones of the Bajocian-Bathonian age (High Tatra Mantle Series): The limestones are composed from crinoidal calcitic monocrystals (crinoidal biosparite). These are known to be high-Mg calcite in recent Crinoidea (GRAF, 1960). The Sr concentrations of recent Crinoidea are ~ 1,450 p.p.m. (GRAE, 1960). (4) Limestones of the Upper Anisian and Ladinian age (Slovak Karst region): They are formed mainly from debris of algal skeletons (Dasycladaceae) which are known to be mainly high-Mg calcite in recent genera and species (CHAVE, 1954). The Sr concentrations of recent Dasycladaceae are not available. There are only few data of Sr concentrations in green algal calcitic skeletons (LOWENSTAM,1963) with about I-1.5 tool ~ of Sr. However these concentrations are very high in comparison with Sr concentrations of other classes and do not agree very well with the known concentration factors of Sr for both high- and low-Mg calcites. (5) Limestones of the Anisian age (High Tatra Mantle Series): By analyzing physicochemical conditions of the first sedimentation cycle in the High Tatra Mantle Series region (VEIZER, 1968b) it was found that sedimentation of this area was partly of hypersaline character because of evaporation in the back-reef (backSediment. Geol., 5 (1971) 5--22
12
J. VIEIZER ET tsl,
bank) area. This conclusion is indicated by: (a) the development of red beds (with gypsum and anhydrite in the southern parts of the West-Carpathian geosyncline) at the beginning and the end of this sedimentation cycle; (b) intercalation oi limestones (especially in Lower Anisian) with sheet dolomites of early diagenetic or primary origin; (c) existence of cavernous "dolomites" with pseudomorphs after gypsum; (d) existence of pseudomorphs after gypsum and NaCI in this limestone described by MIgiK (1968). The evidence is supported by extremely fine texture of the limestones and lack or sporadic occurrence of organisms. The hypersaline conditions are characterized by higher pH as well as Mg/Ca and Sr/Ca ratios which shifts the equilibrium towards physicochemical or biochemical? (bacterial) precipitation of aragonite (ZELLERand WRAY, 1956: WRAY and DANIELS, 1957; GOTO, 1961 ; TAFT, 1962). According to BATHURST(1964), aragonitc is the only physicochemica[ carbonate mineral precipitating IYom sea water. KINSMAN and HOLLAND (1969) found experimentally that aragonite is the o n b mineral precipitating from sea water at temperature above 30 ':C. The Sr concentrations of similar recent facies are ,- 9,000 p.p.m. (KINSMAN, 1969). In agreement with this interpretation are the very fine textures as well as the extremely high Sr concentrations (ODUM, 1957). The conclusions of supposed original mineralogy of the above-discussed populations are summarized in Table Ill. TABLE I11 SUPPOSED ORIGINAL MINERALOGY AND AVERAGE sr CONCENTRATIONS
O F T H E D I S C U S S E D FACIES
Supposed original mineralogy
Sr' Ca. l 0 Sr (p.p.m,)
High Tatra Mantle Series region
Malmian-Neocomian Bajocian-Bathonian
physico-chemical (biochemical?) aragonite mixture of organic low-Mg calcite and organic aragonite organic low-Mg calcite organic high-Mg calcite
Slovak Karst-algal limestones Upper Anisian and Ladinian
organic high-Mg calcite
Anisian Urgonian
760
2.02
167 159 137
0.43 0.42 0.36
116
0.31
DISCUSSION
Sr in recent carbonate sediments occurs mainly in the aragonitic lattice (THoMPSON and CHOW, 1955; ODUM, 1957). KINSMANand HOLLAND (1969) lkmnd that the concentration factor of Sr for aragonite is 1,17 :~: 0.04 (16°C) and (i).88 : 0.03 Sediment. Geol.. ~ II971 )5 22.
SR IN CARBONATE ROCKS AS A PALEOENVIRONMENTAL INDICATOR
13
(80 °C) whereas for calcite it is only 0.11 :~: 0.02 (30°C) and 0.07 :J: 0.004 (95°C) according to OXBURGHet al. (1959). Also St/Ca ratio of inorganic aragonites is higher than that of most organic aragonites (GOLDBERG, 1957). This short review suggests that different mineralogical composition caused by different conditions in sedimentary environments might explain the differences in Sr distribution as given in Tables I-IlI. Comparison of the assumptions regarding original carbonate mineralogy with the average Sr concentrations and the average Sr/Ca ratios (Table I11) shows that both are decreasing in sediments expected to be aragonitic, through mixture of organic aragonite and organic low-Mg calcite, organic low-Mg calcite to organic high-Mg calcite (Fig.6). Sr R.p.m.
1500
1000
--
--
--
4
-
-
Q------
. . . . •
-
ARITHMETIC AVERAGE OF Sr CONCENTRATIONS
STANDARD DEVIATION - VARIATION
--.
COEFFICIENT
._g g "5
"~
-og 500
-o g
~9 -100 °/, '~
300 \
lo~
.....
_o
o
>Y--\~ "
. . . . _......... - . . . . . . . . .
_._
.=
o
2OOlooLs° °~°
g
~
.~o
~
"~
-
N
.o_=
~ o
o
o
a
Fig.6. AverageSr concentrations and supposed original mineralogy of the limestonefacies. Also in limestones of Early Anisian age (Slovak Karst and Gemeridy Unit), which by the senior author (J.V.) are supposed to be of bacterial origin, three analyses showed very high Sr content (740, 832 and 1,110 p.p.m.). Carbonate mineral precipitated by marine bacteria is aragonite (GREENFIELD, 1963). It is very difficult to prove directly the character of the original mineralogy of Sediment. Geol., 5 (1971) 5-22
14
J. VEIZER [-:[ \ i
these sediments because of diagenetic changes, but it is interesting to note that the decreasing Sr content is in agreement with the known concentration factors l~,r these minerals. This indicates that the original mineralogy should be an important factor controlling the present-day Sr concentration of fossil carbonate sediment~. Interesting restalts were obtained using the electron microscope to study the above-mentioned facies. In the limestones of the High Tatra Anisian (aragonite~ grain relicts of elongated shape were tbund (Fig.7), whereas in the M a l m h m Neocomian limestones (low-Mg calcite) the relicts were only of polygonal shape (Fig.8). This mighl be related to the differences in original mineralogy as well.
Fig.7. Electron-microscope photograph of the Anisian limestone (High Tatra Manth: Series region). Note the elongated shape and straight boundaries of the grain in the left centre ~ the picture. (Photo M. Harman: replica technique.)
The assumption that Sr differences are caused by original mineralogy J~ supported by results of FC0GEL and FLOGEL-KAHLI~R(1962) who have found that there are differences in Sr concentrations of the fore-reef and back-reef samples oi the Rhaetian age in the eastern Alps. They concluded that differences were caused S'edinlent,
(,'~,,
~ i l~-i
i "
'
SR IN C A R B O N A T E R O C K S AS A P A L E O E N V I R O N M E N T A L I N D I C A T O R
15
Fig.8. Electron-microscope photograph of the Malmian limestone (High Tatra Mantle Series region). Note the polygonal shape of the grains. (Photo M. Harman; replica technique.) by different assemblages of the organisms in both environments and thus by different original mineralogy of these sediments. Studying Sr concentrations in recent pelecypods (VEIZER and DEMOVI~', 1970b), we found that Sr concentrations of inner layers of the shells are in average two times higher than Sr concentrations of the whole shells (35 exemplars). The inner layer of pelecypod shells is mainly aragonitic (P~vETEAU, 1952). Using Feigel solution to test the mineralogy it was established that the majority of aragonite was already converted to calcite. This indicates that certain partition of Sr in carbonate fraction is possible in spite of conversion of unstable minerals (aragonite, high-Mg calcite) into stable ones (low-Mg calcite and dolomite). However, although the original mineralogy might be the most important factor controlling the present-day Sr concentrations of the above-mentioned facies, it is inevitable to discuss a possible diagenetic influence. During the initial stage of syndiagenesis (FAIRBRIDGE, 1967), which is characterized by squeezing out of the trapped interstitial waters, no substantial Sediment. Geol., 5 (1971) 5 22
16
J. VEIZI-R E l A L
changes should occur, because the composition of the interstitial water is similar to the composition of the water body above the sediment surface. The carbonate minerals are thus in equilibrium with the surrounding media. This conclusion is supported by results of BErNER (1966), who has found that the original mineralogy, is relatively very stable in contact with sea water. A similar feature may be expected also in the areas of hypersaline solutions. According to Berner, the conversion ol unstable minerals into stable ones was observed only in the areas exposed to the influence of brackish or fresh waters. This might be to a certain extent the case of the Urgonian limestones, which were exposed above the sea level during the Lower Albian period. The behaviour of Sr during the later stages of diagenesis (early burial stage, anadiagenesis and epidiagenesis) is not well documented, however it is reasonable to conclude that under higher P and T conditions the unstable carbonate minerals which are converted into stable ones, release part of their Sr into pore solutions. The increased Sr/CI ratio and higher Sr content of these solutions in comparison to sea water has been observed by several authors (CARPENTER and MILLer, 1969: COLLINS, 1969; RITTENHOUSEet al., 1969; and others). At this stage of diagenesis permeability (K.K. Turekian, personal communication, 1969) might be the controlling factor of the Sr movement. Apparently, the more compressible and les.~ permeable fine-grained carbonate sediments may retain higher Sr concentrations, although not necessarily being incorporated into the calcite or dolomite crystal lattice, than the organodetrital ones. Arranging the above-mentioned facies according to this criterion, Ihc succession is as follows: Bajocian-Bathonian (137 p.p.m.) : Urgonian (167) > Slovak Karst (I 16) > > > Malmian-Neocomian (159) ~- Anisian (760). l h e Sr content of the highly permeable and possibly partly recrystallized (fresh-water influence) Urgonian is higher than the Sr content of the less permeable MalmianNeocomian. Also it is very difficult to explain the remarkably different Sr con~ centrations in the two last mentioned facies in spite of their similar permeability Considering the positive correlation between supposed original mineralogy, assumed original Sr concentrations (Fig.8,9) and present-day Sr concentrations ol the facies discussed, one may see that there is approximately a tenfold decrease m the average Sr concentrations regardless of their permeability. The problem to resolve is the nature of this transition. There are two general schools of thought about the transition of unstable carbonate minerals into stable ones. These are the solid-solid transition and the solution-precipitation process. In the light of recent data (FLOGEL and WEDEPOHL, 1967: WEDF~POHL, 1969: KINSMAN,1969; and others) the latter is generally favoured. These authors have developed models in which the Sr concentration of the final phase would depend on the original Sr content, original mineralogy and the nature and character of circulating solutions. Since, during later stages of anadiagenesis compaction of sediments is high Sediment. Gco!
5 (1971~ ~ ?:
SR IN CARBONATE ROCKS AS A PALEOENVIRONMENTAL INDICATOR I~pm. Sr 10000
"..L~ . ~ / / L ' . , ' / ' / . / //',,
1
/ /
f
/
,/,-
///
/,
/.
17
o,ogon~,e ~n
" " " ,
/with sea
.... water
Ii assumed original Sr concentration 5000
opte~ent - day Sr content rahon
]
......
,,, f ,i/, 1000
" +
,
,
.
.
,1 ..... 1
,,
/+/
. ca,. . . . . .
equilibrium 4~ . wlth //. sea waler ,
,
500
I00
Fig.9. A s s u m e d original a n d present-day Sr concentrations of the limestone facies. T h e succession of facies is as in Fig.6.
and porosity low (cf., FAIRBRIDGE, 1967), it is reasonable to suppose that the system acted more or less as a closed system and that the major transitions occurred prior to this period. There should be no substantial changes during the initial stage of syndiagenesis as discussed previously. The stages during which these transitions probably occurred are thus early burial stage of syndiagenesis and early stage of anadiagenesis. These processes during the early burial stage are controlled by entrapped connate waters, which are chemically modified by bacteria and organisms, usually lowering pH values. This might be a period of major transitions within the inorganic and biochemical facies, whereas the organodetrital facies were probably altered during an early stage of anadiagenesis, which is characterized by compaction and maturation of sediments. The very fine-grained texture of the first group would also support an earlier conversion. FLUGEL and WEDEPOHL(1967) developed six models of diagenetic processes, which are in general agreement with KINSMAN'S (1969) data. The closed system model may produce a final phase (low-Mg calcite) with Sr concentrations ~ 700 p.p.m, or more from original aragonites and with ~ 150 p.p.m, or more from original calcites. This would be in excellent agreement with our results. In an open system under the influence of sea water the precipitated calcites should contain ~ 1,000 p.p.m, of Sr, regardless of their original mineralogy. However, the Sr contents of the organodetrital facies are too low to be compatible with this hypothesis. Sediment. Geol., 5 (1971) 5--22
18
J. VEIZER E l AL,
In an open system, which was dominated by fresh waters, the precipitated calcites should have ~ 150-300 p.p.m, of Sr. The original mineralogy does have some influence, but it is generally not very significant. This explanation is incompatible with the high Sr contents observed in the inorganic or biochemical sedi. ments. The role of possible fresh-water influence has already been stressed in the case of the Urgonian facies. With more or less difficulty it would be possible h~ suppose a fresh-water influence for the Bajocian-Bathonian and Stovak Kars~ facies, although no geological evidence is yet available to support this view. This explanation, however, is unlikely for the Malmian-Neocomian sediments, since they were deposited in a pelagic ridge area. They were not exposed above sea level until at least Albian and most probably much later. Thus the minimal period l'oJ lithification of the top part of this suite was ~ 18 million years and of the bottom 51 million years. It is probable that these sediments were already compact and mature before they were exposed to fresh-water influence. A fresh-water influ>~ through seaward-dipping permeable sediments might also be excluded, since the High Tatra Mantle Series ridge was separated from land by the Pieniny trough with radiolarite sedimentation. It would be possible to assume a closed-system model for the "'aragonitic" and Malmian-Neocomian facies and a fresh-water open system for the Urgtmian, Bajocian-Bathonian and Slovak Karst facies (which is a reasonable probability) or to introduce a separate model for each facies. However, the generally equal decrease in Sr concentrations of all facies and the satisfactory agreement with the closed-system model indicates that the facies acted more or less as closed systems (at least within the first group) during their diagenetic history, A closed system of diagenesis might be reasonably assumed for fine-grained carbonate sediments. Since the entrapped water of these s~,diments was very high, the process of diagenesis might cause greater squeezing out of entrapped water and decrease in permeability than an "open"-system circulation of solutions. Such unidirectional movement of connate solutions is also required to explain the pattern of doiomitisation within the Western Carpathians (VEIZER, 1968b) and is in agreement with isotopic data observed by the senior author. The problem is more complicated in the presence of porous sediments with complicated mineralogy in such environments as reefs, banks, etc., which may easily be exposed to fresh-water influence. Nevertheless, the results obtained by the senior author on Australian Precambrian and Palezoic carbonates are very encouraging. As inorganic and biochemical carbonate facies are usually very fine-grained sediments of semirestricted basins with high ionic concentrations (i.e., Sr) and aragonitic mineralogy, they would act as more or less closed systems during the early burial and early anadiagenetic alterations. The chance of retaining Sr concentrations > 700 p.p.m, is thus high and the chance of fresh-water alteration is low, since they are mainly sediments of arid regions and the usually high alkaline Sediment. Geol.. 5 ( 1971 ) 5 22
SR IN CARBONATEROCKS AS A PALEOENVIRONMENTALINDICATOR
19
reaction of ground waters of such regions would not support their solution. This assumption in conjunction with other observations may serve to distinguish such sediments from organodetrital ones, which have a tendency (unless well preserved) to retain lower Sr values. However, the conclusions discussed above need further detailed studies of similar facies and studies of Sr behaviour during diagenetic history. There are two other factors, which might substantially influence the Sr concentration of the carbonate facies. These are the I.R. (insoluble residue) content and composition as well as the degree of recrystallization. It could be argued that there is a substantial partition of Sr in the I.R. which might cause the above-mentioned differences of the whole rock Sr analyses. We did not carry out chemical analyses of the I.R., but we do not think that this interpretation is correct for the following reasons: (1) The average I.R. content and composition of all facies is similar (see Table I). (2) As mentioned earlier there is negative correlation of Sr with I.R. (- 0.29) and MgO (- 0.27) and a positive correlation with CaO ( + 0.37). This indicates that the major part of Sr occurs in CaCO3. (3) The |.R. is composed mainly of a detrital fraction <2]~. The mineralogy of this fraction is uniform in all facies (VEIZER, 1968b). The most abundant mineral is illite, with only sporadic chlorite, montmorillonite and kaolinite. The less abundant fraction > 2/L is composed mainly of quartz with very small amounts of mica and feldspar. (4) The highest value of the Sr concentration in deep-sea clays reported by DASCH (1969) was 452 p.p.m, and less in clays with a higher proportion of illite. The highest Sr concentration in illitic clays analyzed by W. Compston (personal communication, 1969) was 125 p.p.m. The "average" shale of TUREKIAN and KULP (1956) contains ~ 300 p.p.m, of Sr. The average Sr concentration of the Atlantic shales given by WEDEPOHL (19601) is 120 p.p.m. The value reported by TUREKIAN (1964) is 130 p.p.m. This review indicates that the Sr content of shales is lower than that of carbonates. Even a concentration of 500 p.p.m. Sr in the I.R. cannot influence the whole rock Sr concentrations (~ 4 ~ of I.R.) by more than 20 p.p.m. The following reasons support our view that the differences in Sr concentrations are not caused by different degrees of recrystallization: (1) There was no notable difference in the degree of recrystallization in the majority of thin-sections (contact of grains, sparry calcite, shape of grains, etc.). (2) The older sediments of the same area contain higher Sr concentrations than the younger ones and the Sr concentrations of the organodetrital limestones are of the same order in both areas in spite of the different ages. (3) Sediments from the tectonically more disturbed area (High Tatra) contain higher Sr concentrations than the sediments from the less deformed area (Slovak Karst plateau). Sediment. Geol., 5 (1971) 5-22
20
J. VEIZER ET AL.
(4) Any type of recrystallization effects more the fine-grained micritic muds than the coarser remains of organic skeletons. However, the Sr content of the micritic facies is higher or similar to the Sr content of the organodetrital sparitic facies. CONCLUSI()NS
The average Sr concentrations of the supposed original aragonite facies are significantly higher than those of the calcite facies. This succession is in agreemem with known Sr concentration factors for these minerals and thus original mineralogy might be an important factor influencing the present-day Sr distribution of the sedimentary carbonate rocks, although the diagenetic changes may significantly alter this pattern. The Sr concentration, in conjunction with other observations, might serve as ~ valuable tool to distinguish physicochemical (biochemical?) aragonitic carbonate sediments from the organodetrital ones. The Sr concentrations within the organodetrital carbonate facies group are dependent on a great number of t'actor~ and thus are less favourable for diagnostic purposes. ACKNOWLEDGEMENTS
We would like to acknowledge a great debt of gratitude to Drs, S.R. Iaylor, K.A.W. Crook, E, J. Dasch, H. H. Veeh and W. Compston for criticism and specific suggestions. REFERENCES BATHURSr, R. G. C., 1964. Diagenesis and paleoecology: a survey. In: J. IMBRIEand N. Ntz~w~tA IEditors), Approaches to Paleoeeology. Wiley, New York, N.Y., pp.31%-344. BERNER, R. A., 1966. Chemical diagenesis of some modern carbonate sediments. Am. J. Sci.~ 264:1-36. BLACrCMON, P. D. and TODD, R., 1959. Mineralogy of some Foraminifera as related to their classification and ecology. J. Paleontol., 33:1 15. CARPENTER, A. B. and MILLER, J. C., 1969. Geochemistry of saline subsurface water, Saline County (Missouri). Chem. Geol., 4:135-167. CHAVE, K., 1954. Aspects of the biochemistry of magnesium, 1. Calcareous marine organism~;. J. Geol., 62:266-283. COLLINS, G. A., 1969. Chemistry of some Anadarko Basin brines containing high concentration~ of iodide. Chem. Geol., 4:169-187. DASCH, E. J., 1969. Strontium Isotopes in Weathering Profiles, Deep-sea Sediments, and Sedimentary Rocks. Thesis Yale Univ,, New Haven, Conn., 94 pp. DEMOVI~, R., 1968. Geochemistry of Sedimentary Carbonate Rocks and of Some Recent Pelecypoa Skeletons. Thesis Geol. Inst. Slovak Acad. Sci., Bratislava, 203 pp. (in Slovak). FAIRBRIDGE, R. W., 1967. Phases of din.genesis and authigenesis. In: G. LARSEN and G. '~ CHmINGAR(Editors), Diagenesis in Sediments (Developments in Sedimentology, 8). Elsevier. Amsterdam, pp. 19-90.
Sediment. Geol.. 5 (1971) 5 22
SR 1N CARBONATE ROCKS AS A PALEOENV1RONMENTAL INDICATOR
21
FL/.)GEL, E. und FLOGEL-KAHLER, E., 1962. Mikrofazielle und geochemische Gliederung eines obertriadischen Rifles der nordlichen Kalkalpen. Mitt. Bergbau, Geol. Tech., Landesmuseum Joanneum, 24:1-128. FL/SGEL, H. W. und WEDEPOHL, K. H., 1967. Die Verteilung des Strontiums in oberjurassischen Karbonatgesteinen der N6rdlichen Kalkalpen. Beitr. Mineral. Petrog., 14:229-249. GRAE, D. L., 1960. Geochemistry of carbonate sediments and sedimentary carbonate rocks, l ~ . Illinois State Geol. Surv., Circ., 297, 298, 301, 308:250 pp. GOLDBERG, E. O., 1957. Biogeochemistry of trace metals. In: J. W. HEDGPETH (Editor), Treatise on Marine Ecology and Paleoecology, 1. Ecology--Geol. Soc. Am., Mere., 67:345-358. GoTo, M., 1961. Some mineralo-chemical problems concerning calcite and aragonite with special reference to the genesis of aragonite. J. Fae. Sci. Hokkaido Univ., Set. IV, 1(4):571-640. GREENFIELD, L. J., 1963. Aragonite formation by marine bacteria. Bull. Am. Assoc. Petrol. Geologists, 47:p.358 (abstr.). KINSMAN, D. J. J., 1969. Interpretation of Sr 2+ concentrations in carbonate minerals and rocks. J. Sediment. Petrol., 39:486-508. KINSMAN, D. J.J. and HOLLAND, H. D., 1969. The co-precipitation of cations with CaCO3, 4. The co-precipitation of Sr 2~ with aragonite between 16-96 °C. Geochim. Cosmochim. Acta. 33:1-18. KRUMBEIN, W. C. and GRAYBILL, F. A., 1965. An Introduction to Statistical Models in Geology. McGraw-Hill, New York, N.Y., 475 pp. LOWENSTAM, H. A., 1963. Biologic problems relating to the composition and diagenesis of sediments. In: W. DONELLY (Editor), The Earth Sciences--Problems and Progress in Current Research. Univ. Chicago Press, pp.137 195. MAHEI~, M. and BUDAY, T., 1968. Regional Geology o f Czechoslovakia, 2. T/re West Carpathians. 1].I_).G., Prague, 723 pp. MEDVEI~, J., 1967. Quantitative Spectral Analytical MethodJbr Determination o f Mieroelements in Carbonates. Thesis Dept. Econ. Geol. Gecchem., Comenius Univ., Bratislava, 107 pp. (in Slovak). MILLS, F. C., 1956. Introduction to Statistics. Henry Holt, New York, N.Y., 673 pp. MI~iK, M., 1968. Traces of Submarine Slumping and Evidences of Hypersaline Environment in the Middle Triassic of the West Carpathian Core Mountains. Geol. Sb. (Bratislava), 19(l) :205-224. ODUM, H. T., 1957. Biochemical deposition of strontium. Texas Univ., Inst. Marine Sci., 4:39-114. OXBURGH, U. M., SEGNIT, R. E. and HOLLAND, H. O., 1959. Co-precipitation of Sr with calcium carbonate from aqueous solutions. Geol. Soc. Am., Abstr., 60:1653-1654. PIVETEAU, J., 1952. l~tude microseopique et p6trographique de la coquille des lamellibranches. In: J. PIVETEAU, (R6dacteur), Traitd de Paldontologie, 2. Masson, Paris, pp.246 261. R1TTENHOUSE, G., FULTON lit, R. B. GRABOWSKI, R. J. and BERNARD, J. L., 1969. Minor elements in oil-field waters. Chem. Geol., 4:189 209. TAFT, W. H., 1962. Influence of magnesium on the stability of aragonite, high-Mg calcite and vaterite and its control on the precipitation of aragonite. Trans. Am. Geophys. Union, 43:p.477 (abstr.). THOMPSON, Z. G. and CHOW, T. J., 1955. The St/Ca ratio in carbonate secreting marine organisms. Deep-Sea Res., 3:20-30. TURAN, J., 1965. Quantitative manometrische Bestimmung yon Karbonaten des Typs KalkDolomit. Geol. Sb. (Bratislava), 16(1):231-240. TUREKIAN, K. K., 1964. The marine geochemistry of strontium. Geochim. Cosmochim. Acta, 28:1479-1496. TUREKIAN, K. K. and KULP, J. L., 1956. The geochemistry of strontium. Geochim. Cosmoehim. Acta, 10:245-296. VElZER, J., 1968a. High Tatra Mantle Series (Slovak Part)--Stratigraphy and Geology. Thesis Dept. Geology, Comenius Univ., Bratislava, 64 pp. (in Slovak). VE1ZER, J., 1968b. High Tatra Mantle Series ( Slovak Part)--Sedimentary Petrology, Geochemistry, Synsedimentary Tectonic and Facial Development, Tectonogenesis and Orogenesis. Thesis Geol. inst. Slovak Acad. Sci., Bratislava, 244 pp. (in Slovak).
Sediment. Geol., 5 (1971) 5-22
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VEIZER,J. and D~MOW~, R., 1970a. Geochemistry of the sedimentary carbonate rocks of the Western Carpathians region (Slovak Karst and High Tatra Mantle Series). 1. Systematical description. Geol. Sb. ( Bratislava) , in press. VEIZER, J. and DEMOVI~, R., 1970b. Strontium concentrations of some Recent pelecypod shells. Geol. Sb. (Bratislava), in press. WEDEPOHL, K. H., 1960. Spurenanalytische Untersuchungen an Tiefseetonen aus dem Atlantik. Geochim. Cosmochim. Acta, 18:200-231. WEDEPOHL, K. H., 1969. Prim~ire und diagenetische Strontiumgehalte von Karbonatgesteinen. Ber. Geol. Ges. Deut. Demokrat. Rep. Gesamtgebiet Geol. Wiss., 14(1):17 23. WOLF, K. H., CHIUNGAR, G. V. and BEALES, F. W., 1967. Elemental composition of carbonate skeletons, minerals and sediments. In: G. V. CHILINGAR,H. J. BtSSEL and R. W. F air~BRIDGE, (Editors), Carbonate Rocks, B. Elsevier, Amsterdam, pp.23-50. WRAY, J. L. and DANIELS, F., 1957. Precipitation of calcite and aragonite. J. Am. Chem. Soc. 79:2031-2034. ZELLER, E. J. and WRAY, J. L., 1956. Factors influencing precipitation of calcium carbonate Bull. Am. Assoc. Petrol. Geologists, 40:140 152.
Sediment. Geol., 5 (1971)5 22