Tem per a ture and iso to pic re la tions in car bon ate min er als in the Mid dle Ju ras sic si der it ic rocks of cen tral and south ern Po land
Katarzyna JARMO£OWICZ-SZULC1, * and Aleksandra KOZ£OWSKA1
1 Pol ish Geo log i cal In sti tute – Na tional Geo log i cal In sti tute, Rakowiecka 4, 00-975 Warszawa, Po land
Jarmo³owicz-Szulc, K., Koz³owska, A., 2016. Tem per a ture and iso to pic re la tions in car bon ate min er als in the Mid dle Ju ras - sic si der it ic rocks of cen tral and south ern Po land. Geo log i cal Quar terly, 60 (4): 881–892, doi: 10.7306/gq.1323
The pres ent study as sesses the physico-chem i cal char ac ter of the flu ids re spon si ble for the gen e sis of car bon ate min er als in the Mid dle Ju ras sic si der it ic rocks at the north east ern mar gin of the Holy Cross Mts. and in the Czêstochowa re gion. These rocks oc cur at pres ent at depths be tween 30 and 600 m. Fluid in clu sion and iso to pic anal y ses have been per formed in the car bon ate min er als from si der it ic sand stones, clayey siderites and si der it ic coquinas. Sid er ite is the main car bon ate min eral of the si der it ic rocks. Cal cite and an ker ite are also pres ent. The sid er ite is rep re sented by two va ri et ies, Mg-rich sid er ite (sideroplesite, less com monly – pistomesite) and sid er ite. Two gen er a tions of sid er ite have been dis tin guished – an early and a late one. The early sid er ite was formed at tem per a tures of about 20°C in the zone of mi cro bi o log i cal methanogenesis from ma rine wa ters with some in flu ence of me te oric wa ters (d18O from –7.84 to –1.92‰ VSMOW). The late sid er ite crys tal - lized at tem per a tures of about 62–110°C from pore wa ters en riched in 18O (d18O >0‰ VSMOW) as com pared with the iso to - pic com po si tion of the wa ters re spon si ble for the early sid er ite gen er a tion. The con ducted fluid in clu sion anal y ses point to for ma tion of the ce ments from com plex flu ids of brine and car bon di ox ide char ac ter, with den si ties slightly ex ceed ing 1 g/cm3 and sa lini ties vary ing from 10.5 to 16.9 wt.% NaCl eq. and from 6.4 to 14.0 wt.% NaCl eq. in the Holy Cross Mts. and in the Czêstochowa re gion, re spec tively. The ho mog e ni za tion tem per a tures lie in the in ter vals of 62–110°C and 60–97°C, re spec - tively and rep re sent el e vated val ues com pared with data from the Pol ish Low lands. Apart from burial, other heat sources must have been im por tant for the lithogenesis of the Mid dle Ju ras sic de pos its.
Key words: fluid in clu sions, iso topes, car bon ate min er als, si der it ic rocks, Mid dle Ju ras sic.
INTRODUCTION
The term “sid er ite” en com passes min er als of the solid so lu - tion se ries be tween sid er ite and magnesite, most fre quently, sideroplesite and pistomesite (Bolewski, 1982). Most hith erto pub lished pa pers pres ent tem per a ture con di tions re spon si ble for vein siderites or magnesites of hy dro ther mal or i gin (e.g., Hein, 1993; Hurai et al., 2002; Lugli et al., 2002; Schmidt Mumm and Wolfgamm, 2002; Fernández-Nieto et al., 2003;
Strmiæ Palinkaš et al., 2009; Palinkaš et al., 2016). Few pa pers pro vide data on fluid in clu sions in siderites from sed i men tary rocks (Rezaee and Schulz-Rojahn, 1998).
A ba sis for fluid in clu sion stud ies is an as sump tion that dur - ing the crystallisation of pore-fill ing min er als in sed i men tary rocks, small amounts of ba sin flu ids are trapped (Roedder, 1984). Gen er ally, the fluid in clu sions are rel ict por tions of the so lu tions that no lon ger ex ist. There fore, ther mal and iso to pic stud ies may serve to re con struct the pri mary con di tions of min - eral for ma tion and of the com po si tion and den sity of palaeo - fluids (Jarmo³owicz-Szulc, 1999). In for ma tion on the pri mary
vol ume and com po si tion should re main pre served. This is very dif fi cult to con strain in the sed i men tary rocks, which may be deeply bur ied and sub se quently up lifted. Fluid in clu sion bear ers show vari able re sis tance to wards ex ter nal con di tions, which is why tem per a ture re sults ob tained for them may vary in sig ni f i - cance (Jarmo³owicz-Szulc, 2015).
In diagenetic stud ies, ther mo met ric in ter pre ta tion has to take into ac count a num ber of fac tors (Goldstein, 2001). First, the char ac ter of fluid in clu sions (pri mary or sec ond ary) needs to be con sid ered. Next, the mea sured val ues may re flect a wide range of sa lin ity, be cause the crys tals have grown from mixed flu ids. Then, deep burial of de pos its may cause stretch ing and leak age of in clu sions, so the tem per a ture val ues ob tained may not cor re spond to pri mary con di tions of min eral for ma tion (Goldstein, 1986).
The pres ent re search dem on strates the sig nif i cance of fluid in clu sions in re la tion to car bon ate ce ments, mainly sid er ite, lo - cally an ker ite and cal cite. The in clu sion and sta ble iso tope data served as a geo log i cal ther mom e ter. Ad di tion ally, car bon and ox y gen iso tope ra tios in car bon ate min er als have been used for cal cu la tion of the iso to pic com po si tion of the fluid from which these min er als have crys tal lized. Thus, fluid in clu sion anal y sis ac com pa nied by iso to pic stud ies of the car bon ate min er als in the si der it ic rocks from two ar eas of Po land – the north east ern mar gin of the Holy Cross Mts. and the Czêstochowa re gion (Fig. 1) con trib uted to better un der stand ing of the or i gin of these sid er ite de pos its.
* Corresponding author, e-mail:
katarzyna.jarmolowicz-szulc@pgi.gov.pl
Received: June 3, 2016; ac cepted: Oc to ber 12, 2016; first pub lished on line: No vem ber 2, 2016
GEOLOGICAL SETTING AND STUDY AREA
The study area (Fig. 1) rep re sents a south ern part of the Pol ish Ba sin that dur ing the Ju ras sic was the east ern arm of the Cen tral Eu ro pean Ba sin Sys tem (Pieñkowski et al., 2008). The thick ness of the Mid dle Ju ras sic strata at the north east ern mar - gin of the Holy Cross Mts. var ies from 180 m (south-east) to about 800 m (north) (Daniec, 1970). The de pos its are rep re - sented by sand stones and mudstones with interbeds of clay - stones and si der it ic iron ores, mainly of Aalenian, Bajocian and Bathonian age (Koz³owska and Maliszewska, 2015). The thick - ness of the Mid dle Ju ras sic strata in the Czêstochowa re gion changes from 85 m (south) to about 184 m (north) (Kopik, 1998). The de pos its are com posed of Bajocian and Bathonian sandy claystones and mudstones, which lo cally con tain dark claystones with sid er ite (known as ore-bear ing clays; Kopik, 1998). The dif fer ence in the thick ness of the Mid dle Ju ras sic de pos its be tween the two ar eas un der dis cus sion re sults from their palaeogeographic po si tion within the epicontinental ba sin.
It is pre sumed that the north east ern mar gin of the Holy Cross Mts. oc cu pied the cen tral part of the ba sin, whereas the Czêsto - chowa re gion a mar ginal part (Feldman-Olszewska, 1998).
The si der it ic rocks were col lected from two bore holes at the north east ern mar gin of the Holy Cross Mts. (Gutwin and W¹gla - ny k/Opoczna) and from four bore holes in the Czêstochowa re - gion (Biskupice 25BN, £utowiec 135¯, Parkoszowice 58BN and Zrêbice 33BN) (Fig. 1 and Ta ble 1). The de pos its oc cur at depths vary ing from 30 to 600 m. The sam ples stud ied in the Czêstochowa area are from mod er ate depths be tween ~100 m to at max i mum ~380 m (Parkoszowice 58BN – depth from 101.3 to 104.2 m; Biskupice 25BN – depth 134.7 m; £utowiec 135¯ – depth 178.9 m; Zrêbice 33BN – depth 372.7 m), while the sand stones stud ied at the north east ern mar gin of the Holy Cross Mts. lie much deeper, up to about 650 m (Gutwin – depth 201.6 m; W¹glany k/Opoczna – depth from 267.7 to 643.8 m).
Lithological sec tions of the Gutwin and £utowiec 135¯ bore - holes by Koz³owska and Maliszewska (2015) are shown in Fig - ure 2. A sim pli fied sec tion of the Zrêbice 33BN bore hole may be found in Leonowicz (2015). Ac cord ing to Feldman -Olszewska (pers. comm., 2013), the rocks rep re sent var i ous Mid dle Ju ras - sic sed i men tary en vi ron ments, such as the off shore, tran si tion zone, shoreface, deltaic and estuarian re gimes. Sid er ite lay ers and con cre tions, and si der it ic sand stones, are ob served mainly in the Aalenian, Bajocian and Bathonian rocks, at the north east - ern mar gin of the Holy Cross Mts. and in the Bajocian and Fig. 1. Map of lo cal ity of bore holes an a lysed in the pres ent study
Grey col our shows ex tent of the Mid dle Ju ras sic in Po land (af ter Lott et al., 2010, mod i fied)
Bathonian rocks of the Czêstochowa re gion (Koz³owska and Maliszewska, 2015).
There are a num ber of re cent pa pers on the stra tig ra phy, sedimentology, geo chem is try and palaeoenvironments of the Mid dle Ju ras sic strata of the Czêstochowa re gion (e.g., Majewski, 2000; Marynowski et al., 2007; Szczepanik et al., 2007; Wierzbowski and Joachimski, 2007; Zatoñ et al., 2009;
Gedl and Ziaja, 2012; Witkowska, 2012; Leonowicz, 2012, 2013, 2015). The Mid dle Ju ras sic de pos its at the north east ern mar gin of the Holy Cross Mts. were stud ied by Koz³owska and Maliszewska (2015). Their re search was fo cused on the min er - al ogy and pe trog ra phy of the si der it ic rocks. The min er al ogy of the Mid dle Ju ras sic si der it ic con cre tions in the Silesian-Cra cow Monocline was stud ied by Krzykawski (2012) and Witkowska (2015). Siderites in the Car bon if er ous sand stones from the Lublin Graben close to the study ar eas were de scribed by Koz³owska (1997, 2001, 2004).
METHODOLOGY
GENERAL ANALYTICAL PROCEDURES
The an a lyt i cal pro ce dures com prised sam pling and prep a - ra tion, mi cros copy of the min er als and in clu sions, geo chem i cal anal y ses, and auxiliary studies.
Based on ob ser va tions of 276 thin sec tions us ing a Nikon Eclipse LV 100 Pol po lar iz ing mi cro scope, 13 sam ples were se - lected for fur ther study (Ta ble 1). Thin-sec tions were stained with Evamy’s so lu tion to iden tify the car bon ate min er als. Four sam - ples were sub jected to cathodoluminescence anal y sis us ing the so-called “cold cath ode”, CITL MK5 type from Cam bridge Im age
Tech nol ogy Ltd. (volt age 16kV, cur rent 600 mA). The chem i cal com po si tion of the car bon ate min er als was de ter mined on 12 sam ples (Ap pen dix 1*). Microchemical stud ies were per formed us ing an elec tron scan ning mi cro scope LEO 1430, com bined with EDS ISIS. Un cov ered car bon-coated thin -sec tions were ana lysed. Back-scat tered elec tron im ages (BSE) were also made. The stud ies were con ducted in the Pol ish Geo log i cal In sti - tute – Na tional Re search In sti tute in War saw.
PREPARATION AND ANALYTICAL TECHNIQUES FOR FLUID INCLUSION STUDIES
13 sam ples for fluid in clu sion stud ies were pre pared us ing stan dard prep a ra tion tech niques (Shephard et al., 1985;
Jarmo³owicz-Szulc, 2001). Dou ble-sided-pol ished thin sec tions, 0.1–0.2 mm thick, were ob tained for low tem per a ture mount ing.
Mi cro scopic ob ser va tions were con ducted us ing a po lar iz ing mi - cro scope in trans mit ted and re flected (UV) light. The an a lyt i cal steps cor re sponded to a mi cro scopic anal y sis of fluid in clu sions (Leitz Orthoplan), flu o res cence stud ies and microphotography (Nikon mi cro scope and UV de vice) as well as microthermometric anal y ses. The lat ter in cluded heat ing and freez ing us ing a Fluid Inc. Sys tem, mounted on a Leitz Orthoplan mi cro scope and the Linkam equip ment with dig i tal microphotography. The Fluid Inc.
Sys tem and the Linkam stage were cal i brated against melt ing tem per a tures of the pure chem i cals and phase tran si tions in syn - thetic fluid in clu sions (SYNFLINC stan dards; Reynolds 1993).
The un cer tainty lim its are 0.2°C be low –100°C, 0.1°C be tween –100 and +100°C, and 0.2°C above 100°C. Fluid in clu sions in the ce ments were stud ied by freez ing in or der to avoid vol ume changes of the in clu sions. The mea sure ments em braced ho - mog e ni za tion tem per a tures and de ter mi na tions of eutectic and ice melt ing tem per a tures of the brine in clu sions (Ap pen dix 2).
T a b l e 1 Si der it ic sam ples stud ied
Area Bore hole Depth
[m] Age Type
of rocks Vol.%
of sid er ite Type
of sid er ite Vol.% of other
car bon ate min er als Method
North east ern mar gin of the Holy Cross Mts.
Gutwin 201.6 Bj2 sst 28.0 Sdp Pt 12.7 Ak PL EDS FI
W¹glany k/Opoczna
267.7 Bt3 scq 16.0 Sdp 36.3 Ak PL EDS FI
395.2 Bt1-2 cls 57.7 Sdp 0.0 PL EDS FI IS
406.0 Bt1-2 cls 59.7 Sdp Pt 0.0 PL FI
597.2 Aa1 cls 67.4 Sd Sdp Pt 0.0 PL EDS FI
600.2 Aa1 sst 32.7 Sdp Pt 0.0 PL EDS FI IS
643.8 Aa1 sst 43.7 Sdp 0.0 PL EDS FI IS
Czêstochowa re gion
Biskupice 25BN 134.7 Bt1 sst 40.0 Sdp Pt 18.0 Ca PL CL EDS FI IS
£utowiec 135¯ 178.9 Bj1 cls 50.3 Sdp PL EDS FI IS
Parkoszowice 58BN
101.2 Bj2 cls 65.0 Sdp 5.0 Ca PL FI
102.3 Bj2 cls 72.0 Sdp 0.0 PL CL EDS FI IS
104.1 Bj2 cls 76.0 Sdp 3.0 Ca PL CL EDS FI
Zrêbice 33BN 372.7 Bj2 sst 30.0 Sd Sdp 0.0 PL CL EDS FI IS
Ak – an ker ite, Ca – cal cite, Sd – sid er ite, Sdp – sideroplesite, Pt – pistomesite; cls – clayey sid er ite, sst – si der it ic sand stone, scq – si der it ic co quina, mic – micrite, msp – microsparite, sp – sparite, rb – rhombohedron, Sph – spherulite; Aa1 – Lower Aalenian, Aa2 – Up per Aalenian, Bj1 – Lower Bajocian, Bj2 – Up per Bajocian, Bt1 – Lower Bathonian, Bt2 – Mid dle Bathonian, Bt3 – Up per Bathonian; PL – po lar iz ing mi cro - scope, CL – cathodoluminescence, EDS – microprobe anal y sis, FI – fluid in clu sions, IS – iso tope anal y sis
* Supplementary data associated with this article can be found, in the online version, at doi: 10.7306/gq.1323
Tem per a ture of ho mog e ni za tion was ap prox i mated as the tem - per a ture of trap ping due to small pres sure cor rec tion in fluid in - clu sions which ho mog e nize into liq uid phase (Roedder, 1984).
Isochores were cal cu lated with the Flincor pro gram (Brown, 1989) and FLUIDS pack age (Bakker, 2003). Dif fer ent va ri et ies of the FLUIDS pack age, mainly AqSo1e (Bakker and Brown, 2003), were ap plied.
ISOTOPIC STUDIES
Anal y ses of the iso to pic com po si tion of ox y gen and car bon in seven sid er ite and one cal cite sam ples were con ducted in the Iso tope Lab o ra tory of the Maria Cu rie-Sk³odowska Uni ver sity at Lublin (Ta ble 2). The method was de scribed by Durakiewicz and Ha³as (1994) and Durakiewicz (1996). Gas eous car bon di ox ide Fig. 2. Lithological sec tions of the Mid dle Ju ras sic de pos its (af ter Koz³owska and Maliszewska, 2015)
was re leased from car bon ates dur ing re ac tion with phos pho ric acid (Mc Crea, 1950; Al-Aasm et al., 1990). Iso tope mea sure - ments of car bon and ox y gen were con ducted in the mod i fied mass spec trom e ter MI 1305 with a mea sure ment pre ci sion of
±0.08‰ (one sigma). Mea sure ments were con ducted with ref er - ence to in ter na tional stan dards (Durakiewicz,1996). The val ues of d13C were ex pressed at the scale of the VPDB, while d18O re - sults were ob tained in the VPDB and VSMOW scales.
CHARACTERISTICS OF THE SIDERITIC ROCKS
The ma te rial stud ied co mes mainly from clayey siderites and si der it ic sand stones (Fig. 3), lo cally from si der it ic coquinas.
Sid er ite is the main com po nent of the si der it ic rocks. This min - eral rep re sents Mg-rich sid er ite (sideroplesite, less fre quently pistomesite), and lo cally sid er ite.
The clayey siderites con tain micritic, microsparic and spar sid er ite and clay min er als. Sideroplesite is the main sid er ite min eral (micrite, microspar, spar), while pistomesite (micro - spar, spar) and the sid er ite (micrite, spar) ap pear lo cally. The sideroplesites show the fol low ing chem i cal com po si tion (in mol.%): 77.4–85.8 – FeCO3, 6.5–9.3 – MgCO3, 6.6–13.3 – CaCO3 and 0.0–1.5 – MnCO3 (Ap pen dix 1). Clay min er als are rep re sented by kaolinite, berthierine and illite (Koz³owska and Maliszewska, 2015). Cal cite and an ker ite are the other car bon - ate min er als pres ent in the rock. Quartz grains of silt- and sand-size oc cur in vary ing amounts. Feld spar grains, mica flakes, zir con, py rite, he ma tite and the or ganic mat ter are ac - ces sory com po nents. Calcitic, lo cally pyritized, fau nal frag - ments are com mon. Clay and car bon ate ooids were ob served in a few sam ples. The car bon ate ooids are com posed mainly of sparry sideroplesite or pistomesite, rarely of cal cite and an ker - ite. Lo cally, clayey side rites are cut by cal cite, an ker ite and/or py rite veins.
The si der it ic sand stones are rep re sented by fine- to me - dium-grained quartz arenites. Quartz is the main de tri tal ma te rial and feld spars, micas and zir con are sub or di nate. Shell frag - ments and ooids are ob served in vari able amounts. Frag ments
of bi valves, echinoderms, gas tro pods and foraminifers are com - po sed of car bon ate min er als (com monly cal cite, oc ca sion ally of an ker ite and sid er ite) and clay min er als (kaolinite and berthie - rine). Ooids con sist mainly of berthierine, sparitic sidero plesite or cal cite and lo cally of kaolinite and py rite. The main ce ments in the sand stones are car bon ates, as sideroplesite (mi cri tic, micro - sparitic, sparitic) and pistomesite (sparitic), sid er ite (micritic, sparitic), an ker ite and cal cite. The most com mon sidero plesites show the fol low ing chem i cal com po si tion (in mol.%): 75.3–86.3 – FeCO3, 5.9–21.4 – MgCO3, 1.9–16.2 – CaCO3 and 0.0–4.2 – MnCO3 (Ta ble 2). Clay min er als such as berthierine, kaolinite, illite and lo cally chlorite also oc cur (Koz³o wska and Maliszewska, 2015). Lo cally, the si der it ic sand stones are cut by cal cite, an ker - ite, sideroplesite and/or pistomesite veins.
The si der it ic co quina (bioclasts 20% of rock vol ume) from the W¹glany k/Opoczna bore hole is com posed mainly of ooids and bioclast frag ments, such as echinoderms, bi valves, brachi - o pods, gas tro pods and bryo zoans. The berthierine ooids have been re placed to a vari able de gree by an ker ite and sidero - plesite. The ce ment is com posed of microsparry and sparry sideroplesite and an ker ite (Ap pen dix 1).
CHARACTERISTICS OF THE CARBONATE MINERALS STUDIED
Sid er ite is the main car bon ate min eral stud ied in the si der it ic rocks, while cal cite and an ker ite are less fre quent. The Mg-rich sid er ite rep re sents sideroplesite and pistomesite of microspar and spar crys tal size (Fig. 3), very of ten in the form of rhom bo - he dra. Two sid er ite gen er a tions – early and late ones – may be dis tin guished based on the mi cro scopic ob ser va tions. The early gen er a tion is rep re sented by micritic and micro sparitic sideroplesite, lo cally by sid er ite, whereas the late one has sparitic (partly rhombohedric) sideroplesite (Fig. 4A) and rare pistomesite. The rhom bo he dra are more fre quent in the si der it ic rocks at the north east ern mar gin of the Holy Cross Mts. than in the Czêstochowa re gion (Ap pen dix 1). Rhombo hedric crys tals of sideroplesite and pistomesite of ten dis play zonal struc ture, re lated to the vary ing con tents of iron and mag ne sium, as well T a b l e 2 Car bon and ox y gen iso tope data of the car bon ates in the si der it ic rocks
Bore hole Age Depth
[m] Type of car bon ate
Con tent [%] d13C VPDB [‰]
d18O VPDB [‰]
d18O VSMOW
[‰]
*d18O VSMOW H2O S1 S2 [‰]
North east ern mar gin of the Holy Cross Mts.
W¹glany k/Opoczna
Bt1-2 395.2 Sdp msp ce ment, sp ooid 70 30 –17.68 –3.86 26.88 –7.01
Aa1 600.2 Sdp msp ce ment 100 0 –8.63 –7.84 22.78 –11.11
Pt sp rb ce ment 0 100 –9.58 –10.45 20.08 –
Aa1 643.8 Sdp sp rb ce ment 0 100 –10.83 –8.82 21.77 –
Czêstochowa re gion Biskupice 25BN Bt1 134.7 Sdp mic ce ment, Sdp Pt
sp rb ce ment Ca ce ment
60 40 –7.48
–2.01
–2.01 –5.38
28.80 25.32
–5.10 –
£utowiec 135¯ Bj1 178.9 Sdp msp, sp rb ce ment 85 15 –22.85 –1.92 28.89 –5.01
Parkoszowice 58BN Bj2 102.3 Sdp sp ce ment 80 20 –8.87 –3.81 26.94 –6.95
Zrêbice 33BN Bj2 372.7 Sd Sdp Sph msp, sp rb
ce ment 15 85 –11.52 –3.45 27.31 –6.58
*d18O VSMOW wa ter of sideroplesite which crys tal lized at a tem per a ture of 20°C; S1 – early gen er a tion of sid er ite; S2 – late gen er a tion of sid er ite; for ex pla na tions see Ta ble 1
Fig. 3. Pho to graphs in po lar iz ing mi cro scope (PL)
A – sid er ite rep re sented by pistomesite rhom bo he dra (ar row) and an ker ite ce ment (Ak) in si der it ic sand stone (Gutwin bore hole, depth 201.6 m, crossed polars); B – part of photo A; two-phase in clu sions (ar rows) in pistomesite rhombohedron (Pt) and an ker ite (Ak); plane po lar ized light; C – pistomesite ooids (Pt) in clayey sid er ite com posed of sideroplesite micrite (Sdp); pistomesite in the form of rhom bo he dra (W¹glany k/Opoczna bore hole, depth 597.2 m, plane po lar ized light); D – part of photo C; sin gle two-phase in clu sion (ar rows) in pistomesite rhombohedron (Pt);
plane po lar ized light; E – sid er ite ce ment: sparry sideroplesite (ar row) and micrite sideroplesite (Sdp) in si der it ic sand stone (Biskupice 25BN bore hole, depth 134.7 m, crossed polars); F – part of photo E; one-phase in clu sions (ar rows) in sparry sideroplesite (Sdp); plane po lar ized light;
G – sideroplesite ooid (ar row) and micrite sideroplesite (Sdp) in clayey sid er ite (Parkoszowice 58BN bore hole, depth 101.2 m, plane po lar ized light); H – part of photo G; two-phase in clu sions (ar rows) in sparry sideroplesite in ooid (Sdp); plane po lar ized light
seen in BSE im ages (Fig. 4B). The sid er ite min er als can oc cur as a mass of clayey siderites, a ce ment fill ing the pore space in the si der it ic sand stones (Fig. 4B) and a min eral re plac ing berthierine in ooids in the si der it ic rocks (Fig. 4C). Some va ri et - ies of si der it ic min er als con tain fluid in clu sions. This is why sparry in di vid u als, of ten rhom bo he dra, of the sidero plesite and the pistomesite have been mi cro-ther mo met ri cally ana lysed (Fig. 3 and Ap pen dix 2). The micritic sid er ite and sideroplesite, how ever, do not con tain fluid in clu sions. In clu sions in the micro - sparic crys tals are too small to be mea sured. The cal cite and an ker ite ei ther form ce ments in the si der it ic rocks, or fill veins (Fig. 4D). These min er als also con tain fluid in clu sions. How - ever, due to the low abun dance and size of the in clu sions, only some sam ples could have been se lected for tem per a ture mea - sure ments (Ap pen dix 2). The iso to pic anal y ses were con - ducted both in sideroplesite and pistomesite, as well as on cal - cite in the same sam ples (Ta ble 2).
GENERAL CHARACTERISTICS OF THE FLUID INCLUSIONS
The liq uid-vapour in clu sions are small in size and not abun - dant. Their av er age size falls into the in ter val of 1–3 mm that is dif fi cult to ob serve in heat ing and freez ing ex per i men tal modes.
The in clu sion shapes vary, but no form dom i nates. Some in clu -
sions are oval, oth ers are more or less reg u lar in shape, or are shape less. The rare oc cur rence and small sizes of in clu sions are sig nif i cant, oc ca sional stretch ing symp toms may be no ticed. The char ac ter of in clu sions in gen eral is pri mary. The in clu sions are mostly one phase, lo cally with two phases. The fluid to vapour ra - tio var ies, but gen er ally the fluid vol ume pre vails. Oc ca sion ally, the two-phase char ac ter of the in clu sions cor re sponds to a co-pres ence of two liq uid phases (L1 and L2). The fluid in clu - sions are ran domly po si tioned, mean ing ful re la tions with crys tal - lo graphic planes are hard to de ter mine as is clas si fi ca tion of dis - tinct FIAs (Fluid In clu sion As so ci a tion, sensu: Goldstein and Reynolds, 1994; Goldstein, 2003), which is not pos si ble in prac - tice due to the low abun dance of two -phase fluid in clu sions. In some cases, only one-phase in clu sions were ob served (e.g., in the Parkoszowice 58BN bore hole).
TEMPERATURE RESULTS OF FLUID INCLUSION STUDIES
The car bon ates in the si der it ic rocks con tain rare fluid in clu - sions. They ex hibit a pri mary char ac ter, small size, and ei ther one or two phases.
Tem per a ture re sults are shown in Ap pen dix 2. Mi cro pho to - graphs show in clu sions in sideroplesite and pistomesite of se - lected rock sam ples (Fig. 3). As shown in the ta ble, the fol low ing Fig. 4. Pho to graphs by po lar iz ing mi cro scope (PL) and scan ning elec tron mi cro scope (BSE)
A – two gen er a tions of sid er ite – the early gen er a tion (S1 – microsparitic sideoplesite) and the late gen er a tion (S2 – sparitic sideoplesite) in clayey sid er ite (£utowiec 135¯ bore hole, depth178.9 m, crossed polars); B – zonal struc ture in rhombohedric crys tals of sideroplesite (Sdp) and pistomesite (Pt) which form ce ment in sid er ite sand - stone; 1, 2 – num bers of points of anal y sis (Ap pen dix 1) (Gutwin bore hole, depth 201.6 m, BSE im age); C – pistomesite (Pt) ooids with berthierine (Be) relicts in si der it ic sand stone ce mented by micritic sideroplesie (Sdp);
quartz (Q) (W¹glany k/Opoczna bore hole, depth 597.2 m, crossed polars); D – cal cite (Ca) veins in clayey sid er ite with micritic sideroplesie (Sdp) (Parkoszowice 58BN bore hole, depth 101.2 m, crossed polars)
val ues have been mea sured for two-phase in clu sions: tem per - a ture of ho mog e ni za tion (Th), ice melt ing tem per a tures (Tm).
For one-phase in clu sions only Tm val ues were de ter mined, since no metastable con trac tion bub ble was cre ated dur ing the ex per i ment.
Tem per a ture val ues are grouped in col umns in Ap pen dix 2, show ing char ac ter is tic fea tures such as eutectic tem per a ture, ice melt ing, clathrate melt ing and ho mog e ni za tion val ues. The
“Fluid” col umn gives a sug ges tion as to the pos si ble type of the in di vid ual in clu sion-fill, based on the in di vid ual tem per a ture data. Fluid sa lini ties and den si ties in the in clu sions in sim pli fied two-com po nent sys tems are shown in Ap pen dix 2.
Sum ming up the re sults, the num ber of mea sure ments of ho mog e ni za tion tem per a tures (Th) in the sand stones is not large. The val ues of ho mog e ni za tion tem per a tures for the sid - er ite fall into the in ter val be tween 60 and 100°C. Tem per a tures of ice melt ing are rel a tively low and vary be tween –10.0 to –3.4°C. The sa lin ity of flu ids is mod er ately high and var ies with re spect to the type of ce ment and bore hole lo ca tion. The sa lin - ity cor re sponds to in ter vals from 7.8 to 13.9 wt.% NaCl eq. and from 9.2 to 12.9 wt.% NaCl eq. for sid er ite and cal cite, re spec - tively. The den sity of flu ids is close to 1 g/cm3. The eutectic tem - per a tures are also vari able and be tween –40 and –30°C. This sug gests the pres ence of two valent cat ions in the brines, e.g., con tain ing cal cium and/or mag ne sium ions (Shephard et al., 1985; Schmidt Mumm and Wolfgramm, 2002).
ISOTOPIC RESULTS
Iso to pic car bon and ox y gen re sults are shown in Ta ble 2 and in Fig ure 5, re stricted to the sam ples stud ied by the fluid in - clu sion method. They are mostly for sideroplesite, with only some for pistomesite and cal cite. Two sid er ite gen er a tions are of ten ob served co ex ist ing in the rocks, while only a few sam ples con tain just one sid er ite gen er a tion (the early or the late one).
Some iso to pic re sults rep re sent the cu mu la tive prod ucts of vary ing pro por tions of two sid er ite gen - er a tions (Ta ble 2). The sam ples do not co-vary with the depth and age of the rocks.
At the north east ern mar gin of the Holy Cross Mts. the d13 C VPDB val ues in the early sidero plesite of the Aalenian age are –8.63‰ and in the Batonian are –17.68‰. The cor re spond ing d18O VPDB val - ues are –7.84 and –3.86‰. The d13C VPDB val ues in the late sideroplesite and pisto mesite of the Aalenian age are equal to –10.83 and –9.58‰, re - spec tively. The cor re spond ing d18O VPDB val ues are –8.82 and –10.45‰.
In the Czêstochowa re gion the d13C VPDB val - ues change in the Bajocian early sideroplesite from 22.85 to –8.87‰ and the Batonian sideroplesite are –7.48‰. The cor re spond ing d18O VPDB val ues are from –3.81 to –1.92‰ and –2.01‰. The d13C VPDB value in the Batonian cal cite is –2.01 and d18O VPDB value is –5.38‰.
INTERPRETATION AND DISCUSSION
TEMPERATURE MEASUREMENTS
The ma jor ity of car bon ates oc cur ring in the si - der it ic rocks show crypto- or fine crys tal line crys tal
hab its. This is why the in clu sions were ob served only in the sparry sideroplesite and pistomesite crys tals and in the ankeritic and calcitic ce ment in the si der it ic sand stones or clayey siderites.
De ter mi na tion of in clu sion char ac ter re sulted in pri mary and sec ond ary in di vid u als. We have used Roedder’s (1984) cri te - rion: the pri mary in clu sions are rare, ran domly dis trib uted and have no char ac ter is tic po si tion in the ce ments of min er als. That makes the eval u a tion of in clu sion char ac ter and gen e sis dif fi - cult. The size of in clu sions of 1–3 mm, type and lack of clar ity of sam ples also causes dif fi cul ties in tem per a ture mea sure ments and ob ser va tions in the freez ing and heat ing modes. The pro - cesses were some times seen only partly dur ing mea sure ment cy cles on the Linkam stage (Ap pen dix 2).
Tem per a ture re sults ob tained for in clu sions are those eutectic, ho mog e ni za tion and ice melt ing val ues (Ap pen dix 2).
How ever, not all char ac ter is tic tem per a ture val ues were ob - tained for all the sam ples.
At the north east ern mar gin of the Holy Cross Mts., most mea sure ments were per formed on the ce ment-form ing rhom - bo hedric crys tals of pistomesite and sideroplesite in si der it ic rocks from the W¹glany k/Opoczna bore hole (Ap pen dix 2). The ho mog e ni za tion tem per a tures there vary from 62 to 110°C. In the rhom bo he dra of pistomesite ce ment in the si der it ic sand - stone from the Gutwin bore hole ho mog e ni za tion tem per a tures lie in the in ter val be tween 107 and 139°C. In the W¹glany k/Opoczna bore hole the ho mog e ni za tion tem per a tures in the rhombo hedric crys tals of pistomesite in ooid were ~137°C and the spar sideroplesite crys tal in ooid showed 94.7°C. Only one ho mog e ni za tion tem per a ture value was ob tained in an ker ite ce - ment ing a si der it ic co quina (168°C). Other tem per a ture val ues ob tained in the Holy Cross Mts. area cor re spond to the eutectic tem per a tures that point to brine and car bon di ox ide pres ence in the flu ids in the in clu sions. In some cases also clathrate and ice melt ing val ues were mea sured. Based on these data, it seems that in case of sideroplesite ce ment at a depth of ~643 m, the fluid is a brine of sa lin ity be tween 10.5 and 12.9 wt.% NaCl eq.
Fig. 5. Plot of the d18O VPDB ver sus the d13C VPDB in car bon ate min er als n – num ber of anal y ses
and a den sity of 1.03–1.05 g/cm3. The pistomesite ce ment from much shal lower depth dis plays a very low fluid sa lin ity in con - trast to the ankeritic ce ment in the same bore hole which re veals higher sa lin ity and fluid den sity.
The fol low ing fea tures can be de scribed for the si der it ic sam ples from the Czêstochowa re gion in the min er als from the Parkoszowice 58BN bore hole, which oc cur in a rel a tive nar row depth in ter val: one-phase in clu sion as so ci a tions in sidero - plesite, which point to trap ping at tem per a tures of 40–50°C (Goldstein, 2001); vari a tion of ice melt ing tem per a tures in the in ter val from –5.3 to –9.7°C. The Tm re sults for the rhombo - hedric sideroplesite are be tween –5.3 and –6.6°C, while those for the sideroplesite in ooids are from –5.3 to –9.7°C, that cor re - sponds to sa lin ity in ter vals of be tween 7.8 and 10.5 wt.% NaCl eq. and from 7.8 to 13.9 wt.% NaCl eq., re spec tively. The ooids dis play a large scat ter in val ues that may be con nected with a vari a tion of the fluid char ac ter dur ing crystallisation of the in - ner/outer parts of the ooid. How ever, such a dif fer en ti a tion can - not be es ti mated be cause of the low abun dance of fluid in clu - sions. Ho mog e ni za tion tem per a tures have been mea sured for in di vid ual in clu sions. For cal cite they mostly fall into the in ter val be tween 60 and 70°C (depth 104.1 m). The sa lin ity of flu ids in cal cite var ies from 9.2 to 12.9 wt.% NaCl eq.
The fol low ing char ac ter is tics may be pre sented for the sam - ple from the Biskupice 25BN bore hole (depth 134.7 m): sid er ite char ac ter vari abil ity; one- and two-phase in clu sion as so ci a - tions; vari a tion of eutectic tem per a tures for brine in clu sions from –52 to –28°C; vari a tion of ice melt ing tem per a tures (from –3.4 to –10.0°C), whereas most of re sults for sidero plesite fall into the Tm in ter val be tween –7.3 and –10.0°C (in ce ments). Ho - mog e ni za tion tem per a tures vary and fall into the in ter val be - tween 55 and 100°C (sideroplesite). The sa lin ity of flu ids var ies from 10.5 to 13.9 wt.% NaCl eq.
In the sam ple from the £utowiec 135¯ bore hole (depth 178.9 m) one-phase in clu sions have been ob served and a sin - gle ice melt ing value mea sured (–4.4°C), that points to a low fluid sa lin ity of about 6.37 wt.% NaCl eq. and a den sity of 1.05 g/cm3.
The fol low ing fea tures have been rec og nized for the Zrêbice 33BN bore hole (depth 372.7 m) in sideroplesite rhom - bo he dra in ce ment: one-phase fluid in clu sion as so ci a tions;
eutectic tem per a tures of ~–42°C (more com plex sys tem than the two -com po nent brine); vari a tion in ice melt ing tem per a tures (from –6.2 to –9.2°C), that im plies sa lin ity in the in ter val from 9.2 to 12.9 wt.% NaCl eq. and fluid den sity of 1.07 g/cm3; po ten - tial pres ence of car bon di ox ide in two-phase aque ous in clu - sions. That last fea ture is sim i lar to the ob ser va tions re ported by Hurai et al. (2002) for siderites in the Carpathian veins.
Ob ser va tions of fluid in clu sions to gether with vary ing ho - mog e ni za tion tem per a tures of two-phase in clu sions, their vari - able L:V ra tio, sug gest that the tem per a ture data ob tained for them have a ran dom char ac ter not con strain ing the pri mary con di tions of cement formation.
The ice melt ing tem per a ture re sults af ter freez ing are very sig nif i cant and valu able for in ter pre ta tion. Based on these val - ues ob tained in fluid in clu sion stud ies, a com plex char ac ter of flu ids in in di vid ual sam ples may be de duced. The most sim ple way to pres ent these re sults is to ex press them as a wt.% NaCl eq. Us ing stan dard cal cu la tion pro grams for H2O-NaCl sys tem (FLUIDS pack age, AqSo1e pro gram) fluid sa lini ties and den sity have been ob tained, in the in ter val from 8.2 to 14.0 mass%
NaCl and of about 1 g/cm3, re spec tively.
The re la tion ship be tween the ho mog e ni za tion tem per a - tures and fluid sa lin ity for the two-phase in clu sions is shown in Fig ure 6.
The eutectic tem per a tures close to –30°C or even –40°C sug gest (es pe cially in cal cite) a pres ence of more com plex flu - ids than the sim ple sys tem of NaCl-H2O, as for ex am ple H2O-NaCl-CaCl2-MgCl2 (Shephard et al., 1985; Bodnar, 2003).
Based on the AqSo1e (sys tem H2O-NaCl-CaCl2) and AqSo3e (sys tem H2O-NaCl-MgCl2) pro grams such a trial of cal cu la tions for multi-com po nent sys tems has been made, though with sev - eral as sump tions in tro duced. Due to this fact (e.g., lack of ex act mole ra tios), the re sults ob tained af ter the Oakes et al. equa tion (1990, fide: Bakker and Brown, 2003) should be re garded as ap prox i mate.
ISOTOPES
The car bon and ox y gen iso to pic re sults in both re gions stud ied are sim i lar. Most de ter mi na tions con cern the sam ples where the early sid er ite pre dom i nates over the late one (Ta ble 2). Two-iso tope data have been ob tained in the sam ples con - tain ing a late gen er a tion of sid er ite from the same depths as those stud ied for fluid in clu sions.
The re sults of d13C de ter mi na tions for early gen er a tion of sid - er ite-sideroplesite fall within the range of –22.85 to –7.48‰
VPDB. They in di cate that the sideroplesite was formed in the zone of mi cro bi o log i cal methanogenesis, where a bac te rial fer - men ta tion of the or ganic com po nents was the CO2 source (Irvin et al., 1977; Morad, 1998). The d18O val ues range be tween –7.84 and –1.92‰ VPDB. The for mula af ter Carothers et al. (1988) has been used to es ti mate the d18O of the pore wa ter re spon si ble for
Fig. 6. Ho mog e ni za tion tem per a ture ver sus fluid sa lin ity in two-phase in clu sions
n – num ber of anal y ses
crystallisation of the early sid er ite gen er a tion. The d18O val ues sug gest that the early sideroplesite pre cip i tated from wa ter of d18O VSMOW in the range of –11.11 to –5.01‰, as sum ing a crystallisation tem per a ture of about 20°C (Baker et al., 1995;
Rezaee and Schulz -Rojahn, 1998). Such val ues in di cate a mix - ture of ma rine and me te oric wa ters.
The re sults of d13C and d18O de ter mi na tions for the late gen - er a tion of sid er ite were ob tained only for the rocks from the north east ern mar gin of the Holy Cross Mts. The re sults of d13C de ter mi na tions for late gen er a tion of sid er ite – sideroplesite and pistomesite are –10.83 and –9.58‰ VPDB. The late gen er a tion of sid er ite is char ac ter ized by a high mag ne sium con tent. Ac - cord ing to Macaulay et al. (1992), al tered min er als rich in Mg+2, e.g. micas, could have been a mag ne sium source. Ac cord ing to Desborough (1978) the mag ne sium could have been re leased from kerogen dur ing sed i ment burial. It seems that in the rocks un der study, car bon re leased from or ganic mat ter in the ther - mal decarboxylation zone might have been a source of this el e - ment for the late, Mg-rich sid er ite gen er a tion. The same source of car bon for Mg-rich siderites was sug gested by Morad et al.
(1994) and Rezaee and Schulz-Rojahn (1998). The d18O val - ues are –8.82 and –10.45‰ VPDB. The ho mog e ni za tion tem - per a tures for the late sid er ite gen er a tion were 90–110°C and 62–98.8°C, re spec tively (Ap pen dix 2). The tem per a ture data cal cu lated with use of the Carothers et al. (1988) for mula point to pre cip i ta tion of the late sid er ite from the pore wa ters dis play - ing d18O in the in ter val from about –5 to 3.5‰ SMOW, most of - ten >0‰ SMOW (Fig. 7). Such val ues of d18O for pore wa ter sug gested that the late sid er ite has pre cip i tated from wa ters richer in the 18O iso tope in com par i son with the wa ter com po si - tion of the early sid er ite crystallisation. The en rich ment in the ox y gen iso tope con tent in pore wa ters is al ready pos si ble at sev eral hun dred metres of burial due to the wa ter-sed i ment in - ter ac tion (McKay et al., 1995).
The ox y gen and car bon iso to pic val ues in the cal cite ce ment were ob tained for one sam ple from the Czêstochowa re gion. The d13C value points to or ganic mat ter as the car bon source (Baker,
1991). It was im pos si ble to mea sure a ho mog e ni za tion tem per a - ture in this sam ple. Mea sure ments were per formed in the calcitic vein on an other si der it ic rock. The val ues of 59.8 and 67.8°C (Ap - pen dix 2) have been re garded as a prob a ble tem per a ture of cal - cite crystallisation. The iso to pic and tem per a ture val ues for cal - cite have been used in the Fried man and O’Neil (1977) for mula.
For the cal cite crystallisation, they point to the d18O pore wa ter equal to about 0‰ VSMOW.
CONCLUSIONS
1. The main car bon ate min er als of the Mid dle Ju ras sic si der - it ic rocks at the northeast ern mar gin of the Holy Cross Mts. and in the Czêstochowa re gion are rep re sented by sideroplesite, less fre quent pistomesite, and sid er ite. They form ce ments and ooids.
Early and late gen er a tions of sid er ite have been dis tin guished.
Apart from this min eral, cal cite and an ker ite in the form of ce - ments and veinlets are pres ent as well.
2. One-phase in clu sions and as so ci a tions of two-phase in - clu sions with a dif fer ent phase ra tio are pre dom i nant. As com - pared with the Czêstochowa re gion, two-phase in clu sions are more abun dant and the phase ra tios are more ho mo ge neous at the northeast ern mar gin of the Holy Cross Mts.
3. The sa lin ity of flu ids in the in clu sions var ies in the range be tween 1.7 and 16.9 wt.% NaCl eq. for siderites in the rocks from the north ern mar gin of the Holy Cross Mts. The fluid den - sity is close to 1 g/cm3 in the Czêstochowa re gion, and the sa lin - ity os cil lates be tween 6.4 and 13.9 wt.% NaCl eq. It var ies for siderites in form of the ce ments and those oc cur ring as ooids.
The fluid den sity is also close to 1 g/cm3. Com plex chem i cal brine sys tems may oc cur as flu ids, e.g., H2O-NaCl- CaCl2- MgCl2 or H2O-CaCl2-MgCl2 as well as mixed ones (H2O-CO2).
4. Stud ies of two-phase fluid in clu sions pres ent in the crys - tals of the late sid er ite gen er a tion – sideroplesite and pisto - mesite – in the Mid dle Ju ras sic si der it ic sand stones and clayey siderites, dis play ho mog e ni za tion tem per a tures in the in ter val of 55.0–137.1°C. They sug gest crys tal li sa tion in deep burial con di tions. The cal cite in the veinlet showed a tem per a ture of ~60°C. Higher ho mog e ni za - tion tem per a tures of ~168°C were de ter mined in the ankeritic cement of a siderite coquina.
5. The tem per a ture re sults vary with re spect to the bore hole and the type of ce ment in both re gions. The char ac ter of in clu sions and the ho mog e ni za tion tem - per a ture re sults are very dif fer ent. The rocks oc cur at the depth of about 100 to >600 m, and no tem per a ture ten dency may be ob served, ei ther as re gards depth or type of cement.
6. The ho mog e ni za tion tem per a tures in the car - bon ates, are slightly higher than the re sults ob tained in the Mid dle Ju ras sic sand stones in si der it ic rocks in the Pol ish Low lands (Malisze wska et al., 2007). These facts sup port the au thors’ con clu sion that, apart from burial, an other heat source was a cause of in creased tem per a tures char ac ter is tic for the litho genesis of the Ju ras sic de pos its.
7. The iso to pic de ter mi na tions of d13C VPDB (from –22.85 to –7.48‰ VPDB) in the early sid er ite gen er a - tion point to for ma tion of this min eral in the zone of mi - cro bi o log i cal methano genesis. The iso to pic ox y gen com po si tion d18O VPDB (from –7.84 to –1.92‰
VPDB) points to sid er ite pre cip i ta tion from ma rine and also me te oric wa ters at tem per a tures of ~20°C.
Fig. 7. Plot of d18O pore wa ter ver sus tem per a ture for the late gen er a tion of sid er ite (Carothers et al., 1988)
8. The re sults of d13C for the late gen er a tion of sid er ite (–10.83 and –9.58‰ VPDB) sug gest that car bon could have been re leased from the or ganic mat ter in the ther mal decar - boxy lation zone. Based on data com pi la tion of d18O val ues (–8.82 and –10.45‰ VPDB) and of ho mog e ni za tion tem per a - tures (90–110°C and 62–98.8°C) the con clu sion can be drawn that the late sid er ite gen er a tion crys tal lized from pore wa ters of d18O >0‰ VSMOW. The cal cite also pre cip i tated from the pore wa ters with d18O of about 0‰ VSMOW.
9. Val ues of d18O VSMOW of pore wa ter for the late sid er ite and cal cite gen er a tions are higher when com pared with those char ac ter is tic for the wa ter re spon si ble for the early sid er ite
crystallisation. An en rich ment in 18O iso tope might have been caused ei ther by a wa ter-rock re ac tion dur ing burial of the de - posit or by an in flux of the ma rine wa ter to the sed i ment.
Ac knowl edge ments. The au thors are very grate ful to the re view ers of the manu script – L.A. Palinkaš and Z. Saw³owicz, whose crit i cal com ments and cor rec tions im proved the con tent of the pa per. Cor dial thanks are ad dressed to T.M. Peryt for his con stant help and fa vour. The pres ent pa per is a part of the pro - ject No. N N307 330339 fi nanced by the Min is try of Sci ence and High Ed u ca tion, and no. 61.2201.0604.00.0 of the Pol ish Geo - log i cal In sti tute – Na tional Re search In sti tute.
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