Char ac ter is tics of diagenesis, iso to pic re la tions and res er voir prop er ties of the Mid dle Mio cene sand stones in the Carpathian Foredeep (Po land and Ukraine)
Katarzyna JARMO£OWICZ-SZULC1, *, Aleksandra KOZ£OWSKA1 and Marta KUBERSKA1
1 Pol ish Geo log i cal In sti tute – Na tional Re search In sti tute, Rakowiecka 4, 00-975 Warszawa, Po land
Jarmo³owicz-Szulc, K., Koz³owska, A., Kuberska, M., 2015. Char ac ter is tics of diagenesis, iso to pic re la tions and res er voir prop er ties of the Mid dle Mio cene sand stones in the Carpathian Foredeep (Po land and Ukraine). Geo log i cal Quar terly, 59 (4): 750–761, doi: 10.7306/gq.1261
The Up per Badenian and Sarmatian sand stones rec og nized from bore holes in south east ern Po land and west ern Ukraine are very fine to me dium-grained subarkosic and sublithic arenites and wackes. The de pos its un der went diagenesis well be - low 100°C, and their evo lu tion ary path ways of diagenetic and re lated res er voir prop er ties rep re sent eo- and mesodiagenesis. Eodiagenesis here com prised me chan i cal com pac tion, de vel op ment of chlorite, microcrystalline cal cite, py rite, sid er ite, kaolinite and quartz, and dis so lu tion of feld spar and mica grains. Mesodiagenesis in cluded quartz and K-feld - spar overgrowths, albitisation, crystallisation of do lo mite and an ker ite and coarsely crys tal line cal cite, dis so lu tion of feld spar grains and car bon ate ce ment, and illite growth. The iso to pic data of d18OVPDB of car bon ate ce ments sug gest their crys tal li sa - tion from porewater which is a mix ture of ma rine and me te oric wa ters. The d13CVPDB val ues sug gest der i va tion of car bon from mi cro bial methanogenesis of or ganic mat ter. The 87Sr/86Sr val ues in coarsely crys tal line cal cite are higher than those of Badenian sea wa ter. The ra dio genic stron tium may have been sup plied dur ing diagenesis by me te oric wa ters drain ing the con ti nen tal area. The Mid dle Mio cene sand stones show better fil tra tion abil i ties (good and very good) in the west ern part of the study area (Po land) than in the east. Pri mary inter gra nu lar po ros ity is more fre quent than sec ond ary intragranular and intercrystalline po ros i ties.The pri mary po ros ity was di min ished due to com pac tion and ce men ta tion from west to east. Some in crease in po ros ity was caused by dis so lu tion of de tri tal grains and by de cay of soft parts of or gan isms.
Key words: diagenesis, res er voir prop er ties, sand stones, iso to pic anal y ses, Mid dle Mio cene, Carpathian Foredeep.
INTRODUCTION
Changes in res er voir char ac ter is tics of the Mid dle Mio cene strata of the Carpathian Foredeep are im por tant for the in ter - pre ta tion of the geo log i cal his tory and as re gards evo lu tion of oil and gas po ten tial and hy dro car bon pros pects. Hence, de tailed sedimentological, pet ro log i cal, min er al og i cal, iso to pic and fluid in clu sion stud ies on the Up per Badenian and Sarmatian rocks from south east ern Po land and west ern Ukraine have been car - ried out in the last two de cades (e.g., Dziadzio, 2000;
Maliszewska et al., 2001a, b, 2004; Jasionowski and Peryt, 2010; Jarmo³owicz-Szulc et al., 2011; Koz³owska et al., 2011;
Kuberska et al., 2011; Lis and Wysocka, 2012; Jasionowski et al., 2012; Wysocka et al., 2012; Peryt et al., 2014; Galamay et al., 2014). Iso to pic anal y sis and par tic u larly stron tium iso to pic anal y ses have proven a pow er ful chronostratigraphic tool (e.g., McArthur et al., 2001, with ref er ences therein). Fur ther more, iso to pic com po si tion of d18O and 87Sr/86Sr can pro vide use ful in - for ma tion about the or i gin, mix ing pro cesses (Cendón et al.,
2008; Gar cia-Veigas et al., 2013, 2015, amongst many oth ers) and diagenetic evo lu tion of for ma tion wa ters (Sheppard, 1986;
Schultz et al., 1989; Armstrong-Altrin et al., 2009). How ever, diagenesis can al ter 87Sr/86Sr ra tios from their orig i nal val ues, so a de tailed un der stand ing of al ter ation pro cesses is needed to val i date such stud ies (e.g., Kasprzyk et al., 2007).
Mio cene de pos its from twenty one bore holes are the sub - ject of the pres ent syn thetic study (Fig. 1). Their lo ca tion is shown in Fig ure 1.
The aim of the pres ent study is to ana lyse min eral com po si - tions of the sand stones and their ce ments and the re la tion ships be tween var i ous diagenetic pro cesses and the sed i men tary en - vi ron ment, and to de scribe the char ac ter is tics of the hy dro car - bon res er voir rocks. At ten tion was fo cused on ob serv ing pro - cesses over the en tire study area. Over one hun dred sam ples of siliciclastic rock were ex am ined, the re sults be ing pre sented both in ear lier works of the au thors and in the pres ent pa per.
These rocks are un der lain by the evaporitic suc ces sion of the Mid dle Mio cene ba sin (Oszczypko et al., 2006; Peryt, 2006).
Ear lier re sults ob tained for the Mid dle Mio cene sand stones from bore holes in the Tarnogród area (Maliszewska et al., 2001a) have been used for com par i son and dis cus sion. The pres ently ana lysed rock sam ples are mainly the sand stones re - ferred by Garecka and Olszewska (2011) to the Late Badenian and Sarmatian.
* Corresponding author, email: katarzyna.jarmolowicz-szulc@pgi.gov.pl Received: January 20, 2015; accepted: November 18, 2015; first published online: November 25, 2015
GEOLOGICAL SETTING AND DEPOSITIONAL ENVIRONMENTS
The Carpathian Foredeep is a large sed i men tary ba sin de - vel oped on the Carpathian front from the Dan ube River in Aus - tria to the Iron Gates in Ro ma nia (Oszczypko et al., 2006). The fore land ba sin de vel oped as a re sult of Carpathian front move - ment to wards north dur ing Early to Mid dle Mio cene. The in ner part of the Carpathian Foredeep is locateed be neath the Carpathian nappes whereas the outer one is placed in front of the orogen (Ney et al., 1974; Oszczypko et al., 2006).
Ac cord ing to seis mic, magnetotelluric and bore hole data (Oszczypko et al., 2006), the Carpathian Foredeep is asym met - ri cal as a whole, with an ero sional bound ary in the north and a tec tonic bound ary to the south. It is filled in with pre dom i nantly clastic strata of Mio cene age. The molasse de pos its un der lain by the base ment of the East Eu ro pean Plat form are over lain by Perm ian-Me so zoic ter res trial and shelf strata and lo cally by Paleogene de pos its. The plat form base ment with the Mio cene molasse dips south wards be neath the Outer Carpathian units (Oszczypko et al., 2006). The Early to Mid dle Mio cene Carpathian Foredeep de vel oped as a peripherical fore land ba - sin re lated to the mov ing Carpathian front. The Pa leo zoic–Me - so zoic, Paleogene and Neo gene strata of the Carpa thian Foredeep are oil and gas pro duc tive (e.g., Fedyshyn, 1998;
Karnkowski, 1999; Kurovets et al., 2004; Kotarba and Koltun, 2006; Kotarba et al., 2007, 2011a, b; Wiêc³aw et al., 2012).
The west ern part of the Pol ish Carpathian Foredeep Ba sin is char ac ter ized by block struc tures, and the east ern part by deep ero sional struc tures (can yons; Oszczypko et al., 2006;
Peryt, 2012, with ref er ences therein; cf. Krzywiec et al., 2014).
The siliciclastic de pos its (claystones, mudstones and sand - stones) reach a thick ness of 3 km in the west ern part of the study area and up to 6 km in the east ern sec tion (Oszczypko et al., 2006; Kurovets et al., 2004, re spec tively). The lat est Badenian–Early Sarmatian de pos its formed in a va ri ety of depositional en vi ron ments, from deep ma rine (ba sin plain) to shal low ma rine (Lis and Wysocka, 2012). They rep re sent the Machów For ma tion in the Pol ish part (Jasionowski, 1997;
Oszczypko et al., 2006) and the Kosiv and Dashava for ma tions in the Ukrai nian part (Andreyeva- Grigorovich et al., 2008). In gen eral, the sec tion con sists of mudstones and fine-grained sand stones de pos ited pre dom i nantly from grav ity flows. Prox i -
mal fa cies con tain huge sand stone pack ages, while the dis tal ones are dom i nated by mudstones and claystones with thin sand stone beds. The orogen was the main source area for the ma te rial de pos ited in the Carpathian Foredeep Ba sin. The sed i - men tary re cord is in ter preted as ter res trial to ma rine and con - sists pre dom i nantly of fine-grained sand stones, claystones and mudstones (Peryt and Piwocki, 2004, with ref er ences therein).
Lis and Wysocka (2012) dis tin guished four teen lithofacies in the Mid dle Mio cene de pos its within the Pol ish and Ukrai nian parts of the study area. Gen er ally, the sand stones are char ac ter is tic of deltaic and shal low ma rine en vi ron ments.
METHODS
53 core sam ples of sand stones from the depth in ter val of 300–2500 m from 8 bore holes from Po land and 49 sam ples from the depth in ter val of 1250–3200 m from 10 bore holes from Ukraine were col lected. Sedimentological de scrip tions of cores and well-log cor re la tion pan els for both parts of the Carpathian Foredeep are given by Lis and Wysocka (2012). An a lyt i cal pro - ce dures com prised sev eral stages: prep a ra tion, mi cro scopic eval u a tion, pet ro log i cal and min er al og i cal as sess ment and iso - to pic and fluid in clu sion anal y ses.
All pet ro log i cal sam ples were vac uum-im preg nated with blue resin prior to thin sec tion prep a ra tion in or der to in ves ti - gate, op ti cally, the po ros ity. Sand stones un der went min eral count ing us ing a coun ter PRIOR model G. Modal com po si tions of the sand stones were ob tained by count ing 300 points per thin sec tion us ing a po lar iz ing mi cro scope Nikon Eclipse LV 100 Pol. The pore per cent age in sand stones was cal cu lated. Sand - stone microlithofacies were dis tin guished us ing the Pettijohn et al. (1972) clas si fi ca tion (a ver sion of the Dott clas si fi ca tion, mod i fied). Thin sec tions were stained by Evamy so lu tion in or - der to iden tify the car bon ates. Tex tural fea tures, grains of feld - spar and ce ments of car bon ates, quartz and kaolinite were ob - served in se lected pol ished thin sec tions ana lysed within cathodoluminescence (CL) us ing the equip ment with a cold cath ode CCL 8200 mk 3, Cam bridge Im age Tech nol ogy Ltd.
Stud ies of crys tal habit, oc cur rence and paragenetic re la - tion ships were per formed on gold-coated sam ples chips us ing a LEO 1430 scan ning elec tron mi cro scope (SEM) with en - ergy-dispersive X-ray analyser. Back-scat tered elec tron (BSE) Fig. 1. Location of the boreholes studied in the Carpathian Foredeep
im ages were also ob tained with the same SEM. The chem i cal com po si tion of car bon ates and feld spars was de ter mined on twenty-two pol ished, car bon-coated thin sec tions us ing a JEOL JSM-35 scan ning elec tron mi cro scope (SEM) equipped with an en ergy-dispersive X-ray analyser. Min er al og i cal com po si tion of the <2 mm frac tion of the sed i ment (clay min er als) was de ter - mined by X-ray dif frac tion (XRD), us ing a Philips X’Pert PW 3020 diffractometer (Cu Ka ra di a tion and semi con duc tor de tec - tor). The anal y ses were per formed on ori ented air-dried and sub se quently gly col-solvated sam ples, heated at 550°C. The fluid in clu sion anal y sis was con ducted on authigenic car bon - ates in se lected sam ples in twenty dou ble-pol ished thin sec - tions. Ther mo met ric stud ies were per formed us ing a Linkam THMS600 heat ing-cool ing stage mounted on a po lar iz ing mi - cro scope (Nikon Eclipse LV 100 Pol). In the heat ing mode they lead to de ter mi na tion of tem per a tures of min eral crystallisation, since it is as sumed that the ho mogeni sa tion tem per a ture of the pri mary aque ous in clu sions rep re sents a min i mum tem per a ture of fluid trap ping dur ing min eral pre cip i ta tion (Roedder, 1984).
The es ti ma tion of the pres sure and tem per a ture con di tions of the for ma tion of min er als based on the cross ing isochore tech - nique us ing co ex ist ing car bon di ox ide and aque ous in clu sions, fol lowed the method in tro duced by Kalyuzhnyi (1982;
Jarmo³owicz-Szulc et al., 2011). Isochores for the car bon di ox - ide were cal cu lated with both the Flincor pro gram (Brown, 1982) and the FLUIDS pack age (Bakker, 2003).
Car bon and ox y gen sta ble iso tope anal y ses were per - formed on forty-seven cal cite- and eigh teen do lo mite-ce - mented sand stone sam ples. Mea sure ments were con ducted at the Maria Cu rie-Sk³odowska Uni ver sity in Lublin (e.g., Ha³as, 1982). For the iso to pic anal y ses, car bon di ox ide gas was ex - tracted from the sam ples by re ac tion of car bon ate with H3PO4
at 50°C in a vac uum line for at least 24 hours (ac cord ing to the pro ce dure by McCrea, 1950). The gas was pu ri fied of wa ter on a P2O5 trap and col lected on a cold fin ger. Iso to pic com po si - tions were ana lysed us ing a tri ple col lec tor mass spec trom e ter equipped with a gas ion source. Af ter sub se quent nor mal iza tion to mea sured in ter na tional stan dards, the iso to pic com po si tion was ex pressed in per mille rel a tive both to VPDBand VSMOW stan dards. An a lyt i cal pre ci sion of both d13C and d18O in sam - ples and in stan dards was better than ±0.08‰.
Stron tium anal y ses were per formed on eight sand stone sam ples with car bon ate ce ments (10–15 vol.% cal cite) at the Iso tope Geo chem is try Lab o ra tory of the Pol ish Acad emy of Sci ences in Cra cow. Stan dard pro ce dures have been de - scribed, e.g., by Peryt et al. (2010), or by Peryt and Anczkiewicz (2015). Pow dered rock sam ples were dis solved on a hot plate in HCl. Dis solved sam ples were first loaded on a stan dard cat - ion col umn (DOWEX 50W-X12 resin). The col lected Sr frac tion was fur ther pu ri fied on Eichrom Sr-spec resin. Af ter con vert ing to ni trates, anal y ses of the stron tium iso to pic ra tio (87Sr/86Sr) were per formed in a static mode on the MC ICPMS Nep tune with ref er ence to fre quent anal y ses of the SRM987 stan dard.
The mea sured ra tios were in stru men tally cor rected to frac tion - ation ef fect us ing the val ues of 86Sr/88Sr=0.1194 and nor mal - ized with 87Sr/86Sr = 0.710248 (Oslick et al., 1994). Pre ci sion of in di vid ual ra tios re fers to the last sig nif i cant dig its and is at 2se level (Thirlwall, 1991).
Petrophysical mea sure ments of po ros ity, per me abil ity and the pore space pa ram e ters: porosimetric po ros ity, the per cent - age of pores with a di am e ter >1 µm, size of thresh old di am e ter and hys ter esis were con ducted at the Oil and Gas In sti tute in Kraków.
SANDSTONE PETROGRAPHY
The sand stones, as pack ages or lay ers of dif fer ent thick - ness, form interlayers in thick mudstone-claystone thick suc - ces sions. Sand stone fea tures for both parts of the study area are shown in Ta ble 1.
FRAMEWORK GRAIN COMPOSITION
The sand stones are very fine- to me dium-grained, mod er - ate to poorly sorted. The grains are an gu lar to subrounded. The sand stones stud ied rep re sent subarkosic and sublithic arenites and wackes (Fig. 2).
The quartz, the con tent of which ranges from 18.7 to 70.6 vol.%, is the main com po nent of the rock (Ta ble 1).
Monocrystalline quartz pre dom i nates over polycrystalline quartz, which in cludes frag ments of chert (on av er age
~1 vol.%). The quartz grains com monly have sharp edges, and only those of the frac tion of 0.25 mm are partly rounded. Feld - spars oc cur in all sand stone sam ples ana lysed in amounts vary ing from 1.0 to 12.3 vol.%. They are mainly po tas sium feld - spars which show a blue color in cathodoluminescence. The plagioclase, char ac ter ized by a green color in CL, is less fre - quent (Fig. 3A, B). The par tial or to tal re place ment of some feld - spar grains by al bite (non-lu mi nes cent in CL) and/or cal cite as well as dis so lu tion of feld spar is ob served (Fig. 3C). Micas oc - cur in var i ous amounts in both seg ments of the ba sin, with a dis - tinct mus co vite pre dom i nance over bi o tite. Their per cent age is low in the east, only oc ca sion ally ex ceed ing 10 vol.%. In the west ern part of the study area, mica con tent reaches about 18 vol.%. Lithoclasts oc cur in the sand stones stud ied in amounts of up to 11.6 vol.% in the Ukrai nian and up to 18.3 vol.% in the Pol ish seg ments. They are mainly sed i men tary rock frag ments (mudstones, very fine-grained sand stones, claystones, car bon ate rocks in the east ern, and mainly lime - stones, rarely claystones, siltstones and sand stones in the west ern part of the ba sin). The frag ments of meta mor phic rocks (mica and quartz-mica schists), and the frag ments of ig ne ous rocks (granitoids and erup tive rocks, mainly vol ca nic glass) are less fre quent. Cal cite bioclasts were ob served in the sand - stones ana lysed, from 0 to 3.3 vol.%. Foraminifers are the most com mon bioclasts (Fig. 3D), while frag ments of bi valve and brachi o pod shell and echinoderm and branches of bryo zoans are less fre quent. Other com po nents of sand stones with
<2 vol.% in the sand stones are: or ganic mat ter, ac ces sory min - er als (mainly zir con and ap a tite), ooids and glauconite. The glauconite is com mon and forms oval, green grains of var i ous size that ap pear af fected by vary ing de grees of chloritisation and pyritisation. Lo cally, ooids with di am e ter <0.5 m are ob - served (e.g., the Pruchnik 22 bore hole).
Both the ma trix and the ce ment in the Mid dle Mio cene sand - stones are pres ent in vari able amounts. The ma trix is com - posed of fine grains of quartz mud and de tri tal flakes of clay min er als, plus lo cally iron hy drox ides, or ganic mat ter and py rite.
XRD anal y ses of clay min er als have shown the pres ence of smectite, illite, chlorite and kaolinite. Ce ments are mainly built of car bon ates, while quartz and clay min eral ce ments are less fre quent.
CEMENTS AND REPLACIVE MINERALS
Var i ous diagenetic min er als in the Mid dle Mio cene sand - stones (Fig. 3A, B, E–H) were ear lier de scribed by Maliszewska
Sand stone fea tures West ern part (Po land) East ern part (Ukraine)
Quartz [vol.%] 19.0–70.6 18.7–68.0
Feld spar [vol.%] 1.7–12.3 1.0–9.3
Lithoclast [vol.%]
0–18.3 (mudstones, very fine grained sand - stones, claystones, car bon ate rocks, rarely mica schists, quartz-mica shists, granitoids and
vol ca nic glass)
0.3–11.6 (lime stones, rarely claystones, siltstones, sand stones, mica schists, quartz-mica
schists, granitoids and vol ca nic glass)
Micas [vol.%] 0–17.7 0–13.3
Bioclasts [vol.%] 0–3.3 0–2.7
Ooids [vol.%] 0–0.7 0
Glauconite [vol.%] 0–1.3 0–5.3
Ac ces sory min er als [vol.%] 0–1.7 0–0.7
Ma trix [vol.%] 0–49.7 1.7–33.7
Authigenic quartz [vol.%] 0–2.4 0–6.3
Car bon ates [vol.%] 3.0–39.7
(cal cite, do lo mite, an ker ite, sid er ite, rhodochrosite) 4.8–49.3 (cal cite, do lo mite, an ker ite)
Authigenic clay min er als [vol.%] 0–0.3 0–1.7
d13C in do lo mite ce ment [‰ VPDB] n.d. -0.59–2.11
d18O in do lo mite ce ment [‰ VPDB] n.d. –8.25–(–1.70)
d13C in cal cite ce ment [‰ VPDB] –5.72–(–1.71) –7.76–(–1.03)
d18O in cal cite ce ment [‰ VPDB] –8.61–(–5.51) –8.80– (–3.46)
87Sr/86Sr in cal cite ce ment n.d. 0.708661–0.709255*
Th [°C] in cal cite ce ment <50 <50
Sa lin ity wt.% eq. NaCl 13.52 7.53–16.24
Po ros ity in thin sec tion [vol.%] 0–29.4 0–19.3
Ef fec tive po ros ity [%] 14.03–34.76 0.61–28.33
Pores >1 mm [%] 47–91 4–90
Thresh old di am e ter [mm] 3–50 0.2–30
Hys ter esis [%] 21–84 43–82
Per me abil ity [mD] 0.62–332.27 0.10–294.40
Data from Jarmo³owicz-Szulc et al. (2011), Koz³owska et al. (2011) and Kuberska et al. (2011); * – new data; n.d. – not de ter mined T a b l e 1 Sand stone fea tures in the west ern and east ern parts of the study area
Fig. 2. Plot of the mineral composition of the Miocene sandstone (arenites, wackes) samples in the classification triangle of Pettijohn et al. (1972); data from Koz³owska et al. (2011) and Kuberska et al. (2011)
et al. (2001a, b), Koz³owska et al. (2011) and Kuberska et al.
(2011).
The car bon ate ce ments in the study area are rep re sented mostly by cal cite, do lo mite and an ker ite (Figs. 4–9). The sid er - ite was iden ti fied only in the west ern part of the study area. Two types of the cal cite ce ment can be dis tin guished: mi cro- and coarsely crys tal line. The microcrystalline cal cite oc curs on the sur face of grains and in pri mary pores. The coarsely crys tal line to poikilotopic cal cite ce ment oc curs in inter gra nu lar and intragranular po si tion in the sand stones stud ied (Fig. 3A, B).
Ad di tion ally, this ce ment re places feld spar grains and rock frag - ments, of ten form ing pseudo morphs. The coarsely crys tal line cal cite post-dates quartz overgrowths and do lo mite and an ker - ite rhom bo he dra (Fig. 3E). The chem i cal com po si tion of cal cite is: 92.2–99.4 mol.% CaCO3, 0–4.6 mol.% FeCO3, 0–2.5 mol.%
MgCO3 and 0–2.5 mol.% MnCO3 (Fig. 4). It rep re sents mainly Fe-bear ing cal cite char ac ter ized by red-or ange and or ange-yel - low col ors in CL (Fig. 3A, B). The d18O val ues for cal cite range from –8.80 to –3.46‰ VPDB, and the d13C val ues from –7.76 to –1.03‰ VPDB(Ta ble 1; Figs. 5 and 6). Stron tium val ues in the cal cite are shown in Ta bles 1 and 2, Fig ures 8 and 9. The
87Sr/86Sr ra tios in the sand stones stud ied with pre dom i nantly cal cite ce ments range from 0.708661 to 0.709255 (2se of 0.000011, Ta ble 2; Figs. 8 and 9). Fluid in clu sions in the cal cite ce ment in the sand stones are mostly one-phase and ei ther clear trans par ent or dark in col our. Their size ranges from 1 to 2 µm. The one-phase char ac ter of the in clu sions in di cates low tem per a tures of ce ment for ma tion – at about 50°C (Shephard et al., 1985; Burruss et al., 1987; Jarmo³owicz-Szulc et al., 2011). The do lo mite and the an ker ite oc cur in sand stones as pore-fill ing rhom bo he dra (Fig. 3A, E–G). Some of the crys tals show zon ing, with the core poorer in iron than the rims. The chem i cal com po si tion of the do lo mite min er als is:
52.4–61.4 mol.% CaCO3, 18.1–45.0 mol.% MgCO3, 0–21.0 mol.% FeCO3 and 0–2.0 mol.% MnCO3 (Fig. 4). The do - lo mite and an ker ite crys tals are sur rounded by Fe-bear ing cal - cite. The d18O val ues for do lo mite are be tween –8.25 and –1.70‰ VPDB, while the d13C val ues range from –0.59–+2.11‰ VPDB(Ta ble 1; Figs. 5 and 7). The sid er ite oc - curs as scat tered microcrystalline crys tals. Sid er ite var ies widely in com po si tion, be ing en riched in mag ne sium, and rep - re sents sideroplesite (Fig. 4).
The quartz ce ment oc curs com monly in amounts be low 1 vol.% of the whole rock, only rarely reach ing up to 2.4 vol.%. It oc curs as par tial or com plete syntaxial overgrowths around the quartz grains. The bound ary be tween the overgrowths and the de tri tal core is ei ther poorly de fined or de lin eated by fluid in clu - sions or thin clay coat ings. The quartz overgrowths show dark-brown lu mi nes cence or no lu mi nes cence, while the quartz grains have brown and blue col ors (Fig. 3B). The authigenic
quartz overgrowths are rhombohedral crys tals and prisms on de tri tal quartz grains as ob served in SE im ages (Fig. 3H).
The authigenic clay min er als ob served un der the po lar iz ing and scan ning elec tron mi cro scopes are kaolinite, chlorite and illite. The kaolinite oc curs as book lets and vermicular stacked
Fig. 3. Photographs in cathodoluminescence (CL) and scanning electron microscope (SE, BSE) modes
A – frag ment of sand stone, CL im age, orange and yel low-or ange lu mi nes cence of cal cite ce ment (Ca) and no lu mi nes cence of rhom bo he dra of an ker ite (ar row), blue lu mi nes cence of po tas sium feld spar (K-Fs), Jod³ówka 8 bore hole, depth 2406.0 m; B – frag ment of sand stone, CL im age, non-lu mi nes cent quartz overgrowths (ar row) on brown quartz grain (Qd), or ange and yel low-or ange lu mi nes cence of cal cite ce ment (Ca), green lu mi nes cence of plagioclase (Pl) and blue lu mi nes cence of po tas sium feld spar (K-Fs), Jod³ówka 8 bore hole, depth 2403.5 m; C – sec ond ary po ros ity re sult ing from dis so lu tion of feld spar (ar row), Jod³ówka 18 bore hole, depth 2403.5 m, SE im age; D – sec ond ary po ros ity in foraminifer shell (ar row), Jod³ówka 18 bore hole, depth 2104.4 m, SE im age; E – do lo mite grain (Do) with an ker ite (Ak) outer layer en gulfed by cal cite ce ment (Ca), skhidne Dovhe 3 bore hole, depth 1726.9 m, BSE im age; F – rhom bo he dra of do lo mite (Do) with an ker ite (Ak) in the outer parts. Nyklovychi 26 bore hole, depth 1249.7 m, BSE im age; G – rhom bo he dra of an ker ite (Ak) in pore space of sand stone, Jod³ówka 18 bore hole, depth 2403.5 m, SE im age; H – fi brous illite (It) fill ing in sand stone pore space and pris matic authigenic quartz (ar row), Jod³ówka 18 bore hole, depth 1912.6 m, SE im age
Fig. 4. Plot of the el e men tal com po si tion of CaCO3, MgCO3 and FeCO3 + MnCO3 (mol.%) for the car bon ate ce ments from microprobe anal y ses; data from Koz³owska et al. (2011) and Kuberska et al. (2011)
Fig. 5. Plot of the data ob tained for cal cite and do lo mite sam - ples from the car bon ate ce ments in the d18OVPDB ver sus d13CVPDB
di a gram; data from Koz³owska et al. (2011) and Kuberska et al.
(2011)
pseudohexagonal crys tals, the lat ter be ing lo cally dis trib uted in inter gra nu lar and intragranular space of the Mid dle Mio cene sand stones. Blocky hab its were also no ticed in some sam ples.
The kaolinite is sur rounded by quartz overgrowths, so it pre-dates the quartz. Rarely, it re places de tri tal feld spar or mus co vite. Chlorite was iden ti fied only lo cally. Chlorite/chlo - rite-smectite min er als oc cur as small flakes de vel oped into a hon ey comb-like tex ture that coats the frame work grains. Iron con tent is there higher than that of mag ne sium (Koz³owska et al., 2011). Platy and fil a men tous crys tals of illite cover the authigenic quartz and cal cite and infill the pore space in the sand stone (Fig. 3H).
Mi nor diagenetic min er als in clude py rite, feld spars and rhodochrosite. The py rite oc curs as scat tered framboids fill ing pri mary and sec ond ary pores (dis solved bioclasts) in the rock.
Authigenic K-feld spars oc cur as overgrowths on partly to com - pletely albitised and argillitised plagioclase grains. These overgrowths are sur rounded by, and hence pre-date, the quartz overgrowths. The rhodochrosite in nod ules was iden ti fied only in sam ples from the west ern part of the area.
INTERPRETATION AND DISCUSSION
EVOLUTIONARY PATHWAYS OF DIAGENESIS
In the pres ent pa per, a clas si fi ca tion of diagenetic stages af - ter Choquette and Pray (1970) has been ap plied. As shown be - low, two diagenetic stages (eo- and mesodiagenesis) have been dis tin guished.
The eodiagenesis cor re sponds both to the for ma tion of clay min eral rims (mostly chlorite rims on the de tri tal grains) and me - chan i cal com pac tion, ob served as undulose mica flakes or as lo - cal grain re-ar range ment. At this stage the crystallisation of the microcrystalline cal cite and, lo cally, of the sid er ite and the py rite started. The pre lim i nary al ter ation stages of un sta ble com po - nents of the grain fab ric (such as micas and feld spars) led to the kaolinite for ma tion. Tem per a tures of the kaolinite for ma tion may be de ter mined as 25–50°C (Osborne et al., 1994). The pre cip i ta - tion of sil ica may have also started at this tem per a ture.
In the mesodiagenesis, the authigenic quartz over growth for ma tion on quartz grains con tin ued. Feld spar overgrowths on the de tri tal feld spar grains were formed af ter the quartz and prior to coarsely crys tal line cal cite ce ments. The do lo mite and Fig. 6. Plot of the re sults ob tained from pore wa ter in the cal cite
ce ment in the d18O ver sus tem per a ture di a gram (see Fried man and O’Neil, 1977); data from Koz³owska et al. (2011) and Kuberska et al. (2011); tem per a ture of 50°C ob tained from FI (Jarmo³owicz-Szulc et al., 2011)
Fig. 7. Plot of the re sults ob tained from pore wa ter in the dolomitic ce ment in the d18O ver sus tem per a ture di a gram (see Dutton and Land, 1985); data from Kuberska et al. (2011)
Bore hole Depth [m]
d13C [‰ VPDB]
d18O [‰ VPDB]
87Sr/86Sr 2se
(mea sure ment pre ci sion)
Lanivka 1 1456.3 –2.40 –5.76 0.708842 0.000011
Makuniv 1 1847.0 –5.55 –7.66 0.708927 0.000011
Nyklovychi 26 1250.5 –1.30 –4.66 0.708661 0.000011
Nyklovychi 26 1701.3 –4.39 –7.19 0.708859 0.000009
Podil’tsi 1 1231.8 –5.95 –7.24 0.708823 0.000011
Skhidne Dovhe 3 1714.3 –7.76 –8.27 0.708953 0.000009
Skhidne Dovhe 3 1726.9 –6.56 –8.80 0.708887 0.000012
Susoliv 5 2100.5 –1.95 –6.11 0.708783 0.000007
Susoliv 5 2528.2 –2.78 –6.09 0.709255 0.000011
Voloscha 1 2091.2 –6.91 –5.59 0.709163 0.000011
T a b l e 2 Stron tium iso to pic data ob tained for cal cite ce ment in com par i son to car bon and ox y gen
data for the east ern part of the study area
an ker ite rhom bo he dra post date the quartz overgrowths and pre-date the coarsely crys tal line cal cite ce ment, so that ce ment crys tal lised at lower tem per a tures than the cal cite, prob a bly not higher than 50°C.
El-Ghali et al. (2013) sug gested a pre cip i ta tion of do lo mite on a Lower Mio cene shoreface and on deltaic arenites at tem - per a tures of 20–50°C and 42–55°C, re spec tively. The dis so lu -
tion of the cal cite ce ments, the dis so lu tion and albitisation of plagioclases, or the illitisation of the smectite may have been sources for Ca and Fe in the coarsely crys tal line cal cite in the sand stones stud ied (Boles and Franks, 1979; Milliken, 1998;
Morad, 1998). Pro gres sive mesodiagenesis led to a con tin ued dis so lu tion of feld spars, lithoclasts and com po nents of the ear - lier ce ments re sult ing in the for ma tion of sec ond ary, inter gra nu - lar and intragranular, po ros ity. More over, ef fects of the illitisation of kaolinite can be ob served. The for ma tion of authigenic illite took place at tem per a tures of about 100°C (Kantorowicz, 1990). All these pro cesses have been ac com pa - nied by lim ited com pac tion.
DIAGENETIC CONDITIONS OF CARBONATE CEMENTATION
Fluid in clu sions (FI) in the cal cite ce ment in the sand stones stud ied by means of microthermometry in di cate a tem per a ture de pend ence. The eutectic tem per a ture for these in clu sions is gen er ally <–21°C and the ice melt ing tem per a ture is be tween –6.5 to –5.9°C (see: Jarmo³owicz-Szulc et al., 2011).
Microthermometric data of the fluid in clu sions in the coarsely crys tal line cal cite ce ment stud ied in the west of the area (e.g., in the Pruchnik 22 bore hole; Koz³owska et al., 2011) point to low tem per a tures of ce ment for ma tion – <50°C (Shephard et al., 1985; at max i mum 80°C, Jarmo³owicz-Szulc et al., 2011). The eutectic tem per a tures sug gest the NaCl-CaCl2-MgCl2-H2O sys - tem, while the ice melt ing tem per a ture in di cates fluid sa lin ity of
~13.52 wt.% NaCl eq. (Brown, 1982; Burruss, 1987; Bodnar, 1990; Jarmo³owicz-Szulc et al., 2011). In the east ern part of the study area, the microthermometric re sults of one-phase in clu - sions (Skhidne Dovhe 3, Lanivka 1) sug gest sa lini ties of
~9 wt.% NaCl eq., den si ties of ~1.1 g/cm3 trap ping con di tions
<60°C and pres sures of about 375 bars (see Jarmo³owicz-Szulc et al., 2011).
CARBON AND OXYGEN ISOTOPES
The gen er ally pos i tive d13C val ues of do lo mite in the study area in Ukraine in the in ter val from –0.59 to 2.11‰ VPDB and its en rich ment in iron sug gest der i va tion of the car bon from mi - cro bial methanogenesis of or ganic mat ter (Burns et al., 1988;
Morad, 1998). The d18O val ues for do lo mite change most fre - quently from –4.0 to –2.0‰ VPDB(Jarmo³owicz-Szulc et al., 2011; Kuberska et al., 2011). From the frac tion ation equa tion of Dutton and Land (1985) the au thors have used d18O val ues (mainly from –4.62 to –1.70‰ VPDB) and as sumed a crystallisation tem per a ture of about 40–50°C (Fig. 7). The data in di cate the pre cip i ta tion of do lo mite from porewater show ing d18O VSMOW val ues be tween about –3.5 to 1.0‰ which fur ther points to a mix ture of ma rine and me te oric wa ters. El-Ghali et al.
(2013) ob tained sim i lar iso to pic com po si tions of porewater and they as sumed that do lo mite pre cip i tated from brack ish to ma - rine porewaters.
The d13C val ues of cal cite, with an av er age of about –4.0‰
VPDB,sug gest the mi cro bial methanogenesis of or ganic mat ter as a source of the car bon. The FeCO3 con tent in cal cite (0.0–4.6 mol.%; av er age 2.0 mol.%) sug gests pre cip i ta tion in the suboxic zone where the porewaters were de pleted in ox y - gen dur ing pro gres sive burial (El-Ghali et al., 2013). Ac cord ing to Glasmann et al. (1989), the high iron and man ga nese con - cen tra tions in the cal cite in di cate pre cip i ta tion from pore wa ters in re duc ing con di tions. The d18O val ues for cal cite change from –8.80 to –3.46‰ VPDB. If the frac tion ation equa tion of Fried - man and O’Neil (1977) is adopted, a tem per a ture of 50°C for pre cip i ta tion of the coarsely crys tal line cal cite is in di cated Fig. 8. Variation of the 87Sr/86Sr ratio in the calcite cements
with depth
Fig. 9. Plot of the 87Sr/86Sr ratio versus d18OVPDB in calcite cements
(Fig. 6).The d18O cal cu la tion re sults in the cal cite in di cate the pre cip i ta tion of this cal cite from porewater which was a mix ture of ma rine and me te oric wa ters. This fur ther sug gests some dif - fer en ti a tion of d18O VSMOW in the porewaters of (–2.5 to 1.0‰) and (–2.5 to 3.0‰) from the west to the east, re spec tively. The me te oric or mixed, i.e., me te oric and ma rine wa ters, could have been a source for the car bon ates. Czapowski (1976), Ha³as (1982) and Kurzawa (1990) have al ready de scribed se lec tive car bon ate ce men ta tion in the Mio cene de pos its in Po land, al - though in an other geo log i cal con text than given in the pres ent pa per.
STRONTIUM ISOTOPES
A cer tain re la tion ship be tween the 87Sr/86Sr ra tio (0.708661 to 0.709255) in cal cite and the sam pling depth can be no ticed (Fig. 8 and Ta ble 2). In gen eral, the deeper is the sam ple, the higher are the val ues of iso to pic ra tios. The points cor re spond - ing to 87Sr/86Sr val ues seen in the fig ure (Fig. 8) plot on an al - most lin ear trend for the Ukrai nian sam ples, with one ex cep tion (the sam ple from the Podil’tsi bore hole). The sam ples show dis - tinctly lower val ues than those ob tained by Jasionowski and Peryt (2010) for the cal cite from the anhydrite suc ces sion of the Wola Ró¿aniecka bore hole. The 87Sr/86Sr ra tios for the car bon - ates from the depth be tween 1112.9 and 1118.8 m are be tween 0.710276 and 0.71148. In that con text, a de creas ing ten dency eastwards may be ob served in re gional com par i sons of the stron tium ra tios in car bon ates. The pres ent pa per data (0.708661 to 0.709255) also dif fer from the 87Sr/86Sr value re - ported by Dick son et al. (2001) for con tem po ra ne ous ma rine car bon ates. Ac cord ing to Schultz et al. (1989), the car bon ate ce ments have the same stron tium ra tio as those of the pore wa - ter at the time they pre cip i tated. The ra tio of 87Sr/86Sr of sea wa - ter dur ing the Late Mio cene to Early Plio cene lies be tween 0.7089 and 0.7091 (Hodell et al., 1991). Ac cord ing to McArthur et al. (2001) de picted 87Sr/86Sr ra tio vari a tion in the Phanerozoic, sea wa ter val ues lower than about 0.7083 were char ac ter is tic for the time pe riod from the Early De vo nian to the ear li est Mio cene. The 87Sr/86Sr ra tio value in the Badenian sea - wa ter is re ported as 0.708698–0.708817 (Kasprzyk et al., 2007). The sam ples stud ied show av er age 87Sr/86Sr ra tios val - ues of about 0.708915, which is higher than those of the Badenian sea wa ter quoted above. This dif fer ence can sug gest that the cal cium ce ments were formed from brines con tain ing non-ma rine Sr, or with sig nif i cant me te oric wa ter in puts, and also by bac te rial sul phate re duc tion. In gen eral, the non-ma rine wa ters are char ac ter ized by higher 87Sr/86Sr val ues as com - pared with val ues of the nor mal Mio cene sea wa ter (Palmer and Edmond, 1989). In a closed ba sin sys tem, the lo cal, al tered plagioclase and smectite could have been a pos si ble source of stron tium for the cal cite which crys tal lised at a later stage of diagenesis. The 87Sr/86Sr ra tios in plagioclase (av er age of
~0.70663) are lower than those in smectite (av er age of
~0.71073) which can af fect the 87Sr/86Sr value in cal cite (Schultz et al., 1989). In the cal cite stud ied, there is an in crease in stron tium ra tios as com pared with the Badenian sea wa ter val ues.
In the pres ent case, there fore, the plagioclase can not be a source of stron tium. The sam ples stud ied have higher 87Sr/86Sr ra tios than the con tem po rary sea wa ter, in di cat ing a sig nif i cant in put of the ra dio genic 87Sr to the sys tem af ter de po si tion (Armstrong-Altrin et al., 2009). The ra dio genic stron tium may have been sup plied dur ing diagenesis by me te oric wa ters drain ing the con ti nen tal area. Glasmann et al. (1989) stated that the high ra dio genic stron tium level in di cates an in ter ac tion
of the pore-fluid with con ti nen tal sil i cates. As shown in Fig ure 9, there is a gen eral trend to wards higher neg a tive d18O and higher 87Sr/86Sr ra tios. This con firms that con ti nen tal wa ters or a mix ture of ma rine and con ti nen tal wa ters were re spon si ble for these re la tion ships.
Such an in ter pre ta tion is in agree ment with the val ues of
87Sr/86Sr ra tios ob tained re cently in the Badenian pri mary gyp - sum from two bore holes in the Pol ish Carpathian Foredeep Ba - sin (Peryt and Anczkiewicz, 2015) and with the fluid in clu sion and iso to pic stud ies in the Badenian evap o rates that sug gest a mixed ma rine /me te oric or i gin for brines re sult ing in evaporite pre cip i ta tion (Céndon et al., 2008). Peryt and Anczkiewicz (2015) found out that stron tium ra tios are higher than the con - tem po rary sea wa ter value due to sig nif i cant non-ma rine con tri - bu tion of ra dio genic stron tium. The high-grade Archean and Paleoproterozoic ig ne ous rocks of the Ukrai nian shield are re - garded as the source of the higher 87Sr/86Sr ra tios re corded in the pri mary gyp sum.
DIAGENESIS AND POROSITY
The po ros ity and the per me abil ity data ob tained for nu mer - ous Pol ish and Ukrai nian sand stone sam ples shows vari abil ity as shown by Koz³owska et al.( 2011) and Kuberska et al. (2011) and in Ta ble 1. The re sults of lab o ra tory de ter mi na tions of ef - fec tive po ros ity fac tor os cil late from 0,61 to 34.76%. Ac cord ing to the clas si fi ca tion of Jenyon (1990), the Mid dle Mio cene sand - stones can be re garded as hav ing a good and a very good po - ros ity. Curves of cap il lary pres sure were con structed and a thresh old di am e ter de ter mined (from 0 to 50 mm). Val ues of
<3 mm in di cate very low prop er ties, while higher val ues point to good or very good fil tra tion abil i ties of the sand stones ana lysed.
The val ues of the hys ter esis change in gen eral from 21 to 84%, be ing less scat tered eastwards. From anal y sis of these val ues some reg u lar ity in de vel op ment of the pore space may be no - ticed. The per cent age of pores with a di am e ter >1 mm var ies and changes from 4 to 91% (ex ceed ing 50% in most sam ples).
The ma jor ity of the Ukrai nian sam ples show a low per me abil ity – <1 mD. In some sam ples the per me abil ity is of some doz ens mD, oc ca sion ally >200 mD. On the other hand, most of the Pol - ish sam ples are char ac ter ized by a very high per me abil ity, above 100 mD, ac cord ing to the clas si fi ca tion of Levorsen (1956).
The po ros ity mea sured in thin sec tions reaches at max i - mum 19.3.vol% (in the east ern part of the area stud ied) and 29.4 vol.% in the west and cor re sponds mainly to a pri mary inter gra nu lar po ros ity. Sec ond ary intragranular pores were pri - mar ily as so ci ated with the dis so lu tion of de tri tal feld spars (Fig. 3C) and rock frag ments and mi nor bioclasts and cal cite ce - ment. Some sec ond ary pores are in side foraminifer shells (Fig. 3D). Intercrystalline po ros ity (micropores) may be as so ci - ated with the pres ence of clays.
A suc ces sive de te ri o ra tion of po ros ity in the sand stones stud ied with in creas ing depth is ob served (Koz³owska et al., 2011; Kuberska et al., 2011). The pri mary po ros ity of sand - stones de creased due to com pac tion and ce men ta tion. Later, it in creased by dis so lu tion.
The me chan i cal com pac tion in cludes grain re-ar range ment and plas tic de for ma tion of mica and duc tile grains. Point and lin - ear con tacts be tween quartz grains were the only ones ob - served in the sand stones. The car bon ates, the quartz and the authigenic clay min er als play the most sig nif i cant role among the ce ments of the sand stones. The cal cite ce ment is pre dom i - nant. Lo cally, it strongly re duces the po ros ity and de creases per me abil ity down to zero. The early fringe ce ments as the clay
rims and the quartz overgrowths bound the sed i ment, that pre - vented me chan i cal com pac tion, and re sulted in a pres er va tion of a part of the pri mary po ros ity. The plot of the to tal inter gra nu - lar vol ume ver sus the ce ment vol ume (Houseknecht, 1987) re - veals that the ce men ta tion has been more im por tant in the po - ros ity de struc tion than the com pac tion (Fig. 10). The pri mary po ros ity was re duced on av er age due to com pac tion and ce - men ta tion by about 26 and 35%, and by ap prox i mately 36 and 43% in the west ern and east ern parts, re spec tively (Fig. 10).
The dis so lu tion af fects the po ros ity re sult ing in the for ma tion of sec ond ary po ros ity. This pro cess ex erted an ef fect mostly on the feld spar and lithic grains, and also on the car bon ate ce - ment. Some in crease in po ros ity was also caused by a de cay of the soft parts of the or gan isms.
CONCLUSIONS
1. The Mid dle Mio cene sand stones of the Carpathian ba sin rep re sent very fine to me dium-grained subarkosic and sublithic arenites and wackes. Their de tri tal frame work is dom i nated by quartz, feld spar and sub or di nate rock frag ments, micas, glauconite and bioclasts. The dom i nant rec og nized ce ment types are: Fe-bear ing cal cite, quartz overgrowths, do lo mite and an ker ite, and kaolinite. K-feld spar overgrowths, chlorite/chlo - rite-smectite rims, illite, py rite, sid er ite, anhydrite and rhodo - chrosite are mi nor ce ments of the sand stones. Sid er ite and
rhodochrosite have been rec og nized only in the west, and anhydrite in the east.
2. The d18OVPDB data (–8.8 to –1.7‰) of the do lo mite and the coarsely crys tal line cal cite in di cate that the car bon ate ce ments pre cip i tated from the porewater with the d18OVSMOW val ues be - tween ~ -3.0 to 3.0‰ which points to a mix ture of ma rine and me te oric wa ters. The d13CVPDB val ues of car bon ates (–7.8 to 2.1‰), sug gest der i va tion of car bon from mi cro bial methanogenesis of or ganic mat ter. The 87Sr/86Sr val ues (0.7087 to 0.7093) in coarsely crys tal line cal cite, higher than in Badenian sea wa ter, sug gest that pore-fluid had in ter acted with con ti nen tal sil i cates.
3. Fluid in clu sions give in gen eral tem per a tures <60°C (at max i mum 80°C) for the cal cite ce ments, and pres sures of about 375 bars. The fluid was CO2-bear ing, of mod er ate sa lin ity (of
~10% and ~13wt.% NaCl eq.), of mod er ate iso to pic com po si - tion and with a den sity of ~1.1 g/cm3. Petrographic and iso to pic stud ies of ce ments in the sand stones sug gest that the Mid dle Mio cene de pos its un der went diagenetic pro cesses at tem per a - tures not higher than 100°C.
4. Most Mid dle Mio cene sand stones show a good and a very good po ros ity of about 20% and per me abil ity >100 mD.
The po ros ity re duc tion ap pears to be depth-con trolled; the po - ros ity data show a gen eral de crease with an in crease in depth.
Both pri mary inter gra nu lar and sec ond ary intragranular and intercrystalline pore types are pres ent in the sand stones. Pri - mary pores are abun dant and are af fected by com pac tion and ce men ta tion by about 26 and 35% in the west, as well as by ap - prox i mately 36 and 43% in the east, re spec tively. Some in - crease in po ros ity was caused by the dis so lu tion of de tri tal grains (mainly feld spars) and by the de cay of soft parts of or - gan isms. Com par ing the sand stones from the west ern and east ern parts of the Carpathian Foredeep, the first ones show better fil tra tion abil i ties.
5. The his tory of diagenesis of the Mid dle Mio cene sand - stones in the ba sin stud ied in cludes two stages: eo- and mesodiagenesis. Me chan i cal com pac tion (crystallisation of chlorite /chlorite-smectite, microcrystalline cal cite, py rite, sid er - ite, kaolinite and quartz ce ments), as well as the dis so lu tion of feld spars and micas cor re spond to eodiagenesis. The ce men - ta tion of the fol low ing min er als: K-feld spar, do lo mite and an ker - ite, coarsely crys tal line cal cite and illite as well as albitisation, and the dis so lu tion of feld spar grains and car bon ate ce ments cor re spond to mesodiagenesis.
Ac knowl edge ments. Part of the re search was un der taken as pro ject No. UKRAINA/193/2006 of the Min is try of Sci ence and Higher Ed u ca tion car ried out at the AGH Uni ver sity of Sci - ence and Tech nol ogy and in the Pol ish Geo log i cal In sti tute – Na tional Re search In sti tute fi nanced from the sci en tific funds of 2007–2010. The re search was also sup ported by funds of the PGI-NRI, War saw. Thanks are due to Prof. A. Maliszewska for her sug ges tions and fruit ful dis cus sions con cerned with the es - sence of the sub ject. T. Peryt is thanked for his ed i to rial re vi - sions. Cor dial thanks are ad dressed to D.I. Céndon, K. Górniak, G. Leœnak and one anon y mous re viewer, whose crit i cal com - ments, de tailed re vi sions and stim u lat ing sug ges tions sig nif i - cantly im proved the manu script.
Fig. 10. Plot of po ros ity data for the Mio cene sand stones on a di a gram af ter Houseknecht (1987) show ing the ef fect of com - pac tion and ce men ta tion on po ros ity: C – ce men ta tion pre dom - i nance, K – com pac tion pre dom i nance
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