Polyphase Dolomitisation of the Wuchiapingian Zechstein Lime Stone (Ca1) Iso Lated Reefs (Wolsztyn Palaeo-Ridge, Fore-Sudetic Monocline, SW Po Land)

Geo log i cal Quar terly, 2014, 58 (3): 503–520 DOI: http://dx.doi.org/10.7306/gq.1194

Polyphase dolomitisation of the Wuchiapingian Zechstein Lime stone (Ca1) iso lated reefs (Wolsztyn Palaeo-Ridge, Fore-Sudetic Monocline, SW Po land)

Marek JASIONOWSKI1, *, Tadeusz Marek PERYT1 and Tomasz DURAKIEWICZ2, 3

1 Pol ish Geo log i cal In sti tute – Na tional Re search In sti tute, Rakowiecka 4, 00-975 Warszawa, Poland 2 Maria Cu rie-Sk³odowska Uni ver sity, Mass Spec trom e try Labo ra tory , In sti tute of Phys ics, 20-031 Lublin, Poland 3 Los Alamos National Labo ra tory , Los Alamos, New Mex ico 87545, USA

Jasionowski, M., Peryt, T.M., Durakiewicz, T., 2014. Polyphase dolomitisation of the Wuchiapingian Zechstein Limestone (Ca1) iso lated reefs (Wolsztyn Palaeo-Ridge, Fore-Sudetic Monocline, SW Po land). Geo log i cal Quar terly, 58 (3): 503–520, doi: 10.7306/gq.1194

Dolomitisation was the main diagenetic process in the Up per Perm ian Zechstein Lime stone of the Wolsztyn High – dolo mite cemen ta tion (“over-dolomitisation”) also oc curred. The rocks stud ied usu ally have a mixed min er al ogy and rep re sent a con - tin u ous spec trum from pure lime stone to pure do lo mite. This is due to vary ing de grees of dolomitisation, do lo mite ce men ta - tion and dedolomitisation. There are two main types of do lo mite: re place ment do lo mite (mostly pla nar unimodal dolosparite mo sa ics that are mainly fab ric-de struc tive) and ce ment do lo mite (pla nar isopachous rims and pore-fill ing non-pla nar sad - dle-do lo mite crys tals). The tim ing of dolomitisation and do lo mite ce men ta tion is dif fi cult to as cer tain, but com par ing pet ro- graph i cal and geo chem i cal data in di cates that the reef car bon ates were dolomitised shortly af ter de po si tion in a near-sur face sabkha/seep age-re flux and then in burial sys tems. It seems that many of the dolomites gain their present isoto pic compo si - tion when buried in rel a tively high-tem per a ture con di tions, as shown by low ox y gen iso to pic ra tios (d18O as low as –9‰ PDB) and the pres ence of sad dle do lo mite. No iso to pic sup port for a wa ter-mix ing mech a nism is doc u mented.

Key words: Zechstein Lime stone, reefs, diagenesis, dolomitisation, car bon and ox y gen iso topes.

INTRODUCTION Michalik, 2001). As far as early diagenetic dolomites are con - cerned, those from the Zechstein Lime stone (that pre ceded the evaporite de po si tion – Fig. 1) of mar ginal car bon ate plat form fa- Al though the or i gin of do lo mite re mains sub ject to con sid er - cies in SW Po land show a broad range of nearly 7‰ of d18O val- able con tro versy, geo chem i cal data and nu mer i cal mod els sug - ues (av er age –1‰) and a rel a tively nar row range (»3.5‰) of gest that most re gion ally ex ten sive dolomites form(ed) at tem- d13C val ues (av er age +4.6‰) (Magaritz and Peryt, 1994). per a tures around 50–80°, com men su rate with depths of 500 m These dolomites were thought to have formed via me te oric- to a max i mum of 2000 m (e.g., Machel, 2004). How ever, even sea wa ter mix ing (Magaritz and Peryt, 1994) and such an in ter - the small est do lo mite crys tal may be a com pos ite crys tal re sult - pre ta tion for dolomites from the Bonikowo 1 sec tion (lo cated on ing from mul ti ple, time-sep a rated phases of dolomitisation. It is the Wolsztyn High in SW Po land) show ing d18O val ues –0.67 to dif fi cult to as sign par tic u lar petrographic fea tures and/or geo- –7.24‰ was ac cepted by Sylwestrzak (2000). How ever, the chem i cal sig na tures to spe cific phases of dolomitisation (Jones, study of Melim et al. (2004) of mix ing-zone diagenesis com- 2005) as pri mary dolomitisation of a lime stone by basinal flu ids bined with a crit i cal ex am i na tion of lit er a ture data ad vo cates re- gen er ates sim i lar char ac ter is tics to those of a replacive burial do- jec tion of the mix ing-zone dolomitisation model. Dolo mites of lo mite (Machel and Bur ton, 1991; cf. War ren, 2000). In ad di tion, the Zechstein Main Do lo mite (sandwiched be tween evaporites the for ma tion of nu mer ous do lo mite bod ies was driven not by – Fig. 1) in SW Po land show rel a tively large d18O val ues (av er - one, but by sev eral mech a nisms of dolomitisation (e.g., Nader et age 2–3‰), with a broader range of nearly 5‰. d13C val ues al., 2004; Chen et al., 2004; Gar cia-Fresca et al., 2012). show a rel a tively lim ited range (»4‰) but a very large av er age The Up per Perm ian Zechstein dolomites are prod ucts of value (7‰), and are in ferred to have been de rived from very both early and late diagenesis (e.g., Füchtbauer, 1980; Clark, early (near-sur face) re flux of dense, hyper saline, Mg-rich brines 1980; Peryt, 1984, 1987; Tucker and Hollingworth, 1986; Be- (Peryt and Scholle, 1996). cker, 2002) and the pat tern of the oc cur rence of do lo mite is In the basinal fa cies of the Zechstein Lime stone in SW Po- com plex (e.g., Lorenc, 1975; Kijewski, 1981; Peryt, 1984; land, reefs were en coun tered (Fig. 2), and they are sur rounded lat er ally and over lain by evaporites (Dyjaczynski et al., 2001; Dyjaczyñski and Peryt, 2014). The pur pose of this pa per is to * Corresponding author: [email protected] de fine the mech a nisms and tim ing of dolomitisation in those Received: August 1, 2014; accepted: September 8, 2014; first reefs, as con cluded from car bon and ox y gen iso to pic in ves ti ga - published online: September 30, 2014 tions com bined with a petrographic study. 504 Marek Jasionowski, Tadeusz Marek Peryt and Tomasz Durakiewicz

playa lake, aeolian and wadi de pos its up to 1000 m thick ac cu mu lated dur ing Mid dle and the ear li est Late Perm ian times. Those silici clastic rocks are ab - sent from the Wolsztyn Ridge or are re placed by coeval vol canic rocks (Kiersnowski et al., 1995, 2010). De po si tion in the Pol ish Zechstein Basin com- menced with flood ing of the conti nental Rotliegend ba sin (e.g., Peryt et al., 2012a with ref er ences there - in). The first basin-w ide lithological unit is the Kupfers- chiefer, ab sent from most mar ginal parts of the Zechstein Ba sin as well as from more el evated parts of the Wolsztyn Palaeo-Ridge. It is fol lowed by dolomites and lime stones of the first cycle car bonate, the Zechstein Lime stone. In the area stud ied, reef Fig. 1. Stra tig ra phy of basal and middle parts of the Zechstein (Peryt et al., com plexes were formed on more em i nent el eva tions 2010a with refer ences therein) shown on an exam ple of an in terpreted seis mic section controlled by three boreholes (loca tion of the section is re lated to the cen tral part of the Wolsztyn Palaeo- shown in Fig. 2C) Ridge (Dyja czynski et al., 2001; Kiersnowski et al., 2010; Peryt et al., 2012b). The thick ness of reef com - Na3 – Youn ger Halite, Tp1+2 – Lower and Middle Buntsandstein plexes reaches 90.5 m. Biofacies se quence and the dom i nant fauna of those reefs (Raczyñski, 2000; Peryt et al., 2012b) show re mark able sim i lar ity to the iso lated reefs de scribed by Füchtbauer (1980) from NW Ger - many. Coeval basinal sec tions of the Zechstein Lime stone are GEOLOGICAL SETTING very thin in the area studied, of ten <1 m thick, and con sist of lime - stone and/or do lo mite (Dyja czynski et al., 2001; Kotarba et al., The Late Perm ian Pol ish Zechstein Ba sin is a part of the 2006; Peryt et al., 2014; Dyjaczyñski and Peryt, 2014). South ern Perm ian Ba sin ini ti ated in Late Car bon if er ous when, In the sec tions of reef com plexes of the Wolsztyn High within the Variscan orogenic belt and its foredeep, a num ber of zone, five units can gen er ally be distin guished: (i) brec cia (char - sub-de pres sions de vel oped, sep a rated by horsts and ridges. ac ter ized by D. Peryt et al., 2012); (ii) bioclastic grainstones with One of these ridges, the Wolsztyn Palaeo-Ridge, part of the extraclasts, (iii) bioclastic grainstones and packstones with Vari scan externides, sep a rated two Rotliegend sed i men tary abundant anhydrite; (iv) bioclastic wackestones-grainstones bas ins (Zielona Góra Ba sin and the Vari scan Fore land) where with intraclastic brec cia and car bon ate crusts; (v) stromatolitic-

Fig. 2. Lo ca tion map A – Zechstein Ba sin (af ter Smith, 1980, mod i fied by Kiersnowski et al., 2010); 1 – Mid North Sea High, 2 – RingkÝbing-Fyn High, 3 – Texel High, 4 – Bran- denburg-Wolsztyn-Pogorzela High arrow shows the Wolsztyn reefs; B – Zechstein Lime stone Ba sin in Po land (af ter Buniak et al., 2007, in Kiersno wski et al., 2010); C shows the area shown in Figure 2C; C – Wolsztyn reefs in terpreted from 3D seis mic data (after Geofizyka Toruñ, in Kiersno wski et al., 2010) Polyphase dolomitisation of the Wuchiapingian Zechstein Limestone (Ca1) isolated reefs... 505

pisolithic car bon ates (Dyjaczynski et al., 2001; Kiersnowski et The sub se quent depositional and burial his tory of the al., 2010; Peryt et al., 2012b). In places where units (iii) and (iv) Zechstein Lime stone de pos its of the Wolsztyn Palaeo-Ridge are ab sent and de pos its of unit (v) lie di rectly on those of unit was the same as that of the en tire Fore-Sudetic Monocline that (ii), units (iii) and (iv) were ei ther not depos ited or were eroded con sti tuted a part of the Pol ish Ba sin (e.g., Kotarba et al., prior to unit (v) depo si tion (Dyjaczynski et al., 2001). Where 2006). Dur ing Late Perm ian and Me so zoic times, contin ual pres ent, units (iii) and (iv) con sti tute the ma jor part of the sub si dence took place with pe ri ods of ac cel er ated sub si - Zechstein Lime stone sec tion, and unit (v) is mostly several dence, un til the Turonian to Paleocene tec tonic in ver sion of metres thick. the Pol ish Ba sin (see Resak et al., 2007; Krzywiec et al., 2009; Units (i)–(iv) in gen eral re flect de po si tion in sub aque ous and ref er ences therein). At pres ent, the base of the Zechstein envi ron ments, whereas unit (v) orig i nated in very shal low wa - Lime stone lies at a depth of 2.0–2.5 km, and at the end of Ju - ter and a tem porarily subaerial en vi ron ment. Unit (i) is in ter - ras sic it was lo cated at a depth of ca. 3.5 km (Karnkowski, preted as a transgressive systems tract (TST; D. Peryt et al., 1999: fig. 29). The pres ent tem per ature at that depth is ca. 2012), units (ii)–(iv) as a highstand sys tems tract (HST), and 80°C (Karn kowski, 1999: fig. 42). unit (v) as a lowstand systems tract (LST) (Dyjaczynski et al., 2001). The over lying Lower Anhydrite shows a brec cia-like ap - pear ance, nod u lar anhydrite with clasts of red mudstone oc - MATERIAL AND METHODS cur ring, topped by selenitic anhydrite with up ward-fining crystals (Peryt et al., 2010b; Hryniv and Peryt, 2010). The (re- In this paper we re port the re sults of study of the Zechstein crystallised) anhydrite with clear pseudo morphs af ter sel enite Lime stone car bonates in six selected bore holes; two of them are crystals form the greater part of the anhydrite plat form sec - lo cated in the Koœcian Reef (Koœcian 9 and 10), two in the tions that are re lated to the el evated ar eas within the ba sin Paproæ Reef (Paproæ 21 and 29), and two in the Broñsko Reef (among them, reef zones), and in the de pressed area co eval (Broñsko 1 and Kokorzyn 1; Figs. 2 and 3). Of those six bore - halite de pos its have formed (Dyjaczyñski and Peryt, 2014). holes, the Zechstein Lime stone of the Broñsko 1 bore hole was The depo si tion of the PZ1 evaporites lev elled off the ear lier char ac ter ized by Dyjaczynski et al. (2001), and the Kokorzyn 1 exist ing re lief, mak ing the up per sur face of the PZ1 depos its bore hole by Sylwestrzak (2000). Jasionowski et al. (2000) and roughly planar (Dyjaczynski et al., 2001: fig. 2; Dyjaczyñski Jasionowski (2010) pre sented a pre lim i nary in ter pre ta tion of sta - and Peryt, 2014). ble iso tope study of the Zechstein Lime stone in other bore holes.

Fig. 3. Lithological and d13C and d18O logs of selected Zechstein Limestone sections

Tri an gles – d18O, cir cles – d13C, solid symbols – cal cite, open sym bols – do lo mite; units of the Zechstein Lime stone af ter Dyjaczynski et al. (2001) 506 Marek Jasionowski, Tadeusz Marek Peryt and Tomasz Durakiewicz

Thin sec tions (332 in to tal, in clud ing 49 for CL study) were stained with Aliz arin Red S and po tas sium ferri cyanide to as sist in the iden ti fi ca tion of do lo mite and to as sess the Fe con tent of the car bon ates. They were stud ied un der a po lar iz ing mi cro - scope. The petrographic anal ysis was en hanced by cathodo - luminescence obser va tions. In ad di tion, fresh rock sam ples and thin sec tions were exam ined us ing a scan ning elec tron mi - cro scope (SEM), and back scat ter ing and microprobe stud ies were car ried out. To es tab lish the min er al og i cal com po si tion and the stoichiometry of do lo mite, anal yses of 54 sam ples were made us ing the X-ray dif frac tion method in the Cen tral Chem i - cal Lab o ra tory of the Pol ish Geo log i cal In sti tute – Na tional Re - search In sti tute in War szawa. The Philips X-ray Diffractometer Sys tem PW1840 with Cu-tube and solid state de tec tor pro vided with an au to matic com put er ized pow der iden ti fi ca tion sys tem APD 1877 was used. 205 sam ples were stud ied for ox ygen and car bon iso topes at the Insti tute of Physics, Maria Cu rie-Sk³odowska Uni ver sity, Lublin, Po land. For iso to pic anal yses of lime stone, CO2 gas was extract ed from the sam ples by the re ac tion of cal cite with H3PO4 (McCrea, 1950) at 25°C in a vac uum line, fol low ing the stan dard. The gas was pu ri fied of H2O on a P2O5 trap and col - lected on a cold fin ger. Iso to pic com posi tions were ana lysed us ing a mod i fied Rus sian MI1305 tri ple-col lec tor mass spec - trom e ter (Durakiewicz, 1996) equipped with a gas ion source. Iso baric cor rec tion was ap plied. Af ter sub se quent nor mali sa - tion to mea sured cer ti fied ref er ence ma te ri als, the iso to pic com po si tion was ex pressed in per mille (‰) rel ative to the VPDB in ter na tional stan dard and sep a rately to PDB. An a lyt i- cal pre ci sion of both d13C and d18O in a sam ple was ±0.08‰. The tem per a tures of cal cite and do lo mite pre cip i ta tion were in ter preted us ing the tem per a ture-de pend ence of the 18O–16O frac tion ation fac tors be tween cal cite and fluid, and do lo mite and fluid (ox y gen iso tope ther mom e try), ac cord ing to equations given re spec tively by Vasconcelos et al. (2005) and Fried man and O’Neil (1977) for low- and high-tem per ature dolomites. Fig. 4. Calcite, dolo mite and anhydrite content in the samples studied (1–54 – see Appen dix 1) RESULTS ac cord ing to X-ray anal y sis

MINERALOGY stoichio metry and its petrographic fea tures (and or i gin) was en - coun tered. Microprobe study showed that most do lo mite crys- Pet ro graph i cal and X-ray stud ies in di cated that the Zech - tals do not con tain de tect able Fe and Mn ad mixtures that have stein Lime stone rocks usu ally are of a mixed com po si tion and been re corded only in rare crys tals of one dolo mite gen er ation rep re sent a con tin uous spec trum from pure limestone to pure char ac ter ized by banded struc ture. do lo mite (Fig. 4 and Appen dix 1*). This is due to varying de - grees of dolomitisation, do lo mite ce men ta tion and dedolomi - tisation. The rocks con tain var ied amounts of anhydrite (even to PETROGRAPHY more than a half of rock vol ume – Fig. 4 and Ap pen dix 1) and other sub or di nate and ac ces sory authigenic min er als: flu o rite, an ker ite, quartz, celestine, clay min er als, ga lena, sphalerite, The Zechstein Lime stone de pos its were orig i nally com posed py rite, ap a tite, in ad di tion to siliciclastic and volcanogenic clasts of cal cite (mostly high-Mg) and partly aragon ite (a part of bio - re corded es pe cially in the lower unit of the Zechstein Lime stone clasts and synsedimentary ce ments). Pri mary calcite is rare; (cf. D. Peryt et al., 2012). when pres ent, it builds per fectly preserved bioclasts and ce - X-ray study and then the cal cu la tion of molar con cen tra tion ments, thus the diagenetic trans for ma tion was re stricted in such ® of CaCO3 in do lo mite based on the posi tion of peak d104 cases to high-Mg low-Mg cal cite trans for ma tion. Most de pos - (Lumsden, 1979) showed that the dolomites are mostly non - its, how ever, ex pe ri enced in tense diagenesis, and the dolomi - stoichiometric and are char ac ter ized by quite var ied CaCO3 tisation and dolo mite ce men ta tion were the most im por tant pro - con tent, al though most of the val ues are within the range cesses. In ad di tion, dedolomitisation, sev eral phases of cal cite 47–52%, with the dom i nant range 49–50% (Fig. 5 and Ap pen - ce men ta tion, anhydrite ce men ta tion and anhydritisation as well dix 1). No clear re la tion be tween the cal cu lated do lo mite as authigenic min eral for ma tion were re corded (Figs. 6–12).

* Supplementary data associated with this article can be found, in the online version, at doi: 10.7306/gq.1194 Polyphase dolomitisation of the Wuchiapingian Zechstein Limestone (Ca1) isolated reefs... 507

nar (both subhedral and euhedral) (Sibley and Gregg, 1987), and the lat ter are clearly predominant. Pla nar dolomites are com posed of trans par ent crys tals of clear rhomb cross-sec tion with a size of sev eral tens of mi crom - eters. They occur throughout the en tire Zechstein Lime stone sec tion and form usu ally isopachous rims on bioclasts and pore walls (Figs. 6, 7D, 9D and 11D). This ce ment gen er ation fol lows the synsedimentary cal cite ce ments and precedes blocky and other coarse-crystal line cal cite ce ments and non-pla nar do lo - mite ce ment (saddle do lo mite). The lat ter is com posed of dark (due to abun dant in clu sions) cen tre and clear outer zones (Fig. 11), and is char ac ter ized by fan-shaped extinc tion and, in the case of euhedral habit, also by curved crystal walls. They do not show lu mi nes cence due to a high Fe con tent. Sad dle do lo mite is rare, and it usu ally fills large pores or joints, fully (mono - crystals) or partly (druse-like aggregates). There oc cur three va ri et ies of re place ment do lo mite in the Zechstein Lime stone: dolomicrite, fine to me dium-crystal line dolosparite, and dolosparite. The lat ter is rare and the first two va ri et ies are ubiq ui tous, be ing end-mem bers of a continuum. Dolomicrite is char ac ter ized by very fine- or crypto cry stalline tex ture. In some cases it un der went a clear recry stallisation that Fig. 5. His to gram of CaCO3 con tent in do lo mite sam ples (1–54 – see Appen dix 1) re sulted in a unimodal mo saic of rhomb pla nar euhedral do lo mite crystals (sev eral tens of micrometres across). Dolomicrite occurs in sabkha and in pisolithic depos its of the up per most unit of the There are two main types of do lo mite in the Zechstein Lime - Zechstein Lime stone (Fig. 11), as well as in part strongly stone: re place ment do lo mite (mostly unimodal dolosparite mo- dolomitised wackestones, packstones and grainstones forming saic that is mainly fab ric-de struc tive) and cement do lo mite. units (iii) and (iv), both in the ma trix and the mi met i cally Both types show two ba sic tex tural types: non-pla nar and pla - dolomitised bioclasts and other grains (Figs. 8A–D and 10A–D).

Fig. 6. Bryozoan grainstone (b – bryozoan) with sev eral gener a tions of car bonate ce ment The two first gener a tions are syndepositional ma rine ce ments form ing isopachous rims (fc) and bot ry oi dal ce - ment (bc) of most proba bly primary aragonitic min er al ogy. The next ce ment gen er a tion is isopachous rim do lo - mite (dc) in tensely red in CL. Indi vid ual do lo mite rhombs oc cur also within the bot ry oi dal fab ric. The last gen er a tion is coarsely crys tal line calcitic sparry ce ment (cc) showing zoned struc ture in CL that is also subtly ex - pressed in BS, in di cat ing del i cate dif fer ences in chem i cal com po si tion (prob a bly a greater Mn ad mix ture) in dis tin - guish able in microprobe study. Koœcian 10, sam ple 34; A – plane po lar ized light; B – CL; C, D – backsc attered elec tron im age (BS) of a scan ning elec tron mi cro scope thin sec tion 508 Marek Jasionowski, Tadeusz Marek Peryt and Tomasz Durakiewicz

Fig. 7. Fully dolomitised bioclastic grainstone; the pri mary bioclast structures are obliter ated due to fab ric-de struc tive dolomitisation Dolomitised bioclasts are made of fine do lo mite crystals and coated by larger dolo mite ce ment crystals (dc) show ing euhedral forms. Do lo mite is intensely red in CL; the pore space filled with poikilitic cal cite ce ment (pc). Part of the poros ity (black areas in CL and BS images) is pri mary and part is sec ondary (due to dis so lu tion of bioclasts). Paproæ 29, sam ple 74

A – plane po lar ized light; B – CL; C – back scat tered elec tron im age (BS) of a scan ning elec tron mi cro scope thin sec tion; D – SEM photo

Those dolomites could have orig i nated both in near-sur face con - low-green colours that are ac ti vated by Mn (Habermann et al., di tions (early diagenetic dolomitisation re lated to the sabkha 1996). The length of the emit ted waves (and thus the col our) zone), and dur ing burial diagenesis. depends on the po si tion of Mn ions in the crystal lat tice. If it sub - Fine- and me dium-crys tal line dolosparite is usu ally de- sti tutes Mg2+ ions, which is the most com mon case, dolo mite vel oped in the form of a unimodal pla nar mo saic with abun dant shows a red col our, and the po si tion of the maxi mum of emis - in clu sions of crystals sev eral tens of micrometres across. It sion spec trum at about 660 nm wave length. More rare yellow or orig i nated due to the re place ment of cal cite, form ing bioclasts or ange colours are due to the oc cur rence of Mn2+ ions in the po - and micritic depos its which de stroyed the pri mary texture (fab - si tion of Ca2+ ions lead ing to the over lap ping of the spec trum ric-de struc tive dolomitisation). It is com mon in units (ii), (iii), (iv) com ing from the Ca-replac ing Mn (max i mum of about 575 nm) (fully dolomitised grainstones, packstones and wackestones) over the maxi mum of 660 nm (Mg-replac ing Mn) (Habermann (Figs. 7 and 9) and within recrystallised depos its of unit (v) (Fig. et al., 1996). However, microprobe study did not show a detect - 12C, D). Un der cathodoluminescence al most all these dolo - able con tent of trace el ements (in clud ing Mn). mites show an in tense red col our and rarely or ange or yel- Polyphase dolomitisation of the Wuchiapingian Zechstein Limestone (Ca1) isolated reefs... 509

Fig. 8A–D – bioclast-peloid grainstone. Dolomitised grains (red in CL, dark grey in BS) occur within calcitic cement (yel low in CL, light grey in BS). Although the primary microstruc tures are fully recrystallised due to dolomitisation, their outlines are perfectly preserv ed (f – foraminifer). Paproæ 29, sample 72; E–H – dolomitic-calcitic mosaic (in CL dolo mite is intensely red and calcite is yellow -black in CL) with calcitic bryozoan zoarium (b) filled by rim dolo mite ce ment (dc). The zoarium is completely recrystallised; black are pores. Paproæ 29, sample 55

A, E – crossed polars; B, F – CL; C, D, G, H – back scat tered elec tron im age (BS) of a scan ning elec tron mi cro scope in thin sec tion 510 Marek Jasionowski, Tadeusz Marek Peryt and Tomasz Durakiewicz

Fig. 9A–D – fully dolomitised bioclastic grainstone of oblit er ated pri mary struc ture of bioclasts, charac - ter ized by very high pri mary and sec ondary poros ity, party destroy ed by anhydrite ce ment (ac). Much of the do lo mite shows yel low-free colours in CL; rare flu orite crys tals (fl) show a blue col our. Dolomitised grains are coated by rhombohedral euhedral crys tals of do lo mite ce ment (dc); Paproæ 29, sample 62; E–H – biolithite; Koœcian 9, sample 32 (b – bryozoans, o – encrust ing foraminifer). Cav ern filled by anker - ite-do lo mite-cal cite mo saic; ak – anker ite, c – calcite, d – dolo mite. Calcite shows a red colour in CL. Do- lomite crystals show zoning in BS – outer parts of crystals are enriched in Fe and Mn and they are not bright in CL. Crosses 1–3 in D show places of analy ses with microprobe

A, E – crossed polars; B, F – CL; C, G, H – back scat tered elec tron im age (BS) of a scan ning elec tron mi cro scope in thin sec tion; D – SEM photo Polyphase dolomitization of the Wuchiapingian Zechstein Limestone (Ca1) isolated reefs... 511

Fig. 10A–F – bioclastic grainstone, Paproæ 21, sample 2-TMP; a – anhydrite, c – calcite, d1, d2 – do lo - mite. Outer (lighter) zones of do lo mite (d2) crys tals are en riched in Fe and Mn and they are not bright in CL (arrow s); in places they are calcitised (yel low in CL and light in BS im ages)

A – plane po lar ized light; B – CL; C–F – back scat tered elec tron im age (BS) of a scan ning elec tron mi cro scope in thin sec tion

Dolosparite of a banded struc ture usu ally comprises pla - Mea sured val ues of d13C of cal cite and do lo mite in the stud - nar euhedral crystals sev eral tens to ca. 100 mi crom etre ied bore holes are in the ranges shown, ex cept for one sam ple of across, in di vid ual or clus tered in ag gre gates (Figs. 9 E–H and cal cite and do lo mite, of about 0 to +8‰ VPDB (av er age +4.7‰ 10). They show opaque pore cen tres com posed of lu mi nes cent for cal cite and av er age +5.13‰ for do lo mite; Table 1 and Fig. pure do lo mite, show ing cath ode lu mi nes cence, that are sur - 13). The d18O val ues show even greater vari ation from about +3 rounded by a non-lumi nes cent do lo mite rim. This is the youn- to –13‰ VPDB in cal cite (av er age –4.79‰) and from +3 to –9‰ gest do lo mite gen er a tion oc cur ring rarely in some sec tions, VPDB in do lo mite (av er age –3.99‰) (Table 1 and Fig. 13). usu ally in their basal parts. In some cases these crys tals are In the sec tions stud ied of the Zechstein Lime stone, the ver - calcitised (Figs. 9H and 10E–F). ti cal vari a tions in the d13C val ues and es pecially d18O val ues are large, both in cal cite and do lo mite, but show a ran dom pat tern (Fig. 3), al though a slight upw ard in crease trend in d13C val ues STABLE ISOTOPE GEOCHEMISTRY can be ob served. In ad di tion, the iso to pic com po si tion of ox y- gen is con trolled to a greater ex tent by pri mary fa cies and The ox y gen and car bon iso tope com po si tion of cal cite and diagenesis than by the iso to pic com po si tion of car bon. For ex- do lo mite in the sam ples stud ied are listed in Table 1 and shown am ple, the cal cite mo saic at the base of the Zechstein Lime - in Fig ures 3 and 13. stone in the bore hole Paproæ 29 is highly depleted and the 512 Marek Jasionowski, Tadeusz Marek Peryt and Tomasz Durakiewicz

Fig. 11A–D – large pore in dolomicrite sabha depos its filled by monocrystal of sad dle do lo mite (ds). In the dolomicrite, common silt quartz oc curs (darker sharp-edged fields in BS, see arrow s in D). Dolomicrite is cryptocrystalline and only the walls of pores are rimmed by finely crys talline dolo mite cement (dc). Koœcian 10, sample 20

A – crossed polars; B – CL; C, D – SEM pho tos dolomicritic sabkha depos its in the up per most part of the son et al., 1990) that in turn is con trolled by the prox im ity to the Koœcian 9 sec tion are clearly rich in 18O, whereas their d13C val - brine source, zones of rel atively higher po ros ity, and per me abil - ues dif fer only slightly (see Figs. 13 and 14A). ity contrast s, as in di cated by Gar cia-Fresca et al. (2012) for the Perm ian San Andres For ma tion (cf. Carmichael and Ferry, 2008; Carmichael et al., 2008; Al-Helal et al., 2012). In addi tion, INTERPRETATION AND DISCUSSION com plex lime stone-do lo mite dis tri bu tion as ob served in the Zechstein Lime stone reefs re sulted from mul ti ple reflux events, When the om ni pres ent anhydrite is ig nored and only the both in time and space (cf. Garcia-Fresca et al., 2012). car bon ate com po si tion is taken into con sid er ation, most an a - The tim ing of the ex ten sive dolomitisation and dolo mite ce - lysed samples of do lo mite and all an alysed samples of lime - men ta tion are dif fi cult to as cer tain, but com bined pet ro graph i cal stone are not 100% do lo mite or 100% cal cite, re spec tively. This and iso to pic geo chem i cal data (e.g., dom i nance of pla nar and im plies that sharp lime stone-do lo mite con tacts are rare, and spar sity of nonplanar dolomites, rel a tively high d18O val ues) in - this is sup ported by mac ro scopic ob ser va tions. The ge om e try di cates that the reef car bonates were dolomitised soon af ter de - of re place ment do lo mite bod ies can be com plex, as this is a di - posi tion in a near-sur face sabkha/seep age-re flux sys tem. Cal - rect im age of the ge om etry of dolomitising fluid flow paths (Wil - cite was mostly dolomitised in as so ci a tion with low- tem per a ture Polyphase dolomitisation of the Wuchiapingian Zechstein Limestone (Ca1) isolated reefs... 513

Fig. 12A, B – partly recrystallised vadoid grainstone; pores filled by calcite cement (red in CL) and anhydrite ce ment (black in CL). Koœcian 9, sample 16; C, D – sabkha dolo mite com posed of unimodal mo - saic of fine dolo mite crystal rhombs; slightly larger dolo mite crystals occur in pores; q – authigenic quartz, ac – anhydrite cement. Koœcian 9, sample 13 (C), Koœcian 19 (D)

A – crossed polars; B – CL; C, D – SEM pho tos

Fig. 13. Ox y gen and car bon iso topes in the Zechstein Lime stone (Ca1) de pos its of the Wolsztyn High in the reef sections studied (Broñsko 1 after Dyjaczynski et al., 2001) 514 Marek Jasionowski, Tadeusz Marek Peryt and Tomasz Durakiewicz

Ta ble 1

The ox y gen and car bon iso tope com posi tion (in ‰) of cal cite and do lo mite in the sam ples stud ied

Standard Num ber of Min i mum Max i mum Mean Mediane Bore hole Min er al ogy devi a tion anal y ses [‰] [‰] [‰] [‰] [‰] cal cite – d13C 20 2.34 6.94 5.39 5.36 1.01 cal cite – d18O 20 –6.62 –1.8 –4.26 –4.43 1.19 Broñsko 1 do lo mite – d13C 25 3.7 7.09 5.71 5.67 0.79 do lo mite – d18O 25 –8.1 1.18 –3.57 –3.4 2.64 cal cite – d13C 48 2.89 8.26 5.11 5.22 1.08 cal cite – d18O 48 –8.79 2.21 –4.68 –4.86 2.15 Kokorzyn 1 do lo mite – d13C 23 3.72 7.1 5.4 5.48 0.91 do lo mite – d18O 23 –8.97 2.18 –4.64 –5.31 3.59 cal cite – d13C 8 –2.16 3.17 1.23 1.68 1.68 cal cite – d18O 8 –10.13 –1.91 –6.08 –6.14 3.0 Koœcian 9 do lo mite – d13C 22 1.21 7.87 5.18 5.52 1.57 do lo mite – d18O 22 –8.11 3.085 –2.23 –2.55 3.41 cal cite – d13C 20 0.85 5.33 2.80 2.84 1.14 cal cite – d18O 20 –9.39 3.2 –5.06 –5.34 3.05 Koœcian 10 do lo mite – d13C 11 1.83 5.48 4.22 4.26 1.05 do lo mite – d18O 11 –8.88 –0.07 –4.81 –4.93 2.80 cal cite – d13C 12 2.01 5.88 4.35 5.21 1.52 cal cite – d18O 12 –7.34 0.3 –4.05 –4.65 2.46 Paproæ 21 do lo mite – d13C 25 2.33 7.58 5.57 5.52 1.20 do lo mite – d18O 25 –8.87 1.86 –4.74 –5.13 2.70 cal cite – d13C 18 2.7 5.72 4.41 4.46 0.88 cal cite – d18O 18 –12.97 0.37 –5.27 –4.58 4.15 Paproæ 29 do lo mite – d13C 21 –1.11 6.72 4.05 4.56 1.82 do lo mite – d18O 21 –8.84 2.06 –4.28 –4.6 3.20 cal cite – d13C 126 –2.16 8.26 4.37 4.64 1.63 cal cite – d18O 126 –12.97 3.20 –4.79 –4.72 2.65 TOTAL do lo mite – d13C 127 –1.11 7.87 5.13 5.41 1.39 do lo mite – d18O 127 –8.97 3.08 –3.99 –4.74 3.16

seep age re flux dur ing de po si tion of the over ly ing PZ1 sul phate ized by higher heat flow, that sub se quently decreased dur ing de pos its. This pro cess was ac com pa nied by anhydrite pre cip i - the Early Ju ras sic to Late Cre ta ceous (Karnkowski, 1999; ta tion (cf. Rahimpour-Bonab et al., 2010). Kotarba et al., 2006). This dolomitisation was usu ally fabric-s elec tive, or at least The iso to pic com po si tion of dolomites may actu ally reflect a fab ric-re ten tive, as is com mon for low-tem per a ture do lo mite gross rep re sen ta tion of the chem is try of recrystallising flu ids, (Machel, 2004). In con trast, high-tem per ature dolomitisation rather than the com po si tion of the orig i nal flu ids (e.g., Land, is mostly fab ric-de struc tive (cf. Machel, 2004). Machel (2004) 1985; Hardie, 1987), and there fore diagenetic sta bi li za tion af ter con cluded that dolomites that orig i nally form very close to the mul ti ple pe ri ods of dolomitisation pro duces com plex do lo mite sur face and from evaporitic brines tend to recrystallise with tex tures and chem i cal com po si tions (Gao and Land, 1991; time and dur ing burial, and the case studied fully supports Gregg et al., 2001; El-Tabakh et al., 2004). such a con clu sion. This early dolo mite (ei ther of sabkha or re- Very pos i tive car bon iso to pic val ues re corded in the Zech - flux or i gin) was ex ten sively recrystallised dur ing burial with stein Lime stone are typi cal of Perm ian dolomites of ma rine neomorphism and for ma tion of fab ric-de struc tive dolomites, prov e nance ( d13C val ues about +4‰ PDB – Scholle, 1995) and and dolo mite ce ment pre cip i tated from highly saline, hot wa- are prob ably related to changes in the burial rate of or ganic car - ters dur ing Late Perm ian to Tri as sic times that were char ac ter - bon dur ing this pe riod (Scholle, 1995). Those val ues in di cate Polyphase dolomitisation of the Wuchiapingian Zechstein Limestone (Ca1) isolated reefs... 515

Fig. 14A – ox y gen and car bon iso topes in the dolomites of the Zechstein Lime stone of the Wolsztyn reefs set against the d18O val ues of low- and high-tem per a ture dolomites and Permian marine car bonates (after Allan and Wiggins, 1993); B – inter pre ta tion of oxy gen isotopes in dolomites of the Zechstein Lime stone of the Wolsztyn Ridge

18 18 6 –2 The curves are ac cord ing to the equa tion d Odol. – d Owa ter = [3.2 x 10 T ] – 1.5 (Friedman and O’Neil, 1977)

that the basic source for car bon ate ions dur ing diagenesis was A broad range of d18O val ues was found in the dolomites, the Zechstein Lime stone de pos its, and there fore the diagenetic cor re spond ing to both the low- and high-tem per ature dolo - system was closed as far as the car bon is con cerned. Most mites (Fig. 13). Two groups of do lo mite can be dis tin guished mea sured val ues of d13C of cal cite and do lo mite over lap in the (Fig. 14A). range 2–3‰ and thus it is as sumed that in most cases the car - The first group are lam i nated or structureless and cav ern - bon iso tope com po si tion of re place ment do lo mite was in her ited ous sabkha dolomicrites with anhydrite and pisolithic de pos its from its cal cite (Table 1). that were syndepositionally dolomitised in the sabkha en vi ron - 516 Marek Jasionowski, Tadeusz Marek Peryt and Tomasz Durakiewicz ment by solu tions en riched in 18O due to evap ora tion. The d18O be im prob able, even if the iso to pic com po si tion of Late Perm ian val ues are from 0 to +3‰ VPDB. As sum ing a crys tal li sa tion sea water was slightly lighter and the Earth sur face tem per a - tem per a ture of 40°C, sabkha de pos its orig i nated from wa ter tures were much higher than they are today (Chen et al., 2013; char ac ter ized by d18O val ues close to 0‰ SMOW, which cor re - Schobben et al., 2014). In turn, if crys tal li sa tion at a higher tem - sponds to slightly evapo rated ice-free Late Perm ian sea water per a ture is ac cepted, the d18O val ues are more re al is tic. There - (Chen et al., 2013). De pend ing on the tem per ature, an uncer - fore it seems that most of the dolomites gained their pres ent tainty in d18O of fluid of ±1‰ trans lates into an uncer tainty in the iso to pic com po si tion in burial con di tions at rel a tively high tem - tem per a tures re corded by d18O of cal cite or do lo mite of ±5 to per atures (see Fig. 14B), and such a con clu sion is sup ported by ±8°C (Carmichael and Ferry, 2008). the pres ence of sad dle do lo mite that is char ac ter is tic for deeply A part of the iso to pi cally heavier depos its is also rep re - bur ied con di tions with tem per atures rang ing from 60 to 150°C sented by dolomitised grainstones show ing per fectly preserved (Radke and Mathias, 1980). However, the most com mon petro - pri mary fab ric (fab ric-pre serv ing dolomitisation; Fig. 14A). graphic tex ture of do lo mite is pla nar, typ i cal of low-tem per a ture These dolomites might have orig i nated through dolomitisation diagenetic envi ron ments (Sibley and Gregg, 1987) al though in the sabkha envi ron ment or through reflux. Wright et al. (2004) de duced, for the Lower Car bon if er ous of Other dolomites, in de pend ently of pri mary fa cies and Ire land, that pla nar re place ment do lo mite can be produced by diagenesis in ten sity, show low d18O val ues (from –2 do –10‰ mod i fi ca tion of sea water by an increase in tem per ature to a VPDB) that of ten are lo cated within the field of interfingering of min i mum of 50°C and a max i mum of 70°C, and thus was in her - low- and high-tem per a ture dolomites (Fig. 14A) and thus it is ited af ter ear lier, low-tem per a ture phases of do lo mite for ma tion. dif fi cult to con clude their or i gin. As sum ing that dolomites have Jones (2005) showed that the devel op ment of pla nar as op - low-tem per a ture prov e nance (for ex am ple, they orig i nated in posed to non-pla nar bound aries of do lo mite crystals is not al - the mix ing zone), the d18O val ues of water should be very low (in ways de pend ent on the crit i cal rough en ing tem per a ture. The some cases around –10‰ PDB – see Fig. 14B). This seems to num ber of ma jor dolomitisation phases is dif fi cult to as cer tain.

Fig. 15. The plot of d13C and d18O val ues for the Zechstein Lime stone in SW Po land and some data from the other parts of the Zechstein Basin (after Peryt and Magaritz, 1990; Magaritz and Peryt, 1994; Peryt and Scholle, 1996; Becker, 2002; Peryt and Peryt, 2012) includ ing data on brachio pods (after Becker, 2002)

The spread of data is shown by fields supple mented by the loca tion of in di vid ual sam ples show ing di ver gent val ues (these are marked by ‘X’); data on recent Abu Dhabi sabkha depos its (af ter McKenzie, 1981, and War ren, 2000) are shown as well Polyphase dolomitisation of the Wuchiapingian Zechstein Limestone (Ca1) isolated reefs... 517

The dolomites stud ied show a much greater range of d18O CONCLUSIONS val ues and a slightly greater range of d13C val ues than dolo - mites from the mar ginal car bon ate plat form of the Zechstein Lime stone in SW Po land (Fig. 14), and at the same time a sim i - 1. The Zechstein Lime stone sec tions of the Wolsztyn High lar range of d18O val ues and slightly greater range of d13C val - are usu ally of a mixed min er al og i cal com po si tion and rep re sent ues than dolomites from the Hessian Zechstein char ac ter ized a con tin uous spec trum from pure limestone to pure do lo mite. by Becker (2002). He dis tin guished four types of dolomites, This is due to varying de grees of dolomitisation, do lo mite ce - based on pe trog ra phy, cathodoluminescence, trace el ements men ta tion and dedolomitisation. Dolomitisation was the main and car bon and oxy gen iso tope data: diagenetic pro cess and it was ac com pa nied by dolo mite ce - men ta tion (“over-dolomitisation”). – do lo mite 1 formed in a sabkha en vi ron ment and char ac - d18 2. Both main types of do lo mite, re place ment do lo mite and ter ized by O val ues rang ing from –2.4 to 1.5‰; ce ment do lo mite, show two basic tex tural types: non-pla nar and – do lo mite 2 formed due to brine-re flux dur ing de posi tion pla nar (both subhedral and euhedral). 18 of the Lower Werra Anhydrite – it shows d O val ues 3. Pet ro graph i cal and geo chem i cal data in di cate that the from –0.8 to 3.4‰; reefs were dolomitised shortly af ter de po si tion in a near-sur face – do lo mite 3 formed dur ing shal low burial dolomitisation, sabkha/seep age-re flux en vi ron ment, prob a bly from cu mu la tive with d18O val ues from –8.2 to 0.3‰; and the youngest; short-lived events, and then in burial conditions. – sad dle do lo mite, with d18O val ues from –5.7 to –9.3‰ 4. The pres ent iso to pic com po si tion of dolomites was con - (Becker, 2002; Fig. 15). trolled by rel a tively high-tem per a ture burial con di tions as shown d18O val ues of the dolomites from three basinal sec tions lo - by quite low oxy gen iso to pic ra tios (d18O as low as –9‰ PDB) cated close to the reefs studied (Paproæ 28, Koœcian 21 and and the pres ence of sad dle do lo mite. There is no iso to pic ev i - Czarna Wieœ 4 – Peryt et al., 2014) range from –2.4 to 7.1‰ dence for mixing-w ater dolomitisation. and d13C val ues are from 1 to 7.2‰; thus their ranges are smaller. The basinal dolomites show higher d18O val ues com - Ac knowl edge ments. The re search was funded by the pared to the reef sec tions (Fig. 14; Peryt et al., 2014). State Com mit tee for Sci en tific Re search (Grant No. 9 T12B 028 The dolomites of the isolated reefs dif fer from the dolomites 15 to TMP) and the stat utory funds of the PGI-NRI (pro ject No. in reefs related to the mar ginal car bonate plat form in that the 6.20.1382.00.0 to MJ). TD was sup ported by the U.S. De part - lat ter are mostly stoichiometric and well or dered (Magaritz and ment of En ergy, Of fice of Sci ence, Ba sic En ergy Sciences, Ma - Peryt, 1994). Evaporitic dolomites tend to be more stoichio - te ri als Sci ences and En gi neer ing Di vi sion. The Pol ish Oil and metric (Lumsden and Chimahusky, 1980). Kaczmarek and Gas Com pany granted access to core ma te rial and thin sec - Sibley (2011) con cluded that dolo mite does not evolve to wards tions. A. Wójtowicz helped with the anal yses, and K. Ch³ódek more stoichiometric com po si tion, but in stead, more stoichio - of fered lo gis ti cal sup port. We greatly ap pre ci ate com ments and metric dolo mite was formed in so lu tions with higher Mg/Ca. sug ges tions of im prove ments by the jour nal re view ers, M. Kra- jewski and F. Pomoni-Papaioannou.

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