Fluid in clu sions in ha lite from ma rine salt de pos its: are they real mi cro-drop lets of an cient sea wa ter?
Volodymyr KOVALEVYCH and Serhiy VOVNYUK
Kovalevych V. and Vovnyuk S. (2010) – Fluid in clu sions in ha lite from ma rine salt de pos its: are they real mi cro-drop lets of an cient sea - wa ter? Geol. Quart., 54 (4): 401–410. Warszawa.
Eval u a tion of data sets on in clu sion brine com po si tions in ha lite from the Phanerozoic ma rine evaporite de pos its used for the re con struc - tion of an cient sea wa ter chem is try shows that brine anal y sis of pri mary in clu sions from pri mary ma rine ha lite (in the case of proper ge netic type de ter mi na tion) un doubt edly in di cate two mega cy cles in sec u lar vari a tion of sea wa ter chem is try dur ing the Phanerozoic. It is also shown that in side pri mary ha lite, in clu sions formed at later stages of de posit for ma tion lo cally oc cur. Er ro ne ous at tri bu tion of such in clu sions to pri mary ones is the main rea son for de vi a tions ob served in most data sets. It is also ob vi ous that fluid in clu sions in clear (recrystallized) ha lite are un suit able for the re con struc tion of an cient sea wa ter chem is try. Brines from in clu sions prop erly de ter mined as pri mary in pri mary bed ded ha lite are mi cro-drop lets of con cen trated an cient sea wa ter.
Volodymyr Kovalevych and Serhiy Vovnyuk, In sti tute of Ge ol ogy and Geo chem is try of Com bus ti ble Min er als, Na tional Acad emy of Sci - ences of Ukraine, Naukova 3A, 79060 Lviv, Ukraine, e-mail: igggk@mail.lviv.ua (re ceived: De cem ber 03, 2009; ac cepted: Au gust 25, 2010).
Key words: ma rine salt de pos its, ha lite, fluid in clu sions, sea wa ter chem is try.
INTRODUCTION
The idea of steady-state (or close to it) in sea wa ter chem i cal com po si tion over the past 1000 m.y. pre vailed in geo log i cal lit - er a ture un til the end of the 20th cen tury (e.g., Valiashko, 1962;
Borchert and Muir, 1964; Braitsch, 1971; Garrels and Mac ken - zie, 1971; Hol land, 1984) al though some au thors sug gested prob a ble vari a tions of sea wa ter chem is try based on known (and quan ti ta tively de scribed) or pre dicted changes in dif fer ent geo log i cal pro cesses and on the com po si tion of evaporite and car bon ate rocks (Ronov, 1980; Fischer, 1984; Yanshin, 1988;
Spencer and Hardie, 1990; Hardie, 1996). Dur ing last few de - cades, ge ol o gists started to use the re sults of study of in di vid ual brine in clu sion drop lets in ha lite from evaporite for ma tions to solve this prob lem for the Phanerozoic. The brines of pri mary in clu sions in pri mary (sed i men tary) ha lite were con sid ered to be trapped microdroplets of evaporite ba sin brines, i.e. brines sim i lar in com po si tion to con cen trated con tem po ra ne ous sea - wa ter (Holser, 1963; Petrychenko, 1973; La zar and Hol land, 1988; Petrichenko, 1988; Roedder, 1984) and their anal y ses have re sulted in sev eral quan ti ta tively sim i lar mod els of sec u lar vari a tions in evaporite ba sin brines and in sea wa ter chem is try (Kovalevich, 1988; Kovalevich et al., 1998; Zim mer mann,
2000; Lowenstein et al., 2001, 2003; Horita et al., 2002). It was con cluded that sec u lar vari a tions in sea wa ter chem is try were con trolled pri mar ily by fluc tu a tions in the mid-ocean ridge hy - dro ther mal brine flux, which in turn have been driven by fluc - tu a tions in the rate of ocean crust pro duc tion (Spencer and Hardie, 1990; Hardie, 1996).
De spite sig nif i cant prog ress in re con struc tion of sec u lar vari a tions in evaporite ba sin brines and sea wa ter chem is try, some as pects such as: sub stan ti a tion of ge netic types of fluid in - clu sion suit able for anal y sis; com pa ra bil ity of re sults ob tained by dif fer ent meth ods and dif fer ent au thors; meth od ol ogy of cal cu la tions of sea wa ter com po si tion based on data on com po - si tion of ha lite-hosted fluid in clu sions; and scales of lo cal fac - tors im pacting on the chem i cal com po si tion of sea wa ter dur ing its pas sage to re stricted evaporite bas ins or dur ing its evap o ra - tion in the bas ins, still re main a topic of dis cus sion, (Kovalevich et al., 1998, 2005, 2009; Zim mer mann, 2000, 2001; Ayora et al., 2001; Lowenstein et al., 2001, 2003; Horita et al., 2002; Hol land, 2003; Cendón et al., 2003, 2004, 2008;
García-Veigas et al., 2009).
In this pa per we fo cus on the main ev i dence in fa vour of the con cept of sig nif i cant sec u lar vari a tions in sea wa ter chem is try dur ing the Phanerozoic, since se lec tion of the ini tial con cept is very im por tant for in ter pre ta tion of the an a lyt i cal data. In par -
tic u lar, the es ti mate of lo cal fac tors im pact ing on ba sin brine com po si tion (eval u ated from fluid in clu sions in ma rine ha lite) de pends mainly on which sea wa ter (mod ern or an cient) is used as the stan dard for com par i son. There are brine in clu sion data in ha lite that have to be ex cluded from eval u a tion of an cient sea wa ter chem is try, be cause the ha lite in ques tion is a nonmarine de posit, or be cause it co mes from a part of the evaporite sec tion where sea wa ter was not the main source for salt pre cip i tates, as de fined based on palaeo geo graphi cal and geo chem i cal data, in clud ing the bro mine con tent of the ha lite (see, for ex am ple, Ayora et al., 1994; Zim mer mann, 2000;
Cendón et al., 2004). Then we will con cen trate on the prob lems of sub stan ti a tion of the ge netic type of fluid in clu sions suit able for sea wa ter chem is try eval u a tion. The ne ces sity of de tailed con sid er ation of this prob lem re sults from the find ings of later and sec ond ary in clu sions in side many pri mary tex tures of ha - lite (chev ron) in clu sions. These post-sed i men tary in clu sions some times dif fer in chem i cal com po si tion (Kovalevych et al., 2002a, 2009; Vovnyuk and Kovalevych, 2007). We will also make a brief com par a tive de scrip tion of the main meth ods of in clu sion brine anal y sis.
VALIDITY OF CONCEPT OF SECULAR VARIATION IN SEAWATER CHEMISTRY
THE NATURE AND SCALE OF VARIATIONS
Modern ideas con cern ing vari a tions in evaporite ba sin brines and sea wa ter chem is try dur ing the Phanerozoic can be de scribed by quan ti ta tive mod els based on the re sults of ha - lite-hosted fluid in clu sion studies pub lished in re cent de cades (Kovalevich, 1988; Kovalevich et al., 1998; Zim mer mann, 2000; Lowenstein et al., 2001, 2003; Horita et al., 2002). Ac - cord ing to these data, dur ing the Phanerozoic there were two long-term cy cles of vari a tions in chem i cal com po si tion of sea - wa ter and (cor re spond ingly) evaporite ba sin brines. Dur ing each of those cy cles, ba sin brines and sea wa ter dom i nantly of Na-K-Mg-Ca-Cl (Ca-rich) type changed to a Na-K-Mg- Cl-SO4 (SO4-rich) type.
The curve of sec u lar vari a tions of Ca vs. SO4 con cen tra tions inevaporite ba sin brines clearly re flects these changes (Fig. 1).
The curve is a mod i fi ca tion of an ear lier pub lished curve (Kovalevich et al., 1998) and it in cludes data taken from sum - mary pa pers (Zim mer mann et al., 2000; Lowenstein et al., 2001; Horita et al., 2002) and also from many pa pers de voted to in di vid ual bas ins (Brennan and Lowenstein, 2002; Brennan et al., 2004; Cendón et al., 2004, 2008; Kovalevych et al., 2002a, b, 2003, 2006b, c, 2009; Lowenstein et al., 2003, 2005;
Petrychenko and Peryt, 2004; Petrychenko et al., 2005). The in - di vid ual curve for two com po nents re flects a real chem i cal com po si tion of brines evap o rated prior to the pot ash fa cies, when brines, de pend ing on their chem i cal type, con tain ei ther Ca or SO4. This curve shape al lows us to con clude that vari a - tions in Ca and SO4 con cen tra tions in Phanerozoic sea wa ter were syn chro nous and in versely pro por tional.
Fig. 1. Sec u lar vari a tion in Ca and SO4 con cen tra tions (in Jänecke units, mol%) of evaporite ba sin brines dur ing the Phanerozoic es ti -
mated from fluid in clu sions in ma rine ha lite
Solid line is our best es ti mate of age curve based on anal y ses of pri mary fluid in clu sions. Dashed line – parts where the curve could be built only ap - prox i mately due to wide scat ter, sus pect au then tic ity or ab sence of data.
Axis line sep a rates ba sin brines into two chem i cal types: SO4-rich (to the left) and Ca-rich (to the right). Also plot ted are (two col umns on right) tem - po ral dis tri bu tion of pri mary Phanerozoic nonskeletal car bon ate min er als (cal cite vs. ar agon ite; Sandberg, 1983) and pot ash evaporites (MgSO4-rich vs. KCl-rich; Hardie, 1996). SW’ – mod ern evap o rated sea wa ter prior to pot ash fa cies; SW” – an cient evap o rated sea wa ter of Ca-rich type (with Ca con cen tra tion equal to SO4 con cen tra tion in evap o rated mod ern sea wa ter);
NP – Neoproterozoic, CM – Cam brian, O – Or do vi cian, S – Si lu rian, D – De vo nian, C – Car bon if er ous, P – Perm ian, T – Tri as sic, J – Ju ras sic, K – Cre ta ceous, Pg – Paleogene: Pa – Paleocene, Eo – Eocene, Ol – Oligocene;
Ng – Neo gene: Mio – Mio cene; E – early, M – mid dle, L – late
Sec u lar vari a tions of all ma jor ion (Na, Cl, K, Mg, Ca and SO4) con cen tra tions in sea wa ter cal cu lated on the ba sis of the data on the com po si tion of fluid in clu sions in ma rine ha lite are pub lished (Lowenstein et al., 2001, 2003; Horita et al., 2002).
These data show a di rect cor re la tion of Na and Mg with SO4, and Cl with Ca con cen tra tions, al though rel a tive changes in the con - cen tra tion of each ion are sub stan tially dif fer ent. It was as sumed that the over all sa lin ity of sea wa ter and K con cen tra tion did not change. Ex treme com po si tions of two types of sea wa ter: the mod ern SO4-rich type, char ac ter ized by high est SO4 con cen tra - tion and cal cu lated an cient sea wa ter of Ca-rich type, char ac ter - ized by the high est Ca con cen tra tion, are shown in Fig ure 2.
Na and Cl were, ev i dently, the ma jor com po nents of an - cient sea wa ter dur ing the Phanerozoic, mak ing up to 90% of the to tal ion con cen tra tion. Sec u lar vari a tions of these two ions were rel a tively small and they are still in suf fi ciently stud ied;
there fore, they are not shown in Fig ure 2. Thus, the sec u lar vari a tions of sea wa ter chem is try dis cussed were formed mostly by changes in rel a tive con cen tra tion of Ca, SO4 and Mg ions, al though these ions were less than 10% of the to tal ion con cen - tra tion. The Ca ion con cen tra tion in an cient sea wa ter could in - crease (with syn chro nous SO4 de crease) by up to three (or a lit - tle more) times com pared to their con cen tra tion in mod ern sea - wa ter. Dur ing the Phanerozoic, both these ions were con stantly pres ent in sea wa ter re gard less of its chem i cal type and cal cium sul phate de pos its are pres ent in all an cient evaporite for ma tions of ma rine or i gin. Suf fi cient dif fer ences in the min er al ogy and chem is try of ma rine evaporites be come ap par ent only when the brine con cen tra tion reaches fa cies of K-Mg salts pre cip i ta tion.
At these fa cies, in the case of brines of Ca-rich type, K-Mg salts of chlo ride type (KCl at Fig. 1) pre cip i tate, whilst in the case of brines of SO4-rich type, the sul phate K-Mg salts (MgSO4 at Fig. 1) pre cip i tate. The pe ri ods of pre cip i ta tion of these two types of salt can be cor re lated well with pe ri ods of the ex is tence of cor re spond ing types of sea wa ter (Fig. 1; Hardie, 1996;
Lowenstein et al., 2001, 2003).
The Mg con cen tra tion in an cient sea wa ter was in di rect re - la tion with SO4 con cen tra tion and in in verse re la tion ship with Ca con cen tra tion. This kind of re la tion caused sig nif i cant changes of the Mg/Ca ra tio in sea wa ter. Ac cord ing to the re -
sults of study of ha lite-hosted in clu sions this ra tio in sea wa ter was be low ~ 2.0 at pe ri ods of Ca-rich sea wa ter and at pe ri ods of SO4-rich sea wa ter it was above ~ 2.0 reach ing 5.2 (a value typ i - cal of mod ern sea wa ter; Lowenstein et al., 2001, 2003;
Timofeeff et al., 2006). This ra tio thus var ied ap prox i mately be tween 1.0 and 5.2. The value of the Mg/Ca ra tio in sea wa ter ev i dently had a de ci sive im por tance for ma rine car bon ate pre - cip i ta tion and it ex plains the na ture of pe ri ods of so-called “ar - agon ite seas” and “cal cite seas” (Sandberg, 1983; Hardie, 1996; Lowenstein et al., 2001, 2003) which are syn chro nous with pe ri ods when pot ash de pos its are char ac ter ized by MgSO4
and KCl salts re spec tively (see Fig. 1).
Thus, sec u lar vari a tion of sea wa ter chem is try in the Phanerozoic is eval u ated mostly from changes in the rel a tive con cen tra tion of Ca, SO4 and Mg ions. De spite their rel a tively low con tent, vari a tions in their rel a tive con cen tra tions caused sig nif i cant changes in the min er al ogy of ma rine car bon ates and evaporites.
EVIDENCE IN FAVOUR OF THE IDEA OF SECULAR VARIATION IN SEAWATER CHEMISTRY
Cases in fa vour of the idea of sig nif i cant sec u lar vari a tion in sea wa ter chem is try are widely dis cussed (Yanshin, 1988;
Spencer and Hardie, 1990; Kovalevich, 1990; Hardie, 1996;
Kovalevich et al., 1998; Lowenstein et al., 2001, 2003; Horita et al., 2002; Hol land, 2003; Kovalevych et al., 2006a;
Timofeeff et al., 2006). The fol low ing ar gu ments seem to speak for the vari a tion most con vinc ingly:
1. There is a clear strati graphic con trol of changes in evaporite ba sin brine chem is try eval u ated from fluid in clu sions in ma rine ha lite re gard less of the palaeogeographic and tec - tonic con di tions of salt for ma tion, in ten sity of wa ter-rock in ter - ac tion and run off amount. For ex am ple, in the Neo gene, when sea wa ter was un am big u ously of SO4-rich type, brines of all ma rine evaporite bas ins also were only of this type.
2. The changes in the ma jor-el e ment chem is try of an cient sea wa ter cor re late in time with vari a tions in the mineralogies of ma rine nonskeletal lime stones and pot ash evaporites, with vari - a tions of iso to pic com po si tion of some el e ments and many other geo log i cal pro cesses in the Phanerozoic.
3. There is ap par ent lack of ex ten sive con tem po ra ne ous do - lo mite in many evaporite bas ins, that casts doubt on the im por - tance of dolomitization in par ent brine com po si tion.
COMPARATIVE DESCRIPTION OF ANALYTICAL METHODS
Avail able data for the com po si tion of fluid in clu sions in ha - lite are ob tained mostly with three meth ods: (1) ultramicro - chemical anal y sis (UMCA) in tro duced by Petrychenko (1973), (2) microextraction fol lowed by ion chro ma tog ra phy (La zar and Hol land, 1988) or by in duc tively cou pled plasma mass spec - trom e try (ICP-MS; von Borstel et al., 2000), (3) Cryo-SEM-EDS (Ayora and Fontarnau, 1990; Ayora et al., 1994; see also Timofeeff et al., 2000). In as much as de tailed de - scrip tion of these meth ods is widely pub lished, we will con cen -
Fig. 2. Com par i son of Mg, SO4 and Ca con cen tra tions in mod ern sea - wa ter of SO4-rich type (a – af ter Hol land, 1984) and an cient sea wa ter of Ca-rich type (b – cal cu lated af ter Kovalevych et al., 1998;
Lowenstein et al., 2001, 2003; Horita et al., 2002), as two ex treme ver - sions of sea wa ter in the Phanerozoic
It is as sumed that Na and Cl con tents (which made up about 90% of to tal ion con tent in both of sea wa ter chem i cal types) did not change sig nif i - cantly, and K con tent was sta ble
trate on their com par a tive char ac ter is tics, and in par tic u lar on the pos si bil ity of the use of each method for anal y sis of pri mary in - clu sions, which usu ally do not ex ceed 150 mm.
UMCA is the main method used by us. It al lows the ma jor ions (ex cept for Na and Cl) in brine in clu sions to be de ter - mined: K, Mg, Ca and SO4 ions (see Petrychenko and Peryt, 2004, for de tailed dis cus sion). The an a lyt i cal er ror of this method is 15–23% (for Mg and K) and 37–43% (for SO4 and Ca). To re duce er rors, a num ber of anal y ses of each com po nent in in clu sion brines need to be car ried out. Two to three re peated anal y ses de crease the er ror to 16–17% (Petrychenko, 1973).
Gen er ally in clu sions >40 mm in size were used for chem i cal anal y ses. The UMCA method is the only tech nique that al lows ob ser va tion of the be hav ior of in clu sions (>40 mm) in ha lite dur ing their open ing by a nee dle un der the mi cro scope. This es - tab lishes the ap prox i mate pres sure in in clu sions (high or low), and ap prox i mate gas con cen tra tion in the brines. These fea tures are very im por tant for the ge netic char ac ter iza tion of in clu sion types (Roedder, 1984; Kovalevych et al., 2002a, 2009).
The method of microextraction fol lowed by ion chro ma - tog ra phy or by in duc tively cou pled plasma mass spec trom e try is dis tin guished by the most pre cise de ter mi na tion of ma jor con stit u ents (with a pre ci sion of 2 to 5%) and some trace el e - ments (Br, Li), though with a pre ci sion of 3 to 15%. How ever, this method is only ap pli ca ble to large fluid in clu sions (>200 mm in di am e ter), which are rare in chev ron ha lite.
The Cryo-SEM-EDS meth ods per mits the de ter mi na tion of Na, K, Mg, Ca, SO4 and Cl in frozen fluid in clu sions greater than ~15 mm in size, which is an im por tant ad van tage be cause chev ron tex tures are of ten built up with in clu sions smaller than 40 mm. Other ad van tages are a rel a tively small an a lyt i cal er ror (be low 10%) and the pos si bil ity to run many anal y ses of the same opened in clu sion. The method does not al low us to ob - serve the ana lysed in clu sion in trans mit ted light or to es ti mate the in ner pres sure; the de ter mi na tion of ge netic type of the in - clu sion stud ied re mains prob lem atic.
One more method (LA-ICP-MS) ex ists, which al lows anal - y sis of fluid in clu sions big ger than 20 mm with high ac cu racy (Shep herd et al., 1998). Its use is lim ited be cause it only de fines the rel a tive con cen tra tions of el e ments. But good re sults can be ob tained when this method is used to gether with Cryo-SEM-EDS.
GENETIC TYPES OF HALITE HOSTED FLUID INCLUSIONS
The de tailed in ves ti ga tions of salt de po si tion in mod ern salt lakes gave the key to un der stand ing the fea tures of ha lite crys - tal growth and fluid in clu sion for ma tion (Valiashko, 1951, 1962; Dellwig, 1955; Shearman, 1970; Lowenstein and Hardie, 1985). Most of the ha lite tex ture re vealed built up with fluid in clu sions, and also sol i tary in clu sions in clear ha lite from salt lakes, ap peared to be sim i lar to those in an cient ha lite, help - ing to un der stand ing their or i gin. (Wardlaw and Schwerdtner, 1966; Petrychenko, 1973; Petrichenko, 1977; Roedder, 1984;
Lowenstein and Hardie, 1985). How ever, the ge netic clas si fi - ca tion of fluid in clu sions in ha lite re mains prob lem atic ex cept
as re gards pri mary in clu sions in pri mary bed ded (sed i men tary) ha lite (Petrychenko, 1973; Roedder, 1984). In this pa per we also use such am big u ous terms as “in clu sions in recrystallized ha lite”. Some times we di vide these into “early diagenetic” or
“late diagenetic”, tak ing into ac count data on the in ner pres sure and chem is try of these in clu sions. We also use the term “sec - ond ary in clu sions” but only in case of their re la tion to healed faults in crys tals.
PRIMARY INCLUSIONS IN PRIMARY HALITE
Rock salt de pos its, ei ther mod ern or an cient, if not dis - turbed by salt tec ton ics, very of ten con sist of interbedded an - nual lay ers of grainy ha lite. The av er age thick ness of lay ers is 5–8 cm, with grains from sev eral milli metres to sev eral centi - metres in size. An nual lay ers usu ally are sep a rated by thin lay - ers of anhydrite, terrigenous or car bon ate rocks. An nual lay ers are of ten sub di vided into sea sonal/pe ri odic lay ers which dif fer in tex ture, ad mix tures and grain shape and size. There are three ha lite grain tex tures out lined by fluid in clu sions: 1 – py ram i dal hop pers, plates and/or rafts; 2 – chev rons; and 3 – cu bic hop - pers. The first of these – skel e tal ha lite crys tals – orig i nated at the brine/air in ter face. The sec ond one – chev rons – are bot - tom-growth ha lite crys tals with one cube ver tex ori ented up - wards; they form a layer of ver ti cally ori ented elon gated (up to few centi metres) ha lite crys tals, clearly vis i ble in cross-sec tions of an nual ha lite lay ers (Fig. 3A). The third tex ture – cu bic hop - pers – formed at bound ary of two brines of dif fer ent den sity and sat u ra tion (Raup, 1970; Kovalevich, 1978). The in clu sions from the first and the third tex tures are formed in spe cific con - di tions, and thus can not be used to re con struct brine com po si - tion of ha lite fa cies of sea wa ter sat u ra tion. The brines in these in clu sions can dif fer in ma jor ion ra tios from near-bot tom brines, but these in clu sions are suit able for dis tin guish ing be - tween two chem i cal types of brine (Kovalevich, 1990).
Chev ron tex ture is most widely dis trib uted in pri mary bed - ded ha lite. In clu sions in chev ron ha lite nor mally are one-phase (liq uid). They are microdroplets of brine trapped dur ing crys tal growth. In clu sions are ar ranged in bands lo cated par al lel to crys tal growth faces. In thin plates of ha lite cut out par al lel to cleav age one can ob serve bands lo cated in two per pen dic u lar di rec tions. These bands form the chev ron tex ture; the chev ron top shows the growth di rec tion (Fig. 3A, B). In clu sions are of neg a tive cu bic crys tal shape with sides ori ented par al lel to faces of the host crys tal. In clu sions usu ally do not ex ceed 150 mm (cube edge).
The in ter nal struc ture of chev rons can vary sig nif i cantly even within the same sam ple. They may or may not have clear rhyth mic band ing (Figs. 3B and 4A), and lo cally the sides of chev ron can be out lined by in clu sions that dif fer in size (Fig. 4B). Also chev rons can dif fer in in clu sion size and dis tri - bu tion – nor mally they are formed with in clu sions of sim i lar size (ei ther rel a tively small or larger; Fig. 4C), but one can also ob serve chev rons with rare large in clu sions on a back ground of nu mer ous smaller ones (Fig. 4D) or with grad ual in crease of in - clu sion size from chev ron axis out wards (Fig. 4E). Lo cally, a chev ron car ries traces of par tial dis so lu tion thus re cord ing breaks in crys tal growth (Fig. 4F). In po tas sium-bear ing zones,
in clu sions in chev rons of ten con tain daugh ter crys tals of sylvite or car nal lite (Fig. 5A). Nu mer ous pho tos of dif fer ent chev rons have been pub lished by Petrychenko (1973;
Petrichenko, 1977). Here is im por tant to note that all pri mary in clu sions in chev rons (un less they are an oma lously large or con tain daugh ter crys tals) are suit able for the re con struc tion of the an cient sea wa ter chem is try. In some evaporite de pos its, all in clu sions in chev rons con tain gas bub bles, i.e. are two-phase (Fig. 5B). The gas phase in ini tially liq uid in clu sions trapped at the sed i men tary stage can ap pear due to stretch ing or par tial crack ing of the in clu sions af ter their heat ing to above 50°C, as shown by ex per i ments on ar ti fi cial and nat u ral ha lite (Petrychenko, 1973; Holdoway, 1974; Roedder, 1984). The use of such in clu sions for sea wa ter chem is try re con struc tion is dis cussed in the lit er a ture and it is var i ously ac cepted (Kovalevych et al., 2002a, 2009; Vovnyuk, 2007) or de nied (Horita et al., 2002) by dif fer ent au thors. Dis cus sions re sult from the as sump tion that the chem i cal com po si tion of brines in these in clu sions was changed due to depressurizing dur ing their stretch ing or par tial crack ing. This re sulted from in clu sion brine stud ies of chev ron ha lite from de pos its that have dif fer ent in clu sion phase com po si tions in var i ous parts (in one part of the de posit in clu sions are sin gle-phase liq uid and in the other they also con tain a gas phase). As these, in stances are from the Neo gene of Transcarpathia (Kityk et al., 1983; Shaidetska, 1997) and from the Perm ian and Tri as sic of West ern Eu rope (Kovalevych et al., 2002a, b, 2009; Vovnyuk, 2007) we as - sume that salt de posit over heat ing to rel a tively low tem per a - tures (100–120°C) did not re sult in brine chem is try changes sig nif i cant enough to be rec og nized by ex ist ing meth ods. In fact, the anal y ses showed iden ti cal brine com po si tions (ma jor ion ra tios) in these two types of in clu sions in each de posit. In - clu sion brines with a gas phase from Messinian salts of the Red Sea showed a chem i cal com po si tion very close to that of mod - ern sea wa ter, which also in di cates that this type of in clu sion is suit able for an cient sea wa ter chem is try re con struc tion (Kovalevich et al., 1997; Horita et al., 2002). Be fore us ing
two-phase in clu sions for an cient sea wa ter chem is try eval u a tion it is im por tant to make sure that the liq uid/gas phase ra tio is equal in all in clu sions from a given sam ple and that the in ner pres sure is rel a tively low (i.e., it is close to at mo spheric – in such a case the gas bub ble vol ume will not ex ceed 1% of the in - clu sion vol ume).
A very in ter est ing phe nom e non can be re corded in chev ron ha lite from the over heated de pos its – a mi gra tion of in clu sions along a ther mal gra di ent (Roedder, 1984). Larger in clu sions move faster to wards higher tem per a tures and on their way they
“eat” smaller in clu sions, leav ing a trace formed of clear in clu - sion-free ha lite (Fig. 5C). Ob vi ously such an in clu sion can merge with in clu sions of other ge netic types re sult ing in change of its brine com po si tion.
There are the re cords of tec tonic im pact in chev ron ha lite from most an cient salt de pos its, such as chev ron axis dis place - ment along healed microfaults (Fig. 5D) or in di vid ual healed faults vis i ble as chains of in clu sions cross ing the chev ron in ir - reg u lar di rec tions (Fig. 5E). Some times, later, a post - sedimentary or i gin of in di vid ual in clu sions lo cated in side chev rons is shown by the pres ence of a xenogenic phase, oil or bi tu men for ex am ple (see Fig. 5C). This is why the best way to avoid prob a ble er rors is to choose for study, if pos si ble, only ideal chev rons, with out any vis i ble trace of de for ma tion or mi - gra tion, free of healed faults and built up with in clu sions of reg - u lar cu bic shape and sim i lar size.
INCLUSIONS IN RECRYSTALLIZED HALITE
It is dif fi cult to find very well-pre served chev rons in many an cient evaporites. This is ex plained by ha lite’s abil ity to recrystallize eas ily at early stages of diagenesis and dur ing later post-sed i men tary stages, in con di tions of in creas ing pres sure and tem per a ture or tectonism. As the re sult of recrystallization, ha lite grains be come clear and in clu sion-free. Lo cally this pro - cess af fects only pe riph eral parts of the grain, leav ing a relic of
Fig. 3. Thin sec tion pho to graphs of ver ti cally ori ented chev ron crys tals
A – bed ding per pen dic u lar (and growth di rec tion par al lel – up ward) cut through chev ron ha lite grains which are elon gated along the [110] axis, lower Perm ian Solikamsk Ba sin, Rus sia. Un der ly ing Salt Mem ber; B – frag ment of chev ron tex ture with rhyth mic band - ing out lined by tiny pri mary brine in clu sions, lower Perm ian Dnipro-Donets Ba sin, Ukraine. Slovyans’k Suite, Nadbryantsiv Bed, Volodars’k Mine
Fig. 4. Chev ron tex tures with dif fer ent in ner struc ture
A – chev ron tex ture out lined by tiny and rel a tively large pri mary fluid in clu sions (with out rhyth mic band ing), lower Perm ian Dnipro-Donets Ba sin, Ukraine, Slovyans’k Suite, Bryantsiv Bed, Sverdlov Mine; B – frag ment of chev ron tex ture out lined by dif fer ently sized pri mary brine in clu sions, smaller in the right part of the tex ture and larger in its left part, Carpathian Foredeep, Po land, Bochnia de posit, Badenian; C – poorly vis i ble chev ron tex ture out - lined by a few rel a tively large fluid in clu sions, up per Perm ian Del a ware Ba sin, USA, Salado For ma tion, WIPP Stor age, 655.3 m; D – chev ron tex ture with rare large pri mary brine in clu sions on a back ground of nu mer ous small ones, lower Perm ian Dnipro-Donets Ba sin, Ukraine, Slovyans’k Suite, Bryantsiv Bed, Sverdlov Mine; E – chev ron tex ture with grad ual in crease of in clu sion size from chev ron axis out wards, Eocene Navarra Ba sin, Spain, Biurrun bore - hole, sam ple Bi-415; F – frag ment of chev ron ha lite crys tal with a trace of dis so lu tion (ar rowed) dur ing the crys tal growth, up per Perm ian (Zechstein) Ba - sin, Miłoszewo ONZ1 bore hole, depth 1293.0 m (Old est Ha lite Na1)
Fig. 5. Pri mary (sed i men tary) and postsedimentary fluid in clu sions within, or ad ja cent to, chev ron ha lite
A – pri mary fluid in clu sions with daugh ter crys tals of sylvite (ar rowed) in a growth band of chev ron ha lite, up per Perm ian (Zechstein) Ba sin, West Po land, Older Ha lite, Na2, Lelechów 4 bore hole, depth 1066.7 m; B – frag ment of chev ron tex ture out lined by two-phase (liq uid + gas) pri mary in clu sions, gas bub bles (black) are well seen in larger in clu sions, Messinian ha lite from the Red Sea (DSDP site 225; sam ple 23-225-29-3,101-103); C – an oma lously large sec ond ary fluid in clu sion with trails of its mi gra tion within a growth band of chev ron ha lite, bi tu men par ti cles and oil drop let (black) cov ered by bi tu - men crust are vis i ble in the cen tral part of the large in clu sion, lower Perm ian Solikamsk Ba sin, Rus sia, Pot ash mem ber; D – chev ron tex ture of ha lite dis - turbed by microfaults, up per Perm ian (Zechstein) Ba sin (Old est Ha lite, Na1 of Peri-Bal tic area), Po land, Zdrada IG 6 bore hole, depth 867.5 m; E – healed microfault (ar rowed) cross ing a growth band of chev ron ha lite, sec ond ary brine in clu sions lo cated along the frac ture are of ir reg u lar or elon gated shape, in - clu sion-free zone of trans par ent recrystallized ha lite is vis i ble par al lel to the fault, Carpathian Foredeep, Po land, Bochnia de posit, Badenian; F – relic of chev ron tex ture in the mid dle part of a ha lite grain sur rounded by sol i tary gas-brine in clu sions in trans par ent ha lite, up per Perm ian (Zechstein) Ba sin, West Po land, Chartów 2 bore hole, depth 2724.0 m (Basal Anhydrite A2)
chev ron tex ture in the cen tral part of the grain; a relic is sur - rounded by trans par ent clear ha lite (Fig. 5F). But of ten, mostly in salt domes, rock salt con sists of grains of clear, fully recrystallized ha lite. Grain shape be came elon gated along bed - ding, and some times lenses of trans par ent gi ant-crys tal line ha - lite ap pear. In recrystallized ha lite, fluid in clu sions also oc cur, but they are rel a tively rare, sol i tary or in small groups (Fig. 6A–D). Only some times their re la tion to healed faults is vis i ble (Fig. 6B). In di vid ual in clu sions, lo cally reach ing sev - eral milli metres in size, usu ally have ir reg u lar shapes. Of ten in - side these in clu sions anhydrite daugh ter crys tals or gas bub bles are ob served (see Fig. 6A–D). In po tas sium-bear ing zones postsedimentary in clu sions may con tain sylvite or car nal lite daugh ter crys tals, and when salt strata are lo cated close to hy - dro car bon de pos its oil drop lets or bi tu men glob ules may oc cur (Fig. 6C, D; Kovalevych et al., 2008).
The above-de scribed va ri ety of ha lite-hosted postsedi - mentary in clu sions can be lo cated in side a chev ron tex ture and thus they are very dif fi cult to de ter mine in as much as healed faults are not al ways vis i ble, and the shape of these in clu sions can be close to the shape of pri mary in clu sions. There fore, the de ter mi na tion of the ge netic type of such in clu sions should be
based on other cri te ria, such as in ner pres sure, brine sat u ra tion with gases, phase com po si tion, and the chem i cal com po si tions of brine and gases. Pri mary in clu sions, formed at the sed i men - tary stage, are char ac ter ized by low pres sure (close to at mo - spheric) and their brine com po si tion is close to those of other pri mary in clu sions from the same de posit (or from the other de - pos its of the same age). The chemistry of gases dis solved in postsedimentary in clu sion brines is of ten char ac ter ized by an el e vated meth ane con tent. Thus, there is a set of cri te ria for the pri mary or i gin of fluid in clu sions in ha lite, but they re quire de - tailed re search into both chev rons and in di vid ual in clu sions.
Un for tu nately, con vinc ing ev i dence of the pri mary or i gin of stud ied in clu sions are rather the ex cep tion than the rule in the lit er a ture, and in some cases the pri mary or i gin of in clu sions is based only on their lo ca tion in side chev rons.
In evaporite de pos its where pri mary in clu sions con tain a gas phase due to over heat ing, the later postsedimentary in clu - sions will also have this, but these in clu sions will dif fer from pri mary ones by el e vated in ner pres sure. Some times the open - ing of such in clu sions pro vokes the mo men tary “boil ing up” of brines or even their ejec tion.
Fig. 6. Fluid in clu sions of dif fer ent phase com po si tion in recrystallized ha lite
A – group of vari ably-sized liq uid in clu sions with gas bub bles (ar rowed) in recrystallized ha lite. Anisotropic crys tals (a) (anhydrite ?) oc cur in some of the in clu sions. Many in clu sions, es pe cially large ones, are of ir reg u lar or slightly elon gated shape.
Also, a chain of some in clu sions re lated prob a bly to a healed crack can be traced. Lower Cam brian, East ern Of fi cer Ba sin, South Aus tra lia, Manya 6 bore hole, depth 1329.7–1349.8 m, crossed polars; B – large sol i tary fluid in clu sions of ir reg u lar shape with ap par ent re la tion to a healed frac ture along the bound ary be tween two ha lite grains. Lower Cam brian East Si be ria Ba sin, Rus sia, Tyret’ De posit, com plex V; C – sol i tary three-phase in clu sion with a bi tu men glob ule (1) and a gas bub ble (2), in trans par ent ha - lite crys tal from the salt suc ces sion over ly ing a hy dro car bon ac cu mu la tion, up per Perm ian (Zechstein) Ba sin West Po land, Barnówko 5 bore hole, depth 3063.1 m (Basal Anhydrite A2); D – large sol i tary fluid in clu sions (in recrystallized ha lite) with gas bub bles (ar rowed) and car nal lite crys tals (c), crossed polars, Up per Or do vi cian Can ning Ba sin, West ern Aus tra lia, Gingerah Hill 1 borehole, depth 1345.8–1345.9 m
EVALUATION OF DATA SETS AND CONCLUSIONS
An a lyt i cal data avail able in lit er a ture have been ob tained by dif fer ent au thors and by dif fer ent meth ods. Ev i dently all these data are close to the true ion com po si tion in in clu sions (within an a lyt i cal er rors), in as much as all the meth ods were ver i fied on ar ti fi cial brines or on in clu sions in mod ern ha lite of known brine com po si tion. Fur ther more, an a lyt i cal data au then tic ity is shown by re cent stud ies con ducted us ing two meth ods (UMCA and Cryo-SEM-EDS) on the same sam ples (Kovalevych et al., 2005), and also by iden ti cal re sults, ob tained by dif fer ent au thors (and dif fer ent meth ods) for the same for ma tions or the for ma - tions of the same age (see, for in stance, Kovalevich et al., 1998;
Zim mer mann, 2000; Horita et al., 2002). This is shown also by reg u lar pat tern of sec u lar vari a tions of ma jor ion ra tios in Phanerozoic evaporite ba sin brines (Kovalevich et al., 1998;
Lowenstein et al., 2001, 2003; Horita et al., 2002).
Er rors in anal y ses of in di vid ual in clu sions or groups of in - clu sions usu ally oc cur due to er ro ne ous ge netic type de ter mi - na tion. This es pe cially con cerns large in clu sions (>250 mm across) when they are con sid ered pri mary. In clu sion brine com po si tion in the same ha lite crys tal can dif fer de pend ing on in clu sion ge netic type (Kovalevych and Hauber, 2000;
Kovalevych et al., 2002b, 2009). Ap par ently these in di vid ual er rors cause the vari abil ity in pub lished data sets. These dif fer - ences be come ev i dent dur ing anal y sis of nearly all data sets, ir -
re spec tive of method used or age of stud ied evaporite de pos its, al though they be come par tic u larly ap par ent when large in clu - sions were stud ied. These in di vid ual er rors in side large sets of data on pri mary in clu sion brines usu ally do not im pact av er age val ues used for global con clu sions. The av er age val ues based on small num bers of anal y ses should be con sid ered with care when they do not fit the known pat tern of chem i cal evo lu tion of ba sin brines. For eval u a tion of small de vi a tions be tween evaporite de pos its that are close in age it is needed to have a con sid er able num ber of an a lyt i cal re sults and only those in clu - sions that are un doubt edly pri mary can be used for anal y ses.
These cri te ria for an a lyt i cal data eval u a tion are based on the as sump tion that evaporite ba sin brines did not un dergo sig nif i - cant changes of ma jor ion ra tios dur ing ha lite pre cip i ta tion (up to K-Mg salt fa cies) when sea wa ter was the main source for salt pre cip i ta tion. Pri mary in clu sions in pri mary bed ded ha lite are real rel ics of con cen trated sea wa ter or are very close to it as re - gards ma jor ion com po si tion. De spite the im pact of lo cal fac - tors, data on in clu sion brine com po si tion in ma rine ha lite are rep re sen ta tive for eval u a tion of two cy cles in chem i cal evo lu - tion of sea wa ter dur ing the Phanerozoic and for de tailed re con - struc tions of some time pe ri ods.
Ac knowl edg ments. We thank D. I. Cendón and G. Czapowski for their help ful re views and T. Peryt who pro - vided many sug ges tions to im prove the manu script.
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