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STU DIA GEO LOGICA PO LO NICAVol. 126, Kraków 2006, pp. 5–76.Hydrogeology and HydrogeochemistryEd ited by J. Dowgia³³oPart IIDorota KAC ZOR 1The sa lin ity of ground wa ter in Meso zoic and Ce no zoicaq ui fers of NW Po land – ori gin and evo lu tion 2(Figs 1–33; Tabs 1–4)Abstract. Chemi cal com po si tion of sa line ground wa ters oc cur ring in the Meso zoic de pos its of NWPo land, based on 285 ar chi val chemi cal analy ses from 113 deep bore holes, shows much simi lar itywithin par ticu lar aq ui fers. These are mostly chloride- sodium wa ters. Chloride- sodium- calciumwa ters pre domi nate only within the Lower Tri as sic aq ui fer. Chloride- sodium- magnesium wa tersap pear only at iso lated lo ca tions. All the wa ters stud ied are typi cal of a high min er ali za tion (TDS), thelat ter in creases with the aq ui fer depth up to a maxi mum of 328 g/dm 3 (Ob jez ierze IG-1 well). TheTDS of these brines, meas ured sys tem ati cally over the last 40 years at pro duc tion wells in the healthre sorts Ko³obr zeg, Ka mieñ Po mor ski, Œwi nou jœcie and Po³czyn Zdrój, is nearly con stant and di rectlypro por tional to the con cen tra tion of Cl – ion.The brines in Meso zoic aq ui fers of NW Po land are poly ge netic. Their main com po nents are fos silsea wa ter and me te oric wa ter. Holo cene in fil tra tion wa ter is a lo cal ad mix ture in the up per part of theMeso zoic suc ces sion only.The hy dro chemi cal in di ca tors (Br – :J – , Cl – :J – , Cl – :Br – , Ca 2+ :Sr 2+ , rNa + :rCl – ) and the iso topera tios of oxy gen, hy dro gen and stron tium sug gest that the sa lin ity of wa ters in the Meso zoic de pos itsis re lated to their ma rine ori gin and, to a lesser ex tent, to the dis so lu tion of Zechstein and Tri as sic salts.Dis so lu tion of Zechstein salts could oc cur in con tact zones with ground wa ters within the Meso zoicun til the chemi cal bal ance be tween them has been es tab lished. Such con tacts are cur rently ob served atbase of the Lower Tri as sic rock as well as in 18 salt struc tures pierc ing the Tri as sic aq ui fers. Brineswithin the Tri as sic rock con tain an ad mix ture of re sid ual (evaporite- related) liq uids as so ci ated withthe Zechstein and Tri as sic salt se ries.The sa line wa ters within the Meso zoic rock com plex are un der pres sure, which en ables theirup ward mi gra tion through a sys tem of frac tures and faults to wards the Ce no zoic aq ui fers. Thispro cess is most in tense in hydro geo logi cal win dows de vel oped in ar eas of ero sional re duc tion of theover ly ing Oli go cene clays on up lifted tec tonic blocks and salt- cored an ti clines.The ex tent of in creased ground wa ter sa lin ity zones in Ce no zoic de pos its de pends on flowdi rec tions in the ac tive cir cu la tion zones. There fore, these sa lin ity zones, which oc cupy 33% of thestudy area, do not al ways co in cide with the zones of brine as cen sion.1 In sti tute of Geo logi cal Sci ences, Pol ish Acad emy of Sci ences, ul. Twarda 51/55,00- 818 Warszawa, Po land; e- mail: dkacz@op.pl2 Manu script re ceived Oc to ber 16, 2006. Manu script ac cepted for pub li ca tion De cem ber 4th 2006.

6 D. KACZORThe as cent of sa line wa ter is haz ard ous to the qual ity of Ma jor Ground wa ter Res er voirs (MGR).This con cerns the MGRs of Uznam (101) and Wo lin is lands (102), Roœc ino (103) and Dêbno (134), aswell as large mu nici pal ground wa ter in takes, such as those in Œwi nou jœcie (“Wydrzany”), Wo lin,Trze bi atów, Gry fice, Ko³obr zeg (“Roœciêc ino” and “Bo gu cino”), Koszalin, Go leniów, Nowo gard,Gry fino (“Tywa” and “Dolna Odra”), Krzypnica, Star gard Szcze ci ñski, Choszc zno, Wa³cz andCzarnków lo ca tions.Key words: Ground wa ter, sa lin ity, brine as cen sion, NW Po land.INTRODUCTIONThe knowl edge of the ori gin, chemi cal com po si tion, and con di tions of oc cur -rence of sa line ground wa ters in the Meso zoic de pos its of NW Po land is im por tantfor proper ground wa ter man age ment. These wa ters have been util ized for salt pro -duc tion in Ko³obr zeg since the 8th cen tury (Le cie jewicz, 1960). Be gin ning fromthe 19th cen tury, they have been ex ploited for thera peu tic pur poses in the health re -sorts of Ko³obr zeg, Ka mieñ Po mor ski, Œwi nou jœcie and, af ter World War II, also atPo³czyn Zdrój. By the end of the 20th cen tury, brines from the Meso zoic de pos itshave be come the sub ject of in ter est as a source of ther mal en ergy, e.g. in geo ther malheat ing plants at Pyrzyce and Star gard Szcze ci ñski. Pro duc tion of this en ergy is fa -voured by suit able geo logi cal con di tions in the area.The knowl edge of geo logi cal con di tions un der which the brines oc cur has a cru -cial sig nifi cance for proper man age ment of fresh ground wa ter. As cend ing brinesare haz ard ous to the qual ity of us able aq ui fers (Kac zor, 2005). Due to this pro cess, anumber of ground wa ter in takes have al ready been closed in West Pom era nia, e.g.those at Œwi nou jœcie, Ka mieñ Po mor ski, Strze¿ewo, ¯ó³cin, and Bia³ogard. There -fore, the rec og ni tion of zones of as cen sion of sa line wa ters and the de ter mi na tion ofmecha nisms of this pro cess are of par ticu lar im por tance for the pro tec tion of us ableground wa ter re serves.The main pur pose of this pa per is to elu ci date the ori gin of sa lin ity of ground wa -ters in the Meso zoic de pos its of NW Po land, and to char ac ter ize sa lin ity of the as so -ci ated Ce no zoic aq ui fers that are in flu enced by as cend ing brines. The study areacov ers ap proxi mately 26,000 km 2 , be ing con fined by the Bal tic Sea coast line, thestate bor der with Ger many, the Warta and No teæ River val leys, and the me rid ian 17E (Figs 1, 2). The pa per sum ma rizes data con cern ing the chemi cal com po si tion ofground wa ters in the Meso zoic aq ui fers and in the health re sort in takes (the lat terwere collected over the last 40 years). The pa per also ad dresses im por tant prob lemsof sa lin ity caused by an thro po genic con tami na tion, as well as the sa lin ity re lated tocoastal in tru sions of Bal tic sea- water. The avail able hy dro chemi cal data were care -fully se lected and veri fied in an at tempt to elimi nate meas ure ments in di cat ing thatthe sa lin ity origi nates from the above- mentioned sources. Pos si ble haz ard to theMa jor Ground wa ter Res er voirs and to the main ground wa ter in takes due to de vel -op ment of the up ward mi gra tion of sa line wa ters from the Meso zoic aq ui fers isdiscussed.

SALINITY OF GROUNDWATER, NW POLAND 7Fig. 1. Geo log i cal map of NW Po land with out Ce no zoic de pos its (af ter Dadlez ed., 2000)The main sub ject of in ter est of the pres ent pa per is ground wa ter from Meso zoicfor ma tions, with ref er ence to the defi ni tion of sa line wa ter pre sented in the Hydro -geo logi cal Glos sary (Dow gia³³o et al., ed., 2002). For Ce no zoic aq ui fers, ground -wa ter with con cen tra tion of chlo ride ion >30 mg/dm 3 , caused by brines as cend ingfrom the Meso zoic com plex, was taken into con sid era tion. This bound ary value iscon sid ered to be in dica tive of a de vel op ing pro cess in sali ni za tion of us able freshground wa ters (Ma cioszc zyk, 1991; Grube, 2000; Gór ski, 2001).PREVIOUS RESEARCHSci en tific pa pers pub lished in the 18th and 19th cen tu ries gave de scrip tions ofnu mer ous nat u ral springs and out flows of sa line wa ters, sin gle chem i cal anal y ses of

8 D. KACZORFig. 2. Sketch map of tec tonic units of the study area (af ter Po¿aryski, ed., 1974)brines as well as in di cated halophyte sites near Mrze¿yno, Ko³obrzeg, Bia³ogard,Pyrzyce and Miedwie Lake (Brüggemann, 1799; Ascherson, 1859; Deecke, 1898).Halophytes are salinity indicator plants for near-surface groundwater. Research onand prospection for ther a peu tic wa ters, bi tu mens and ther mal wa ters gave rise to anum ber of re ports de scrib ing oc cur rence con di tions of sa line wa ters in the Pol ishLow lands (Œwidziñski, 1954; Kolago, 1957, 1964; Dowgia³³o, 1961, 1965a, b;Bojarski & Depowski, 1963; Pazdro & Agopsowicz, 1964; Depowski et al., 1965;Bojarska & Bojarski, 1968; Bojarski, 1966, 1970, 1993; Bojarski et al., 1977;D¹browski, 1973; P³ochniewski & Stachowiak, 1980; Soko³owska & Soko³owski,1990; Górecki (ed.), 1995; Górecki & Szczepañski, 1991; Soko³owski et al., 1993,1995; Bojarski & Soko³owski, 1994; Soko³owski, 1997; Kapuœciñski et al., 1997:Bojarski & Sadurski, 2000).The prin ci pal pro cesses con trol ling the for ma tion of sa line wa ters and brines arethe fol low ing ones: sea wa ter evap o ra tion, dis so lu tion of salt-bear ing rocks, re ac -tions be tween wa ter and the rock, and mem brane fil tra tion (Land & Prezbindowski,1981; Leœniak, 2005; Stoessell & Moore, 1983; McCaffrey et al., 1987; Con nollyet al., 1990a; Fisher & Boles, 1990; Fontes & Matray, 1993a, b; Nativ, 1996; Chi &Savard, 1997; Davisson et al., 1994; Davisson & Criss, 1996; Branks et al., 2002;Tijani, 2004). Sea wa ter re tained in the rock and dis so lu tion of ha lite are the sources

SALINITY OF GROUNDWATER, NW POLAND 9of ground wa ter sa lin ity, most of ten re ported by re search work ers (Egeberg &Aagaard, 1989; Fisher & Boles, 1990; Davisson et al., 1994; Nativ, 1996; Chi &Savard, 1997; Branks et al., 2002; Tijani, 2004).There are two dom i nant hy poth e ses in the de bate on the causes of sa lin ity in wa -ters within Me so zoic aqui fers of the Pol ish Low lands. In nu mer ous, par tic u larlyear lier pa pers, a view was ex pressed that the sa lin ity re sulted from dis so lu tion ofZechstein salts by me te oric wa ter cir cu lat ing within the rock mass – see Samsonowicz(1928, 1954), Œwidziñski (1954), Kolago (1957, 1964), Dowgia³³o (1965a),Kleczkowski (1966), Prochazka (1970), Zuber & Grabczak (1991), Krawiec(1999a, b), Krawiec et al. (2000), Kwaterkiewicz et al. (1999, 2000). An es sen tialrole of fos sil sea wa ter in the evo lu tion of chem i cal com po si tion of brines was pos -tu lated by Dowgia³³o (1965b, 1971, 1988), Paczyñski & Pa³ys (1970), Dowgia³³o& Tongiorgi (1972), Kleczkowski (1979), Macioszczyk (1979), Weil (1981), andSzpakiewicz (1983). Re sults of iso to pic in ves ti ga tions of ground wa ter, first car riedout on sam ples from Po land by Dowgia³³o (1971), had a fun da men tal sig nif i cancefor this hy poth e sis. De ter mi na tions of ox y gen, hy dro gen and sul phur sta ble iso topera tios gave rise to a con cept that sa line wa ters in Me so zoic de pos its of NW Po landare of a mixed or i gin (fos sil and me te oric wa ters) with a pre vail ing con tri bu tion ofcon nate sea wa ter or sea wa ter which in fil trated into consolideted rocks dur ingtrans gres sion pe ri ods (Dowgia³³o, 1971; Dowgia³³o & Tongiorgi, 1972; Ró¿-kowski & Przew³ocki, 1974). The hy poth e sis that the main com po nent of ground -wa ter within in the Me so zoic is a mix ture of fos sil wa ters, and that only groundwa -ters within the Triassic are dominated by residual (evaporite-related) liquids, wasconfirmed by the later work of Dowgia³³o (1988).The geogenic sa lin ity of wa ters within Ce no zoic aqui fers in the Pol ish Low -lands was ini tially seen as a re sult of dis so lu tion of salt struc tures (Gumu³ka, 1964;Prochazka, 1970). Sub se quently, some au thors pointed out to a pos si bil ity of up -ward mi gra tion of brines from Me so zoic rocks. Their chem i cal com po si tion in -volved mix ing of rel ict sea wa ter with so lu tions formed by leach ing of rock salt(Macioszczyk et al., 1972, 1980; Macioszczyk, 1973, 1979, 1980; Gmurczyk,1999). In the cen tral Wielkopolska re gion (West ern Po land), the de vel op ment ofground wa ter sa lin ity in the Mio cene aqui fer is re lated to faults and tec tonic de pres -sions ob served at the top of the Me so zoic se quence, whereas in the case of Pleis to -cene aqui fers – to discharge zones along river valleys (Górski, 1989).The pro cess of sa line wa ter as cen sion from Me so zoic rocks might have been in -ten si fied by Pleis to cene glacioisostatic move ments (Michalski, 1985; Michalski &Starnawska, 1987; Boniecka et al., 1988; Dowgia³³o et al., 1988a, 1990; Dowgia³³o& Nowicki, 1991, 1997). In the Bal tic coastal zone, wa ter sa lin ity in the Ce no zoicaqui fers could orig i nate from both the as cent of sa line ground wa ter and in gres sionsof Bal tic sea wa ter, as re ported by Matkowska (1983), K³yza (1988), Kucharski &Twarogowski (1993), Kachnic (1999), Krawiec (1999c), Kozerski & Kwaterkiewicz(1984, 1988, 1997), Zuber et al. (1988), Dowgia³³o et al. (1988b), Burzyñskiet al. (1999) and Kwaterkiewicz et al. (1999, 2000).A syn thetic char ac teri sa tion of sa line wa ters of Po land was also pre sented in a

10 D. KACZORnum ber of at lases (Dowgia³³o et al., 1974; Turek, ed., 1977; Górecki, ed., 1995;Bojarski, 1996; Paczyñski & P³ochniewski, 1996). Ar eas of in creased sa lin ity inus able aqui fers were shown in the Hydrogeological Map of Po land, scales1:200,000 and 1:50,000 pub lished by the Pol ish Geo log i cal Institute.DATA SOURCES AND RE SEARCH METH ODSThe pres ent re search was based on both un pub lished (ar chi val) and pub lisheddata, as well as on au thor’s own in ves ti ga tions.Un pub lished data were col lected from the fol low ing sources: Cen tral Geo log i cal Ar chives inWar saw, ar chives of the Oil & Gas Drill ing Com pany in Pi³a and Zielona Góra, BPiUBU “Balneoprojekt”in War saw, Geo log i cal En ter prise “Polgeol” in War saw, health re sorts of Kamieñ Pomorski,Ko³obrzeg and Po³czyn Zdrój, “Geotermia” En ter prises at Pyrzyce and Stargard Szczeciñski,Szczecin Voivodship Of fice and HY DRO Bank Da ta base (CBDH) in War saw. Ar chi val ma te ri alsin cluded pri mar ily geo log i cal logs and re sults of chem i cal anal y ses of ground wa ter from deepbore holes drilled by pe tro leum com pa nies (68) and the Pol ish Geo log i cal In sti tute (22), from healthre sort wells (13), geo ther mal drillings (6) and other wa ter wells (7650). Some in for ma tion was alsode rived from geo log i cal and hydrogeological documentations and re ports. Out of pub lished re ports,the fol low ing were used: “Pro file g³êbokich otworów wiertniczych Instytutu Geologicznego”(Bojarski, 1972 – Kamieñ Pomorski IG-1; Bojarski, 1973 – Szczecin IG-1; Bojarski, 1975 – WolinIG-1; Bojarski, 1977a – Chociwel IG-1; Bojarski, 1977b – Koszalin IG-1; Bojarski, 1979 – Po³czynIG-1; Bojarski, 1986 – Ustronie IG-1). The re search was also based on re sults of pub lished chem i calanal y ses (Dowgia³³o, 1965a, 1969; Szmytówna, 1970; Jarocka, ed., 1976) and iso to pic de ter mi na -tions (Dowgia³³o 1971; Dowgia³³o & Tiongiorgi 1972; Dowgia³³o, 1988; Zuber & Grabczak 1991;Krawiec 1999a, b, 2005; Krawiec et al., 2000; Krawiec & Dulski, 2004).The pres ent au thor also used re sults of 42 chem i cal anal y ses of ground wa tersam ples col lected by her self from Ce no zoic de pos its dur ing map ping work on themap sheets of Goleniów (191), Jenikowo (192) and Tucze (193) for pur poses of theHydrogeological Map of Po land, scale 1:50,000. These anal y ses were car ried out atthe Cen tral Geo log i cal Lab o ra tory of the Pol ish Geo log i cal In sti tute in War saw.The range de ter mi na tions in cluded: pH, con duc tiv ity, al ka lin ity, HCO 3 , SO 4 , Cl,NO 3 , NO 2 , F, HPO 4 , SiO 2 , NH 4 , Ca, Mg, Na, K, Fe, Mn, Zn, Cr, Cu, Pb, Sr, Ba, Aland B. Mea sure ments of sta ble ox y gen and hy dro gen iso tope ra tios were also donefor 3 wa ter sam ples col lected from the Li assic aqui fer of the geo ther mal wells GT-1at Pyrzyce (2 sam ples) and GT-1 at Stargard Szczeciñski (1 sam ple), and for 1 sam -ple from the Up per Cre ta ceous aqui fer of a well at Pniewo. In ad di tion, the ra tios ofstron tium iso topes87 Sr/ 86 Sr were mea sured in 2 sam ples taken from the Li assicaqui fer in well GT-1 at Pyrzyce and well “Ed ward II” at Kamieñ Pomorski. Iso to picre search was con ducted at the laboratories of the Institute of Geological SciencesPolish Academy of Sciences.The use of un pub lished ma te ri als was pre ceded by the as sess ment of their re li -abil ity. As far as data from wa ters oc cur ring within Me so zoic rock com plexes areconcerned, the results of chemical analyses performed by petroleum companieswere treated with spe cial cau tion. The pro cess of data se lec tion in cluded also a ver i -fi ca tion car ried out by Bojarski (1996) dur ing con struc tion of the “Hydrochemical

SALINITY OF GROUNDWATER, NW POLAND 11and hy dro dy namic at las of the Palaeozoic and Me so zoic and ascensive salinity ofground waters in Polish Lowlands”.The as sess ment of re li abil ity of wa ter data for in di vid ual Ce no zoic ho ri zons re -lied on elim i na tion of those re sults of anal y ses which could in di cate that wa ter sa -lin ity was caused ei ther by Bal tic sea wa ter in gres sions or by anthropogenicpollution.In elim i nat ing anal y ses which could sug gest the con tam i na tion by the Bal ticsea wa ter of chem i cal com po si tion of groundwaters in Ce no zoic aqui fers, depth tothe sam pled aqui fer and the Cl – ion con cen tra tion, were the main fac tors con sid -ered. The au thor used the same mode of in ter pre ta tion of the or i gin of ground wa tersalinization in coastal ar eas as that pre vi ously ap plied by Kwaterkiewicz et al.(1999, 2000) in the nearby £eba re gion. Ac cord ing to that in ter pre ta tion based oniso to pic de ter mi na tions, it was pos si ble to find out that the sa lin ity of the first, un -con fined, aqui fer is a re sult of the Bal tic sea wa ter in flu ence, whereas in the sec ondaqui fer, con fined by a sev eral tens of centi metres thick till layer, sa line ground wa -ter co mes from Me so zoic rocks. Fol low ing this as sump tion, the re sults of chem i calanal y ses of wa ter sam ples col lected from the un con fined aqui fer were elim i nated.The only mea sure ments used, were those of chlo ride con cen tra tion ex ceed ing theav er age ob tained for the Bal tic sea wa ter, i.e. 4000 mg/dm 3 (K³yza, 1988).Par tic u lar at ten tion was paid to the re sults of anal y ses of ground wa ter ex tractedfor pub lic use in cit ies where the prob a bil ity of anthropogenic pol lu tion of ground -wa ter is high. The ba sic in di ca tor of anthropogenic or i gin of chlo rides in ground -wa ter is an in creased con cen tra tion of sulphates and ni tro gen com pounds, as sug -gested by Macioszczyk (1991) and Górski (2001). Mea sure ments show ing theamount of ni trates in wa ter of >0.1 mg/dm 3 , and that of sulphates of >40 mg/dm 3 incon fined aqui fers, and 75 mg/dm 3 in unconfined ones, were rejected.Depths to the sam pled aqui fers and the lo cal land use pat tern were ad di tional cri -te ria taken into con sid er ation. The as sess ment of vari abil ity of chlo ride con cen tra -tions com bined with the depth to the aqui fer (Kaczor, 2005) shows that the de creasein Cl – con cen tra tions to the amount be low 30 mg/dm 3 takes place at depths of about25–35 m be low the sur face in the area con sid ered. In creased con cen tra tions of chlo -rides, re corded at greater depths, should rather be re lated to saline groundwater rise.To il lus trate chem i cal com po si tion of sa line ground wa ter within Me so zoic for -ma tions, 285 chem i cal anal y ses per formed in the years 1881–2002 were used. Thecol lected data en abled iden ti fi ca tion of chem i cal types of the wa ters us ing the clas -si fi ca tion of Shchukarev-Priklonsky (Priklonsky & Laptev, 1955). This clas si fi ca -tion is based on the most com monly de ter mined ions: Cl – , SO 4 –2 , HCO 3 – , Na + , Ca 2+and Mg 2+ found in amounts ex ceed ing 20% meq, assumintg that the to tal sums ofthese an ions and cat ions equiv a lents equal 100% each. The con cen tra tions of Na +and K + are pre sented jointly due to the usu ally small con tent of the K + and the dif fi -culty in its de ter mi na tions. The pres ent pa per de scribes the spa tial vari abil ity of theground wa ter chem i cal com po si tion in 8 ma jor Me so zoic aqui fers, pro vid ing mapsfor the best doc u mented aqui fers namely the Lower Triassic (see Fig. 6) and theLower Jurassic (see Fig. 7) ones.

12 D. KACZOROne of the au thor’s aims was to iden tify the re la tion ships be tween vari a tions inchem i cal com po si tion of ground wa ter and the tec ton ics of the Perm ian–Me so zoicstruc tural com plex. Thus, hydrochemical data are pre sented against the back -ground of the fault pat tern and salt tec tonic struc tures, in clud ing also the poorly de -vel oped ones (see Fig. 3). The pa per pro vides also char ac ter is tics of spa tial andtemporal variations in the total water mineralization of Mesozoic aquifers. The ver -ti cal vari abil ity in to tal min er al iza tion is pre sented on geo log i cal-hydrochemicalcross-sec tions (see Fig. 9–12) and in the graph show ing the ra tio be tween wa termin er al iza tion and depth (see Fig. 8). The tem po ral vari abil ity over the last 40 yearsis il lus trated in graphs show ing the vari a tion in to tal min er al iza tion of brines frompro duc tive wells in the Œwinoujœcie, Kamieñ Pomorski, Ko³obrzeg and Po³czynZdrój health resorts (see Fig. 13).An at tempt to ex plain the or i gin of ground wa ter sa lin ity of Me so zoic aqui ferswas based mainly on anal y sis of ge netic hydrochemical and iso to pic in di ca tors in -clud ing the most com monly ap plied ra tios: Br – :J – , Cl – :J – , Cl – :Br – , Ca 2+ :Sr 2+ andrNa + :rCl – . Re sults of four au thor’s own de ter mi na tions of sta ble iso topes of ox y genand hy dro gen, and 20 cou ples of pub lished de ter mi na tions (Dowgia³³o 1971;Dowgia³³o & Tiongiorgi 1972; Dowgia³³o 1988; Zuber & Grabczak 1991; Krawiec1999a, b, 2005; Krawiec et al., 2000; Krawiec & Dulski, 2004) were also used (seeTab. 2). The re la tions be tween 18 O to 2 H (see Fig. 18), 18 O and to tal min er al iza -tion (see Fig. 19), and be tween 18 O and the depth to the sam pled aqui fer (see Fig.20) were ana lysed. An at tempt was also made to cal cu late the 87 Sr to 86 Sr ra tio inground wa ter, com par ing the re sults with the av er age value of this ra tio in mod ernsea wa ter and in Phanerozoic sed i men tary rocks (see Figs 21, 22). The char ac teri sa -tion of ground wa ter sa lin ity in Ce no zoic de pos its is based on 7747 mea sure mentsof Cl – con cen tra tion, and on maps of Cl – con cen tra tion in groundwaters of Qua ter -nary (see Fig. 24), and Neo gene and Palaeogene aqui fers (see Fig. 32). The vari a -tion in sa lin ity dis played by groundwaters from Ce no zoic lay ers was dis cussedagainst the back ground of both the tec tonic set ting of Perm ian–Me so zoic formationsand a scheme of ground wa ter cir cu la tion sys tem in Ce no zoic de pos its(Paczyñski, ed., 1993).GEOLOGICAL SETTINGSub-Me so zoic base mentThe Zechstein salt-bear ing de pos its, which form the sub-Me so zoic base ment,are the most im por tant for ma tion in volved in the dis cus sion on the or i gin ofsalinization of ground wa ter. The Zechstein sec tion in cludes rocks of the Werra,Stassfurt, Leine and Aller cyclothems (Marek & Pajchlowa, eds, 1997). The top ofthe Zechstein strata lies at depths rang ing from 500 m be low sea level in the north -ern part of the Pom er a nian Synclinorium to > 4000 m be low sea level in theSzczecin Synclinorium, ris ing over the Goleniów salt stock up to 690 m be low sealevel (Jaskowiak-Schoeneichowa, ed., 1979). The Zechstein suc ces sion is rep re -

SALINITY OF GROUNDWATER, NW POLAND 13sented by rock salt and po tas sium-mag ne sium salts with lime stone, anhydrite, do -lo mite and clay in ter ca la tions.Me so zoic for ma tionsLower Tri as sic de pos its are rep re sented by a mudstone-claystone-sand stonecom plex. The Röth (Lower Tri as sic) sec tion of the Szczecin Synclinorium in cludestwo evaporitic se ries com posed of rock salt and an hyd rites with in ter ca la tions ofdolomites, marls and clastics, 5 to 47 m thick (Jaskowiak-Schoeneichowa, ed.,1979). In the Pom er a nian Anticlinorium and Synclinorium, claystones with anhydriticcon cen tra tions are equiv a lent to the evaporitic se ries (Dadlez, ed., 1976;Raczyñska, ed., 1987). Mid dle Tri as sic de pos its are rep re sented by marly lime -stones with clastic ad mix ture, and by claystones and dolomites with abun dantanhydritic con cen tra tions. These rocks oc cur through out the whole re gion, ex ceptfor the area of well de vel oped salt diapirs in the cen tral part of the SzczecinSynclinorium (Marek & Pajchlowa, eds, 1997). The Up per Tri as sic sec tion con -sists of the Keuper sand stone-claystone de pos its with plant re mains, the lower gyp -sum beds (claystones with anhydrite, gyp sum, do lo mite and sand stone in ter ca la -tions) and the up per gyp sum beds (claystones with anhydrite and gyp sum con cen -tra tions). The two lat ter are sep a rated by sand stone-mudstone rocks of the “reedsand stone” (Dadlez, ed., 1976; Jaskowiak-Schoeneichowa, ed., 1979; Raczyñska,ed., 1987). The over ly ing Rhaetian rocks are rep re sented largely by var ie gateddolomitic claystones with con glom er ate and sand stone in ter ca la tions and con cen -tra tions of coalified plant de tri tus.The Lower Ju ras sic de pos its are com posed of quartz sand stones, most fre -quently fine-grained, dolomitic, si der it ic and cal car e ous, interbedded by claystoneand mudstone con tain ing plant re mains, py rite con cre tions and spherosiderites.Thick ness of the Li assic suc ces sion var ies from 20 m in the Pom er a nian Synclinoriumto 1100 m in the Pom er a nian Anticlinorium. Near Œwidwin, and close to theGoleniów salt diapir, these rocks were re moved by ero sion (Dadlez, ed., 1976;Jaskowiak-Schoeneichowa, ed., 1979; Raczyñska, ed., 1987). The Mid dle Ju ras sicde pos its are rep re sented mainly by claystones and mud shales ac com pa nied byfine-grained sand stones with plant de tri tus, rang ing in thick ness from about 10 m toover 500 m. The Upper Ju ras sic rocks are pre served in the Szczecin and Pom er a -nian synclinoria, in the east ern part of the Fore-Sudetic Monocline, along slopes ofthe Pom er a nian Anticlinorium, and in the Trzebiatów Syncline (see Fig. 1). Theycon sist of mudstones, marls, sand stones and claystones over lain by car bon ates,marls, mudstones, and fine-grained sand stones with glauconite, as well as bydolomites, marls and lime stones. An evaporitic se ries (Up per Portlandian) rep re -sented by gyp sum and anhydrite beds is ob served in the south-east of the SzczecinSynclinorium and near Szczecinek.The Cre ta ceous de pos its oc cur in the Szczecin and Pom er a nian synclinoria, theFore-Sudetic Monocline and in the Trzebiatów Syncline of the Pom er a nian Anticlinorium(see Fig. 1). Lower Cre ta ceous com plex is rep re sented by marly

14 D. KACZORclaystones and sandy-cal car e ous mudstones with bi valve shell de tri tus, over lain byclaystones with sid er ite in ter ca la tions and fine-grained sand stone. The Up per Cre -ta ceous suc ces sion is com posed of car bon ate rocks (chalk, marls, lime stones withflints), gaizes, marly claystones and mudstones com monly con tain ing glauconiteand quartz grains. Lo cally sandstones and sandy limestones occur.The above-de scribed li thol ogy of the Me so zoic suc ces sion makes it pos si ble todraw some palaeohydrogeological con clu sions con cern ing the area un der con sid -er ation. Through most of the Me so zoic era, ma rine con di tions pre vailed over thearea under consideration. Thus, mainly seawater filled the sedimentary basins,while intercalations of salt and sulphate rocks indicate periodical increases in watersa lin ity due to in tense evap o ra tion. Only dur ing the Late Rhaetian and, pe ri od i -cally, dur ing the Early and Mid dle Ju ras sic and the Early Cre ta ceous, non-ma rinecon di tions pre vailed over the area, while the ma rine ba sin was con fined to the deep -est zones of the Mid-Pol ish Trough (Marek & Pajchlowa, eds, 1997). In fil tra tion ofrain wa ter, caus ing re moval of con nate sea wa ter from the top most part of the geo -log i cal sec tion, was possible only during relatively short periods.Cenozoic depositsThe Palaeogene and Neo gene sed i men tary cover of the Me so zoic com plexshows nu mer ous ero sional hi a tuses (see Figs 24, 32). The lon gest one cov ers north -ern part of the Pom er a nian Synclinorium (Ciuk & Piwocki, 1988), shorter hi a tuseshave been rec og nized over the Szczecin Synclinorium near Œwinoujœcie and oversalt-cored anticlines of Nowe Warpno, Szczecin, Gryfino and Choszczno (Kurzawa,2000, 2003). The Palaeogene and Neo gene de pos its, 100 to 200 m thick, arerep re sented mostly by sands, grav els, muds and clays (Ciuk, 1972). The LowerOligocene (Rupelian) clays and claystones (“septarian clays”), and brack ish siltstonescor re spond ing to the “Toruñ clays” (Peryt & Piwocki, ed., 2004), which sep -a rate Ce no zoic aqui fers from the Me so zoic ones con tain ing sa line wa ters, are im -por tant in terms of sa lin ity of Ce no zoic wa ters caused by ground wa ter as cent. The“septarian clays” are best de vel oped over the Szczecin Synclinorium with the av er -age thick ness of 62 m, lo cally ex ceed ing 100 m. In the east of the study area, thereoc cur the “Toruñ clays” (Czempiñ For ma tion), from sev eral m. to over 50 m thick.In the south-east ern area, ground wa ter occuring within Qua ter nary sed i ments ispro tected by up to 50 m-thick Lower Plio cene clays and muds, the so-called “var ie -gated clays”.The Qua ter nary de pos its are a con tin u ous com plex com monly less than 100 mthick (max i mum 237 m), de creas ing to sev eral tens of metres and even be low 10 min the up lifted north ern area of the Pom er a nian Anticlinorium and over salt-coredanticlines (Kurzawa, 2000). The Pleis to cene suc ces sion in cludes 10 gla cial till ho -ri zons rep re sent ing the Narew, San, Nida, Odra, Warta and Vistula glaciations, andac com pa nied by sandy-grav elly and muddy-clayey glaciofluvial and ice-dam lakese ries (Mojski, 1984). The Ho lo cene sec tion con sists mainly of organogenic de pos -

SALINITY OF GROUNDWATER, NW POLAND 15its (peat and gyttja) and a sev eral metres thick sandy-muddy se ries filling rivervalleys and lake basins.Tectonic settingAs far as the sub-Perm ian struc tural pat tern is concerned, the study area is lo -cated within the West Eu ro pean Palaeozoic Plat form, and its east ern ex tremes ad -join the mar ginal zone of the East Eu ro pean Pre cam brian Plat form (Dadlez, 1974).The area in cludes parts of the four sec ond-or der tec tonic units: the Pom er a nian andSzczecin synclinoria, the Pom er a nian Anticlinorium and the Fore-Sudetic Monoclinealong with the Gorzów Wielkopolski Block (Po¿aryski, ed., 1974). Bound arybe tween the Pom er a nian Synclinorium and the Pom er a nian Anticlinorium runsalong the Karlino-Szczecinek fault zone, be tween the Pom er a nian Anticlinoriumand the Szczecin Synclinorium – along the Œwinoujœcie-Drawsko fault zone, andbe tween the Szczecin Synclinorium and the Fore-Sudetic Monocline – along thePyrzyce-Krzy¿ zone. The south ern bound ary of the Gorzów Wielkopolski Blockruns along the Lower Warta fault zone as iden ti fied on seis mic pro files (Fig. 2).The trends, na ture and pa ram e ters of the ma jor fault zones are in ad e quatelyknown. The most com pre hen sive char ac ter is tics re fers to those sec tors of faultswhich sep a rate the Pom er a nian Anticlinorium from the Szczecin and Pom er a nianSynclinoria; this ar eas was well ex plored by seis mic sur veys. These faults cross thePalaeozoic base ment and the en tire Me so zoic se quence, and their pres ence is man i -fested by var ied re lief and struc tural fea tures of the top sur face of the Me so zoiccom plex. The scale of up lift or throw along the fault planes, de fined by Dadlez(1987) as the in ver sion di men sion, is 1500–2000 m in the coastal Bal tic Sea re gion,and up to 3000 m in cen tral and south-east ern parts of the Pom er a nian Anticlinorium.The downfaulting and shift ing of faulted blocks re sults in for ma tion of asystem of mobile blocks.The Mid-Pol ish Trough de vel oped at the end of the Car bon if er ous be tween themar ginal zone of the East Eu ro pean Plat form and the Variscan orogen. Its ax ialzone ap prox i mately co in cides with the pres ent-day po si tion of the Pom er a nianAnticlinorium (Marek & Pajchlowa, eds, 1997). Since the Zechstein, through theLate Cre ta ceous, the Mid-Pol ish Trough was the main path way for ma rine trans -gres sions, be ing sub ject to load-in duced sub si dence due to in creas ing burial. Dur -ing the Late Cre ta ceous, the trough be gan to in vert, re sult ing in an up lift of the Pom -eranian Anticlinorium. Intense erosional processes affected the Cretaceous andJurassic rocks during Early Tertiary times.Typ i cal tec tonic fea tures of the north ern area of the Pom er a nian Anticlinoriumare synsedimentary grabens de vel oped dur ing the Late Tri as sic and Early Ju ras sic(Dadlez, 1987). The graben-bound ing faults show a near-me rid i o nal ori en ta tionand are ob served in the ar eas of Kamieñ Pomorski, Trzebiatów and Ko³obrzeg (Fig.3). In this sec tor of the Mid-Pol ish Trough, the most in tense fault ing, reach ing deepbase ment, oc curred dur ing the Perm ian. Dur ing Late Cre ta ceous, these faults be -came re ac ti vated (Krzywiec, 2000). The best sur veyed Perm ian–Me so zoic faults

16 D. KACZORwhich fol low the sub-Perm ian frac ture sys tem are those in the Pom er a nian Anticlinorium(Dadlez, ed., 1976). Trends of youn ger faults only partly co in cide withsub-Perm ian dis con ti nu ity zones, be ing of ten in de pend ent of older faults. Alsofault throw di rec tions have changed through time. Ac tive faults transecting the Me -so zoic for ma tions could play a role of mi gra tion path ways for brines, al though, insome cases, they could also act as hy dro dy namic bar ri ers. Closer iden ti fi ca tion oftheir sig nif i cance for the de vel op ment of salinization affecting groundwater inMesozoic aquifers is, however, difficult.Block move ments of the sub-Zechstein base ment trig gered pro cesses of mi gra -tion of Zechstein salt. These pro cesses have con tin ued since Late Tri as sic, re sult ingin de for ma tion of the over ly ing rock se ries (Dadlez, 1979). Salt move ments gaverise to the for ma tion of salt struc tures, i.e. con vex forms such as salt-cored anticlinesand domes (Dadlez & Jaroszewski, 1994). The salt body may partly or com -pletely pierce the over ly ing rocks, or oc curs as swells with out break ing the con ti nu -ity of the over ly ing strata. When pierc ing the over bur den, the salts form salt plugs(salt diapirs) that in clude salt stocks (oval in plan view) and salt walls (elon gated inshape). Domed salt bod ies which de vel oped with out pierc ing through the over bur -den are re ferred to as salt pil lows (more or less iso met ric forms) or salt walls (ani so -met ric in shape). In the area of the max i mum thick ness of Zechstein de pos its,within the so-called cen tral zone of salt tec ton ics, there are salt walls and stocks partlypierc ing the Me so zoic overburden, mostly the Lower Triassic rocks (see Fig. 3).These are salt plugs of: Grzêzno, Oœwino, Maszewo, Drawno, Goleniów, Wierzchos³awiec,Nowogard, Ostrzyca, Dominikowo, Cz³opa and Szamotu³y, and small, close-to-faults salt in tru sionsnear Przytór, Miêdzyzdroje, Dargob¹dz and Kodr¹b. Poorly de vel oped struc tures, rep re sented by saltwalls and pil lows not pierc ing Me so zoic rocks, oc cur in the so-called mar ginal zone of salt tec ton ics.These are salt pil lows of: Po³czyn, Barwice, Lotyñ, Œwidwin, Rokita, Resko, £obez, Drawsko, Pi³a,and the salt walls of Krajenka and Miros³awiec-Trzcianka, lo cated in the east ern mar ginal zone. Saltpil lows of Nowe Warpno, Krakówko, Maszewo, Gryfino, Pyrzyce, Marianowo, Recz, Choszczno,Widuchowa, Banie, Lipiany, Karsk, Pe³czyce, Drezdenko, Chojna, Myœlibórz, Dêbno, Cedynia andCzelin, and salt walls of P³awno and Szczecin were de vel oped in the west ern marginal zone.The move ment of salt, largely be long ing to the cyclothem Z2 (Leine), oc curredsince the Late Tri as sic. The pro cess was most in tense dur ing the Late Tri as sic andLate Cre ta ceous times. A first gen er a tion of salt walls and pil lows de vel oped withinthe cen tral zone of salt tec ton ics dur ing the Late Tri as sic. Sub se quently, theyevolved into salt stocks and walls dur ing the Late Cre ta ceous (Dadlez, 1979). Qua -ter nary glacioisostatic pro cesses as so ci ated with ice-sheet load ing-deloading cy -cles (Liszkowski, 1993), reactivatied salt tec tonic move ments, as ev i denced bythick ness re duc tion and strati graphic hi a tuses ob served in the Pleis to cene sec tionabove salt-cored anticlines as compared with synclinal areas (Kurzawa, 2003).HYDROGEOLOGICAL CONDITIONSWa ter-bear ing Me so zoic de pos its, rep re sented largely by sand stones withinterbedding mudstone-claystone se ries, and by Mid dle Tri as sic, Ju ras sic and Cre -

SALINITY OF GROUNDWATER, NW POLAND 17ta ceous car bon ate rocks, oc cur over most of the study area, ex cept for the north ernand cen tral parts of the Pom er a nian Anticlinorium where Cre ta ceous and Mid dle toUp per Ju ras sic de pos its were re moved by ero sion. Near Œwidwin and Czaplinek,there are also small ar eas lack ing Lower Ju ras sic and Up per Tri as sic de pos its. In thewest of the Fore-Sudetic Monocline, no Mid dle to Up per Ju ras sic and Lower Cre ta -ceous rocks oc cur. The Me so zoic rocks con tain pre dom i nantly sa line wa ters andbrines. Nonsaline (fresh) groundwaters have been found only in the north ern part ofthe Pom er a nian Anticlinorium which is de void of Palaeogene and Neo gene de pos -its and cov ered only by a thin Pleis to cene se quence. Depths to the nonsaline wa tersrange here be tween 300 and 500 m be low sur face, as for ex am ple near Œwidwin,Szczecinek and Pi³a (Turek, ed., 1977). Of par tic u lar sig nif i cance is the Li assicaqui fer be ing the ma jor res er voir of ther mal wa ters in the Pol ish Low lands, withgeo ther mal gra di ents rang ing from 1.5 to 5.5°C/100m (Górecki, ed., 1995). Theper cent age con tri bu tion of thick ness of wa ter-bear ing sand stone lay ers in theLower Ju ras sic sec tion var ies be tween 50 and 80%. Con sid er able re sources of ther -mal wa ters are also stored in the Lower Cre ta ceous aqui fer.Water-bearing Cenozoic deposits are represented mainly by Miocene sands,subordinately by Oligocene sands and Pleis to cene glaciofluvial sands interbeddedby poorly per me able gla cial tills. They are sat u rated with fresh wa ters re charg ingus able aqui fers. Only in ar eas of slow wa ter ex change, these groundwaters are col -oured and show in creased min er al iza tion and oxidability (Macioszczyk et al.,1972; Górski, 1989). Groundwaters are con fined, ex cept of shal low aqui fers, mostof them oc cur ring in river valleys (Malinowski, ed., 1991).Both re gional and lo cal ground wa ter sys tems may be ob served in the study area.A re gional sys tem con sists of sa line wa ters stored in Me so zoic de pos its. It is re -charged di rectly through in fil tra tion of me te oric wa ter in ar eas of aqui fer out cropslo cated in the Fore-Sudetic Monocline, the north ern mar gin of the Holy Cross Mts,the Suwa³ki-Mazury El e va tion and the £eba El e va tion (Bojarski & Sadurski, 2000;Malicki & Szczepañski, 1991). In di rect re charge oc curs by in fil tra tion of wa terthrough Ce no zoic de pos its. The vari abil ity in re duced ground wa ter heads of theLower Ju ras sic (Fig. 4) and the Lower Cre ta ceous aqui fers (Fig. 5) sug gests thatbrines of the Me so zoic com plex mi grate very slowly north wards, to wards the Bal -tic Sea. These groundwaters are con fined and their head gra di ent ranges be tween0.9x10 3 and 1.1x10 3 hPa/10m (Bojarski, 1996). The ground wa ter ta ble in most ofthe tested wells sta bi lizes within Ce no zoic de pos its above the top of the Me so zoicrocks. In the wells Kamieñ Pomorski IG-1, Ustronie IG-1 (see Fig. 9), Huta Szklana1 (see Fig. 12), “Ed ward II” in Kamieñ Pomorski, “Józef” in Dziwnówek,“Anastazja” in Podczele (see Fig. 9), B-1 and B-2 in Ko³obrzeg, Jatki II, GoœcinoIG-1, Ko³obrzeg PN1, Jarkowo 1, Gorzów Wielkopolski IG-1, Marianowo 1 (seeFig. 10) and Pi³a IG-1 (see Fig. 11), spon ta ne ous out flow of brines was ob served, oreven oc curs at pres ent. This in di cates fa vour able con di tions of their as cent to wardsus able aqui fers. Through close-to-faults and highly frac tured zones, the brines mi -grate up wards, from Me so zoic into the Ce no zoic aqui fers, to be mixed with freshwa ters in the ac tive cir cu la tion zone. Wa ters of this zone form lo cal ground wa ter

18 D. KACZORFig. 4.1995)Hy dro dy namic field of the Lower Ju ras sic geo ther mal wa ter res er voir (af ter Górecki, ed.,sys tems in clud ing ei ther par tic u lar aqui fers or their groups. The de gree of ground -wa ter salinization within Ce no zoic de pos its due to the as cent of brines de pends onthe dis tance trav elled by sa line so lu tions which un dergo di lu tion within the ground -wa ter res er voir. There fore, the up ward mi gra tion of brines does not ev ery- wherelead to no tice able salinization of us able aquifers.Flow di rec tions of groundwaters within the Ce no zoic com plex of the study areaare con trolled both by the po si tion of the Odra and Warta river val leys and by the vi -cin ity of the Bal tic Sea coast – see Fig. 24 (Paczyñski, ed., 1993). In lower-or derground wa ter res er voirs, these di rec tions are re lated to the po si tion of lo cal re chargeand dis charge zones. The Drawsko Lakeland is such a re charge area sup ply ingground wa ter to the Ce no zoic aqui fers, where the high est re corded ground wa ter ta -ble al ti tude reaches 140 m above sea level (Paczyñski, ed., 1993). This is also anarea of deep in fil tra tion of fresh wa ters into Me so zoic aqui fers (Dowgia³³o, 1965a),as ev i denced by the Po³czyn 2 well ex tract ing an al most fresh wa ter from the Up perTri as sic aqui fer at depths of 711–767 m below the surface (Krawiec & Dulski,2004).

SALINITY OF GROUNDWATER, NW POLAND 19Fig. 5. Hy dro dy namic field of the Lower Cre ta ceous geo ther mal wa ter res er voir (af ter Górecki,ed., 1995)CHEMICAL COMPOSITION OF GROUNDWATERSIN MESOZOIC AQUIFERSCom po si tion of groundwaters oc cur ring within Me so zoic aqui fers is based onthe re sults of 285 chem i cal anal y ses. These wa ters are mostly of the Cl-Na, type al -though the Cl-Na-Ca wa ter is dom i nant in the Tri as sic aqui fer (Tab. 1). Only thewa ter anal y ses from the bore holes Przytór 1 and Sadlno 1 (Lower Tri as sic aqui fer),Cz³opa 3 and Dargob¹dz 2 (Lower Ju ras sic aqui fer) re vealed the pres ence ofCl-Na-Mg type wa ter with high Mg (>20 meq%). In Cre ta ceous aqui fers, a lo cal in -flu ence of fresh meteroric wa ter in fil tra tion is marked. It re sults in the for ma tion ofCl-HCO 3 -Na wa ters (Oœwino IG-1, Biesiekierz 1 and Rokita IG-1 bore holes). Sa -line groundwaters in Me so zoic aqui fers are char ac ter ised by a high to tal min er al -iza tion reach ing 328 g/dm 3 (Objezierze IG-1 bore hole – see Fig. 6). Their chem i calcom po si tion shows much sim i lar ity within both par tic u lar strati graphic units andma jor struc tural units within the Me so zoic com plex (see Tab. 1). The most fre quentare Cl – an ions with con cen tra tion rang ing from 54.2 to 99.7 meq% (see Tab. 1). Bi -

20 D. KACZORAquiferUpperCretaceousUpperJurassicMiddleJurassicLowerJurassicUpperTriassicMiddleTriassicTable 1Chem i cal com po si tion of sa line groundwaters in Me so zoic aqui fersChemical typeofgroundwaterNumberofanalysesTDSg/dm 3Cl-Na 8 5.5 - 63.9Cl-HCO 3-Ca-Na1 3.8Cl-HCO3-Na 2 1.0 - 1.9Cl-Na 1214.0 -125.7Cl-Na 12 4.7 - 104.4Cl-Na 27 8.8 - 161.7Cl-Mg 1 169.0Cl-Na 54 3.0 - 173.9Cl-Na-Ca-Mg 1 148.0Cl-Na-Mg 1 65.0Cl-Mg-Na 1 112.0Cl-Na 29Cl-Na-Ca 449.8 -299.244.0 -199.9Cl-Na-Mg 1 170.9Cl-Na 531.0 -140.4Cl-Na 2 88.8 - 96.7Cl-Na-Ca 1 32.8Abridged notation of chemical compositionmeq %IodineBromineconcentrationconcentramg/dm3mg/dm 3Cl 74.7-99.1 SO 4 0.7-6.1 HCO 30.0-15.7Na 80.7-97.6 Ca 1.2-10.1 Mg 0.1-9.0 3.0 - 532.8 0.5 - 1.5Cl 58.7 SO 4 13.6 HCO 326.8Na 40.2 Ca 59.8 33.3Cl 54.2-77.7 SO 4 0.1-3.4 HCO 322.2-42.3Na 85.1-89.2 Ca 5.7-7.1 Mg 3.5-8.4 2.0Cl 92.2-99.2 SO 0.2-5.8 0.0-5.84 HCO 3 10.0 -Na 83.9-96.7 Ca 0.6-8.5 Mg 0.2-9.8 325.02.1 - 3.6Cl 90.4-99.1 SO 4 0.6-4.9 HCO 30.2-8.5Na 74.6-96.7 Ca 3.7-11.9 Mg 2.0-15.4 7.9 - 106.6 3.9Cl 84.8-99.5 SO 4 0.0-6.2 HCO 30.0-10.4Na 82.6-95.3 Ca 3.8-13.2 Mg 1.4-9.1 9.0 - 120.0 2.0 - 7.1Cl 91.5 SO 4 7.7 HCO 30.2Na 14.9 Ca 2.3 Mg 82.7 1492.0Cl 84.7-99.4 SO 4 0.2-7.2 HCO 30.0-11.4Na 69.8-97.6 Ca 1.5-13.1 Mg 0.9-19.8 1.3 - 239.7Cl 99.0 SO 4 0.5 HCO 30.1Na 48.8 Ca 23.5 Mg 27.7 729.4Cl 94.0 SO 4 2.9 HCO 33.0Na 61.9 Ca 6.9 Mg 30.2 114.4Cl 91.6 SO 4 7.2 HCO 30.4Na 21.4 Ca 3.8 Mg 74.8 879.1Cl 85.4-99.7 0.4SO -6.9 0.0-8.54 HCO 3 39.9 -Na 63.7-97.6 Ca 1.9-18.0 Mg 0.8-17.8 479.5Cl 97.8-98.9 SO 0.8-1.5 0.0-0.54 HCO 3 136.5 -Na 68.3-74.1 Ca 21.2-23.7 Mg 2.1-9.1 670.0Cl 94.7 SO 4 4.8 HCO 30.3Na 71.2 Ca 4.0 Mg 24.5 466.2Cl 96.9-98.7 SO 1.1-2.2 0.0-1.24 HCO 3 59.9 -Na 71.7-91.6 Ca 6.9-18.0 Mg 1.5-10.3 366.0Cl 96.3-96.6 SO 3.2-3.4 0.14 HCO 3 193.0 -Na 78.2-79.5 Ca 14.3-14.60 Mg 5.5-7.1 233.0Cl 98.8 SO 4 0.4 HCO 30.6Na 64.7 Ca 20.4 Mg 14.9 53.2LowerCretaceous0.3-16.02.2 -10.72.52.7 - 3.1

SALINITY OF GROUNDWATER, NW POLAND 21car bon ates and sulphates show a much smaller con tri bu tion, com monly below1 meq%. In creased con cen tra tions of bi car bon ates above 20 meq% were re cordedonly in sev eral ground wa ter sam ples taken from Cre ta ceous de pos its, and the max i -mum value re corded was 42.3 meq% (Oœwino IG-1 bore hole). The high est amountof sulphates – 526 meq/dm 3 (18.5 meq%) – was found in the Lower Tri as sic aqui fer(Gozd 3 bore hole). The most com mon cat ion Na + , is dom i nant in all aqui fers. Itsshare var ies be tween 14.9 to 97.6 meq% (see Tab. 1). The cal cium con tri bu tion issmaller, rang ing from sev eral to a dozen or so meq% (1619 meq/dm 3 in the LowerTri as sic aqui fer – Huta Szklana 1 bore hole). The share of Mg +2 is 0.2–30.2 meq%,ex cept for the Mid dle and Lower Ju ras sic aqui fers where it amounts to 82.7 meq%and to 74.2 meq%, re spec tively (the Dargob¹dz 2 bore hole, see Tab. 1). Sa line wa -ters within the Me so zoic com plex are char ac ter ised by high con cen tra tions ofbiophile el e ments such as bro mine and io dine. The max i mum bro mine con cen tra -tion reaches 2000 mg/dm 3 (Po³czyn IG-1 bore hole), the io dine con cen tra tion co -mes up to 17.0 mg/dm 3 (Moracz IG-1 bore hole). Both max ima were found in theLower Tri as sic aqui fer (see Tab. 1). Chem i cal anal y ses of cu ra tive wa ters pro ducedby wells in health re sorts pro vided also data on the con cen tra tions of stron tium(39.0–285.0 mg/dm 3 ), lith ium (

22 D. KACZORshows the min er al iza tion of 58.6 g/dm 3 , while at a depth of 1436–1441 m be low thesur face in the same aqui fer – 298.4 g/dm 3 (see Fig. 11). Such an in crease in min er al -iza tion along a rel a tively short depth in ter val sug gests the de vel op ment of a min er -al iza tion au re ole due to leach ing of salts from the Cz³opa salt wall. Sim i lar signs ofthe Zechstein salts leach ing can be in ferred from brine anal y sis of the Wolin IG-1borehole where, in the Lower Jurassic aquifer, the maximum water mineralizationof 173.9 g/dm 3 (see Fig. 12) was re corded at a depth of 1240–1309 m be low the sur -face. This bore hole was drilled close to a small close-to-fault salt struc ture ofMiêdzyzdroje, within which the top of Zechstein salt oc curs at the depth of 1460 mbe low the sur face, and is di rectly over lain by Up per Ju ras sic de pos its. A dis tinct in -crease in wa ter min er al iza tion was also ob served in brines from the Up per Ju ras sicaqui fer of the bore holes Grzêzno 5 (89 g/dm 3 ), Oœwino IG-1 (96 g/dm 3 ) andChociwel 3 (104.4 g/dm 3 ) – see Fig. 10, drilled near the Grzêzno and Oœwino saltdiapirs (see Fig. 3). In the case of other salt struc tures con sid ered, no rep re sen ta tivedata are avail able. In ar eas of weakly de vel oped salt walls and pil lows, no dis tinctin crease in wa ter min er al iza tion has been ob served. This is best pro nounced in theLower Tri as sic aqui fer which is in a di rect con tact with salts of these struc tures (seeFig. 6). How ever, the lack of drillings above the salt walls and pil lows does not al -low to prove such re la tion ship. Highly min er al ized ground wa ter of 314 g/dm 3 wasob served only near the P³awno salt wall (Huta Szklana 1 bore hole), sug gest ing oc -cur rence of salt dis so lu tion (see Fig. 6). High min er al iza tion val ues (>200 g/dm 3 )were re corded also above the Drezdenko (Strzelce Krajeñskie IG-1 bore hole),Rokita (Rokita IG-1 and Moracz 1 bore holes) and Po³czyn salt pil lows (Po³czynIG-1 bore hole) – see Fig. 6.Re la tion ship be tween the min er al iza tion of sa line groundwaters in Me so zoicaqui fers and depth of their oc cur renceMin er al iza tion vari abil ity of wa ters within the Me so zoic com plex, in con nec -tion with depth of their oc cur rence, was ana lysed tak ing into ac count 220 de ter mi -na tions dis played as points on a graph (Fig. 8). A re gres sion line is de ter mined bythe lin ear equa tion: M = 0.08H –2.4 (where M stands for min er al iza tion, H – for thedepth to the sam pled aqui fer). This re la tion ship is most ap par ent within the depthin ter val of 800 to 1800 m be low the sur face within which the great est num ber ofpoints is grouped close to the re gres sion line. The in crease in min er al iza tion withdepth is less pro nounced at depths less than 800 m be low the sur face, which may bea re sult of me te oric wa ter re charge. Sim i larly, the re la tion ship is less pro nounced atdepths be low 1800 m be low the sur face. There are only few points sit u ated near there gres sion line, the other ones (those cor re spond ing to sam ples col lected mainlyfrom the Lower Tri as sic aqui fer) are shifted to the right of the line. This can sug gestan in creas ing min er al iza tion caused ei ther by an ad mix ture of strongly min er al izedre sid ual liq uids of the Zechstein ba sin (and, pos si bly, smaller, Tri as sic ba sin un der -go ing evap o ra tion), or by a con tact of these wa ters with Zechstein salts. The graph(see Fig. 8) also shows the re gres sion lines cal cu lated by Dowgia³³o (1971) for

SALINITY OF GROUNDWATER, NW POLAND 23Fig. 8.The re la tion ship be tween ground wa ter min er al iza tion and depth of oc cur rencegroundwaters in Me so zoic aqiufers of north ern Po land, and by Weil (1981) formin er al ized groundwaters oc cur ring within the War saw Trough. Com par i son ofthe curves in di cates that the in crease in min er al iza tion of groundwaters in Me so -zoic aqui fers with depth is most dis tinctly ex pressed in north-west ern Po land. Thisre la tion is also il lus trated in hydrogeochemical cross-sec tions (Figs 9–12) show ingthat wa ter min er al iza tion does not de pend ei ther on lith o logic or strati graphic fac -

24 D. KACZORtors. The con tours of ground wa ter min er al iza tion, cor re spond ing to the val ues of50, 100, 200 and 300 g/dm 3 , cross the bound aries of lithological com plexes andstrati graphic units. Ex am ples of a dis tinct in crease in min er al iza tion with depth areob served in the Ko³czewo 1, Ustronie IG-1 (see Fig. 9), Chociwel 3, Oœwino IG-1(see Fig. 10), Chabowo 3, Cz³opa 3, Cz³opa 1 and Pi³a IG-1 bore holes (see Fig. 11).The phe nom e non of min er al iza tion in creas ing with depth is typ i cal of deep sed i -men tary bas ins (Rittenhouse et al., 1969). It is of ten ex plained by the pro cess ofultrafiltration which re lies on pref er en tial sep a ra tion (re tain ing) of some ions,which are con tained in ground wa ter, by clay sed i ments act ing as semipermeablemem branes (Berry, 1969; Dowgia³³o, 1971, Hanshaw & Coplen, 1973; Kharaka &Berry, 1973; Graf, 1982; Philips & Bentley, 1987; Kharaka & Carothers, 1986;Hem, 1989; Drever, 1997). The course of this pro cess de pends pri mar ily on elec tro -chem i cal prop er ties of clay min er als, as well as on pres sure and tem per a ture withinthe res er voir, in par tic u lar dur ing com pac tion of sed i ments. Out of the ions con -tained in the brines in ves ti gated, Na + and Cl – ions are the most susceptible ones tobe retained.On the other hand, how ever, the ef fec tive ness of ultrafiltration pro cess and, firstof all, its abil ity to pro duce con sid er able vol umes of brines, has been chal lenged bysome au thors (Knauth & Beeunas, 1986; Egeberg & Aagard, 1989; Con nolly et al.,1990a; Fontes & Matray, 1993a; Hanor, 1994; Tijani, 2004). The main counter -argu ments against the sig nif i cance of the ultrafiltration pro cess are the lack of suf fi -ciently high pres sures, un usual in nat u ral geo log i cal con di tions (Knauth &Beeunas, 1986; Tijani, 2004), and the lack of clay de pos its in the lith o logic pro file(Land & Prezbindowski, 1981). Nev er the less, high pres sures oc cur withincompressional zones as so ci ated with tec tonic ac tiv ity. Such a compressional zoneex isted at the end of the Me so zoic in north-west ern Po land, as ev i denced both bythe de vel op ment of in ver sion faults cut ting the Perm ian–Me so zoic struc tural com -plex and its base ment, and by the evo lu tion of salt struc tures (Marek & Pajchlowa,eds, 1997; Krzywiec, 2000). The ultrafiltration pro cess in the area of in ter est couldhave also been fa voured by the lithological types of Me so zoic de pos its rep re sentedmainly by mudstone-claystone-sand stone com plexes. Car bon ate rocks are dom i -nant only in the Middle Triassic, uppermost Upper Jurassic and Upper Cretaceoussections.Vari abil ity in time of sa line ground wa ter min er al iza tionin Me so zoic aqui fersData con cern ing the vari abil ity in time of the to tal ground wa ter min er al iza tion,and its re la tion ship with the con cen tra tion of chlo rides, orig i nate from sys tem aticmon i tor ing car ried out dur ing the pe riod of 1959–2002 by the “Balneoprojekt” En -ter prise on me dic i nal wa ters in takes: “Ed ward II” at Kamieñ Pomorski, “B-1” and“Emilia” (No 6) at Ko³obrzeg, “Jantar” at Œwinoujœcie and Po³czyn IG-1 at Po³czynZdrój. The anal y ses are shown in the form of graphs il lus trat ing both vari a tions inmin er al iza tion and con cen tra tions of Cl – ion as a function of time (Fig. 13).

SALINITY OF GROUNDWATER, NW POLAND 25Fig. 13. Tem po ral vari abil ity in to tal min er al iza tion, and chlo ride ion con cen tra tion in brines frombore holes: “Ed ward I”, “Ed ward II” (A), Po³czyn IG-1 (B), “Jantar“ (C), B-1 (D), and “Emilia“ (E)

26 D. KACZORThe re sults of 6 anal y ses of brines from the Li assic aqui fer sam pled in the bore -hole “Ed ward I”, per formed in 1881–1961 (Dowgia³³o, 1965a) were also taken intocon sid er ation. Dur ing that pe riod, an ini tial in crease in the ground wa ter min er al -iza tion was ob served. It could have been a re sult of ex trac tion of sa line groundwa -ters from the aqui fer un til a bal ance be tween the well’s pro duc tion rate and in flowof min er al ized groundwaters has been es tab lished (Dowgia³³o, 1971). Since 1973,in ves ti ga tions of ground wa ter from this aqui fer were con tin ued in the bore hole“Ed ward II”, which re placed the well “Ed ward I”, as may be seen on the graph (seeFig. 13), min er al iza tion val ues fluc tu ate be tween 35.7 and 33.5 g/dm 3 , show ing noclear in creas ing or de creas ing trends. Small vari a tions of the or der of up to 1 g/dm 3in the years 1978, 1984 and 1987–1989 could also be a re sult of a higher wa ter with -drawal rate. The Cl – con cen tra tion was also al most con stant, rang ing be tween 21.4to 20.0 g/dm 3 , and its small vari a tions cor re late ex actly with fluc tu a tions in to talmin er al iza tion. The data show that the chem i cal com po si tion of sa line groundwa -ters from the Lower Ju ras sic aqui fer ex ploited at Kamieñ Pomorski is constant, andthere is no indication of an increased inflow of fresh meteoric waters.Ob ser va tions of brines from the Up per Tri as sic aqui fer sam pled at the Po³czynIG-1 bore hole in the Po³czyn Zdrój health re sort, re fer to in ves ti ga tions con ductedin the pe ri ods of 1966–1970, 1972–1975, 1983–1987, 1990–1992, 1994 and 1997.The to tal min er al iza tion and con cen tra tion of Cl – ion were nearly con stant throughthe whole pro duc tion pe riod (see Fig. 13), the first one vary ing be tween 76.6 g/dm 3(in 1985) and 74.0 g/dm 3 (in 1973). Even the change in the pro duc tion rate from 7m 3 /h to 2.3 m 3 /h, af ter the well ren o va tion in 1991 (Paczyñski & P³ochniewski,1996), did not af fect the chem i cal com po si tion of ex tracted ground wa ter. Thus, itcan be as sumed, that brines un der con sid er ation are well iso lated from other aqui -fers, in par tic u lar from the over ly ing Up per Rhaetian one, where in the wellPo³czyn 2 at a depth of 711–770 m be low the sur face fresh ground wa ter with themin er al iza tion of 0.74 g/dm 3 was found (Krawiec & Dulski, 2004). Wa ter anal y sesfrom the “Jantar” bore hole (depth of in flow 227.3–237.3 m), drilled in theŒwinoujœcie health re sort, were car ried out dur ing the years 1936–1967, 1969–1971, 1975 and 1992 (Jarocka, ed., 1976; Paczyñski & P³ochniewski, 1996). Thewa ter oc curs in a Lower Cre ta ceous aqui fer. Be fore 1967, its to tal min er al iza tionwas al most con stant rang ing from 34.3 to 35.0 g/dm 3 . Af ter 1969, it in creased to 42g/dm 3 , but over the next years it did not change con sid er ably, as ev i denced by anal -y ses car ried out in the years 1975 and 1992 (see Fig. 13). A pro nounced in crease inmin er al iza tion in 1969 might have been a re sult of an ad mix ture of ground wa tercom ing from a new, deeper well “Teresa” (No VI), ex tract ing wa ter of a highermin er al iza tion from the lower lower parts of the aqui fer. The con cen tra tion of Cl –ion in the Lower Cre ta ceous aqui fer changes pro por tion ally to the to tal min er al iza -tion. It means that in creased sa line ground wa ter production from the LowerCretaceous aquifer, did not cause any inflow of fresh bicarbonate groundwaterfrom overlying aquifers.Anal y ses of cu ra tive wa ter from the wells “Emilia” (No 6) and “Barnim” (B-1)were car ried out sys tem at i cally at Ko³obrzeg. The wa ter co mes from the Mid dle Ju -

SALINITY OF GROUNDWATER, NW POLAND 27ras sic aqui fer. Dur ing the first years of pro duc tion (1964–1968), a slight de crease inwa ter min er al iza tion was ob served in the B-1 well. Since 1969, the TDS has notchanged sig nif i cantly os cil lat ing around 54 g/dm 3 (see Fig. 13). In the years1990–1993, small fluc tu a tions in to tal min er al iza tion were ob served. They can beex plained by poor tech ni cal con di tion of the well which was about to be closed. Thechanges in Cl – con cen tra tion were pro por tional to the to tal min er al iza tion changes.Only in 1971, there was a dis pro por tional in crease in con cen tra tion of chlo rides inre la tion to the TDS. This might be a result of an analytical error.A de crease in min er al iza tion from 59 to 54 g/dm 3 , which oc curred dur ing the pe -riod of 1964–1968, was in ter preted by Dowgia³³o (1971) as caused by fresh en ing ofgroundwaters from the Li assic and Dogger aqui fers. Ac cord ing to this au thor, thefresh en ing might have been prop a gated from the out crops of Tri as sic rocks at thesub-Ce no zoic sur face ex tend ing near Czaplinek. How ever, re sults of the later in -ves ti ga tions con ducted over the next 25 years did not show any de crease in min er al -iza tion which could in di cate a fresh en ing of groundwater during that period.Re sults of chem i cal anal y ses of ground wa ter from the well “Emilia” were ini -tially show ing an in crease fol lowed by a de crease in to tal min er al iza tion (see Fig.13). The chem i cal com po si tion was sta ble only in 1976. The con cen tra tion of chlo -rides in the wa ter is pro por tional to the vari abil ity in total mineralization.The above data, col lected dur ing sev eral tens of years, show a con stant chem i calcom po si tion of brines ex tracted from the Lower Cre ta ceous, Mid dle Ju ras sic,Lower Ju ras sic and Up per Tri as sic aqui fers in the health re sorts con sid ered. The to -tal min er al iza tion was chang ing no tice ably only in the ini tial stages of brines pro -duc tion from the wells “Ed ward I” at Kamieñ Pomorski and B-1 and “Emilia” (no6) at Ko³obrzeg. These changes can be re lated to dis tur bances within the aqui fers,caused by in tense ground wa ter with drawal and its con strained in flow into the well;these dis tur bance events were fol lowed by rel a tively long pe ri ods of re dressed bal -ance of wa ter with drawal rate and its chem i cal com po si tion. The vari a tions in wa terTDS in the above-men tioned wells is gen er ally pro por tional to the vari a tions in Cl –con cen tra tion. It means that the pre sented data can not be a proof of mod ern in fil tra -tion of me te oric wa ters af fect ing the chem i cal com po si tion of brines. Thus, the de -crease in the to tal wa ter min er al iza tion ob served in the B-1 well at Ko³obrzeg doesnot seem to con firm the existence of a general saline water freshening process aspostulated by Dowgia³³o (1971).ORIGIN OF GROUNDWATER SALINITYWITHIN THE ME SO ZOIC COM PLEXHydrochemical indicesThe method of com par ing some ionic ra tios in sa line groundwaters with thesame av er age ra tios typ i cal of ocean wa ter is widely con sid ered to be a valu able toolin de ter min ing the or i gin of ground wa ter com po nents and of wa ter it self. Ac cord -ing to the com monly ap plied in ter pre ta tion, these ra tios, which are equal to, orlower than those of mod ern sea wa ter, are in dic a tive of the ma rine or i gin of the

28 D. KACZORFig. 14.Per cent age con tri bu tion of mea sure ments with val ues smaller than sea wa ter averageground wa ter. Cer tainly, ionic ra tios can not be con clu sive for univocal de ter mi na -tion of ground wa ter or i gin, es pe cially in case of a com plex palaeohydrogeologicalhis tory of a given area. Nev er the less, their in ter pre ta tion al lows in many cases tothrow some light on the his tory of wa ter, es pe cially within deep aqui fers, de privedof con tact with me te oric wa ter.Cl – /J – and Br – /J – ra tios. The Cl – /J – ra tios, based on 61 chem i cal wa ter anal y ses,vary from 682 to 41433, ly ing much be low the value of 3.8*10 5 which is typ i cal ofsea wa ter (Fig. 14). Br – /J – ra tios, cal cu lated from 60 wa ter anal y ses, range be tween

SALINITY OF GROUNDWATER, NW POLAND 291 and 633, and are con sid er ably smaller than the value of 1300 which re fers to theocean wa ter (see Fig. 14). Low val ues of these in di ces in re la tion to the val ues typ i -cal of ocean wa ters are as so ci ated with high con tents of io dine and bro mine ions de -rived from ac cu mu la tions of ma rine bio mass which re mains in res er voir sed i men -tary rocks (Rittenhouse, 1967; Dowgia³³o, 1969; Pich & Turek, 1972; Col lins,1975). These val ues re flect the ma rine or i gin of ground wa ter which re mains in con -tact with or ganic mat ter un der go ing de com po si tion. It can also in di cate the pres -ence of connate seawater preserved in Mesozoic deposits.Cl – /Br – ra tio. This is one of the most com mon in di ces used for iden ti fi ca tion ofthe or i gin of wa ters and their chem i cal com po si tion (White, 1965; Dowgia³³o,1971; Rittenhouse, 1967; Bojarski, 1996; D¹browski, 1973; Car pen ter, 1978; Con -nolly et al., 1990a; Zuber & Grabczak, 1991; Fontes & Matray, 1993a; Nativ, 1996;Drever, 1997; Razowska, 1999; Branks et al., 2002; Ró¿kowski, 2002; Tijani,2004). The sig nif i cance of this in dex re lies on the fact that its value is con stant insea wa ter un til the mo ment when pre cip i ta tion of ha lite be gins. More over, the pro -por tions be tween the two ions in sea wa ter do not change, even af ter its di lu tion byfresh in fil tra tion wa ter (Dowgia³³o, 1971; Fontes & Matray, 1993b). Due to par tic -u larly con ser va tive mode of be hav iour of Cl – and Br – ions in so lu tion, pro cesses oc -cur ring be tween wa ter and their res er voir rocks usu ally do not change their con cen -tra tions (Fontes & Matray, 1993b). The ex cep tions are the dis so lu tion of halite orthe alteration of organic matter trapped in rocks.The Cl – /Br – ra tios, cal cu lated on the ba sis of 179 anal y ses, vary be tween 25.6 to8477.0 show ing con sid er able vari a tions in par tic u lar Me so zoic aqui fers (see Fig.14). The cal cu lated val ues sug gest, gen er ally, the ma rine or i gin of ground wa terwithin Tri as sic aqui fers, and con firm, to a lesser ex tent, a dom i nant con tri bu tion offossil seawater within the Jurassic and Cretaceous aquifers. The predominance ofma rine wa ter in the Tri as sic aqui fers is cor rob o rated by the fact that the Cl – /Br – ra -tios are be low 300, i.e. be low the value char ac ter is tic of ocean wa ter. This con cerns85% of sam ples from the Lower Tri as sic aqui fer, 67% from the Mid dle Triassicaquifer and 70% from the Upper Triassic aquifer (see Fig. 14).Very low val ues of the Cl – /Br – ra tio (be low 200) were ob tained from 43 anal y ses(52%). This sug gests the pres ence of an ad mix ture of re sid ual (mother) liq uids ingroundwaters of the Tri as sic com plex; these liq uids could re main af ter the pre cip i -ta tion of Zechstein and, pos si bly, Tri as sic evaporites. Such re sid ual liq uids arechar ac ter ized by an es pe cially high con cen tra tion of bro mine and a low Cl – :Br – ra -tio (Sonnenfeld, 1984). The av er age con cen tra tion of bro mine in sea wa ter is 65mg/dm 3 . It in creases dur ing the evap o ra tion pro cess up to 10 000 mg/dm 3 (Col lins,1975). The con cen tra tion of bro mine in groundwaters can also in crease due torecrystallization of ha lite (Land & Prezbindowski, 1981; Stoessell & Car pen ter,1986; Land & Macpherson, 1992). How ever, in strongly min er al ized brines, bro -mine released from halite cannot significantly change their chemical compositionbecause the concentration of Br – in ha lite in the ini tial stage of its for ma tion ismerely 65–75 ppm, and in the fi nal stage – 200 ppm (Holser, 1979). The Cl – /Br – ra -tios in wa ters from the Tri as sic aqui fers con firm the as sump tions of Dowgia³³o

30 D. KACZOR(1971, 1988) and Szpakiewicz (1983), who postulated that these waters are amixture of fossil seawater and residual liquids.The chem i cal com po si tion of brines in Tri as sic aqui fers was also af fected by thedis so lu tion of Zechstein and Tri as sic salts, as ev i denced by high val ues of Cl – :Br –ra tio rang ing from 341 to 8477 in wa ters sam pled from the bore holes: Warnowo 1,Wysoka Kamieñska 4, Dargob¹dz 1, Bia³ogard 5, Czaplinek IG-1, Obrzycko 2,Strzelce Krajeñskie IG-1, Cz³opa 1, Chociwel 3, Pi³a IG-1, Brojce IG-1, Wierzchowo3 and Wierzchowo 9. The Warnowo 1, Wysoka Kamieñska 4, Dargob¹dz 1bore holes are close to salt stocks bor der ing on faults. The Cz³opa 1, Chociwel 3 andObrzycko 2 bore holes are sit u ated near the Cz³opa, Oœwino and Szamotu³y saltdiapirs. The Strzelce Krajeñskie IG-1 and Czaplinek IG-1 bore holes are close tosalt pil lows (see Fig. 3). All this sug gests that salt in these struc tures was un der go -ing dis so lu tion by groundwaters of the Tri as sic aqui fers. High Cl – :Br – ratios(1–853), typ i cal of ground wa ter from the Pi³a IG-1, Brojce IG-1, Wierzchowo 3and Wierzchowo 9 bore holes (see Fig. 3), might rather be re lated to leach ing theUp per Keuper sa lifer ous com plex close to the Midle Keuper “reed sandstone”aquifers.The Cl – :Br – ra tios, based on 74 anal y ses of ground wa ter taken from Ju ras sicaqui fers, are some what am big u ous as far as their con nec tion with fos sil seawaters iscon cerned. Only 23% of the to tal num ber of these ra tios are lower than 300, be ingthe typ i cal up per limit for sea wa ter. The per cent age con tri bu tions of such val uescal cu lated for the Lower, Mid dle and Up per Ju ras sic aqui fers are 23%, 18%, and33%, re spec tively (see Fig. 14). 77% of the to tal num ber of Cl – /Br – ra tios show val -ues >300. These val ues are com monly in ter preted as in dic a tive of the pres ence ofground wa ter whose chem i cal com po si tion was de ter mined by dis so lu tion of salts(Dowgia³³o, 1971; Sonnenfeld, 1984). How ever, groundwaters from the Ju ras sicaqui fers in the area are con sid ered not to be in a di rect con tact with Zechstein salts,so this in ter pre ta tion can not be ac cepted in dis crim i nately. The pro cess of salt rocksleach ing could oc cur only in the case of the Goleniów, Grzêzno, Oœwino andMiêdzyzdroje salt plugs pierc ing the Tri as sic se quence up to its top (see Fig. 3). Thehigh wa ter sa lin ity, re lated to leach ing these struc tures, has been doc u mented byanal y ses of ground wa ter from the bore holes: Wolin IG-1 near the Miêdzyzdrojesalt diapir; Oœwino IG-1 and Chociwel 3 near the Oœwino diapir (see Fig. 10);Grzêzno 5 over the Grzêzno salt plug (see Fig. 12). The Cl – /Br – ra tios de ter mined inground wa ter from these bore holes vary be tween 559 to 6687. Sim i larly, in groundwaters from the Cz³opa 1, Cz³opa 2 and Cz³opa 3 bore holes, drilled on the Cz³opasalt diapir (see Fig. 11), the Cl – /Br – ra tios range be tween 321 and 1744, also sug -gest ing the influence of salt rock dissolution on the chemical composition of waterswithin the Jurassic complexes.In the re main ing cases, high Cl – /Br – ra tios can not be un equiv o cally in ter pretedas a re sult of the dom i nant con tri bu tion of palaeoinfiltration wa ter to ground wa terin the Ju ras sic aqui fers, ei ther. Pen e tra tion of me te oric wa ter into highly con cen -trated so lu tions of chem i cal com po si tion cor re spond ing to that of brines due to pro -cesses of wa ter-rock in ter ac tion is com monly con sid ered as lit tle likely to oc cur

SALINITY OF GROUNDWATER, NW POLAND 31(Weil, 1981; Land & Prezbindowski, 1981. The in crease in con cen tra tion of Cl –ions in groundwaters within Ju ras sic aqui fers (as com pared to Br – ) with re la tion topri mary sea wa ter could have oc curred as a re sult of the ultrafiltration pro cess. Dur -ing this pro cess, an in crease in con cen tra tion of halo gens in wa ter oc curs ac cord ingto the fol low ing se quence: Cl – >Br – >J – >F – (Berry, 1969; Kharaka & Berry, 1973).The Cl – :Br – ra tios may also change due to the mix ing of so lu tions from dif fer ent,hy drau li cally connected aquifers and of different chemical compositions (Fontes &Matray, 1993a).In groundwaters from Cre ta ceous aqui fers, the Cl – /Br – ra tios were cal cu latedbas ing on 23 anal y ses; only 6 of them sup plied val ues

32 D. KACZORFig. 15.The re la tion ship be tween log [Cl – ] vs. log [Br – ] of sa line groundwaters in Tri as sic aqui fersFig. 16.The re la tion ship be tween log [Cl – ] vs. log [Br – ] of sa line groundwaters in Ju ras sic aqui fers

SALINITY OF GROUNDWATER, NW POLAND 33Fig. 17.aqui fersThe re la tion ship be tween log [Cl – ] vs. log [Br – ] of sa line groundwaters in Cre ta ceouslu tion of salt in well de vel oped diapirs by groundwaters. The graphs il lus trat ing there la tion ship be tween log a rithms of Cl – and Br – of groundwaters within the Ju ras sic(see Fig. 16) and Cre ta ceous aqui fers (see Fig. 17) show that the ma jor ity of pointsare situated above the seawater evaporation line, generally indicating the salt leach -ing pro cess (Car pen ter, 1978; Szpakiewicz, 1983; Con nolly et al., 1990a; Tijani,2004). How ever, due to the lack of any con tact of groundwaters col lected from theJu ras sic and Cre ta ceous aqui fers with Zechstein salts, it should be as sumed that themain rea son for their sa lin ity is a range of hydrochemical processes which havetaken place within the Upper Permian–Mesozoic system.meqNa + /meqCl – ra tio. An other in dex also fre quently used for ex pla na tion ofthe or i gin of groundwaters and their chem i cal com po si tion is the meqNa + /meqCl –ra tio (Dowgia³³o, 1971; Bojarski, 1996; Land & Prezbindowski, 1981; Egeberg &Aagaard, 1989; Con nolly et al., 1990a; Fisher & Boles, 1990; Zuber & Grabczak,1991; Davisson & Criss, 1996; Nativ, 1996; Tijani, 2004). It de fines the de gree ofal ter ation of ground wa ter’s chem i cal com po si tion. The al ter ation con sists in ionex change be tween so dium pres ent in the so lu tion and cal cium which is a rock com -po nent. This pro cess oc curs un der con di tions of ground wa ter long-term iso la tionfrom the zone of ac tive wa ter ex change, and it re sults in a de crease of Na + concentration with a si mul ta neous in crease in Ca 2+ con cen tra tion in wa ter in re la tion to itsother com po nents. This pro cess is man i fested by a de crease in the meqNa + / meqCl –ra tio. This de crease also oc curs as a re sult of albitization of plagioclases and po tas -sium feld spars (Land & Prezbindowski, 1981). Ac cord ing to Dowgia³³o (1971), ade crease in meqNa – /meqCl – ra tio with depth may in di cate an in creased res i dence

34 D. KACZORtime of groundwaters but it can also sug gest an in creased con tri bu tion of con natesea wa ter to the chem i cal com po si tion of groundwaters. The de crease in this ra tiowith in creas ing depth to the aqui fer is also typ i cal of groundwaters within the Me -so zoic for ma tions con sid ered in the pres ent study (see Fig. 14). It means that thechem i cal com po si tion of groundwaters from deeper-seated aqui fers was morestrongly al tered. An in creas ing num ber of meqNa + /meqCl – ra tios be low 0.86 mayalso be ob served in these aqui fers. This in di cates a grow ing role of fos sil sea wa terin brines of the lower part of the Me so zoic struc tural com plex. The pre dom i nanceof primary seawater is most distinctly accentuated by the chemical composition ofbrines within Tri as sic aqui fers, as ev i denced by the fact that in 80% of 97 wa teranalyses, the meqNa + /meqCl – ra tios are be low 0.86. In particular aquifers, thepercentages of such ratios are as follows: Lower Triassic – 90%, Middle Triassic –75%, Upper Triassic – 56% (see Fig. 14).De spite the ex is tence of con tacts of wa ters within the Tri as sic aqui fers androck-salt no meqNa + /meqCl – ra tio is close to 1, that is to the value com monly ac -cepted as in di cat ing the pro cess of salt leach ing by me te oric wa ters (Dowgia³³o,1969; Eugster & Jones, 1979). Rec og ni tion of this pro cess is here hin dered byion-ex change re ac tions caus ing the de crease in Na + con cen tra tion in the watersconsidered.The meqNa + /meqCl – ra tios in wa ters sam pled from the Lower Ju ras sic aqui ferare less un am big u ous, be cause for only 21% out of 59 anal y ses they were lowerthan 0.86, sug gest ing a ma rine or i gin of these wa ters. The per cent age con tri bu tionof such val ues for the Lower Ju ras sic is 20%, for the Mid dle Ju ras sic – 27%, and forthe Up per Ju ras sic – 14% (see Fig. 14). For groundwaters in the Cre ta ceous strata,only 4 of 28 anal y ses show the meqNa + /meqCl – ra tio be low 0.86, pre sum ably in di -cat ing a still smaller con tri bu tion of fossil seawater (see Fig. 14).The above-dis cussed meqNa + /meqCl – ra tios re flect the vari abil ity in chem i calcom po si tion of groundwaters within the Me so zoic com plex. Lower parts of this se -quence con tain groundwaters with a greater con tri bu tion of sea wa ter. Their chem i -cal com po si tions are al tered as com pared to those of mod ern ocean wa ter (meqNa + /meqCl – ra tio is com monly

SALINITY OF GROUNDWATER, NW POLAND 35IG-1, Oœwino IG-1 and Miêdzychód IG-1 bore holes (see Fig. 3) these ra tios ex ceed1, sug gest ing the pres ence of younger meteoric water admixture.Ca 2+ : Sr 2+ ra tio. The Ca 2+ :Sr 2+ ra tios cal cu lated for 27 ground wa ter sam plesvary from 0.5 to 194.2. In 77% of sam ples, these ra tios are be low 30.8, this valuebe ing typ i cal of ocean wa ter. This con firms fairly un am big u ously the pres ence offos sil sea wa ter in groundwaters of Me so zoic for ma tions (see Fig. 14). An in creasedcon cen tra tion of stron tium in the Tri as sic can also be re lated to the oc cur rence of re -sid ual liq uids, since the con cen tra tions of stron tium in the form of SrSO 4 de velop atthe ini tial stages of halogenesis (Dowgia³³o, 1969). En rich ment of wa ters in stron -tium, in di cated by Ca 2+ :Sr 2+ ra tios lower than 30.8, can also oc cur as a re sult of dis -so lu tion of gyp sum and anhydrite by me te oric wa ters. How ever, the Up per Tri as sicevaporitic com plex in the study area is not in con tact with such wa ters, which pre -cludes this kind of stron tium source. High con cen tra tions of cal cium and stron tiumin ground wa ter, as com pared to sea wa ter, can also be the re sult of diagenetic pro -cesses, mainly the dolomitization of cal cite (Stoessell & Moor, 1983; Fontes &Matray, 1993a). Car bon ate rocks are pre dom i nant in the Mid dle Tri as sic, Up per Ju -ras sic and Up per Cre ta ceous sec tions of the Mesozoic rock sequence (Jaskowiak-Schoeneichowa, ed., 1979; Marek & Pajchlowa, eds, 1997).Iso to pic in di ca tors of ground wa ter or i ginThe to tal num ber of ox y gen and hy dro gen iso to pic anal y ses in groundwaterscon sid ered avail able for the pres ent study was 24 pairs. The re sults are shown inTab. 1.On the graph (Fig. 18), the sta ble iso tope com po si tion of par tic u lar wa ter sam -ples con tent are plot ted along the cal cu lated line ful fill ing the equa tion 2 H=6.8 18 O–4.7, which runs be low the Global Me te oric Wa ter Line (GMWL). This de -viation indicates that waters considered are isotopically heavier than the recent me-Fig. 18.The re la tion ship be tween 18 O and 2 H vs. the global me te oric wa ter line (GMWL)

36 D. KACZORNoTable 2Deu te rium and 18 O in wa ters of the Me so zoic aqui fers from north-west ern Po landBoreholeTestintervaldepth mbelowsurfaceDate ofsamplingStratigraphyTDS(g/dm 3 ) 18 O(‰) 2 H(‰)Datasource(according toreferences)1 2 3 4 5 6 7 8 91 Po³czyn IG-11a22aPo³czyn IG-1Kamieñ Pomorski IG-1(Miêdzywodzie)Kamieñ Pomorski IG-1(Miêdzywodzie)3 Ko³obrzeg B-118.07.1968 1175.0 -1235.011.09.2000UpperTriassic(Keuper)74-3.3 -26-3.7 -27.2Dowgia³³o, 1971;Dowgia³³o &Tongiorgi, 1972Krawiec & Dulski,200419.07.-4.5 -33 Dowgia³³o, 19711968 977.0 - Middle93.51035.0 Triassic1997 -4.8 -36.0 Krawiec, 1999 b17.07.1968-5.4 -44Dowgia³³o, 1971;Dowgia³³o &Tongiorgi, 19723a Ko³obrzeg B-1 1973 -5.3 -38 Dowgia³³o, 198884.5 - Middle553b Ko³obrzeg B-1 1974 101.5 Jurassic-5.4 -49 Dowgia³³o, 19883c Ko³obrzeg B-1 1980 -6.7 -50Zuber & Grabczak,19913d Ko³obrzeg B-1 1997 -6.5 -49.0 Krawiec et al., 20004 Kamieñ Pom "Edward I"18.07.1968 LowerJurassic38-7.4 -56Dowgia³³o, 1971;Dowgia³³o &Tongiorgi, 19724a Kamieñ Pom "Edward I" 1973 -7.0 -52 Dowgia³³o, 198855a5b5cKamieñ Pom. "EdwardII"Kamieñ Pom. "EdwardII"Kamieñ Pom. "EdwardII"Kamieñ Pom. "EdwardII"19736 Dziwnówek "Józef" 19971980 -8.2 -59364.0 - Lower35.5400.0 Jurassic1985 -8.2 -58-6.6 -47 Dowgia³³o, 1988Zuber & Grabczak,1991Zuber & Grabczak,19911997 -8.1 -61.5 Krawiec, 1999718.5 -790.0LowerJurassic65.9 -6.1 -50.0Krawiec, 1999;Krawiec et al., 20007 Œwinoujœcie 5 "Jantar " 1973 240.0 - Lower 42 -5.8 -44 Dowgia³³o, 19887a Œwinoujœcie 5 "Jantar " 1997 270.0 Cretaceous -8.6 -62.4 Krawiec et al., 20008 Œwinoujœcie 6 "Teresa" 1973225.0 -266.0LowerCretaceous45 -7.5 -58 Dowgia³³o, 1988

NoBoreholeSALINITY OF GROUNDWATER, NW POLAND 37Testintervaldepth mbelowsurfaceDate ofsamplingStratigraphyTDS(g/dm 3 ) 18 O(‰) 2 H(‰)Ta ble 2 continuedData source(according toreferences)1 2 3 4 5 6 7 8 99 Pyrzyce GT-19aPyrzyce GT-110 Stargard GT-111 Pniewy - water well10.06.2001 1498.0 -15.08. 1620.0200112.04.200212.10.20012428.0 -2670.035.0 -81.0LowerJurassicLowerJurassicUpperCretaceous119.0-4.02 -31.84-4.08 -31.99120 -4.06 -30.771.9 -9.2 -66.01Dowgia³³o et al., inpressING PAN,Warszawa, 200412 Rainwater in NW Poland -9.4 -66 D'Obyrn et al., 199713 Pi³a IG-1 1999997.0 -1022.0LowerJurassic6.5 -8.82 -62.4 Krawiec, 2005te oric wa ters, and may con tain the fos sil sea wa ter com po nent. A sim i lar func tion,i.e. 2 H=6.9 18 O–4.5, was cal cu lated by Dowgia³³o (1988) for chlo ride wa ters ofthe Me so zoic com plex in the Pol ish Low lands, and in ter preted as in di ca tion that wehave to do with a mix ture of dif fer ent sub types of rel ict wa ters. On the ba sis of thesame de ter mi na tions, Zuber & Grabczak (1991) claimed that the heavy com po nentis formed of me te oric wa ters in fil trat ing in pe ri ods in which the cli mate was warmerthan the pres ent one.The points rep re sent ing ground wa ter sam ples from the geo ther mal wells atPyrzyce and Stargard Szczeciñski (points 9, 9a and 10 in Fig. 18), plot fairly closeto the 0 point cor re spond ing to the Vi enna Stan dard Mean Ocean Wa ter (VSMOW). It may in di cate that these groundwaters are fos sil seawaters pre served in Li -assic sed i ments. These high-tem per a ture brines, how ever, might be one of the rea -sons of high 18 O con tent in wa ter due to iso tope ex change be tween wa ter and car -bon ate min er als. On the other hand, the points 1 and 1a, rep re sent ing the brine atPo³czyn Zdrój (Up per Tri as sic) are still closer to the VSMOW point, al though thetemperature here is below 20°C.At Pyrzyce, ground wa ter tem per a ture at a depth of ap prox i mately 1600 m be -low the sur face is 60°C, in Stargard Szczeciñski – 90°C at 2500 m. Dur ing the pro -cess of iso tope frac tion ation, ground wa ter be comes en riched in heavier ox y gen iso -topes, while the con cen tra tion of deu te rium re mains con stant (Dowgia³³o 1970;Sheppard, 1986; Clark & Fritz, 1997; Drever 1997). The points rep re sent ing 18 Oval ues in groundwaters of Pyrzyce GT-1 and Stargard GT-1 bore holes are, how -ever, dis trib uted along the same line as the points char ac ter is ing brines at low tem -per a tures of about 10–13°C (see Fig. 18). It might sug gest that groundwaters withinthe Li assic com plex show no signs of iso tope frac tion ation.

38 D. KACZORFig. 19.The re la tion ship be tween 18 O and min er al iza tion of ground wa ter in Me so zoic aquifersPoint No 1 in Fig. 18 is sit u ated very close to the GMWL and to the mean iso to -pic com po si tion of re cent me te oric wa ter in NW-Po land (d’Obyrn et al., 1997). Thewa ter sam ple taken at Pniewo from the Up per Cre ta ceous aqui fer (depth: 31–80 mbe low the sur face) is rep re sent ing wa ter of me te oric or i gin cir cu lat ing in the zone ofactive exchange.The depth-re lated in crease in con cen tra tion of the heavy ox y gen iso tope 18 O ingroundwaters, along with the in crease in to tal min er al iza tion, is il lus trated in Fig.19. The pres ence of this phe nom e non in the Me so zoic se quence of the Pol ish Low -lands was de scribed by Dowgia³³o (1971) who claimed that also an in crease in con -tri bu tion of con nate wa ters and of ma rine wa ters which in truded into con sol i datedsed i ments dur ing trans gres sion pe ri ods has been ob served with in creas ing depthand min er al iza tion. This is also re lated to the de creas ing in flu ence of the me te oriccon tri bu tion. Such in ter pre ta tion is sup ported by the re sults of sub se quently pub -lished iso tope de ter mi na tions in wa ters taken from the bore holes: B-1 at Ko³obrzeg,“Ed ward II” at Kamieñ Pomorski (Dowgia³³o, 1988; Zuber & Grabczak,1991; Krawiec, 1999b), Kamieñ Pomorski IG-1 and “Józef” at Dziwnówek (Krawiec,1999b), “Jantar” at Œwinoujœcie (Krawiec et al., 2000), “Teresa” at Œwinoujœcie(Dowgia³³o, 1988), Pi³a IG-1 (Krawiec, 2005), as well as by mea sure mentscar ried out in the Pyrzyce GT-1 and Stargard GT-1 bore holes, and the Pniewo wa terwell (see Tab. 2). Only the re sults from the Po³czyn Zdrój brine (Nos 1 and 1a – seeFig. 19) de part from the rule. In this case, the high 18 O val ues do not cor re spond tothe high est to tal min er al iza tion. This can be ex plained by the pres ence of re sid ual

SALINITY OF GROUNDWATER, NW POLAND 39Fig. 20.The re la tion ship be tween 18 O and depth of the tested aqui ferliq uids that re mained in Keuper de pos its af ter Tri as sic evap o ra tion un der a hot andarid cli mate (Dowgia³³o, 1988).The vari abil ity in iso to pic com po si tion of the ana lysed groundwaters ver susdepth is il lus trated in Fig. 20 which shows a dis tinct in crease in the 18 O val ues within creas ing depth to the tested aqui fers. The low est one ( 18 O = –9.2‰) was re -corded in an above-men tioned ground wa ter sam ple from Pniewo. One of the high -est val ues ( 18 O = –4.06 ‰) was found in the wa ter from the Li assic at StargardSzczeciñski and Pyrzyce. It should be noted that 18 O val ues, at Pyrzyce GT-1(point No 9) and Stargard GT-1 (point No 10) bore holes, are al most iden ti cal whilethe dif fer ence in depths to the tested aqui fers amounts to nearly 1000 m (see Fig.20). There fore, it can be sug gested, that the iso to pic com po si tion of groundwaterswithin the Li assic aqui fers had been es tab lished be fore such a great dif fer ence indepths was reached, i.e. prior to the for ma tion of the Chabowo salt anticline piercedat its crest by the Pyrzyce GT-1 bore hole, and of the Ina syncline where the StargardGT-1 bore hole is lo cated (see Fig. 10).

40 D. KACZORFig. 21. 87 Sr/ 86 Sr ra tio cal cu lated for ground wa ter from the Li assic aqui fer of the “Ed ward II” andPyrzyce GT-1 bore holes ver sus 87 Sr/ 86 Sr ra tio (sim pli fied graph) in Phanerozoic sed i men tary rocksaf ter Veizer (1989)An ex cep tion to the rule of in creas ing heavy iso topes con tent in groundwatersalong with in creas ing depth are the re sults ob tained in the Keuper aqui fer at depthsof 1175–1235 m be low the sur face at Po³czyn (points Nos 1 and 1a on Fig. 20). Therecorded 18 O value is –3.3‰, al though the depth to the tested aqui fer is by ca 300m smaller than that at Pyrzyce (points No 9 and 9a) and by about 1300 m smallerthan that at Stargard (point No 10). An ex pla na tion for this de vi a tion can also besought in tec tonic pro cesses oc cur ring af ter the iso to pic com po si tion of wa terwithin the Keuper aqui fer was ashieved. The Po³czyn IG-1 bore hole was drilled inthe Pom er a nian Anticlinorium, i.e. within the deep est zone of the Mid-Pol ishTrough dur ing Tri as sic times, sub se quently up lifted at the end of the Cre ta ceous(Dadlez, 2001). So, if we as sume that the groundwaters, which are to-day storedwithin the Keuper aqui fer of the Po³czyn area, ac cu mu lated be fore the in ver sion ofthe Mid-Pol ish Trough, then it is ob vi ous that they were richer in heavy iso topesthan groundwaters within the Li assic aqui fer of the Pyrzyce and Stargard ar eas, ac -cu mu lated in ar eas ly ing close to the trough’s mar gins which were at greater al ti -tudes at those times.De ter mi na tion of the87 Sr/ 86 Sr ra tios was done in brine sam ples taken from theLi assic aqui fer, in the bore holes “Ed ward II” at Kamieñ Pomorski, and PyrzyceGT-1. The 87 Sr/ 86 Sr ra tio vari a tions through geo log i cal time are an in di ca tor pro -vid ing in for ma tion about re ac tions oc cur ring be tween rock and wa ter trapped insed i ments, about the ground wa ter flow sys tem, and about the or i gin of ground wa ter

SALINITY OF GROUNDWATER, NW POLAND 41Fig. 22.87 Sr/ 86 Sr ra tio cal cu lated for ground wa ter from the Li assic aqui fer of the “Ed ward II” andPyrzyce GT-1 bore holes ver sus 87 Sr/ 86 Sr ra tio (sim pli fied graph) in sea wa ter af ter Burke et al. (1982)and its sa lin ity (Chaudhuri, 1978; Con nolly et al. 1990b; Clark & Fritz, 1997). The87 Sr/ 86 Sr val ues ob tained from the Pyrzyce and Kamieñ Pomorski brines (0.708328and 0.708867, re spec tively), were com pared to the sea wa ter ra tio of 0.709 (Faure,1986) and the value es tab lished by Veizer (1989) for Phanerozoic rocks of dif fer entages (Fig. 21). The re sults ob tained are sim i lar to the value typ i cal of re cent sea wa -ters, but they are higher than the iso to pic ra tio value typ i cal of Ju ras sic rocks. Fur -ther more, the re sults of both mea sure ments were re ferred to the curve pro duced byBurke et al. (1982), de fin ing the 87 Sr/ 86 Sr iso to pic ra tio value in sea wa ters of dif fer -ent geo log i cal pe ri ods (Fig. 22). If the points cor re spond ing to the re sults of mea -sure ments are away from the sea wa ter time-curve, then it is in ter preted as an in di ca -tor of chem i cal al ter ation of ground wa ter due to wa ter-rock in ter ac tion (Chaudhuri,1978; Con nolly et al., 1990b). The ra tio val ues for the Pyrzyce and KamieñPomorski brines are sit u ated away from the curve. This can be in ter preted as an ev i -dence for a con sid er able mod i fi ca tion of the chem i cal composition of brines withinthe Jurassic complex due to chemical processes occurring between seawater andreservoir rocks.GROUNDWATER SALINITY IN CENOZOIC DEPOSITSDUE TO BRINES ASCENTChem i cal com po si tion of ground wa ter in Ce no zoic aqui fersGround wa ter of the Ce no zoic aqui fers is rep re sented mostly by HCO 3 -Ca in fil -tra tion wa ter of me te oric or i gin. Its chem i cal com po si tion de pends on the ground -

42 D. KACZORwa ter cir cu la tion sys tem, re charge and dis charge con di tions, li thol ogy of wa -ter-bear ing rocks, pro cesses oc cur ring in the vadose and sat u ra tion zones, and alsoon anthropogenic fac tors. The Qua ter nary aqui fers are the ma jor us able ones in thestudy area, while the Neo gene and Palaeogene aqui fers play such a role on a lo calscale only. The un con fined aqui fers which are re charged di rectly by pre cip i ta -tion are char ac ter ized by low min er al iza tion rang ing from 150 to 300 mg/dm 3 ,whereas groundwaters from con fined aqui fers iso lated by aquitards show the min -er al iza tion amount ing up to 500 mg/dm 3 (Macioszczyk, 1989). The qual ity of wa terin shal low aqui fers is af fected largely by anthropogenic pol lu tion, re sult ing in anin creased con tent of chlo rides, ni tro gen com pounds and sulphates (Górski, 2001).Groundwaters within intertill and subtill de pos its com monly con tain con sid er ablecon cen tra tions of man ga nese and iron, rang ing be tween 1 and 5 mgFe/dm 3 , and be -tween 0.1 and 0.5 mgMn/dm 3 (P³ochniewski, 1972). The chem i cal com po si tion ofgroundwaters is also in flu enced by hy dro dy namic con di tions, usu ally ob served inwa ter catch ments lo cated in river and ice-mar ginal val leys. Changes in ground wa -ter level con trib ute to an in crease in total mineralization, concentrations of sul phates,iron, manganese, as well in the pH (B³aszczyk & Górski, 1977; Górski, 1981).Out of Neo gene and Palaeogene aqui fers, the Mio cene aqui fer is best ex plored.Its ground wa ter is char ac ter ized by a dis tinct brown col our and a high oxidability,especially in areas where brown coal intercalations occur. Anomalously colouredwa ters orig i nate from re duc ing en vi ron ments, and of ten show in creased con cen tra -tions of chlo rides ex ceed ing 60 mg/dm 3 (Macioszczyk, 1973). Sa lin ity is a se ri ousprob lem in us ing groundwaters in this re gion, and has been a sub ject of re search.Sur face man i fes ta tion of ground wa ter sa lin ityEx am ples of oc cur rence of sa line ground wa ter in shal low aqui fers were re -ported al ready in 19th cen tury lit er a ture. The names of many lo cal i ties con tain ingan el e ment which is a Ger man, Latin or Old-Sla vonic equiv a lent to the word salt(kol. hol) were re lated to the oc cur rence of sa line wa ters (Deecke, 1898). Anaxample is Ko³obrzeg (in Ger man Kolberg) mean ing a salt moun tain. An other aresalt-lov ing plant sites, in di ca tors of in creased wa ter sa lin ity within shal low aqui fers(Fig. 23). Halophyte sites were re ported from Stró¿ewo and Brodogóry nearPyrzyce (Schmidt, 1840; Ascherson, 1859; Soenderop, 1911), to the south ofHeringsdorf on the Uznam (Usedom) is land (Deecke, 1898), near Bia³ogard, in thevil lages of Pêkanino and Kroszal (Hesemann, 1939), and also in Ko³obrzeg and itsvi cin i ties (Preuss, 1910; Dibbelt, 1930). Piotrowska (1961, 1974), re port ing on themain salt-lov ing plant sites along the Bal tic Sea coast, men tioned the lo cal i ties ofŒwinoujœcie, Karsibór, Ognica, Przytór, £unowo, Dro¿kowe £¹ki, Dziwnów,Chrz¹szczewo is land, Mrze¿yno and Ko³obrzeg (see Fig. 23). Salt marsh floragrows there in low land and boggy ar eas, mainly close to big river mouths, wherebackflow of the Bal tic sea wa ter may oc cur. The flora is also as so ci ated with nat u ralsalt wa ter springs char ac ter ised by the oc cur rence of Salicornietum patulae phytocoenosis.This spe cies has been found, e.g., on Chrz¹szczewo is land and in Ko³obrzeg.Nat u ral changes in veg e ta tion, re lated both to drain ing of mead ows in or der

SALINITY OF GROUNDWATER, NW POLAND 43Fig. 23.Salt-lov ing plant sites and nat u ral brine out flowsto con vert them to pas tures, and to the de vel op ment of ur ban ag glom er a tions arethreats to salt-lov ing plants. These fac tors are be lieved to be re spon si ble for the ex -tinc tion of 10 halophyte spe cies over the past cen tury. To con serve the plants, astrictly pro tected na ture re serve was es tab lished at Ko³obrzeg in 1965. The re servein cludes 2 patches of salt marsh, 0.9 ha in area, sit u ated on the right bank of theParsêta River, 1.7 km away from the sea (Bosiacka & Stêpieñ, 2001). Salt-lov ingplant sites were also re ported from the south-west ern part of the study area atStró¿ewo near Pyrzyce (Wiœniewski 3 , 1970) and at Staw near Myœlibórz (Bojanowski4 , 1970).3 Wiœniewski, J., 1970. Zagadnienie zasolenia wód podziemnych w okolicy Stró¿ewa – powiatpyrzycki (The prob lem of ground wa ter sa lin ity near Stró¿ewo, Pyrzyce dis trict – in Pol ish). Pracamagisterska. Wydzia³ Geologii Uniwersytetu Warszawskiego. (Type script. Fac ulty of Ge ol ogyof Warsaw University).4 Bojanowski, M., 1970. Zasolenie wód pierwszego poziomu wodonoœnego w miejscowoœci Staw,województwo szczeciñskie. (Ground wa ter sa lin ity of the shal low est aqui fer in the lo cal ity odStaw, Szczecin Voivodship – in Pol ish). Praca magisterska. Wydzia³ Geologii UniwersytetuWarszawskiego. (Type script. Fac ulty of Ge ol ogy of War saw University).

44 D. KACZORThe ground wa ter sa lin ity in Qua ter nary aqui fers is ev i denced by ar te sian flowsof sa line wa ter at Dobropole, Rekowo, Margowo, Szumi¹ca, Œwierzno, Sulikowoand Œwiêtoujœæ near Kamieñ Pomorski (Gumprecht, 1846; Deecke, 1898) – seeFig. 23. Out flows of sa line wa ter at Œwierzno, con tain ing over 1000 mg/dm 3 ofchlo ride ion, were re con firmed by Dowgia³³o (1965a). The larg est amount of dataon sa lin ity in shal low groundwaters co mes from the Ko³obrzeg area. The brines ex -tracted in the health re sort show the to tal min er al iza tion of up to 54 g/dm 3 , re cordedin the “Edelquelle” spring on Salt Is land (Karsten, 1846). The sa lin ity of ground wa -ter in the Qua ter nary aqui fers was also re ported from the Bia³ogard, Koszalin,Œwinoujœcie, Wolin, Szczecin and Pyrzyce areas (Dowgia³³o, 1965a).Ground wa ter of sa lin ity zones in Ce no zoic aqui fersA ground wa ter salinization zone within a Ce no zoic aqui fer is un der stood as agroup of wells with con cen tra tion of chlo ride ion in wa ter ex ceed ing 30 mg/dm 3 .Such val ues have been re corded in 1988 anal y ses of ground wa ter in Qua ter naryaqui fers, out of the to tal num ber of 7103 wa ter anal y ses avail able. The map (Fig.24), how ever, pres ents only 754 wells be cause only the most rep re sen ta tive wellsare shown in ar eas of high wells con cen tra tion.The dis tri bu tion of sa lin ity zones is re lated to fault zones, salt tec tonic struc turesand to the lithological vari abil ity typ i cal of the Ce no zoic cover.Ground wa ter sa lin ity zones in Pleis to cene aqui fers above fault zonesGroundwater sa lin ity is clearly ev i dent in the north ern part of the Pom er a nianAnticlinorium char ac ter ized by geo log i cal con di tions fa vour ing the as cent ofbrines from Me so zoic de pos its.Due to ero sional re moval of Oligocene and Neo gene aquitards, the stronglyfaulted brine-bearing Mesozoic formations are in immediate contact with Quater -nary aquifers.Among the best known are oc cur rences of sa line ground wa ter within the Qua -ter nary cover of the Ko³obrzeg Anticline (Deecke, 1898; Dowgia³³o, 1965a, b;Krawiec, 1999c). Up to 4 m deep hand drillings, made in this re gion, show thatchlo ride con cen tra tions lo cally reach up to 15 g/dm 3 (Dowgia³³o, 1965a). The pres -ent-day con tin u a tion of the pro cess of brine as cent up to the sur face is ev i denced byar te sian flows of brines with the min er al iza tion rang ing be tween 45 and 54 g/dm 3 ,re corded in the springs No 18, 35 and 31, in the bore holes B-1 and B-2 inKo³obrzeg, and “Anastazja” in Podczele. The sa lin ity of ground wa ter within Qua -ter nary aqui fers is now ob served in the wells 16A (215.5 mgCl/dm 3 ) and 16B(500.6 mgCl/dm 3 ) at the min eral wa ter bot tling plant “Per³a Ba³tyku”, ex tract ingground wa ter from a Pleis to cene aqui fer from the depths of 40.5–64.0 m be low thesur face (Fig. 25). The re sults of chem i cal anal y ses per formed by the “Balneoprojekt”En ter prise in 2001–2002, also show an in creased con cen tra tion in other el e -ments such as bro mine (0.7–1.7 mg/dm 3 ), io dine (0.11–0.21 mg/dm 3 ), stron tium(0.74–1.3 mg/dm 3 ) and bar ium (0.04–0.06 mg/dm 3 ), in di cat ing the pro cess of

SALINITY OF GROUNDWATER, NW POLAND 45Fig. 25.Hydrogeological cross-sec tion I–I’ground wa ter as cent. The re sults of mea sure ments of sta ble ox y gen and hy dro geniso topes as well as of tri tium in groundwater from the 16A well did also confirm thisprocess (Krawiec, 1999c).High wa ter sa lin ity in the Qua ter nary aqui fers is ob served in wells lo cated atBia³ogard and its en vi rons transected by the Karlino-Szczecinek fault zone, whichsep a rates the Pom er a nian Anticlinorium from the Pom er a nian Synclinorium, andby a num ber of mi nor faults (Fig. 26). In creased con cen tra tions of chlo ride ion werealso re corded in wa ters from a num ber of wells at K³opotowo, Œwiemino, Pêkanino,Kozia Góra, Lubiechowo, Kowañcz, Karlino, Lulewice, Krukowo, Bia³ogard,

46 D. KACZORFig. 26. An ex am ple of ground wa ter sa lin ity zone in the Qua ter nary aqui fer against the tec ton ics ofPerm ian–Me so zoic struc tural com plex along the Karlino–Szczecinek fault zoneRobuñ, Dêbczyno, Rychowo, Ramlewo, Skoczów, Wrzosowo, Mierzyn, Nosówko,Koœciernica, Dargikowo, Moczy³ki, Czarnowêsy, Zagórze, Siñce and Karœcino.The high est con cen tra tion of chlo rides (1900 mg/dm 3 ) was mea sured in theLulewice bore hole at a depth of 35 m be low the sur face. In Bia³ogard, high con cen -tra tions of chlo rides (315–1320 mg/dm 3 ) were re corded in 4 wa ter wells at depthsof 20–28 m be low the sur face. An in crease in chlo ride con cen tra tions through timeis ev i denced by mon i tor ing of chem i cal com po si tion of ground wa ter in the Pleis to -cene aqui fer (wa ter well at K³opotowo, depth 62 m be low the sur face) – see Fig. 26.In 1966, the con cen tra tion of chlo rides was here 10 mg/dm 3 , and sub se quently in -creased to 230.4 mg/dm 3 in 1999.A dis tinct cul mi na tion of in creased chlo ride con cen tra tions is vis i ble in Qua ter -nary aqui fers along the Œwinoujœcie – Drawsko fault zone which sep a rates thePom er a nian Anticlinorium from the Szczecin Synclinorium, par tic u larly be tweenNowogard and £obez (Fig. 27). In 55 wa ter wells scat tered through out this area at:Wiewiecko, Dalno, £obez, Dobieszewo, Lesiêcin, Gardno, Zajezierze, Runowo,Stare Wêgorzyno, Wêgorzyno, Borkowo Wielkie, Rogowo, ¯elmowo, Dargomyœl,Rekowo, Mielno, Zwierzynek, Nowogard, Wierzbiêcin, Kulice, Jarchlino,Osowo, Sienno Dolne, Mieszewo, Sielsko, Konarzewo, Œwierczewo, Karsk, Miêtnoand Trzechel, chlo ride con cen tra tions vary be tween 31 and 569 mg/dm 3(Kaczor, 2005). All of these wells sup ply ground wa ter from aqui fers lo cated atdepths be low 20 m. The high est sa lin ity was re corded in 1970–1978 in the al readyaban doned well at Konarzewo near Nowogard, where the con cen tra tion of chlo ride

SALINITY OF GROUNDWATER, NW POLAND 47Fig. 27. An ex am ple of ground wa ter sa lin ity zone in the Qua ter nary aqui fer against the tec ton ics ofPerm ian–Me so zoic struc tural com plex along the Œwinoujœcie–Drawsko fault zoneions was 569 mg/dm 3 in well No 2 screened at a depth of 28.5–32.0 m, and 322mg/dm 3 in well No 1. When con sid er ing the mea sure ments which can in di cate thegeogenic or i gin of ground wa ter sa lin ity in the Qua ter nary aqui fers, it is nec es saryto quote once again the value of 110 mg/dm 3 re corded at the depth of 120.5 m inwell No 1 lo cated at the Lesiêcin col lec tive farm (near £obez). An in ter est ing caseis a dis tinct in crease in con cen tra tion of chlo ride ion from 34 do 89.7 mg/dm 3 , re -corded through the pe riod of 1970–1999 in wa ter from the Pleis to cene aqui fer at adepth of 59 m in the well No 1 at Rogowo. The anal y sis car ried out in 1999 hasshown a small con cen tra tion of ni trates (

48 D. KACZORNoWa ter wells with in creased con cen tra tions of chlo ride ion, area be tween £obezand ŒwidwinWell locationChlorideconcentration(mg/dm 3 )Depth to theaquifer top(m)Table 3Year ofanalysis1 Œwidwin – south district 31.0 51.0 19772 Osowo – water supply system/well 1 165.0 33.0 19713 Osowo – water supply system/well 2 42.0 41.0 19764 Klêpnica – water supply system/well 1 67.0 35.0 19715 Worowo – water supply system/well 1A 49.0 35.0 19846 Worowo – water supply system/well 1 50.0 33.5 19707 Koszanowo – agriculture farm 52.5 39.0 19898 S³onowice – water supply system/well 2 55.0 41.0 19829 S³onowice – water supply system/well 1 68.0 46.0 196810 Mo³stowo – water supply system/well 2 64.0 30.0 199911 Be³czna – water supply system/well 2 36.0 32.3 199512 Poradz – water supply system/well 1 38.0 31.0 197413 Poradz – water supply system/well 2 35.0 32.0 196614 Karwowo – water supply system/well 1 60.0 109.0 196715 Dalno – water supply system/well 1 130.0 28.0 196516 Dalno – water supply system/well 2 99.0 24.0 197417 Rusinowo – water supply system/well 1 42.0 58.0 198018 Rusinowo – water supply system/well 2 35.0 58.0 1982merely 10–40 m in this area. More over, the lack of the Palaeogene seal ing de pos -its and the oc cur rence of ar te sian flows in the brine – pro duc ing wells (“Ed ward II”at Kamieñ Pomorski, Jatki II and “Józef” at Dziwnówek), as well as nat u ral brineout flows re ported from Œwierzno (Schulte, 1921), con firm the pos si bil ity of up -ward mi gra tion of sa line ground wa ter to wards the Qua ter nary aqui fers. The max i -mum con cen tra tion of chlo rides in the Qua ter nary aqui fer of the Kamieñ Pomorski,area amount ing to 2970 mg/dm 3 , was re corded in 1972 in well No1 (state farm at¯ó³cino) at a depth of 28.5 m be low the sur face. These hydrogeological con di tionscause fre quent events of in creas ing ground wa ter sa lin ity due to ex ces sive wa ter ex -trac tion. One of the ex am ples is the H-1 well, a mu nic i pal wa ter in take for the townof Kamieñ Pomorski, ex tract ing ground wa ter from the Qua ter nary aqui fer at adepth of 20 m be low the sur face, in which con cen tra tions of chlo rides in creasedfrom 35 to 498 mg/dm 3 dur ing the pe riod of 1987–1999. Sta ble ox y gen and hy dro -gen iso tope mea sure ments car ried out in 1997, con firmed the pre vi ous sup po si tion

SALINITY OF GROUNDWATER, NW POLAND 49Fig. 28. An ex am ple of ground wa ter sa lin ity zone in the Qua ter nary aqui fer against the tec ton ics ofPerm ian–Me so zoic struc tural com plex, Kamieñ Pomorski regionthat wa ter sa lin ity in this well is as so ci ated with the as cent of ground wa ter(Krawiec, 1999b). An other ma jor prob lem is ground wa ter sa lin ity in the “Wydrzany”mu nic i pal wa ter well in Œwinoujœcie (Fig. 29). Since 1973, this well pro -duced wa ter from the Pleis to cene aqui fer sit u ated at a depth of 20–30 m be low thesur face. The wa ter sa lin ity was ex plained by in tru sion of the Bal tic seawaters(Kucharski & Twarogowski, 1993), although there are also interpretations relatingthe problem to the ascent of saline groundwaters from the Cretaceous (Matkowska,1983; Kachnic, 1999).Ground wa ter sa lin ity zones in Pleis to cene aqui fers above salt struc turesClusters of wells sup ply ing wa ter with in creased chlo ride con cen tra tion arefrom Qua ter nary aqui fers sit u ated over 31 out of 49 salt anticlines con sid ered,namely, the Szczecin, Krakówko, Gryfino, Chabowo, Maszewo, Marianowo,Choszczno, Recz, Dominikowo, £obez, Œwidwin, Grzêzna, Woœwino, Pi³a,Cz³opa, Po³czyn, Barwice, Lotyñ, P³awno, Drezdenko, Pe³czyce, Karsk, Myœlibórz,Dêbno, Czelino, Widuchowa, Lipiany, Banie, Miêdzyzdroje, Dargob¹dz andKodr¹b anticlines (see Fig. 24). This in di cates that salt anticline crests are ar eas ofintense ascent of saline groundwater towards these shallow aquifers. Areas situatedabove the crests of most of these anticlines show most of ten the lack, or re ducedthick ness of poorly per me able Palaeogene clays. The main con fin ing strata, iso lat -ing the Qua ter nary aqui fers from as cend ing brines, are Lower Oligocene (Rupelian)clays. In the south-east ern part of the stud ied area, such role can also be playedby the Lower Plio cene “var ie gated clays”. An ti cli nal zones, up lifted as a re sult ofneotectonic move ments, were sub jected dur ing Pleis to cene to strong ero sion andgla cial exaration which re moved Palaeogene and Neo gene de pos its. Re moval ofseal ing clays, or their re duc tion in thick ness, could re sult in the for ma tion ofhydrogeological win dows within which the up ward mi gra tion of brines to wards the

50 D. KACZORFig. 29.Hydrogeological cross-sec tion II–II’Ce no zoic aqui fers oc curred through a sys tem of frac tures. Ver ti cal salt move mentsre sulted in the de vel op ment of extensional zones on the up lifted anticline crests andin the for ma tion of frac tures and lo cal tec tonic grabens (Kasiñski, 2004).The ground wa ter sa lin ity in the Qua ter nary aqui fer above the Chabowo saltanticline, caused by as cend ing brines, is ev i denced by an in creased con cen tra tionof chlo rides found in wells pro duc ing wa ter from the aqui fer lo cated be neath a sev -eral metres-thick over bur den of gla cial tills. This cover isolater the aqui fer fromanthropogenic pol lu tion (Fig. 30), thus wa ter salinizatioon is cer tainly geogenic.During test pump ing of a well at ¯elis³awiec per formed in 1968, ground wa tercon tain ing 420 mg/dm 3 of chlo rides was ex tracted from a depth of 95–100 m be lowthe sur face. In creased con cen tra tions of chlo rides (rang ing from 31 to 180 mg/dm 3– see Fig. 30), were also re corded in 35 wells at Gardno, Kartno, Stare Czarnowo,Bêdgoszcz, Chabowo, Gi¿yn, Bielice, Linie, Ryszewko, ¯abów, Myœliborki,Kosin, Okunica, Lubiatowo, Stary Przylep, Reñsko, Barnim, Wójcin and ¯elêcino.Chlo ride de ter mi na tions were done in ground wa ter col lected from depths of 2 to 46m be low the sur face. As for most of shal low wells, the dis cussed wa ter chem i cal

SALINITY OF GROUNDWATER, NW POLAND 51Fig. 30. An ex am ple of ground wa ter sa lin ity zone in the Qua ter nary aqui fer against the tec ton ics ofPerm ian–Me so zoic struc tural com plex, Chabowo salt anticline areaanal y ses are in com plete, it can not be pre cluded that wa ter sa lin ity ob served in sev -eral causes de pends on anthropogenic fac tors. How ever, the pos si bil ity that sa lin ityin the shal low aqui fers is re lated to the as cent of brines is in di cated by the 19th and20th cen tury Ger man lit er a ture re port ing the pres ence of brines or highly sa line wa -ters in both hand-dug and drilled wells (Rich ter, 1926). Natural near-surface occurrencesof sa line wa ter are also in di cated by halophytic flora sites near the vil lages ofStró¿ewo and Brody north of Pyrzyce (Schmidt, 1840; Soenderop, 1911; Wiœniewski,1970 5 ) – see Fig. 23.It can be sup posed that some shal low oc cur rences of sa line wa ter, re ported priorto the be gin ning of the 20th cen tury, dis ap peared due to in tense land rec la ma tionlast ing al ready more than 150 years.Oc cur rence of hydrogeological win dows and oc cur rence of rel a tively shal lowsa line ground wa ter was re ported from Up per Cre ta ceous de pos its which di rectlyunderly the Qua ter nary cover above the Szczecin salt anticline crest (Fig. 31). Forex am ple, brine with min er al iza tion of 48 g/dm 3 (Linstow, 1913) was ex tractedfrom the Cre ta ceous strata lo cated at a depth of 92 m at the Szczecin Port, on the£asztownia Is land (Linstow, 1913). The oc cur rence of brines in this area was sub -se quently con firmed by the re sults of a 114 m-deep drill ing per formed in 1956, inwhich a con sid er able in crease in chlo ride con cen tra tion along with depth was ob -served (Dowgia³³o, 1965a). The con cen tra tion of chlo ride ion of wa ter in Qua ter -5 See footnote 3, p. 43

52 D. KACZORFig. 31.Hydrogeological cross-sec tion III–III’nary de pos its lo cated at a depth of 86.9 m was 228 mg/dm 3 , and in Cre ta ceous rocksat 100 m it in creased to 2692 mg/dm 3 (see Fig. 31).Sa line ground wa ter in Qua ter nary de pos its was also re ported from nu mer ouswa ter wells drilled in the Szczecin city cen tre. Sa line wa ter (TDS=4.6 g/dm 3 , 2449mgCl – /dm 3 ) was also found in Pleis to cene de pos its at a depth of 89 m be low the sur -face near the non-ex tant stock ex change build ing close to the City Hall (Deecke,1906).Fur ther data on ground wa ter sa lin ity in Szczecin are those con cern ing a welldrilled in 1959 for a dairy at the Jagielloñska street (aqui fer depth amount ing to95–99.6 m be low the sur face). The ground wa ter TDS was here 4.2 g/dm 3 and thechlo ride con cen tra tion amounted to 2535.5 mg/dm 3 (Dowgia³³o, 1965a). Ground -wa ter sa lin ity in the Pleis to cene aqui fer is also con firmed by chem i cal anal y ses ofwa ter in the well No 4, drilled in 1968 and 1973, where the con cen tra tion of chlo -rides at the depth of 20.9–35.7 m was 105 mg/dm 3 . In an other well drilled in 1971for the “Delfin” Com pany at the Œciegienny street, 200 m away from well No 4, thecon cen tra tion of chlo ride ion in the Pleis to cene aqui fer at a depth of 84–95 m be lowthe sur face was 282 mg/dm 3 (see Fig. 31). In a well drilled in 1984 for PKP Rail way

SALINITY OF GROUNDWATER, NW POLAND 53Hos pi tal in Wyzwolenia street, the con cen tra tion of chlo rides in the Qua ter naryaqui fer at a depth of 54–58 m be low the sur face was 318 mg/dm 3 , TDS=896mg/dm 3 , whereas at a depth of 79 m, the Cl – con cen tra tion in creased to 1400mg/dm 3 (Kaczor, 2005).The high con cen tra tion of wells pro duc ing wa ter with in creased chlo ride con -cen tra tion con tinue into ar eas of neigh bour ing syn clines, spread ing ac cord ing toground wa ter flow di rec tions (see Fig. 24). The pre sented scheme of ground wa tercir cu la tion within Ce no zoic aqui fers is based on the Hydrogeological At las of Po -land, scale 1:500,000 (Paczyñski, ed., 1993). The brines mi grat ing up ward fromMe so zoic rocks are di luted by ground wa ter cir cu lat ing in the up per part of the geo -log i cal pro file. The so lu tions formed in this way flow to wards dis charge zones, i.e.to wards river val leys. There fore, the ground wa ter sa lin ity zones do not alwayscoincide with the zones of ascending brines.Ground wa ter sa lin ity zones in Palaeogene and Neo gene aqui fersThe Palaeogene and Neo gene aqui fers have rarely been used in the study area asa source of us able wa ter. Scat tered hydrogeological data pro vide knowl edge aboutwa ter sa lin ity only in sin gle mea sur ing points thereby giv ing no ba sis for char ac ter -iz ing the ground wa ter sa lin ity over larger ar eas (Fig. 32).In creased chlo ride con cen tra tions were re corded in 132 wa ter wells out of 644 wells sam pled forwa ter anal y ses. These wells are sit u ated at Borzys³aw, Barzkowice, Sulino, ¯elis³awiec, Koszewo,Stobno, Pi³a, Chojna, Krzymów, Ch³opowo, Trzciñsko Zdrój, Otanów, Krzy¿ Wielkopolski, Ciszkowo,Brzozowo-Goraj, Stajkowo, Stare Dzieduszki, Œciechów, Górecko, Drezdenko, UstronieMorskie, Wieniatowo, £opienica, Skibno, Koszalin, Mielno, Unieœcie, Kleszcze, Mierzyn, Karlino,Bia³ogard, Podwilcze, Nowe Ledzisko, Smolnica, Kamionka, Czarnków, Chodzie¿, Michor, Smolary,Klempicz, Stajkowo, Tarnówko, S³opanowo, Kobylniki, B¹blin, Goœciejewo, Or³owo, Boruchowo,Ruda, Garbatka, We³na, Ro¿nowice, Parkowo, S³onawy and Kowanówko (see Fig. 32), thedepths of wells rang ing from 50 to 100 m be low the surface.The only zone of con firmed sa lin ity, doc u mented by a group of 30 wells pro -duc ing wa ter from the Mio cene aqui fer at depths of 48–177.2 m be low the sur face,oc curs around the Szamotu³y salt struc ture. Val ues of chlo ride con cen tra tionsrange there be tween 32.0 and 1835.0 mg/dm 3 . The up ward mi gra tion of brines is re -lated, most likely, to ac tive faults transecting the salt struc ture up to the top of theMe so zoic suc ces sion. An in creased con cen tra tion of chlo rides, re corded in wellslo cated to the south and west of this struc ture, may re sult from a flow of ground wa -ter trans port ing chlo rides from the zone of as cend ing brines to wards the WartaRiver val ley. A sim i lar ground wa ter as cent zone may also oc cur at the crest of theRogoŸno salt anticline sit u ated to the south-east of the Szamotu³y zone, just be yondthe limits of the area of interest (Kaczor, 2005).The high est con cen tra tion of chlo rides (4300–6600 mg/dm 3 ) is ob served in thePalaeogene and Mio cene aqui fers in 6 wa ter wells lo cated at Mielno near Koszalin,sup ply ing wa ter from the depths of 78.0–86.0 m be low the sur face (see Fig. 32).Con cen tra tions of chlo rides in these wa ters are higher than the av er age for Bal ticsea wa ter, amount ing to 4000 mg/dm 3 (K³yza, 1988). This in di cates that ground wa -

54 D. KACZORFig. 32.Dis tri bu tion of in creased chlo rides con cen tra tion in Palaeogene and Neo gene aqui fers

SALINITY OF GROUNDWATER, NW POLAND 55ter sa lin ity in the Mielno area is re lated to a re gion of as cend ing brines. Both nu mer -ous faults in this area, and the ar te sian flow of brine ob served in the nearby JamnoIG-3 bore hole (see Fig. 32), con firm the oc cur rence of fa vour able con di tions forground wa ter as cent. Ex am ples of high chlo ride con cen tra tions in the Mielno –Unieœcie wells were also quoted by Dowgia³³o (1965a). In two wells, the Cl – con -cen tra tions in wa ters sam pled at the depth 54.1 m and 75.0 m were 2005 mg/dm 3 ,and 2600 mg/dm 3 , respectively.As sess ment of risk to Ma jor Ground wa ter Res er voirs and se lectedgroundwater intakes due to groundwater ascent-related salinity20 Ma jor Ground wa ter Res er voirs (MGR) num bered: 101–104, 118–120, 122,123, 125–127, 134–139, 146 and 147, have been dis tin guished over the study area(Kleczkowski, ed., 1990). They were iden ti fied mainly in Qua ter nary river-val leysed i ments and in intermorainic de pos its. The res er voirs num bered 126, 127, 134and 146 in clude also Neo gene and Palaeogene de pos its. While de lim it ing the re -charge ar eas for par tic u lar MGRs, the thick ness and li thol ogy of the aqui fer’s over -bur den were con sid ered the main pro tec tion cri te ria. Anthropogenic pol lu tion wasas sumed to be the larg est threat to groundwater quality (Kleczkowski, ed., 1990).Ac cord ing to the pres ent au thor, also the sa line wa ter as cent is a po ten tial haz ardto the qual ity of MGRs in many ar eas. This prob lem is il lus trated in the map of vul -ner a bil ity of Ce no zoic aqui fers to as cend ing sa line wa ters (Fig. 33). The mapshows all the 20 above-listed MGRs along with the above-dis cussed zones of con -firmed sa lin ity and zones of po ten tial salinization haz ard to ground wa ter within Ce -no zoic aqui fers. As the zones of po ten tial haz ard caused by salinization are con sid -ered both the ar eas sit u ated above the crests of salt anticlines and above up lifted tec -tonic blocks, over which a con fin ing layer of Palaeogene clays is thin or miss ing.These blocks are of ten transected by a sys tem of faults favouring the upwardmigration of brines.These geo log i cal con di tions be came a ba sis for iden ti fi ca tion of MGRs threat -ened by as cend ing sa line groundwaters. These are, first of all, the fol low ing ones:Uznam Is land res er voir – 101, Wolin Is land res er voir – 102 (threat ened also by Bal tic sea wa terin tru sions), Roœcino (103) and Dêbno (134) res er voirs, al most en tirely sit u ated within the zones ofcon firmed ground wa ter sa lin ity (see Fig. 33). In the coastal area, in zones of slow wa ter ex change, thesa lin ity may also be as so ci ated with young fos sil wa ters be ing the rem nant of the Littorina Sea(Kozerski & Kwaterkiewicz, 1984, 1988). Also parts of the MGRs. Nos 118, 119, 120, 125, 126, 127,122, 123, 135, 137, 138, 146 and 139, are lo cated in zones of po ten tial and con firmed risk due tosalinization. The ground wa ter res er voirs of Sianowo (104), Dobiegniewo (136) and Warta Riverval ley (147) are sit u ated out of the zones of con firmed and po ten tial ground wa ter salinization,show ing no ev i dence of po ten tial dam age to water quality due to brines ascent from the Mesozoiccomplex.The threat from as cend ing sa line wa ters to the larg est ground wa ter in takes in there gion with the to tal well dis charge ex ceed ing >100 m 3 /h (see Fig. 33) was ana lysed

56 D. KACZORFig. 33.Ar eas of salinization haz ard to Ce no zoic aqui fers

SALINITY OF GROUNDWATER, NW POLAND 57in a sim i lar way. The anal y sis was based on chlo ride con cen tra tion mea sure mentssince the times of wells con struc tion. Only in a few cases chem i cal anal y ses per -formed for the Hydrogeological Map of Po land, scale 1:50,000, were ad di tion allyused. Wa ter in takes, threat ened by brine as cent, in clude 16 wells lo cated in zones ofcon firmed ground wa ter sa lin ity. These are the fol low ing ones:Œwinoujœcie (“Wydrzany”), Wolin, Ko³obrzeg (“Bogucino” and “Roœciêcino”), Koszalin, Gryfino,Nowe Czarnowo, Czarnków, Gryfice, Nowogard, Krzypnica, Stargard Szczeciñski, Wa³cz,Trzebiatów, Goleniów and Choszczno. The ground wa ter in takes at Stargard Szczeciñski, Ko³obrzeg,Gryfice, Trzebiatów, Gryfino, Wolin, Czarnków, Goleniów and Krzypnica are sit u ated in dis chargezones. This fa vours the mi gra tion of chlo rides from ar eas of con firmed brines as cent to wards rivervalleys where the water intakes are installed.Low-vul ner a bil ity wa ter in takes in clude wells at Po lice, Resko, Ko³baskowo,Pilchowo, Œwierczewo and Pi³a, lo cated in ar eas of po ten tial salinization-re latedrisk. The wells which are free of risk are those sit u ated at Dêbczyno, Drawno,Œwidwin, Drezdenko, Barlinek and Wronki.DISCUSSIONThe in ter pre ta tion of re sults of 285 chem i cal anal y ses from 113 bore holes al -lowed for more detailed characterization of the chemical composition of salineground wa ter from Me so zoic rocks, than those pre vi ously pub lished (see Turek,ed., 1977; Bojarski, 1996; Bojarski & Sadurski, 2000). The main dif fer ence is thatthis pa per pres ents a re gional ap proach tak ing into con sid er ation a de tailed im ageof the geo log i cal struc ture of the Perm ian–Me so zoic struc tural sys tem, as well aspoorly de vel oped salt struc tures, namely nu mer ous salt pil lows and walls.The chem i cal com po si tion of brines within the Me so zoic rocks shows muchsim i lar ity within par tic u lar strati graphic units and within the main Perm ian andMe so zoic struc tural units. Ac cord ing to the Shchukarev-Priklonsky clas si fi ca tion(Priklonsky & Laptev, 1955), ap plied in the pres ent study, these are Cl-Na andCl-Na-Ca groundwaters. A high to tal min er al iza tion (TDS) par tic u larly typ i cal ofthe Buntsandstein se quence, reaches its max i mum (328 g/dm 3 ) in the Lower Tri as -sic aqui fer of the Objezierze IG-1 borehole (see Fig. 6).The vari abil ity in to tal min er al iza tion shows a cer tain re la tion ship with the ar -range ment of tec tonic units. The min er al iza tion changes are sim i lar in all Me so zoicaqui fers. The high est min er al iza tion is ob served in brines from the cen tral part ofthe Szczecin Synclinorium, the low est TDS val ues are typ i cal of brines oc cur ring inthe Pom er a nian Synclinorium and the Fore-Sudetic Monocline. An in crease inmin er al iza tion can be in flu enced by the pres ence of salt diapirs partly pierc ing Me -so zoic rocks, which oc cur in the cen tral area of the Szczecin Synclinorium. Saltleach ing dur ing the rise of these struc tures could have con trib uted to an inrease inground wa ter min er al iza tion marked above all in Tri as sic aqui fers. Con sid er ablylower TDS val ues are ob served in brines where salt struc tures (salt pil lows andwalls) are poorly de vel oped, al though it should be emphasized that these areas areexplored by drilling to a lesser extent.

58 D. KACZORThese ob ser va tions con firm the con clu sions of Dowgia³³o (1971) and Bojarski(1996) about the re la tion ship be tween the in crease in min er al iza tion and the oc cur -rence of more de vel oped salt diapirs partly pierc ing Me so zoic rocks, within whichsalts are in con tact with the aqui fers. On the other hand, how ever, the cen tral area ofthe Szczecin Synclinorium is a re gion where the depth to the sub-Me so zoic base -ment is the great est one within the whole north-west Po land; hence the ob served in -crease in min er al iza tion may be as so ci ated, at least in part, with an in crease of depthto the aqui fers (see Fig. 8). The oc cur rence of this phe nom e non in the Pol ish Low -lands, of ten in ter preted as be ing the re sult of ultrafiltration, was pre vi ously re -ported by Dowgia³³o (1971), Weil (1981), Bojarski (1996), and Bojarski &Sadurski (2000).A syn the sis of new hydrochemical data also al lowed for a new in sight into theprob lem of pro gres sive fresh en ing of the groundwaters within Me so zoic aqui fersin north-west Po land, al ready dis cussed by Dowgia³³o (1971). In the light of40-years mon i tor ing, the to tal min er al iza tion and con cen tra tion of chlo rides inbrines ex tracted from Me so zoic aqui fers by health re sort wells at Œwinoujœcie,Kamieñ Pomorski, Ko³obrzeg and Po³czyn Zdrój, is nearly con stant (see Fig. 13),while slight fluc tu a tions are re lated to vari a tions in the groundwater extraction rate.Con sid er ing the or i gin of ground wa ter sa lin ity in the Me so zoic for ma tions itshould be borne in mind that sed i men tary rocks com pos ing these for ma tions werede pos ited mainly in ma rine en vi ron ments. That is why the chem i cal com po si tion ofgroundwater of Mesozoic aquifers is referenced to seawater, the chemical composi -tion of which has been al most iden ti cal since the Cam brian (Holser, 1979; Hol land,1984). A char ac ter is tic fea ture in the study area is the oc cur rence of Zechstein saltsun der ly ing the Me so zoic suc ces sion. There fore, the pres ent pa per in cludes an at -tempt at ex plain ing the role of these two fac tors which de ter mine the or i gin andevo lu tion of salinization of groundwaters within Me so zoic aqui fers. The es sen tialcon tri bu tion of fos sil sea wa ter to the chem i cal com po si tion of groundwaters in Me -so zoic aqui fers is cor rob o rated by the val ues of hydrochemical in di ces and re sultsof sta ble iso topes de ter mi na tion. How ever, the amount of the pri mary sea wa tercon tri bu tion, con spic u ous by its al tered chem i cal com po si tion as com pared to there cent ocean wa ter, seems to dif fer from one aqui fer to an other. The most un am big -u ous re sults were ob tained for wa ters in Tri as sic aqui fers. Most of Cl – /J – , Br – /J – ,Cl – /Br – , Ca 2+ /Sr 2+ and meqNa + /meqCl – ra tios sug gest that these groundwaters orig -i nate from fossil seawater (see Fig. 14). The percentage of values of particularindices, lower than those typical of seawater, is shown in Tab. 4.A high con cen tra tion of bro mine in brines of the Tri as sic aqui fers, and thus thelow Cl – :Br – ra tio, sug gests the pres ence of an ad mix ture of re sid ual (evaporite-re -lated) liq uids which re mained af ter the de po si tion of Zechstein and Tri as sic salt se -ries. This in ter pre ta tion is con sis tent with the con clu sions pre sented by Dowgia³³o(1971, 1988) and Szpakiewicz (1983) with re gard to groundwaters in Me so zoicaquifers of the Polish Lowlands.Less un equiv o cal val ues were ob tained from Ju ras sic aqui fers. The Cl – /J – , Br – /J –and Ca 2+ /Sr 2+ ra tios quite clearly sug gest a ma rine or i gin of sa lin ity in these

SALINITY OF GROUNDWATER, NW POLAND 59Table 4Percentage contribution of hydrochemical indices lower than the seawater averageRatiosAquiferCl – :J – Br – :J – Cl – :Br – Ca 2+ :Sr 2+ rNa + :rCl –%Triassic 100 100 78 60 80Jurassic 100 100 23 86 21Cretaceous 100 100 26 100 14groundwaters (see Fig. 14). The per cent age con tri bu tions of all anal y ses, for whichthese ra tios are lower than typ i cal sea wa ter val ues, are shown in Tab. 4. For theCl – /Br – ra tio, how ever, this per cent age is only 23%, and for the meqNa + /meqCl – ra -tio only 21%. This can sug gest the dom i nant role of wa ter of an other or i gin (for ex -am ple of fos sil me te oric wa ter), in the for ma tion pro cess of chem i cal com po si tionof groundwaters within Ju ras sic rocks. It is even more prob a ble that these val ues ofhydrochemical in di ces are due to al ter ations of the chem i cal com po si tion as a re sultof pro cesses oc cur ring within the Me so zoic se quence, such as ultrafiltration andion ex change. A high de gree of al ter ation is com monly typ i cal of ground wa ter iso -lated for a long time from the ac tive cir cu la tion zone which is the case of wa terwithin the Ju ras sic aqui fers. Only lo cally, in the Pom er a nian Anticlinorium, whereJu ras sic for ma tions are over lain by Ce no zoic de pos its only, a con tact is pos si blebe tween in fil tra tion wa ters and wa ters within the Ju ras sic aqui fers. In this case, thelast-men tioned ones are char ac ter ized by both a low to tal min er al iza tion and themeqNa + /meqCl – ra tio >1. The high meqNa + /meqCl – ra tio may be due to diageneticprocesses affecting the concentration of Na + ions in wa ter. The illitization ofsmectite in clays and dis so lu tion of al ka line feld spars (al bite) in sand stones, es pe -cially if there is a con tri bu tion of fresh me te oric wa ter, are con sid ered to be suchpro cesses. The pos si bil ity that groundwaters in the Ju ras sic aqui fers were sub ject tocon sid er able chem i cal al ter ation seems to be con firmed by the re sults of stron tiumiso topes de ter mi na tions. The87 Sr/ 86 Sr ra tios in the Pyrzyce and Kamieñ Pomorskibrines are close to the typ i cal value of re cent sea wa ter (see Fig. 21), but are higherthan the value typ i cal for Ju ras sic de pos its. The dis tinct dif fer ence be tween87 Sr/ 86 Sr ra tios in brines of the Ju ras sic aqui fers and that es tab lished for the Ju ras sicocean also suggests considerable modification in chemical composition of groundwaters in Jurassic aquifers due to reactions occurring between the water and thereservoir rocks (see Fig. 22).Sim i larly am big u ous re sults were pro vided by hydrochemical in di ces ingroundwa ters of the Cre ta ceous aqui fers. The Cl – /J – , Br – /J – and Ca 2+ /Sr 2+ ra tiosclearly in di cate the pres ence of fos sil sea wa ter. In stead, Cl – /Br – and meqNa + /meqCl – ra tios, con firm such in ter pre ta tion only to a lim ited ex tent (see Fig. 14).

60 D. KACZORMerely 26% of the Cl – /Br – ra tios yielded val ues lower than than that of sea wa ter,whereas for meqNa + /meqCl – ra tios it was only 14% (see Tab. 4). By anal ogy togroundwaters in Ju ras sic aqui fers it may be sup posed that the chem i cal com po si -tion of groundwaters in the Cre ta ceous aqui fers, in ferred from the ionic ra tio val -ues, was also de ter mined mainly by hydrochemical pro cesses such as ultrafiltrationand ion ex change. How ever, their po si tion at the top most parts of the Me so zoic suc -ces sion in di cates their higher sen si bil ity to the in flu ence of me te oric wa ters. This iscor rob o rated by the fact that 71% of TDS val ues are here be low 35 g/dm 3 , i.e. theyare lower than the seawater average.A con sid er able con tri bu tion of fos sil sea wa ter to the chem i cal com po si tion ofgroundwaters within the Me so zoic com plex is also con firmed by sta ble ox y gen andhy dro gen iso tope de ter mi na tions. Af ter in ves ti gat ing brines from the bore holesPo³czyn IG-1, “Jantar” in Œwinoujœcie, B-1 in Ko³obrzeg, “Ed ward I” and “Ed wardII” in Kamieñ Pomorski and Kamieñ Pomorski IG-1, Dowgia³³o (1971) claimedthat these were mixed ma rine and me te oric wa ters, in which the con tri bu tion of fos -sil con nate sea wa ter in creased with depth. The con clu sion that fos sil sea wa ter is themain com po nent of the groundwaters in Me so zoic aqui fers is in ferred from iso to picstud ies of brines from Lower Ju ras sic rocks sam pled in the Pyrzyce GT-1 andStargard GT-1 geo ther mal bore holes (Dowgia³³o et al., in press). The con tent offos sil sea wa ter in the Pyrzyce and Stargard Szczeciñski ther mal brines is mark edlyhigher than in wa ters de scribed in pre vi ous pa pers (see Tab. 2). On the graph of the18 O and 2 H re la tion ship, the re sults of mea sure ments of the Pyrzyce and StargardSzczeciñski brines appear to be almost the closest ones to the VSMOW point (seeFig. 18).The re sults of iso to pic in ves ti ga tions and the syn the sis of chem i cal data con firmthe the sis about a con sid er able con tri bu tion of con nate sea wa ter to the chem i calcom po si tion of min er al ized groundwaters of the Pol ish-Ger man Low lands, as pre -sented, e.g., by Paczyñski & Pa³ys (1970), Dowgia³³o (1971, 1988), Weil (1981),Szpakiewicz (1983), Lehmann (1974), Gerhardy & Hahn (1979) and Kleczkowski(1979). How ever, the re sults of these in ves ti ga tions do not en able us to dis tin guishun am big u ously be tween in di vid ual types of seawaters which are the com po nentsof the brines within Me so zoic aqui fers (Dowgia³³o, 1971). No avail able in for ma -tion makes it pos si ble to dis tin guish con nate wa ters from wa ters in trud ing into sed i -ments af ter their lithification. This is the more so as the chem i cal com po si tion ofcon nate wa ters is sub jected to con sid er able al ter ations, es pe cially due to the pro -cesses of re duc tion of sulphates, ox i da tion of or ganic com po nents, dolomitizationand albitization pro cesses within the aqui fers, as well as ion ex change and ul trafil -tra tion (White, 1965; Dowgia³³o, 1971; Kharaka & Berry, 1973; Leœniak, 1989,2005; Land & Prezbindowski, 1981; Liszkowska, 1985; Con nolly et al., 1990a;Sadurski, 1989; Tijani, 2004).The waters considered contain a certain admixture of meteoric palaeoinfiltrationwa ters, as ev i denced by dif fer ent dis tances of in di vid ual iso to pic val ues fromthe VSMOW point (see Fig. 18). These wa ters could pen e trate into the res er voirrocks in a large vol ume within up lifted tec tonic blocks. Giv ing a de scrip tion of the

SALINITY OF GROUNDWATER, NW POLAND 61ef fects of Ju ras sic and Late Cre ta ceous move ments of block struc tures across theNor we gian shelf, Egeberg & Aagaard (1989) ex pressed an opin ion that a pe riod ofsev eral mil lions of years could be suf fi cient for the res er voir rocks, lo cated withinar eas of up lifted tec tonic blocks, to have been com pletely filled with me te oric wa -ter. Based on this ex am ple, it might be pre sumed that a sim i lar sit u a tion could haveoc curred in the ana lysed seg ment of the Dan ish-Pol ish Trough. In par tic u lar, itseems prob a ble, tak ing into ac count pe ri ods when con ti nen tal con di tions pre vailed,namely the Late Rhaetian and partly also the Early Jurassic, and Early Cretaceous(Marek & Pajchlowa, eds, 1997).An other cru cial dif fi culty in dis tin guish ing par tic u lar ge netic types of wa ters isthe fact that they mixed with one an other as a re sult of mi gra tion trig gered by in -creas ing pres sure within the geo log i cal sys tem, re lated to tec tonic move ments. Thewaters migrate over considerable distances towards low-pressure areas, throughac tive fault zones and per me able interlayer path ways (Land & Prezbindowski,1994; Tijani, 2004). Thus, it can be sup posed that the in ver sion of the Mid-Pol ishTrough might have had an equally sig nif i cant in flu ence on the mi gra tion ofgroundwaters in Me so zoic aqui fers. Brines from the Kujawy re gion, typ i cal of highmin er al iza tion ex ceed ing 300 g/dm 3 and den sity of 1.211 g/cm 3 ,as, e.g., those fromthe vi cin ity of the Wapno salt diapir (Górski, 2000), could have also migrated intothis area.An as sump tion con cern ing the dom i nant role of fos sil me te oric wa ters played infor ma tion of re cent chem i cal com po si tion of groundwaters within Me so zoic rocksof the Pol ish Low lands, pre sented by Zuber & Grabczak (1991), was ac cepted byKrawiec et al. (2000). It is based pri mar ily on in ter pre ta tion of ox y gen and hy dro -gen iso tope ra tios. Ac cord ing to that in ter pre ta tion, brines of the Me so zoic aqui ferswere formed mainly by palaeoinfiltration of me te oric wa ters which pen e trated intothe sys tem dur ing geo log i cal pe ri ods warmer than to-day’s cli mate. Ac cord ing tothese au thors their sa lin ity is prin ci pally re lated to the dis so lu tion of Zechsteinsalts. In the dis cus sion on the or i gin of wa ter sa lin ity in Me so zoic aqui fers oneshould take into con sid er ation that the dis so lu tion of Zechstein salts could oc curonly in case when there was a con tact be tween un sat u rated wa ters and salts. Thestruc ture of the Perm ian–Me so zoic se quence (Dadlez, ed., 1976; Dadlez, 2001)shows that there is a con tact be tween salt bod ies and groundwaters of Tri as sic aqui -fers. How ever, the val ues of hydrochemical in di ca tors of these groundwaters arecloser to those char ac ter iz ing sea wa ter than to the val ues typ i cal of so lu tionsformed as a re sult of salt dis so lu tion. The re sults of stable oxygen and hydrogenisotopes measurements in the groundwaters also indicate a larger contribution ofseawater.The Cl – /Br – ra tios in groundwaters from the Lower Tri as sic aqui fer, which is inthe di rect con tact with Zechstein salts, com monly vary within the range of100–200, thus the groundwaters nei ther ex hibit any fea tures of so lu tions formeddue to ha lite pre cip i ta tion (the Cl – /Br – ra tio in such wa ters is close to 69) nor arethey typ i cal sea wa ters in which this ra tio is close to 300. There fore, it can be sup -posed that they are mix tures of dif fer ent types of wa ters in which, e.g., an ad mix ture

62 D. KACZORof re sid ual liq uids, con tain ing con sid er able amounts of bro mine, could re duce thevalue of Cl – /Br – ra tio in the case when Cl – ions were de rived from salt dis so lu tionpro cesses. Thus, low Cl – Br – ra tios, typ i cal of brines within the Tri as sic aqui fers,cannot give ground for precluding halite leaching.The dis so lu tion of salts could have oc curred if brines of the Me so zoic aqui fershad taken an ac tive part in ground wa ter cir cu la tion and had not reached the state ofsat u ra tion. In that sit u a tion, the leach ing of salts could take place even at pres ent.How ever, the brines of the Me so zoic in the Pol ish Low lands are iso lated from theac tive cir cu la tion zone, as in di cated by the meqNa + /meq Cl – ra tio which amounts toless than 1 in al most all (93%) of the 230 wa ters ana lysed. The leach ing of saltsmight have oc curred in the study area dur ing Me so zoic times un til there was nochem i cal bal ance be tween the salts and the wa ters re main ing in con tact with them.As far as groundwaters from the Ju ras sic aqui fers are con cerned, they are in di rectcon tact with Zechstein salts only in the vi cin ity of the Miêdzyzdroje, Goleniów,Oœwino and Grzêzno salt struc tures partly pierc ing the aqui fers. The the salt leach -ing pro cess was con firmed only in cases of bore holes: Cz³opa 1, Cz³opa 2, Cz³opa3, Warnowo 1, Wysoka Kamieñska 4, Dargob¹dz 1, Chociwel 3, Obrzycko 2,Wolin IG-1, Oœwino IG-1 and Grzêzno 5. The con firm ing ar gu ment were theCl – /Br – ratios, ranging between 412 and 8477.Un equal dis tri bu tion across the area of data-pro vid ing bore holes, in par tic u larthose pierc ing the top of the Zechstein se quence, and the lack of bore holes close tosome salt struc tures, make it dif fi cult to carry out de tailed in ves ti ga tions of the saltdis so lu tion process.The lack of con tem po rary pro cesses of salt dis so lu tion in the area is also ev i -denced by the lack of re ported events of sub si dence ob served at the sur face, as in di -cated by Dowgia³³o (1971). Dis so lu tion of rock-salts, re sult ing in de crease of theirvol ume, would cause de for ma tion of the land sur face. Such events have been re -ported from the neigh bour ing area ex tend ing be tween Poznañ and £ódŸ, where lo -cal de pres sions/grabens/troughs, filled with thick Palaeogene and Neo gene de pos -its, have developed (Kasiñski, 2004).Nu mer ous ex am ples of dis so lu tion of salt diapirs dur ing the Ho lo cene areknown from north ern Ger many (Glander, 1970; Lehmann, 1974; Putscher, 1978).The salt diapirs pierce through the Me so zoic rocks and are in con tact with wa terscir cu lat ing within the aqui fer sys tem. The leach ing of the Sperenberg salt struc turenear Berlin caused a con sid er able low er ing of the area that re sulted in dam ages tobuildings (Putscher, 1978).There are no salt struc tures be ing at such a ma ture stage of de vel op ment in thestudy area. The only ex cep tion is the Goleniów salt diapir partly pierc ing Ju ras sicde pos its, whose salts were sub jected to leach ing pro cesses dur ing the Palaeogene,as ev i denced by an oma lously large thick ness (>400 m) of the over ly ing de pos its ofthis age (Jaskowiak-Schoeneichowa, ed., 1979). Within the is struc ture, the top ofZechstein rocks oc curs at a depth of ap prox i mately 700 m be low the sur face. Forthe rest of the salt struc tures in the study area, the top of the Zechstein lies muchdeeper, con sid er ably deeper than the top of fresh groundwaters, with the max i mum

SALINITY OF GROUNDWATER, NW POLAND 63depth of 700 m be low the sur face at Po³czyn Zdrój. Thus, it can be as sumed that thesa lin ity of groundwaters in Ce no zoic aqui fers is not a re sult of the cur rently on go -ing pro cess of dis so lu tion of salt bod ies, but is pri mar ily as so ci ated with the as centof fos sil sa line wa ters from the Me so zoic de pos its. In this area, the pro cess of brinesas cent is fa voured by hy dro dy namic con di tions. The brines oc cur un der highpiezometric pres sure oc ca sion ally re sult ing in their ar te sian out flows at the sur face.The ex am ples are the ar te sian out flows of brines re ported from the bore holes:Kamieñ Pomorski IG-1 (see Fig. 9), “Ed ward II” at Kamieñ Pomorski, Jatki II,“Józef” at Dziwnówek (see Fig. 9), Grzybowo 1, Jarkowo 1, Marianowo 1 (see Fig.10), Ustronie IG-1 (see Fig. 9), Jamno IG-3, Biesiekierz 1, Pi³a IG-1 (see Fig. 11),B-1 and B-2 at Ko³obrzeg and “Anastazja” at Podczele (see Fig. 9).An in tense as cent of sa line ground wa ter has been ob served in the north ern partof the Pom er a nian Anticlinorium, where there is no Oligocene clay cover, andwhere Me so zoic rocks, cut by nu mer ous faults, con tain sa line wa ters be ing in con -tact with wa ters from the Pleis to cene aqui fers. Clus ters of mea sure ment points rep -re sent ing the in creased chlo ride con cen tra tions in groundwaters of Pleis to ceneaqui fers oc cur along the Karlino-Szczecinek fault zone (be tween Ko³obrzeg andBia³ogard) – see Fig. 26, and the Œwinoujœcie – Drawsko fault zone (be tweenNowogard and £obez) – see Fig. 27.Ar eas of chlo ride con cen tra tions ex ceed ing 30 mg/dm 3 within Ce no zoic aqui -fers also oc cur above most of the salt anticlines con sid ered, prov ing that those arezones of an in tense as cent of sa line groundwaters from the Me so zoic com plex. Therole of salt struc tures in the pro cess of ground wa ter salinization re lies pri mar ily onthe fact that ar eas of re duced thick ness of Oligocene (Rupelian) clays, iso lat ing sa -line groundwaters from fresh groundwaters, oc cur above the crests of salt struc -tures. Hydrogeological win dows which de vel oped in these ar eas are con sid ered themain zones of brine as cent in north ern Ger many (Glander, 1970; 1982; Grube,2000; Grube et al., 2000). Mi gra tion of brines oc curs through strongly frac turedMe so zoic rocks cap ping salt anticline crests. Such a hy poth e sis was pos tu lated byMacioszczyk (1980) and Dowgia³³o and Nowicki (1997) who con sid ered thestrong frac tur ing of rocks above salt diapirs as the main rea son for the de vel op mentof chlo ride anom a lies in groundwaters of Oligocene and Miocene aquifers in theMazowsze Trough.A re la tion ship of ground wa ter sa lin ity in the Mio cene aqui fer of the Cen tralWielkopolska Re gion with the oc cur rence of faults in the sub-Ce no zoic base mentwas also pos tu lated by Górski (1989). In the study area, how ever, zones of clus tersof points show ing in creased con cen tra tions of chlo rides in ground wa ter con tinue toap pear also in neigh bour ing syncline ar eas, as wa ter is spread ing con cor dantly tothe di rec tions of ground wa ter flow. Ground wa ter, cir cu lat ing in the up per parts ofthe sys tem, di lutes brines as cend ing from the Me so zoic base ment, and the so lu tionsformed in this way flow to wards dis charge zones, i.e. to wards river val leys. As a re -sult of sa line groundwaters oc cur rence in Ce no zoic aqui fers, this is fre quently ob -served out side hydrogeological win dows which are the main zones of brine ascentfrom Mesozoic deposits.

64 D. KACZORCONCLUSIONS1. The sa line groundwaters of the Me so zoic in NW Po land are poly gen etic.Their main com po nents are fos sil (con nate and in tru sive) seawaters and fos sil me -te oric (in fil tra tion) wa ters. Only lo cally, in the up per parts of the Me so zoic se -quence, Qua ter nary in fil tra tion wa ters pro vide a small con tri bu tion.2. The or i gin of ground wa ter sa lin ity in Me so zoic rocks is pri mar ily re lated totheir ma rine or i gin and, to a lesser ex tent, to the dis so lu tion of Zechstein and Tri as -sic salts. The dis so lu tion of Zechstein salts oc curred in con tact zones with groundwaters of the Me so zoic and lasted un til there was no chem i cal bal ance be tween therock-salt and wa ter. Re cently, such a con tact zone ex ists only at the base of theLower Tri as sic strata and around 16 salt struc tures pierc ing the Tri as sic aqui fers.Brines in Tri as sic aqui fers con tain an ad mix ture of re sid ual (evaporite-re lated) flu -ids as so ci ated with the Zechstein and Triassic salt series.3. The chem i cal compostion of sa line groundwaters within Me so zoic aqui fers isvery sim i lar within par tic u lar aqui fers and par tic u lar Me so zoic tec tonic units.These groundwaters are rep re sented mostly by the Cl-Na wa ter type; Cl-Na-Mgtype wa ters are spo radic. Cl-Na-Ca wa ter type is dom i nant only in the Lower Tri as -sic aqui fer. Among an ions, chlo ride ions are pre dom i nant oc cur ring in the amountsof 54.2–99.7 meq%. Bi car bon ates and sulphates make a con sid er ably smaller con -tri bu tion com monly be low 1 meq%. Among cat ions, so dium pre dom i nates, withthe av er age con tent rang ing be tween 14.9 and 97.6 meq%. The cal cium con tentvar ies be tween 0.2 to 33.3 meq%, that of mag ne sium – be tween 0.2 to 30.2 meq%.Sa line groundwaters of the Me so zoic com plex are char ac ter ized by a con sid er ablecon tent of trace el e ments with bro mine and io dine pre dom i nat ing. The chem i calcom po si tion of groundwaters in Me so zoic rocks was subjected to significantalterations in general due to water-rock interaction.4. Dur ing a 40-year pe riod of mon i tor ing the health re sort wells, the chem i calcom po si tion of brines in Me so zoic aqui fers has not changed, as in di cated by the al -most con stant to tal min er al iza tion be ing pro por tional to the vari abil ity in the con -cen tra tion of chloride ion.5. The sa lin ity of groundwaters in Ce no zoic aqui fers, com monly con sid ered asbe ing the main prob lem re gard ing the us age of groundwaters along the coastalzone, is dis tinctly marked also through out a con sid er able part of NW Poland.6. The salinization of groundwaters within the Ce no zoic aqui fers oc curs due tothe as cent of sa line wa ters from Me so zoic for ma tions. This as cent oc curs whenthere is a high piezometric pres sure of brines, caus ing their flow to wards fresh wa -ter aqui fers through a sys tem of frac tures. This pro cess de vel ops best withinhydrogeological win dows formed in zones of re duced Oligocene clay cover abovethe up lifted salt-cored anticlines and tectonic blocks.7. The ex tent of ground wa ter sa lin ity zones in Ce no zoic aqui fers is de pend enton flow di rec tions of groundwaters which di lute the brines mi grat ing up wards fromMe so zoic rocks. That is why the ar eas of con firmed sa lin ity are not al ways co in ci -dent with the ground wa ter ascent zones.

SALINITY OF GROUNDWATER, NW POLAND 658. Up ward mi gra tion of brines is haz ard ous to ground wa ter qual ity of 4 out of 20Ma jor Ground wa ter Res er voirs iden ti fied across the study area: Usedom Is -land-101, Wolin Is land-102, Roœcino-103, Dêbno-134. The re main ing MGRs areonly slightly threat ened be cause they co in cide only in part with the ar eas of con -firmed or sup posed ground wa ter salinization. The to tal area of con firmed sa lin ity is8600 km 2 , i.e. 33% of the whole area of in ter est. The area of po ten tial salinizationhaz ard, cor re spond ing to ar eas where the Oligocene clay seal is re duced in thick -ness or com pletely lack ing, is 4900 km 2 , i.e. 19% of the study area.9. The wa ter salinization is also haz ard ous to 16 ma jor ground wa ter in takesyield ing more than of 100 m 3 /h of water.AcknowledgementsThis pa per pres ents the re sults of doc toral re search per formed dur ing the pe riod of 2000–2004 atthe Post-Grad u ate Stud ies of the Pol ish Acad emy of Sci ences in War saw. The au thor would like toex press cor dial thanks to her promotor, Pro fes sor Jan Dowgia³³o, for point ing at this sci en tificprob lem and for sev eral years of sci en tific su per vi sion. She also wishes to ex press her grat i tude to allper sons and in sti tu tions help ful in col lect ing data and sam ples from wells. Spe cial thanks are due toMgr B. Krawczyk from Ko³obrzeg, Ing. S. Kêpczyñski from Po³czyn Zdrój and Ing. S. Pietraszukfrom Kamieñ Pomorski for mak ing ar chi val data ac ces si ble, to M.Sc. ing. N. Maliszewski from“Geotermia Pyrzyce” and M.Sc. ing. W. Gil from “Geotermia Stargard” for their help in brinesam pling from geo ther mal wells. Thanks are also due to Dr A. Porowski and Dr G. Zieliñski from theIn sti tute of Geo log i cal Sci ences of the Pol ish Acad emy of Sci ences for performing isotopicinvestigations of water samples.REFERENCESAscherson, P., 1859. Die Salzstellen der Mark Brandenburg in ihrer Flora nachgewiesen. Zeitschriftder deutschen Geologischen Gesellschaft, 11: 90–100.Berry, F. A. F., 1969. Rel a tive fac tors in flu enc ing mem brane fil tra tion ef fects in geo logic en vi ron -ments. Chem i cal Ge ol ogy, 4: 295–301.B³aszczyk, T. & Górski, J., 1977. Œrodowisko hydrogeochemiczne w utworach pradolinnych orazjego przeobra¿enia w warunkach zmian re¿imu wód podziemnych (Hydrogeochemical en vi ron -ment in ice-mar ginal val ley de pos its, and its al ter ations in duced by changes in ground wa ter flowre gime – in Pol ish). Biuletyn Instytutu Geologicznego Uniwersytetu Warszawskiego, Warszawa,21: 217–227.Bojarska, J. & Bojarski, L., 1968. Jurajskie solanki termalne Polski pó³nocnej i zachodniej (Ju ras sicther mal brines in north and west Po land – in Pol ish). Kwartalnik Geologiczny, 12 (3): 576–588.Bojarski, L., 1966. Jod i brom jako wskaŸniki hydrochemiczne wystêpowania wêglowodoróww mezozoiku i paleozoiku Polski pó³nocnej i zachodniej (Io dine and bro mine as hydrochemicalin di ca tors of hy dro car bons in Me so zoic and Palaeozoic de pos its in North and West Po land – inPol ish). Kwartalnik Geologiczny, 10: 177–193.Bojarski, L., 1970. Ocena hydrochemiczna mo¿liwoœci wystêpowania wêglowodorów w nadba³tyckiejczêœci antyklinorium i synklinorium pomorskiego (Hydrochemical es ti ma tion of hy dro car -bons occurence in the peri-Bal tic port of the Pom er a nian Anticlinorium and Synclinorium – inPol ish). Kwartalnik Geologiczny, 1: 88–98.Bojarski, L., 1972. Wyniki opróbowania poziomów zbiornikowych (Re sults of aqui fer tests – inPol ish). In: Dadlez R. (ed.), Pro file g³êbokich otworów wiertniczych Instytutu Geologicznego(Deep bore holes of the Pol ish Geo log i cal In sti tute – in Pol ish), Zeszyt 1, Kamieñ Pomorski IG-1.Wydawnictwa Geologiczne, Warszawa: 134–145.

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GERMANYKo³ obrzegJamnoPodczeleAnticlineSarbinowo1 IG 3“Anastazja”Jamno IG 1UstronieKamieñGrzybowo 1“B1,B2” IG 1TrzebiatówPomorskiDŸwirzyno1Koszalin A’SynclineAnticlineIG 1Ko³obrzeg 1DziwnówekBiesiekierz1 Manowo1 Wyszebórz1Polanów1O17 00’Wise³kaKamieñKo³czewo1 “Józef” Sadlno1 Karcino 1Dygowo1K³anino2 Polanów2SynclinePom.IG1Dunowo1Okunino1Wolin IG 1Gorzys³aw14“Jantar”GoœcinoKarsina1WarnowoGostyñ IG 1“Teresa” Przytór1IG 1Gozd3 B’Karlino11Grzybnica IG 1A“Edward II”Jarkowo1Jatki IIBia³ogard 5 Chociwle2Gozd1DMiastko1Rymañ12Bobolice3 Drzewiany1Rec³awSamlino1IG 1Brojce IG 1Wierzchowo5Bia³y Bór7Dargob¹dz1Wierzchowo3 Bobolice2RokitaIG 1 Wysoka Kamieñska4Wierzchowo9 Bia³y Bór1Wysoka Kamieñska1Bia³y Bór3Brzezie1Po³czyn 2GoleniówPo³czyn IG 1IG 1Œwinoujœcie1Œwinoujœcie4OdraPrzytórMiêdzyzdrojeCedyniaBALTIC SEANoweWarponChojnaC zelinDargob¹dzSzczecinIG 1GoleniówCChabowo 3BanieGrzêzno5Grzêzno2GrzêznoOœwino IG 1Chociwel 3Marianowo2Marianowo1GT 1Stargard GT 2 Marianowo3Chabowo 1DêbnoKodr¹bWierzch os³awiecGryfinoWiduchowaKra kówkoSzczecinChabowo 2GT 2GT 4GT1PyrzyceGT 3LipianyMyslibórzWysokaRokitaMaszewoNowogardC habow oMyœlibórz 1KarskReskoOstrzycaC h oszcznoChociwelIG 1Mari a no w oPe³czyceRe c z£ob e zOœwinoIñskoP³awno1DrawnoGeo3Drawno1Œ w idwinDr a wk s oRadêcin1Dre z de n koStrzelceKrajeñskie IG 1DrawnoP³ awnoPOME R AN I AN A NTICLI N ORI U MCzaplinek IG 2Cz³ o paHutaSzklana1Po³czynMê¿yk1P O ME R ANIAN SYNCLIN O RIUMM i ros³awiec - T r zc i an k aominikow oDCz³opa3Czaplinek IG 1Pi³a IG 10 10 kmFORE -S UDET IC MONO CLINEGorzów WielkopolskiIG 1B(G OR ZÓW B LOCK )Miêdzychód IG 1SZ Z CIN YNC N RIUMCz³opa2Cz³opa1Barw ice Lo yC E S LI OSzamotu³yK raj e nkoC’Pi³at ñExplanations:Permian-Mesozoic structural elements after Po¿aryski (ed.), 1974;Dadlez (ed.), 1976, 1998; Dadlez, 1987, 1979Salt structures:confirmed faults presumed faultsBorehole tested for aquifer of:Cretaceous Jurassic TriassicA A’not piercing Triassic depositspartly piercing Triassic depositspiercing Triassic depositsnames of salt structuresC zelinboundaries of major tectonic unitsoutlines of the Wise³ka and Trzebiatów Synclinesoutlines of the Kamieñ Pomorski and Ko³obrzeg Anticlinescentral zone of salt tectonicsgeological and hydrochemical cross-section lineO52 35’Obrzycko2D’Obrzycko1ObjezierzeIG 1Fig. 3. Geological inventory sketch

GERMANYOdraUstronieJamnoIG 1 114.5IG 1K o³obrzeg210.0DŸwirzyno1Jamno 93.5O186.0 206.0 251.0 IG 3 KOSZALIN17 00’Ko³obrzeg PN 1152.2-220.9Dygowo1Karsina1Warnowo1 Ko³czewo1 255.0198.0Dunowo1104.2 70.4Goœcino IG 1228.0Sadlno1124.0253.0115.9Polanów2264.0 Gorzys³aw14 158.0 Karlino1Grzybnica 174.7223.0201KamieñJarkowo1Bia³ogard 5IG 1 Gozd3 133.0Pom.2248.0160.099.2Samlino1Miastko1189.0BrojceBobolice3 167.0Przytór1199.0Rymañ1162.0Chociwle2Dargob¹dz1 250.0IG 1248.0ŒwidwinWysoka Kam.4MoraczIG 1Œwinoujœcie0 10 kmO52 35’GryfinoBALTIC SEA250.0RokitaIG 1GoleniówSZCZECINStargardSzczeciñskiPyrzyceMyœlibórzDêbnoNowogardStrzelceKrajeñskieIG 1£obezChoszczno253.0280.0 GORZÓW WLKP.Gorzów Wielkopolski IG 1DrawnoFORE-SUDETIC M ON OCLINE(GORZÓW BLOCK)PO M ERANIAN SYNCLI N O R IUM174.0Czaplinek IG 2Czaplinek IG 2314.0229.0Po³czyn IG 1PO M ER A NIAN A N TICLINORIUMHutaSzklana1CzaplinekCzaplinek IG 1192.0Wa³czPI£ASZC Z E C IN SYN C LINORI U M109.0Obrzycko 2ObjezierzeIG 1328.0Explanations:Permian-Mesozoic structural elements after Po¿aryski (ed.), 1974;Dadlez (ed.), 1976, 1998; Dadlez, 1987, 1979Salt structures:174.7Gozd 3Dêbno3Total mineralization intervals, in g/dm :20 % mval)Cl-NaCl-Na-CaCl-Na-Mg. Cl-Mg-Na150 - 200200 - 250250 - 300300 - 350Cl-Na-Ca-MgHCO -Ca 3Fig. 6. Chemical composition of groundwaters from the Lower Triassicaquifer against the background of the Permian-Mesozoic structuralcomplex3

G E R MANYJamnoPodczele IG 3“Anastazja”69.760.9 64.6Ko³obrzeg33.6 Koszalin IG 1Ustronie 68.91.4 B-2Dziwnówek Ko³obrzegPN1IG 1 88.0 KOSZALIN“Józef”Biesiekierz164.20.5Gostyñ IG 189.9Goœcino IG 1Wolin34.00.4“Edward II”Œwinoujœcie1 IG 1173.9101.010.0KamieñJarkowo1 Bia³ogard112.0Jatki II 16.0Pomorski92.3Dargob¹dz280.4 Brojce IG 177.2 Samlino1Wierzchowo3Rec³aw IG 153.2-67.0Rokita IG 1ŒwidwinPo³czyn ZdrójOœwino 99.6SZCZECINIG 1Chociwel 3116.7-121.0 120.7-129.9120.0 119.5 Marianowo 2GT 1Marianowo 1125.7Stargard GT 2 Marianowo 3Chabowo 270.6-98.0Odra0 10 kmO52 35’BALTIC SEAGoleniów76.5-114.0Chabowo 3GT 2 115.6-125.8GT1 GT 4Pyrye zc GT 3MyœlibórzDêbno55.8Jeniniec 2ChoszcznoFO R E-SUDETI CMONOCLINE(GORZÓWBLOCK)97.997.0P³awno1109.0Drawno1StrzelceKrajeñskie IG 1GORZÓW WLKP.64.4Gorzów Wielkopolski IG 194.0Radêcin1106.072.0-94.6 Cz³opa265.0 Cz³opa1Cz³opa3107.0Mê¿yk1POME R ANIANSY N CLINORIUM6.9Pi³a IG 1148.0Bia³y Bór3POME R ANIAN A NTICLIN O RIUMPI£ASZCZ E CI NSY NC L IN OR IU MO17 00’109.0Obrzycko 2Dnêbo localitiesextent of Lower Jurassic deposits (after Dadlez, 1979)location and name of well testedthe number denotes total mineralization in g/dmfor other explanations see Fig.6.Fig. 7. Chemical composition of groundwaters from the LowerJurassic aquifer against the background of the Permian-Mesozoicstructural complex3

WNW ESE SW NE WNW ESE W Em a.s.l. Przytór Warnowo Kamieñ Pom. GostyñKarcino Ko³obrzeg Podczelem a.s.l.Œwinoujœcie Wolin Ko³czewo DziwnówekSadlno Gorzys³aw DŸwirzyno “Anastazja” Ustronie JamnoIG 1IG 1 “Józef”Sarbinowo1 1 J 3 KIG 11 1 K 21 IG 1 K 1 1 K 2 14 1 1 1 B2K 1 1 IG 3 IG 1 20 K 60.902J 2 J 3J 64.6K 2J 21J 64.2J JJ12 J3 J J 3K 2 K 2J 3250m21 J1350mJ J J21J2J2 K150J2133.6T 72.2101.0J 783m69.71J3JJ11T1J 231T 3-1000189.0 101.5 -1000173.088.8 T 289.4 T 3 T89.974.92 TT 124.0 93.43T33J 1T 2 93.5T 154.0114.42T 223.0 T 2 252.03124.4T2001 T 1T 1609mT 288.21696m1T 3-2000T 1T 3T 11T 1 1985m-2000T 2T 1P210.0 3000mPPT3020m 2582m 1T12722m255.60 10 km-3000 3357m3000m3280m 2819m 3182.4m 3100m 3000m-30003180.6m- 4000Explanations:CenozoicJ 3 Upper Jurassic T 3K 2 Upper Cretaceous Middle Jurassic T 2K 1 Lower Cretaceous J 1 Lower Jurassic T 1faults confirmedfaults presumed4447mUpper TriassicMiddle TriassicLower TriassicP50J 260.9100Permianborehole borehole located off the sectionFig. 9. Geological and hydrochemical cross-section A-A'3Total mineralization isolines in g/dm3Groundwater mineralization measured in g/dmGroundwater table( stated; stabilised)- 4000SSENNW S N W E SW NE WSW ENE SWNEMarianowoBobolice 2Gorzów Wlkp. Myœlibórz 1 Pyrzyce Stargard Szcz.Chociwel 3 OœwinoOkunino 1m a.s.l.Czaplinek Po³czyn Zdrój Wierzchowo Drzewiany m a.s.l.IG 1GT 3 GT 2 GT 1 1 2 3IG 1IG 2 IG 1 23 1001.0 J30.0 K1K 2K1T2J30.7 J 3 J32 42.0K501K 1 K3J 1JK 1 K 11K1JJ 31T 770m23 T J- 1000502 23.2 37.02-100064.492.3100J 94.0T 1J 2T 3J 1J 13 125.8 115.61001630m1640m119.5 121.0 96.0TJ 125.7174.13 104.4 J T223T 1T 1- 200099.61873.2m -2000280.0 T 2JT 3T 1 2045m2 120.5125.0228.82100mT160.01 283.3 T T 1TT 231 T 1Oœwino5020m2705m T 1 2482m- 30002672mT 1-3000MyœlibórzChabowo2917m199.9 salt£obez Po³czyn3100.5m P salt pillow3361m3304mP salt pillow Marianowo diapirP salt pillow salt pillow- 4000salt pillow-40003893m0 10 km(For explanations see Fig.9)Fig. 10. Geological and hydrochemical cross-section B-B'300200020

NWNESE WS WSWENEm a.s.l.m a.s.l.Chabowo 3 PyrzyceP³awno 1 Radêcin1 Cz³opa Pi³aGT 1 GT 4IG 13 1 2 J 2J 20KK K 2K 122K K 1 2 J 1J 172.0JKJ 5012J 3 J 3 6.9- 10003 94.6 J 3- 100076.5J 294.0J 2 114.0117.6 124.3 97.03K 1J 65.0 T1106.03299.2T298.4J 1 3T 3 T 3- 2000 140.4T 3T - 2000T3JT 21T22T 1T 1T 3T 1T 1T 1 T 1T 2- 3000Trzcianka- 3000P³awnoChabowoT salt pillowsalt pillow1salt pillowP3524m Cz³opaPi³a3555m salt diapir salt pillow- 4000- 40000 10 km5482mFig. 11. Geological and hydrochemical cross-section C-C'(For explanations see Fig.9)1000205 0100200030NWSENSNWSEm a.s.l. Dargob¹dzHutaWolinRec³aw Goleniów Grzêzno Chociwel Drawno Radêcin Szklana Mê¿yk ObrzyckoIG 1 IG 1 532J 3IG 1 IG 111 1 1 10 J 3J2100J 2 K 2 40.0K 2J 1112.0-1000 173.9 J1 77.2K 294.075.0 63.589.0125.7K 109.0KJ 11J 3 K11J 363.9 K JT 3 T 1T 3J 2 T 221620m104.4K 3-2000T1J 11900m 2 J 2125.0J 3T 22T 3T 1J 1 T Grzêzno 160.0P3J 1PsaltT-3000 2819.1m GoleniówT 3T1T 2T32 diapir2767.0m314.0199.92906.1m3116.7m saltT 2TT 123228.2m Drawno3129.0mdiapirP 3361mP³awnoT T 11T 1salt salt pillowP-40003649mdiapir0 10 kmP4434.0m 4381.7m02050100200300m a.s.l.0-1000-2000-3000-4000Fig. 12. Geological and hydrochemical cross-section D-D'(For explanations see Fig.9)

G E R MANYŒwinoujœcieIIII’GryfinoSzczecinLagoonPoliceBALT IC SEAIII’SZCZECINIIIKami eñPomorskiPyrzyceGoleniówMrze¿ynoTrzebiatówGryficeNowogardRegaReskoStargard SzczeciñskinIaI I’Ko³obrzegChoszcznoDrawnoŒwidwinb£oezMielnoKOSZALINBia³ ogardDêbczynoTucznoP o³ cz ynZdrójKalisz PomorskiPa rs êt aCzaplinekWa³ czPad e wPI£AO17 00’W ie pra zSzczecinekGwdaExplanations:Permian-Mesozoic structural elements after Po¿aryski (ed.), 1974;Dadlez (ed.), 1976, 1998; Dadlez, 1987, 1979Salt structures:I I’not piercing Triassic depositspartly piercing Triassic depositspiercing Triassic depositsflow directions within Cenozoic aquifers (after Paczyñski - ed., 1993)boundaries of major tectonic unitsfaults confirmed faults presumedsurface watersheds (after Czarnecka - ed., 1987):first ordersecond order3chlorides concentration in Pleistocene aquifers >30 mg/dmarea devoid of Palaeogene and Neogene deposits(after Ciuk & Piwocki, 1988)hydrogeological cross-section lineDrawaRu rz yc aT yw aNoteæP³o n iaChojnaMyœlibórzOdra0 10 kmO52 35’MyœlaDêbnoWartaGORZÓWWLK.StrzelceKrajeñskieNo te æWartaCzarnkówkWroniRyczywó³Fig. 24. Distribution of increased chlorides concentrations in Quaternary aquifers