Indus­tri­al waters of the Pre-Carpathi­an depres­sion

Indus­tri­al waters nat­u­ral­ly con­tain dis­solved micro­com­po­nents and their salts. They can be ther­mal and used for heat ener­gy; asso­ci­at­ed oil­field waters are enriched with trace ele­ments that accom­pa­ny oil and gas explo­ration; methane waters indi­cate a high­ly increased con­tent of iodine, bromine, and some­times lithi­um; nat­ur­al brines and bit­tern are min­er­al salts—table salt, soda, potash.

Indus­tri­al waters come in dif­fer­ent types: bromine, iodine, stron­tium, boron, iodine-bromine, lithi­um, iodine-boron, ura­ni­um. The main com­po­nents extract­ed from these waters are the cor­re­spond­ing chem­i­cal ele­ments and their salts. Nat­ur­al brines and bit­tern are also types of indus­tri­al waters, com­mon­ly found in the Pre-Carpathi­an depres­sion. His­tor­i­cal­ly, salt was pro­duced (boiled) in the Pre-Carpathi­an region in well-known salt­works in the cities of Doly­na, Dro­hobych, and Bolekhiv. Fac­tors con­tribut­ing to the sta­ble chem­i­cal com­po­si­tion of indus­tri­al waters include their for­ma­tion and depo­si­tion at sig­nif­i­cant depths, move­ment along tec­ton­ic faults, and cir­cu­la­tion through cracks and pores in rock for­ma­tions.

In the Pre-Carpathi­an depres­sion, in the oil and gas-bear­ing areas of the Bilche-Volyt­s­ka SFA and the Boryslav-Pokut­sky SFA, man­i­fes­ta­tions of indus­tri­al waters are encoun­tered. Com­plex tec­ton­ic dis­rup­tions and the geo­log­i­cal struc­ture in the cross-sec­tion of oil, gas, and salt-bear­ing deposits serve as a habi­tat for these waters, appear­ing in forms with defined geo­chem­i­cal types of water, spe­cif­ic indi­ca­tors such as min­er­al­iza­tion, the pres­ence of sul­fates, trace ele­ments, and tem­per­a­ture. The pres­ence of bar­i­um, radi­um, stron­tium, molyb­de­num, gold, mer­cury, ura­ni­um, ger­ma­ni­um, and oth­ers in oil­field water indi­cates the pres­ence of oil and gas, while their con­cen­tra­tion points to the loca­tion of oil and gas deposits in the cross-sec­tion and the type of indus­tri­al water. Under­ground waters, found at sig­nif­i­cant depths, have ele­vat­ed tem­per­a­tures and trans­port heat as they move, poten­tial­ly being used as geot­her­mal ener­gy sources.

The brines of the Doly­na deposit are char­ac­ter­ized by high qual­i­ty, sta­ble chem­i­cal com­po­si­tion, and min­i­mal impu­ri­ties. Pre­dic­tive indi­ca­tors in plat­form con­di­tions sug­gest a chlo­ride-sodi­um type of under­ground water with high min­er­al­iza­tion, while in mod­ern tec­ton­ic con­di­tions of the Alpine fold­ing, a reli­able indi­ca­tor would be the type of bicar­bon­ate-sodi­um water with low min­er­al­iza­tion. The geo­log­i­cal age of under­ground waters ranges from the Cam­bri­an, Upper Juras­sic, Upper Cre­ta­ceous, Pale­o­gene, to the Neo­gene. The full age range of indus­tri­al man­i­fes­ta­tions of under­ground waters is present in the Bilche-Volyt­s­ka and Boryslav-Pokut­sky oil and gas-bear­ing regions. Indus­tri­al brines and bit­tern are known in the salt-bear­ing deposits of the Vorotyshne and Bal­it­s­ka lay­ers of the Neo­gene peri­od. The bal­ne­o­log­i­cal resources of the Pre-Carpathi­an arte­sian basin are rep­re­sent­ed by a vari­ety of salt com­po­si­tions, which define their prop­er­ties as geot­her­mal and min­er­al raw mate­ri­als.

Indus­tri­al waters have estab­lished indus­tri­al stan­dards. For boron waters to be clas­si­fied as indus­tri­al, they must con­tain 300–500 mg/dm³ of boron; bromine waters must have a bromine con­tent of at least 250 mg/dm³ for selec­tive extrac­tion; iodine waters must have a min­i­mum iodine con­cen­tra­tion of 18 mg/dm³ for selec­tive extrac­tion; iodine-bromine waters have low­er con­cen­tra­tion thresh­olds for iodine, boron, and bromine, while in indus­tri­al water for com­plex extrac­tion, the iodine con­tent must be 10 mg/dm³, B₂O₃–150 mg/dm³, and for boron con­cen­trate preparation—200 mg/dm³, bromine—200 mg/dm³; iodine-boron waters have low­er thresh­olds when B₂O₃ is 150 mg/dm³ and iodine 10 mg/dm³, and for boron con­cen­trate preparation—20 mg/dm³; iodine-bromine brines must con­tain no less than 200 mg/dm³ of bromine and no less than 10 mg/dm³ of iodine. Under­ground waters show high con­cen­tra­tions of bromine and iodine, less com­mon­ly boron, which in some places exceed mod­ern indus­tri­al stan­dards by sev­er­al times.

Bromine and iodine manifestations of industrial waters

The man­i­fes­ta­tions of indus­tri­al con­di­tions of bromine waters have been iden­ti­fied in the Kalush and Staru­nia areas, where chlo­ride-sodi­um brines with a min­er­al­iza­tion of 319–321 g/dm³ and a bromine con­tent of 374–496 mg/dm³ are found.Industrial con­di­tions of iodine have been iden­ti­fied in three man­i­fes­ta­tions: Liskivsky, Nizh­niys­tru­tyn­sky, and Grabivsky‑1. These are rep­re­sent­ed by chlo­ride-sodi­um brines with a min­er­al­iza­tion rang­ing from 53 to 119 g/dm³ and an iodine con­tent of 26–50.7 mg/dm³. Most iodine and bromine waters are strong saline solu­tions with min­er­al­iza­tion up to 230 g/dm³.

Iodine-bromine manifestations of industrial waters

These iodine-bromine waters (brines) are the most wide­spread among oth­er indus­tri­al waters. The brines are of chlo­ride-sodi­um and chlo­ride cal­ci­um-sodi­um com­po­si­tion with min­er­al­iza­tion rang­ing from 43 to 383 g/dm³. In the Bilche–Volynska SFA, the most iodine and bromine-rich brines have been tapped by wells with­in the Hrynivske gas field, among Cam­bri­an, Juras­sic, Cre­ta­ceous, and Neo­gene deposits at depths of 898‑2350 m. Iodine con­tent ranges from 22.8 to 88.8 mg/dm³, bromine from 220 to 531.4 mg/dm³, with total min­er­al­iza­tion between 92 and 184 g/dm³, and well yields rang­ing from 400 to 690 m³/day. In the Boryslav-Pokut­sky SFA, self-flow­ing well yields are small—200 to 500 m³/day, with water min­er­al­iza­tion vary­ing from 50 to 300 g/dm³, iodine con­tent from 12.7 to 53 mg/dm³, and bromine from 254 to 804 mg/dm³. These waters are rep­re­sent­ed by the fol­low­ing man­i­fes­ta­tions: Yasen­evet­sky, Ivanivsky, Dzvinyatsky‑I, Maid­an, Dzviny­atsky-III, Starunsky‑I, and Starun­sky-III. The Dzviny­ach-Staru­nia area encom­pass­es the name­sake oil and gas fields.

Under­ground waters from Pale­o­gene and Neo­gene deposits are high­ly min­er­al­ized (220–383 g/dm³) and heav­i­ly meta­mor­phosed, of chlo­ride cal­ci­um-sodi­um com­po­si­tion. They are char­ac­ter­ized by high bromine content—from 400–550 to 804 mg/dm³; iodine—from 12–20 to 37 mg/dm³; and B₂O₃ up to 200–456 mg/dm³. Well yields on self-flow­ing wells amount­ed to 200–500 m³/day. Brine over­flow has been observed for many years from old wells in the form of gryphons, indi­cat­ing high reserves of reser­voir ener­gy. The Dzviny­ach-Staru­nia area, due to the high yields of wide­spread iodine-bromine waters, can be con­sid­ered one of the most promis­ing in the Boryslav-Pokut­sky SFA.

Iodine-boron-bromine manifestations of industrial waters

Brines spread in the area of the Dzviny­ach and Staru­nia oil and gas fields, and the Naza­vyziv area. The brines are of chlo­ride sodi­um, chlo­ride cal­ci­um-sodi­um com­po­si­tion with a min­er­al­iza­tion of 263–292 g/dm³, con­tain­ing: I — 5–38.0 mg/dm³; B₂O₃ — 200–456.8 mg/dm³; Br — 200–461.9 mg/dm³. These brines are found in deposits of the Vorotyshne (Neo­gene) and Nyzh­nyvsky (Upper Juras­sic) hori­zons. The Pre-Carpathi­an region is one of the old­est salt-pro­duc­ing areas. Nat­ur­al chlo­ride-sodi­um brines, wide­spread in areas of salt-bear­ing deposits, have been used as raw mate­ri­als. Only the nat­ur­al brines of the Doly­na deposit, locat­ed on the east­ern out­skirts of Doly­na city, meet the approved stan­dards. The Doly­na deposit is rep­re­sent­ed by high-qual­i­ty brines with a sta­ble chem­i­cal com­po­si­tion and min­i­mal impu­ri­ties. The main com­po­nent of the brines is NaCl, with oth­er salts includ­ing CaSO₄, MgSO₄, and KCl.

Extrac­tion and uti­liza­tion of com­po­nents from indus­tri­al waters Indus­tri­al waters, hav­ing indus­tri­al stan­dards and tech­ni­cal-eco­nom­ic jus­ti­fi­ca­tion of their urgent need in var­i­ous indus­tri­al sec­tors, are extract­ed using known and mod­ern tech­nolo­gies and meth­ods, such as evap­o­ra­tion, crys­tal­liza­tion, chem­i­cal pre­cip­i­ta­tion, sorp­tion on ion-exchange resins, extrac­tion with organ­ic sol­vents, elec­tro­chem­i­cal meth­ods. They are used to obtain I, Br, Ba, B, Ra, Sr, and com­pounds con­tain­ing organ­ic sub­stances, gas­es (hydro­car­bons, nitro­gen, hydro­gen sul­fide, car­bon diox­ide). Leach­ing meth­ods are used to process solu­tions from well-based under­ground salt dis­so­lu­tion (salt min­ing).

Boron and its salts. In indus­try, nat­ur­al borates are fused with soda to obtain borax, which is used as an anti­sep­tic in med­i­cine, a com­po­nent of pes­ti­cides for plant irri­ga­tion, influ­enc­ing their growth, and a med­i­c­i­nal agent for the human body. The Pre-Carpathi­an arte­sian basin con­tains var­i­ous ther­a­peu­tic waters with dif­fer­ent salt com­po­si­tions: sul­fur-con­tain­ing ther­a­peu­tic brines, min­er­al waters (Truskavets, Mor­shyn, and Shk­lo resorts), Beskid low-moun­tain regions (Skhid­nyt­sia and Verkhnye Syn­ovydne), and Roz­tochchia and Opil­lia (Nemyriv, Velykyi Lyu­bin, and Rozdil). Iodine and bromine waters are espe­cial­ly inten­sive­ly used. Min­er­al waters con­tain­ing up to 5 mg/dm³ of iodine can be used in med­i­cine. The most valu­able bromine waters are those with the low­est ratio of chlo­rides to bromine and over­all min­er­al­iza­tion to bromine. The great­est ben­e­fit comes from a jus­ti­fied con­cen­tra­tion of bromine in min­er­al waters—25 mg/dm³.

Iodine and bromine min­er­al waters are known in all tec­ton­ic zones of the Ukrain­ian Carpathi­ans. Such waters are dis­cov­ered at dif­fer­ent depths or emerge on the sur­face as springs (vil­lages of Hrebeniv, Bytkiv, Novose­lyt­sia, etc.). The most inter­est­ing waters were found at depths of 322–390 m in the Karshiv­s­ka depres­sion (Pre-Carpathia): their min­er­al­iza­tion is 11.9 g/dm³, with a bromine con­cen­tra­tion of 24.9 mg/dm³ and iodine 15.2 mg/dm³. Bromine is main­ly extract­ed from asso­ci­at­ed oil­field waters from oil and gas deposits. Bromine and its com­pounds are used in pho­tog­ra­phy, med­i­cine, dye pro­duc­tion, tech­nol­o­gy, and oil extrac­tion.

Chlo­ride-sodi­um brines are used to pro­duce high-grade table salt at the Bolekhiv and Dro­hobych salt fac­to­ries. The extrac­tion is car­ried out from a mine at a depth of 64 m. The mine’s pro­duc­tiv­i­ty is 60–78 m³/day. When brine reach­es sat­u­ra­tion, min­er­als and salts are extract­ed under con­di­tions of phys­i­cal-chem­i­cal equi­lib­ri­um. Nat­ur­al car­bon­ates are rep­re­sent­ed by the min­er­als cal­cite and dolomite. They are used for indus­tri­al and med­i­c­i­nal pur­pos­es. Grown car­bon­ates, such as soda ash, potash, and lime­stones, chalk, and mar­ble, are wide­ly used in con­struc­tion, the chem­i­cal indus­try, optics, etc.

Iodine. Indus­tri­al amounts of iodine are found in the waters of oil and gas deposits. In indus­try, iodine is obtained by reduc­ing sodi­um iodate. Iodine prepa­ra­tions are used in med­ical prac­tice for ther­a­peu­tic and diag­nos­tic pur­pos­es.

Lithi­um is extract­ed from hydrother­mal raw mate­ri­als and is rarely encoun­tered. The aver­age indus­tri­al con­cen­tra­tion of lithi­um in Ukraine is 4–6.5 mg/dm³. Today, lithi­um is one of the alter­na­tive pow­er sources (bat­ter­ies, accu­mu­la­tors).

Oil and gas extrac­tion is accom­pa­nied by large quan­ti­ties of oil­field and asso­ci­at­ed oil­field waters, which are sources of indus­tri­al con­di­tions for wide­spread chem­i­cal ele­ments such as iodine, boron, bromine, lithi­um, and oth­ers. Even­tu­al­ly, the deposits are deplet­ed, but the water remains, and if re-eval­u­at­ed and researched using new­er devel­op­ment tech­nolo­gies, research method­olo­gies, and analy­ses, the poten­tial of these waters could be recon­sid­ered for dis­cov­er­ing new deposits.

Explo­ration and devel­op­ment of oil and gas deposits bring about the dis­cov­ery of new man­i­fes­ta­tions and deposits of indus­tri­al waters. The Insti­tute of Geol­o­gy offers sub­soil users the devel­op­ment and sup­port of a pack­age of doc­u­ments for obtain­ing a Per­mit for sub­soil use, from geo­log­i­cal explo­ration to extrac­tion.