Chemical geothermometry: application to mud volcanic waters of the Caucasus region

doi:10.1007/s11707-019-0810-8

Front. Earth Sci.

2020, Vol. 14

Issue (4) : 738-757 https://doi.org/10.1007/s11707-019-0810-8

RESEARCH ARTICLE

Chemical geothermometry: application to mud volcanic waters of the Caucasus region

Olga E. KIKVADZE^1,²(

), Vasilii Yu. LAVRUSHIN^1,², Boris G. POLYAK¹

¹. Geological Institute, Russian Academy of Sciences, Moscow 119017, Russia
². V.S.Sobolev Institute of Geology and Mineralogy, Siberian Branch of the RAS, Novosibirsk 630090, Russia

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Abstract

The generation temperatures of gas-water fluids released from mud volcanoes in different provinces of the Caucasian region have been constrained using Mg/Li (Т_Mg/Li) chemical geothermometry. Mud volcanic fluids in the Taman Peninsula (Kerch-Taman mud volcanic province) were generated at temperatures (Т_Mg/Li) from 41 to 137°С. The depths of the respective mud reservoirs estimated from Т_Mg/Li values and local geothermal gradient are in a range of 1.0 to 3.4 km which spans the Maykop Formation of marine shale. For the South Caspian province, the Т_Mg/Li values of waters vary from 18 to 137°C and the respective root depths Н_Mg/Li of mud volcanoes range from ~ 0.85 to 6.5 km. The obtained T_Mg/Li values for the analyzed mud volcanic waters from Caucasian provinces are in positive correlation with НСО₃⁻ contents and water oxygen isotope compositions ( $δ 18 O H 2 O$ and Δ $δ 18 O H 2 O$ ) and in high negative correlation with Cl⁻. The increase of Т_Mg/Li toward the Greater Caucasus Range, as well as the lateral T_Mg/Li patterns in the Taman and South Caspian mud volcanic provinces, support the idea that mud volcanic fluids generate at temperatures increasing progressively toward the Alpine orogenic belt.

Keywords mud volcano fluid chemical geothermometry stable isotopes Caucasus region

Corresponding Author(s): Olga E. KIKVADZE

Online First Date: 03 June 2020 Issue Date: 08 January 2021

Cite this article:

Olga E. KIKVADZE,Vasilii Yu. LAVRUSHIN,Boris G. POLYAK. Chemical geothermometry: application to mud volcanic waters of the Caucasus region[J]. Front. Earth Sci., 2020, 14(4): 738-757.

URL:

https://academic.hep.com.cn/fesci/EN/10.1007/s11707-019-0810-8
https://academic.hep.com.cn/fesci/EN/Y2020/V14/I4/738

Fig.1 Tectonic sketch map of Caucasus, simpliﬁed after (Milanovskii and Koronovskii, 1973). 1 – Scythian Plate; 2 – Indol-Kuban (IKF) and Terek-Caspian (TCF) foredeeps; 3 – Greater Caucasus orogen; 4 – Rioni (RB) and Kura (KB) intermontane basins; 5 – Lesser Caucasus orogen; 6 – centers of recent Ca-alkaline volcanism; 7 – Kerch-Taman (I), South Caspian (II) and Kakhety (III) MV provinces.

Fig.2 Location map of mud volcanoes in the Taman peninsula, Kerch-Taman MV province, according to (^{Shnyukov et al., 1986}). 1-2 – sampled (1) and non-sampled (2) mud volcanoes. Sampling sites numbers are same as in Table 1.

Fig.3 Location map of mud volcanoes in the South Caspian MV province, Azerbaijan. 1 – mud volcanoes; 2 – Neftechala oil well; 3-6 –petroleum areas: Fore-Caspian (3), Apsheron (4), Shemakha-Gobustan (5), ForeKura (6), according to (^{Jakubov et al., 1971}). Sampling sites numbers are same as in Table 1.

MV No.	ºN lat.	ºE long.	Sampling site	Sample number*	VSMOW/‰			Data source^***
					δ¹⁸O	δD	?δ¹⁸О^**	Data source^***
Kerch-Taman Province (see Fig. 2)
1	44.90111	37.59833	Semigor MV	14-1/09	10.3	−25	14.7	1
1	44.90111	37.59833	Semigor MV	14-3/09	10.0	−27	14.6	1
2	45.00561	37.72372	Gladkov MV, seepage 4	2/09BG	5.0	−21	8.9	1
3	45.07058	37.61042	Shugo MV, seepage 1	3-1/09BG	5.2	−31	10.3	1
4	45.02836	37.58561	Vostok MV, central seepage	15/09	3.3	−29	8.2	1
5	45.11867	36.89775	Bugaz MV, central seepage	4-1/09	10.1	−26	14.6	1
5	45.11867	36.89775	Bugaz MV, flank seepage	4-2/09	10.2	−28	15.0	1
5	45.11867	36.89775	Bugaz MV, eastern seepage	4-3/09	8.9	−27	13.5	1
7	45.20233	36.78258	Karabetova Gora MV, western seepage	1/09	14.2	−24	18.5	1
8	45.26925	36.96256	Shapur MV, central seepage	6-1/09	3.2	−33	8.6	1
9	45.18939	37.18353	Yuzhno-Neftyanoi MV, seepage with oil films	7/09	−3.2	−33	2.2	1
10	45.27808	37.38744	Miska MV, central seepage	10/09	1.2	−34	6.7	1
12	45.30942	37.03928	Tsymbaly-Vostok MV, seepage 1	17/09	2.9	−35	8.5	1
14	45.43231	36.92253	Kuchugur MV, central seepage	13-1/09	5.4	−22	9.4	1
15	45.35414	36.71381	Chushka MV, flank seepage	12-1/09	5.0	−33	10.4	1
15	45.35414	36.71381	Chushka MV, central seepage	12/09	3.0	−22	7.0	1
19	45.25181	37.43917	Gnilaya MV, central seepage near lake	9-2/09BG	1.5	−34	7.0	1
19	45.25181	37.43917	Gnilaya MV, southern group of seepages	9-3/09	0.9	−39	7.0	1
21	45.32461	37.17114	Sopka MV	11/09BG	−3.4	−35	2.2	1
South Caspian Province (see Fig. 3)
Fore-Caspian area
37	41.00317	49.19772	Zarat (Khydyrzyndy-2) MV	29/10	7.2	−25	11.6	2
47	41.15500	48.98386	Kaynardja MV	18/12	0.1	−28	4.9	1
Apsheron area
3	40.46239	49.57422	Uchtepe MV	3/10	7.4	−21	11.3	2
12	40.25767	49.55056	Pelpelya-Garadag MV	10/10	3.1	−19	6.7	2
21	40.35197	49.55944	Shorbulag MV	17/10	2.1	−22	6.1	2
23	40.38189	49.58417	Davaboynu MV	19/10	3.2	−24	7.5	2
42	40.49294	49.70328	Cheildag MV	34/10	6.2	−13	9.1	2
Shemakha-Gobustan area
1	40.48053	49.44811	Pirekyashkyul MV, northern group of seepages	1/10	3.1	−12	5.9	2
2	40.46625	49.46950	Pirekyashkyul MV, northern group of seepages	2/10	2.8	−21	6.7	2
4	39.99550	49.40642	Dashgil MV, central mud breccia field	4-1/10	2.0	−17	5.4	2
5	39.99561	49.40278	Dashgil MV, large seepage	4-2/10	2.5	−29	7.4	2
6	39.99861	49.47442	Bakhar MV	5/10	4.1	−26	8.6	2
7	40.00100	49.47031	Bakhar MV, northern group of seepages	5-1/10	2.5	−23	6.6	2
8	39.97019	49.34731	Saryboga MV, western group of seepages	6/10	3.2	−31	8.3	2
9	39.97358	49.35978	Goturdag MV	7/10	2.3	−31	7.4	2
10	39.99452	49.30911	Airantekyan MV	8/10	n.d.	n.d.	n.d.	2
22	40.31267	49.43722	Shakhigaya MV	18/10	1.9	−22	5.9	2
24	40.25078	49.24558	Galendarakhtarma MV	20/10	5.6	−14	8.6	2
25	40.35258	49.18122	Eastern Nardaran-Akhtarma MV	21/10	5.4	−15	8.5	2
26	40.82756	48.58558	Demirchi MV	22-1/10	10.4	−23	14.5	2
27	40.82756	48.58558	Demirchi MV	22-2/10	n.d.	n.d.	n.d.	2
28	40.51019	49.03208	Malyi Mereze MV	23/10	7.0	−21	10.9	2
31	40.29842	49.25425	Cheildag MV	26/10	4.9	−20	8.7	2
32	40.30089	49.26419	Cheildag MV, northern group of seepages	26-1/10	4.7	−12	7.5	2
33	40.30750	49.23358	Cheildag MV, western group of seepages	26-2/10	6.6	−14	9.6	2
34	40.30208	49.24000	Cheildag MV, southern group of seepages	26-3/10	5.4	−22	9.4	2
38	40.18611	49.23956	Gylych MV	30/10	4.8	−22	8.8	2
39	40.20617	49.21006	Agdam MV, group of seepages	31/10	2.7	−29	7.6	2
40	40.18083	49.18961	Arzani MV	32/10	5.1	−20	8.9	2
41	40.22075	49.16239	Shekikhan MV	33/10	8.2	−24	12.5	2
48	40.25131	48.84189	Kalamadyn MV, western group of seepage	1/12	4.8	n.d .	n.d .	1
49	40.30642	48.09720	Northern Inchabel MV	2/12	3.0	n.d.	n.d.	1
49	40.30642	48.09720	Northern Inchabel MV	3/13	1.3	−33	6.7	1
50	40.48044	49.03178	Shikhzarli MV	9/12	6.3	−27	10.9	1
45	40.81014	48.70581	Northern-Astrakhanka MV	10/12	10.3	−28	15.1	1
51	40.17442	48.96256	Kyrlyh MV	12/12	3.0	−20	6.8	1
52	40.08844	48.95444	Malyi-Kharami MV	13/12	1.7	n.d.	n.d.	1
53	40.43525	48.74017	Gushchu MV	15/12	1.0	−32	6.3	1
54	40.60908	48.56597	Matrasa MV	16/12	1.7	−26	6.2	1
55	40.21864	49.04072	Dashmardan MV, central seepage	19/12	5.4	−25	9.8	1
55	40.21914	49.04569	Dashmardan MV, flank seepage	19-1/12	3.6	−27	8.2	1
56	40.74378	48.43914	Baskal MV, northern group of seepages	20/12	2.8	−23	6.9	1
57	40.54942	49.30064	Weis MV	21/12	8.8	−20	12.6	1
58	40.52700	48.70000	Melikchoban MV	1/13	n.d.	n.d.	n.d.	1
59	40.58800	48.01000	Kelakhana MV	2/13	n.d.	n.d.	n.d.	1
60	40.52500	48.01800	Charkhan MV	4/13	n.d.	n.d.	n.d.	1
Fore-Kura area
11	39.86128	49.29592	Khydyrly MV	9/10	1.0	−30	6.0	2
13	39.51211	49.10772	Duruvdag MV	11/10	1.2	−23	5.3	2
14	39.38161	49.14611	Duzdag MV, small seepage	12/10	2.0	−16	5.3	2
15	39.38161	49.14611	Duzdag MV, central seepage	12-1/10	3.3	−21	7.2	2
16	39.31475	49.18442	South-Neftechala MV	13/10	−0.6	−32	4.7	2
17	39.31833	49.18711	Oil well near South-Neftechala MV	13-1/10	n.d.	−32	n.d.	2
18	39.94703	49.07764	Malyi Mishovdag MV	14/10	2.3	−23	6.4	2
19	39.95308	49.05206	Bol'shoy Mishovdag MV	15/10	2.5	−16	5.8	2
20	39.88431	48.95014	Yandere MV	16/10	3.0	−18	6.5	2
29	39.92097	49.26481	Kalmaz MV	24/10	4.4	−16	7.7	2
35	40.19606	48.87050	Akhtarma-Pashaly MV	27/10	1.5	−21	5.4	2
43	39.70417	49.41172	Biandovan MV	35/10	3.7	−25	8.1	2
66	40.19036	48.90350	Bol'shoy Kharami MV, central seepage	14/12	2.7	−25	7.1	1
66	40.19030	48.90432	Bol'shoy Kharami MV, eastern group of seepages	14-2/12	2.4	−26	6.9	1

Tab.1 Locations of sampling sites and oxygen and hydrogen isotope compositions of mud volcanic waters

MV No.	Sample	T/°C	pH	TDS/(g·L⁻¹)	Concentration/(g·L⁻¹)			Concentration/(mg·L⁻¹)
MV No.	Sample	T/°C	pH	TDS/(g·L⁻¹)	НСО₃	Сl	Na	SO₄	K	Mg	Ca	Si	Li×1000	CO₂	T/°C calc.	Depth/km	source^*
Taman area of the Kerch-Taman Province
1	14-1/09	22.3	7.95	10.58	5.25	2.13	2.71	36.0	19.9	27.6	13.7	4.85	1.21	17.4	87	2.18	1, 2
1	14-3/09	23.0	8.25	11.47	5.61	2.13	3.01	176.1	16.3	27.9	8.1	5.34	1.16	8.0	86	2.15	1, 2
2	2/09BG	n.d.	6.93	20.07	0.61	11.35	5.84	1.5	229.6	114.9	1560.0	6.68	13.26	1.7	136	3.40	1, 2
3	3-1/09BG	21.0	7.76	18.03	3.54	7.80	5.73	119.8	65.9	77.2	29.8	18.2	11.18	4.5	137	3.43	1, 2
4	15/09	n.d.	8.67	10.87	3.90	3.19	3.01	353.4	41.1	42.7	15.9	6.69	0.54	6.9	63	1.57	1, 2
5	4-1/09	20.0	7.94	13.34	6.22	2.62	3.83	35.5	79.7	101.8	24.6	17.7	2.00	6.4	83	2.08	1, 2
5	4-2/09	23.2	8.27	15.02	6.83	3.05	4.41	64.4	55.6	107.9	19.7	24.1	1.83	n.d.	80	2.01	1, 2
5	4-3/09	n.d.	8.00	14.30	6.10	3.19	4.41	30.7	36.4	78.3	10.2	16.0	1.58	n.d.	81	2.02	1, 2
7	1/09	17.9	8.02	15.44	9.25	1.46	3.82	23.9	55.2	63.2	21.0	9.65	1.97	22.0	89	2.23	1, 2
8	6-1/09	21.6	7.73	18.42	4.27	5.74	8.01	61.3	30.0	53.2	14.6	3.91	1.09	n.d.	76	1.91	1, 2
9 10	7/09 10/09	30.3 n.d.	6.60 7.81	0.80 12.09	0.37 2.39	0.14 5.29	0.11 4.30	26.9 46.1	9.3 14.0	7.3 31.6	114.2 22.0	9.67 5.07	0.02 0.22	5.3 1.9	18 47	0.46 1.18	1, 2 1, 2
12	17/09	25.0	n.d.	11.87	3.29	4.47	3.90	11.8	30.8	34.0	30.9	6.36	1.08	n.d.	82	2.05	1, 2
14	13-1/09	n.d.	6.98	16.05	3.78	4.96	4.81	1462.1	29.6	115.9	173.1	12.8	1.02	16.9	66	1.65	1, 2
15	12/09	17.8	7.82	11.63	3.05	4.26	4.12	8.4	30.9	33.3	30.5	6.09	1.07	3.7	82	2.04	1, 2
15	12-1/09	18.2	7.81	10.96	3.90	3.26	3.60	n.d.	25.3	35.6	34.5	8.82	0.84	5.3	75	1.87	1, 2
19	9-2/09BG	n.d.	8.79	13.10	2.44	5.82	4.60	24.0	5.8	13.3	4.6	2.74	0.11	0.8	41	1.02	1, 2
19	9-3/09	n.d.	8.66	13.12	2.56	5.53	4.75	48.3	6.1	5.8	3.3	4.39	0.12	0.5	51	1.28	1, 2
21	11/09BG	25.5	8.84	9.59	1.83	3.05	2.90	1200.6	12.8	10.9	9.7	2.98	0.20	6.7	56	1.41	1, 2
Fore-Caspian area of the South Caspian Province
37	29/10	13.1	7.42	35.3	2.04	21.56	10.92	14.3	186.4	123.4	123.0	6.62	14.08	2.4	137	6.52	1, 3
47	18/12	17.4	6.69	63.8	0.89	37.59	23.22	n.d.	94.9	654.8	813.4	2.68	3.61	5.6	75	3.57	1
Apsheron area of the South Caspian Province
3	3/10	18.9	7.77	10.7	5.06	2.41	2.92	10.1	8.3	28.3	15.3	6.83	0.69	1.1	73	3.48	1, 3
12	10/10	n.d.	8.65	20.5	5.80	7.66	6.56	59.7	7.8	66.9	18.8	2.01	0.59	0.2	60	2.85	1, 3
21	17/10	14.2	7.82	13.2	1.37	5.82	4.38	961.9	15.8	75.3	107	3.52	0.36	1.5	48	2.29	1, 3
23	19/10	15.6	7.65	19.4	1.36	10.78	6.73	13.5	25.3	214.8	94.0	7.58	1.30	2.2	64	3.06	1, 3
42	34/10	13.7	8.27	9.6	2.53	3.17	2.98	7.7	11.1	11.5	8.5	3.96	0.38	0.6	70	3.32	1, 3
Shemakha-Gobustan area of the South Caspian Province
1	1/10	15.0	8.00	18.7	8.10	3.98	5.67	454.5	20.9	81.3	13.0	6.09	0.87	2.9	66	3.16	1, 3
2	2/10	16.0	8.00	13.2	6.07	2.46	3.80	13.4	13.3	37.3	6.3	10.2	0.77	4.0	73	3.46	1, 3
4	4-1/10	19.0	7.45	24.0	0.49	12.74	7.50	9.3	17.2	362.3	217	4.51	0.46	1.0	37	1.78	1, 3
5	4-2/10	19.6	7.49	38.2	1.76	15.89	11.70	3168.1	24.0	351.6	83.2	4.48	1.17	2.2	57	2.69	1, 3
6	5/10	20.0	7.84	14.7	2.47	6.07	4.83	29.3	10.8	14.0	13.2	4.39	0.41	2.5	69	3.30	1, 3
7	5-1/10	19.0	7.92	34.7	2.50	16.89	11.78	466.0	18.4	159.0	18.2	3.15	0.24	0.9	33	1.57	1, 3
8	6/10	18.5	7.88	14.5	1.40	7.55	5.27	5.1	9.7	65.3	25.0	5.82	0.39	0.6	51	2.43	1, 3
9	7/10	19.6	7.58	18.4	4.15	6.48	5.55	84.7	15.4	111.0	31.7	6.80	0.90	0.8	63	3.02	1, 3
10	8/10	17.5	7.58	18.1	3.23	7.47	5.91	236.4	11.8	119.9	29.0	5.77	0.49	3.0	50	2.37	1, 3
22	18/10	14.7	7.60	34.0	0.57	15.37	9.41	553.0	9.3	392.3	244	4.58	0.21	0.3	23	1.07	1, 3
24	20/10	13.9	7.99	15.2	7.02	2.49	4.23	72.2	7.1	25.4	6.3	4.17	0.78	3.2	77	3.69	1, 3
25	21/10	13.0	7.52	16.3	5.30	4.26	4.86	650.1	15.3	80.3	43.7	7.76	0.67	4.3	60	2.88	1, 3
26	22-1/10	10.0	8.02	8.6	3.97	1.41	2.38	67.0	9.4	22.8	9.2	4.71	2.00	3.6	103	4.91	1, 3
27	22-2/10	9.0	7.60	8.6	4.24	1.27	2.36	3.4	17.9	18.1	13.8	5.59	2.78	3.5	116	5.53	1, 3
28	23/10	11.1	7.98	10.0	3.08	3.27	3.23	59.6	8.8	31.8	11.3	4.88	0.26	1.2	50	2.38	1, 3
31	26/10	16.1	8.46	13.4	5.72	3.08	4.03	31.7	18.1	59.1	10.6	4.76	1.68	2.0	86	4.09	1, 3
32	26-1/10	15.4	8.12	12.5	6.01	1.91	3.35	2.5	18.0	65.2	14.1	2.65	0.98	2.0	71	3.40	1, 3
33	26-2/10	14.5	7.82	10.6	4.15	2.31	3.01	68.8	10.8	32.7	9.5	6.45	0.96	3.6	79	3.77	1, 3
34	26-3/10	14.8	7.82	11.8	4.54	3.07	3.62	45.7	28.0	37.9	18.3	6.79	1.88	4.7	95	4.50	1, 3
38	30/10	15.9	7.48	17.5	5.26	5.78	5.45	6.4	39.6	107.9	49.8	10.8	2.58	10.4	89	4.25	1, 3
39	31/10	14.8	8.10	22.9	5.14	8.02	6.97	187.4	24.5	113.3	15.8	4.99	0.17	1.8	29	1.40	1, 3
40	32/10	16.8	7.66	15.7	5.73	4.22	4.74	8.6	33.0	64.6	19.8	14.7	2.19	6.5	92	4.36	1, 3
41	33/10	14.4	8.00	9.9	3.72	2.54	2.97	128.1	21.0	43.5	42.3	4.73	0.55	2.3	63	3.00	1, 3
48	1/12	18.5	8.05	13.9	1.15	7.17	4.91	21.1	12.0	81.9	19.0	2.88	0.07	1.3	18	0.84	1
49	2/12	18.0	7.37	16.8	0.85	8.92	5.84	3.1	24.4	63.8	112	8.23	0.48	2.2	56	2.66	1
49	3/13	n.d.	8.50	15.0	2.07	5.74	4.56	734.4	22.3	131.7	25.0	4.41	0.07	0.8	12	0.59	1
50	9/12	14.0	7.99	8.8	3.26	1.31	2.33	628.7	12.0	19.8	9.5	5.96	0.28	2.2	57	2.70	1
50	5/13	n.d.	8.10	8.6	4.17	1.31	2.38	27.5	11.0	15.5	13.1	4.89	1.52	8.6	101	4.81	1
45	10/12	12.6	8.02	9.0	4.92	0.70	2.29	2.5	17.1	4.6	2.0	6.52	0.49	3.8	87	4.14	1
51	12/12	20.8	7.88	26.2	1.74	14.97	10.00	2.7	8.7	174.0	15.4	5.51	0.39	3.6	41	1.96	1
52	13/12	18.5	7.58	25.1	0.85	14.38	9.43	2.7	25.6	67.7	59.6	3.74	0.27	2.2	43	2.05	1
53	15/12	18.3	7.46	20.4	0.99	10.74	7.06	7.5	36.9	90.1	74.1	4.58	1.21	3.2	73	3.46	1
54	16/12	23.8	7.56	24.0	5.63	10.28	8.47	5.3	34.0	139.1	27.1	7.16	1.99	9.7	79	3.78	1
55	19/12	n.d.	7.76	11.9	2.70	3.28	3.30	463.4	15.0	20.5	21.3	10.0	0.63	n.d.	75	3.56	1
55	19-1/12	17.5	7.35	11.8	2.65	4.16	3.72	378.5	13.6	42.0	62.4	9.55	0.37	5.8	55	2.62	1
56	20/12	17.4	7.63	7.6	0.40	2.09	1.67	508.9	11.8	15.1	31.9	5.28	0.67	1.7	80	3.81	1
57	21/12	20.9	7.96	11.5	5.82	1.53	3.17	103.6	21.0	21.7	14.3	11.8	0.46	3.6	67	3.18	1
58	1/13	n.d.	8.20	6.7	0.71	3.49	2.50	31.1	11.1	9.0	18.6	4.74	0.25	0.5	63	3.01	1
59	2/13	n.d.	8.10	12.7	4.92	2.27	3.17	6.9	31.2	63.2	19.2	9.28	1.55	4.4	83	3.95	1
60	4/13	n.d.	7.80	17.7	2.99	7.35	5.25	5.4	46.2	251.1	125.7	21.1	1.37	5.9	64	3.04	1
Fore-Kura area
11	9/10	17.9	7.47	28.3	0.11	16.17	8.78	9.0	15.6	259.2	1085.4	2.70	0.19	2.9	24	1.60	1, 3
13	11/10	19.9	7.89	37.1	1.36	19.92	13.23	13.0	16.2	84.0	20.3	3.97	0.03	0.5	n.d.	n.d.	1, 3
14	12/10	20.3	7.61	47.3	1.10	20.40	13.21	3.3	18.2	170.2	82.1	6.36	0.12	0.5	21	1.39	1, 3
15	12-1/10	n.d.	7.41	25.6	1.13	12.81	8.59	6.6	15.2	41.2	43.0	9.45	0.17	0.6	39	2.59	1, 3
16	13/10	19.0	6.51	84.3	0.41	46.07	24.29	12.6	73.5	981.0	3326.2	14.6	1.20	3.5	47	3.10	1, 3
17	13-1/10	22.6	n.d.	40.4	0.12	24.60	13.71	8.0	40.1	465.3	1195.3	11.3	0.61	3.4	41	2.71	1, 3
18	14/10	17.5	7.46	20.3	3.25	8.30	6.28	n.d.	22.3	145.2	36.1	6.27	0.59	2.0	51	3.42	1, 3
19	15/10	16.0	7.60	14.6	2.14	6.48	4.79	6.1	16.6	92.3	31.2	4.23	0.16	0.5	30	2.03	1, 3
20	16/10	17.5	7.69	12.2	1.02	5.99	4.05	n.d.	10.2	86.0	43.1	5.95	0.13	1.2	27	1.83	1, 3
29	24/10	16.0	7.97	16.6	2.26	7.61	5.62	26.0	11.6	66.7	37.0	6.73	0.49	9.5	56	3.70	1, 3
35	27/10	15.5	7.29	16.8	3.54	6.62	4.78	n.d.	18.0	359.5	133.2	18.4	0.66	1.6	45	2.97	1, 3
43	35/10	15.5	7.76	25.1	1.25	11.10	7.42	n.d.	19.5	78.4	72.7	4.62	0.54	3.3	56	3.73	1, 3
66	14/12	18.7	8.00	18.4	2.11	8.68	6.32	3.7	13.2	40.7	11.1	5.26	0.10	2.7	29	1.90	1, 3
66	14-2/12	n.d.	8.09	24.3	3.43	9.55	7.40	17.5	13.5	38.1	5.0	4.52	0.06	3.5	21	1.39	1, 3

Tab.2 Chemistry of mud volcanic waters from the Caucasus region and the fluid generation temperatures based on Mg/Li geothermometry.

Fig.4 Major ions composition of mud volcanic waters from different Caucasian MV provinces (mg-equ %). А – Kerch-Taman province, B – South Caspian province.

Fig.5 Correlation of CO₂ (vol.%) in free gases and HCO₃⁻ (g/l) in MV waters from the Caucasian MV provinces. А – Kerch-Taman province, B – South Caspian province. Straight lines are statistically significant correlation trends.

Fig.6 Oxygen and hydrogen isotope compositions of water from the Caucasus region. 1-3 – MV waters of the Kerch-Taman (1), South Caspian (2), and Kakhety (3) provinces; 4 – fresh water, 5 – sea water, after (Dubinin and Dubinina, 2014) (AS= Sea of Azov, CS= Caspian Sea, BS= Black Sea), 6-7 – pore waters from hydrocarbon reservoirs, after (Seletskii, 1991), Azov-Kuban basin (6) Neftechala oil field in the South Caspian basin (7); 8 – CO₂-rich springs from the Elbrus area; 9 – CO₂-rich springs from West Caucasus; 10 – boreholes from the North Caucasus (8-10 – after Seletskii, 1998; Lavrushin, 2012; Dubinina, 2013). Dash line is Craig line of meteoric water composition (Craig, 1961). Solid line is statistically significant correlation trend inferred from the Taman MVs data. Black dots in two insets are all data set on MV waters from the Caucasus region.

Tab.3 Oxygen and hydrogen isotope compositions of MV water in comparison with pore water, sea water and spring water (the Caucasus region)

Fig.7 Constrained MV fluid generation temperatures (T_Mg/Li) and depths (H_Mg/Li) of mud volcanic reservoirs within the South Caspian province. Dash lines – the boundaries of MV areas. 1 – MV waters with HCO₃^-<25 mg-equ %, 2 – MV waters with HCO₃^->25 mg-equ %; 3-5 – distribution areas of different MV water types: 3 – HCO₃-Cl/Na type, 4 – Cl-HCO₃/Na type, 5 – Cl/Na type; 6 – the Great Caucasus, 7 – zone of high seismicity (Kadirov et al., 2012), 8 – general thrust direction after Reilinger et al. (2006) and Mosar et al. (2010), 9 – ranges of estimated T_Mg/Li and H_Mg/Li values. The specific values see in Table 4.

Fig.8 Correlation of calculated T_Mg/Li(°C), Cl and HCO₃ contents, and δ¹⁸O_H2O values in MV fluids. 1, 2 and 3, 4 are data points (1, 3) and trend (2, 4) in the Kerch-Taman and South Caspian provinces, respectively. Letters S, G and Y mark anomalous data points at Shugo, Gladkov, and Yuzhno-Neftyanoi mud volcanoes (Numbers 2, 3 and 9 in Tables 1 and 2, respectively).

Tab.4 Mg/Li temperature and depth constrains for mud volcano reservoirs in the Caucasus region (mean and extreme values, standard deviation)

Fig.9 Constrained MV fluid generation temperatures (T_Mg/Li) and depths (H_Mg/Li) of mud volcanic reservoirs of the Kerch-Taman province. Sketch map of the Crimea and Taman Peninsulas modified from Shnyukov et al. (1986). 1-2 – MVs: 1 – authors data, 2 – extra data are according to (Ershov and Levin, 2016; Sokol et al., 2019); 3 – Cenozoic sedimentary strata, 4 – Oligocene-Early Miocene shales (Maykop Formation), 5 – Cretaceous sedimentary strata, 6 – the Greater Caucasus orogeny, 7 – anticlinal folds, 8 – faults; 9 – isopachitis of the Maykop strata, km (Tugolesov, 1985); 10 – ranges of estimated T_Mg/Li and H_Mg/Livalues. The specific values see in Table 2.

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