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Geochemistry of mineral water and gases of the Razdolnoe Spa (Primorye, Far East of Russia)
Applied Geochemistry 59 (2015) 147–154
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Geochemistry of mineral water and gases of the Razdolnoe Spa (Primorye, Far East of Russia) George Chelnokov ⇑, Natalya Kharitonova, Ivan Bragin, Oleg Chudaev Far East Geological Institute, Far East Branch of Russian Academy of Sciences, Laboratory of Hydrogeochemistry, 690022, Prospect 100-letya Vladivostoka 159, Vladivostok, Primorsky Kray, Russia
a r t i c l e
i n f o
Article history: Available online 9 May 2015 Editorial handling by M. Kersten
a b s t r a c t New isotopic and chemical data on the sodium bicarbonate water and associated gases from the Razdolnoe Spa located in the coastal zone of Primorsky Kray of the Russian Far East, together with previous stable isotope data (d18O, dD, d13C), allow elucidation of the origin and evolution of the groundwater and gases from the spa. The water is characterized by low temperature (12 °C), TDS – 2.5–6.0 g/L, high contents of B (5 mg/L) and F (4.5 mg/L) and low contents of Cl and SO4. Water isotopic composition indicates its essentially meteoric origin which may comply with an older groundwater that was recharged under different (colder) climatic conditions. Major components of bubbling gases are CH4 (68 vol%), N2 (28%) and CO2 (4%). The obtained values d13C and dD for CO2 and CH4 definitely indicate the marine microbial origin of methane. Thus the high methane content in the waters relates to the biochemical processes and presence of a dispersed organic matter in the host rocks. Based on the regional hydrogeology and the geological structure of the Razdolnoe Spa, Mesozoic fractured rocks containing Na–HCO3 mineral water and gases are reservoir rocks, a chemical composition of water and gases originates in different environmental conditions. Ó 2015 Elsevier Ltd. All rights reserved.
1. Introduction A wide variety of mineral groundwater types occur in the Primorsky Kray in the Far East of Russia and can be grouped into: (a) high pCO2 mineral waters; (b) thermal waters and (c) saline waters. The high pCO2 springs are situated in central and western Primorye closely associated with major structural lineaments (Chudaeva et al., 1999). Thermal water (<35 °C) is represented by two major groups in the East of Primorsky Kray. Saline waters are located in coastal zone of the south of Primorye region. The Razdolnoe Spa field is located about 4 km southwest of the Razdolnoe settlement in the valley of the Razdolnaya River (Fig. 1). During prospecting drilling for energetically useful thermal waters carried out in this area in 1989–1993, the HCO3–Na waters with a salinity of 2.5–6.0 g/L were discovered and the field was named Razdolnoe (Voznyakovskaya and Shamin, 1993). These mineral waters are bottled as drinking medicinal-table waters and are used for balneological treatment. The origin and conditions of cold mineral groundwater with the N2–CH4 gas composition have almost not been studied in the Far East of Russia. According to Korobova (1972), this type of waters ⇑ Corresponding author. Tel.: +7 9146624835. E-mail address: [email protected] (G. Chelnokov). http://dx.doi.org/10.1016/j.apgeochem.2015.05.001 0883-2927/Ó 2015 Elsevier Ltd. All rights reserved.
has been met during the exploration work on oil–gas in Primorye. The first attempt to elucidate the genesis of cold mineral waters in Primorye was made in 1995 in the framework of a joint Russian–British project (Chudaeva et al., 1999). The main goal of this paper is to investigate the geochemistry of the Razdolnoe Spa mineral water and associated gases. The genesis of groundwater and gases is discussed on the base of regional hydrogeological conditions, water and gas composition, water– rock interaction, d18O and dD of mineral and meteoric waters, and carbon isotopic composition in CO2 and CH4. 2. Geological setting The area of the Razdolnoe Spa is located in the junction zone of large geomorphologic structures: the West Primorye flatland with the Razdolnaya River valley, the easternmost tip of the East Manchurian upland (Borisovskoe plateau), and the western branches of Sikhote-Alin’ (Rinkov, 1988). Geological structure of area can be divided on two structural levels: lower-Mesozoic and upper-Cenozoic (Fig. 2). The Mesozoic rocks are the oldest formation in the area and compose the bottom and walls of the Pushkin depression. Jurassic, Triassic and Cretaceous rocks are mainly represented by terrigenous rocks (sandstones, siltstones). They do not outcrop within the area and were trapped during
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the drilling. The thickness of the Mesozoic rocks is more than 400 m. Cenozoic deposits with a sharp angle unconformity overlay the Mesozoic rocks. The Neogene sequence includes the UstDavydovka (N1ud) and Ust-Suifun (N1us) formations of the Miocene. The deposits of the Ust-Davydovka Formation are represented by sandstones, siltstones, and mudstones with thin lens of lignite. Sandstone is generally quite porous and has a good permeability. The sediments of the Ust-Suifun Formation are mainly gravel–pebble deposits with sandy joining material. The thickness of the Cenozoic deposits is no more than 100–120 m. Recent beds overlap all the older rocks and consist of loam, clay sand, sands, marine alluvium and gravel–pebble sediments from 6 to 20 m thick. Tectonically, the area is confined to the eastern wall of the Pushkin depression, which is bordered in the east by the Nizhnii-Suifun submeridional deep-seated fault traceable from the mouth of the Razdolnaya River to the north on 30 km. In addition, the western wall of the Razdolnaya River valley is cut by the Eastern Kedrovskii fault. The submeridional faults are complicated by a series of subsidiary faults; i.e., the study area is located in a complex tectonic environment. Tectonic processes affected as Mesozoic rocks also the Cenozoic rocks. The active geological processes in this area were presumably completed with extinction of the volcanic activity (Pliocene), which produced a large basaltic plateau to the NW of the studied area. 3. Hydrogeological conditions Hydrogeologically, the study area belongs to the central part of the southern Primorye artesian basin (Rinkov, 1988). The basin occupies an area of 5000 km2 from the Amursky Bay coast to middle Razdolnaya River flow. It is the Mezozoic depression filled up with Cenozoic terrigenous and marine sediments. The Neogen basaltic lava plains lie on the western and eastern margins of basin. The depression has a block structure and is confined by tectonic dislocations (Voznyakovskaya and Shamin, 1993). The regional
aquifer system is divided into two distinct water bearing units represented by Cenozoic sedimentary-rock aquifer and Mesozoic consolidated rock aquifer. The Cenozoic sedimentary-rock aquifer is usually comprised of poorly consolidated to unconsolidated sediments where water typically occurs in unconfined conditions. Distinguished for their adverse hydrogeological conditions, the porous-stratal water basins are predominantly composed of Palaeogenic and Neogenic rocks with sub-constituents such as sand, sandy clay, sandstone, siltstone, coal beds add silt. Unconfined waters lie in the river valleys and troughs at the depth of 2–91 m, flow rates of the wells range between 0.05 and 5.4 l/s. The groundwater has a wide range in the type and amount of dissolved chemical constituents. Most water having less than 600 ppm of dissolved solids is either calcium or sodium bicarbonate. Such water is used for the water supply of Vladivostok city. Water containing more than 10,000 ppm is either sodium chlorate or sodium-chlorate–bicarbonate and wide spread in coastal area. The origin of this type of water is connected with late Paleozoic transgression when sea level exceeded the modern over 10–12 m. The Mesozoic confine aquifer represents fractured sandstones, siltstones with thickness up to 800 m. A confined aquifer mostly occurs at depth intervals of 110–350 m, piezometric levels are 10–40 m below the ground surface, well water discharge range between 0.05 and 7.4 l/s. The groundwater signed to upper fractured zones and tectonic dislocations. The groundwater flow is dominantly fracture-controlled. A chemical composition of the groundwater of the Mesozoic aquifer is either fresh HCO3–Ca–Na or HCO3–Cl–Ca–Na (Kuznetsov, 1963). The regional recharge area in respect of the southern Primorye artesian basin is on the highlands – Shufanski Basaltic Plateau located on the west and east of the territory. The regional groundwater flow pattern shows overall NE trending flow lines. Most of the groundwater circulation is thought to take place within the Cenozoic aquifer and upper part of the Mesozoic aquifer. This however, does not indicate that there is no deep circulation or mixing of groundwater from the lower
Fig. 1. Location map showing study area.
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part of Mesozoic aquifer since regional hydrogeological conditions were studied only for depth up to 200 m (Voznyakovskaya and Shamin, 1993). Deep drilling data (Kuznetsov, 1963) show that fresh water with TDS of 0.4 g/L exists at a depth up to 1300 m. Other deep well (Korobova, 1972) shows that TDS rises up to 21 g/L and water has a HCO3–Cl–Na composition. Hydrogeology of the Razdolnoe Spa is ascribed based on data of third wells (2-E, 2-B and 1-Al) drilled within limits of study area. The basin is characterized by a complex hydrogeological structure and by groundwater of diverse geochemical composition. Well No. 1-Al (30 m deep) is located on recharge zone and discloses Pliocene volcanogenic aquifer (N2). Wells No. 2-E (314 m deep) and No. 2-B (500 m deep) are disclosed the following aquifers (from top to the bottom): (1) Quaternary alluvial sediments (aQIV); (2) Quaternary deltaic sediments (amQIV); (3) Miocene sedimentary aquifer consisting of the Ust-Suifun (N1us) and Ust-Davydovka (N1ud) Formations; (4) Mesozoic sediments (MZ). A cross-section demonstrating the hydrogeological conditions of the Razdolnoe Spa is shown on Fig. 2. Hydrogeological characteristics of major aquifers presented within the study area are showed below: (I) An upper, unconfined aquifer which is the nearest to the surface consists of upper quaternary-modern alluvial sediments-fine sands, pebble bed, and gravel, often with a
(II)
(III)
(IV)
(V)
149
sandy clay filler. Wide-spread throughout river valleys, this unit has thickness of 10–15 m and the maximum depth of water level in this aquifer is 3 m from the surface. In the Razdolnoe area, the water of this aquifer flows toward the Razdolnaya River and its feeders. An unconfined aquifer of quaternary marine deltaic sediments- sea mud, pebble bed, and gravel. Spread throughout Razdolnaya River valley over 30 km from the coast, has thickness of 10–20 m. Sediments were accumulated during the transgression. A confined Pliocene volcanogenic aquifer (N2) is restricted to the basaltic plateau occupying the northwestern and eastern parts of the area (Fig. 2). The regime of aquifer is inconstant and strongly depends on the atmospheric precipitation. Natural discharge goes to the adjacent and underlying water-bearing horizons. The maximum depth of the water level on watersheds is 100 m, and within depression areas is 2 m from the surface. Basaltic abundance of the water is very low and irregular. Wells discharge is about 2–5 l/s, the water is fresh, of sodium and calcium hydrocarbonate types. The Pliocene volcanogenic aquifer is characterized by well 1-Al (30 m deep) data. A Miocene sedimentary aquifer consisting of the Ust-Suifun (N1us) and Ust-Davydovka (N1ud) Formations; the groundwater has HCO3–Mg–Na–Ca composition and low salinity, except the area of Razdolnaya River Valley, where a saline groundwater of Cl–Na type with TDS (3–14 g/L) was locally disclosed during the drillings. Unfortunately, we presently have no opportunity to determine the water isotopic composition of the Miocene aquifer, as boreholes, which trapped it, was conserved. Mesozoic sediments. The deepest Mesozoic sedimentary aquifer spreads in Triassic, Jurassic and Cretaceous rocks, as they have similar lithology and represent a single hydraulic system. The aquifer is located at the depths of more than 100 m and has a very complex structure, where underground waters are confined to wide fracture zones and zones of tectonic disruptions. The groundwater is characterized by HCO3–Na composition, but mineralization of the aquifer varies from 2.5 to 14 g/L. Well No. 2-E in interval of depths 135– 280 m disclosed HCO3–Na water with TDS of 2.5–6.0 g/L and at depths of 500 m well No. 2-B revealed waters with TDS of 14 g/L. The variations of mineralization and wells discharge indicate the complexity and heterogeneity of the hydrogeochemical section of the study object.
4. Sampling and analysis
Fig. 2. Geological scheme and hydrogeological cross-section of the Razdolnoe Spa (from Voznyakovskaya and Shamin, 1993). (1) Upper Quaternary alluvial aquifer; (2) Quaternary deltaic sediments; (3) aquifer of Pliocene volcanogenic rocks (basalts); (4) Miocene sedimentary aquifer (pebbles, gravels, sands); (5) Mesozoic terrigenous-sedimentary aquifer (siltstones, sandstones); (6) area of Cl–Na type of water (TDS 5.4–14.0 g/L); (7) area of HCO3–Na type of water (TDS 2.5–6.0 g/L); (8) area of HCO3–Mg–Na–Ca type of water; (9) rock-fracture zone; (10) boreholes: number in the top, depth- in the bottom (m); (11) faults; (12) recharge area.
The mineral waters and gases of the Razdolnoe occurrence were studied in 2008–2014. Water samples were collected from boreholes, Razdolnaya River and its estuary. Groundwater samples were pumped from wells and collected in acid-washed, high-density polyethylene sample bottles. Before sampling, all water samples were filtered through 0.45 lm cellulose filters. Waters for cation analysis were acidified to pH < 2 with ultrapure HNO3. Water temperature, conductivity and pH were measured directly in the field. Major cations and anions were analyzed by ion chromatography. Carbonate species were titrated in the field with 0.1 N HCl. Trace element and rare earth elements (REE) concentrations in groundwater were determined by ICP-MS (Agilent 4500) analysis at the Analytical Center of Far East Geological Institute (Vladivostok, Russia). Analytical precision for the REEs, except for Ce and Pr, was better than 5% vs. RSD; for Ce and Pr, precision was 6% and 9% vs. RSD, respectively. Stable isotope compositions of waters (D/H and 18O/16O ratios) were determined by isotope-ratio mass spectrometry at the Analytical Center of Far
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Table 1 Representative chemical analyses of studied waters. Components
Units
Razdolnaya River
Boreholes No. 1-Al
No. 2-E
Depth T pH Eh TDS HCO3 Cl SO24 Na+ R+ Mg2+ Ca2+ Fetot Al Si Li As Ba I Br B F Mn La Ce Pr Nd Sm Eu Gd Tb Ho Er Tm Yb Lu
m °C
Surface 10 6.6 168 0.25 165 3.5 9.6 32 4.7 12.6 25.0 1.5 0.13 3.54 0.01 0.0009 0.02 – – – 0.1 0.01 1.12 2.02 0.19 0.69 0.12 0.025 0.074 0.019 0.023 0.061 0.010 0.057 0.012
20 10 6.53 290 0.115 74.5 11.5 7.9 13.0 3.0 4.25 13.56 0.1 0.25 43.6 0.001 0.001 0.006 0.00001 0.05 0.05 0.3 0.001 0.0048 0.002 0.001 0.0047 0.0011 0.021 0.0028 0.0005 0.0013 0.0021 0.0006 0.0021 0.0006
135 12 6.56 58 4.56 3252 89 0.4 1347 4.8 15.4 14.8 0.1 0.01 6.2 2.2 0.001 0.6 0.05 0.25 4.8 4.53 0.008 0.05 0.04 0.006 0.01 0.035 0.40 0.012 0.008 0.005 0.036 0.007 0.030 0.005
mV g/L mg/L
lg/L
Bay-head estuary waters Surface 23 6.8 + 7.31 143 3160 274 1787 63.3 199.8 95 0.06 0.009 0.8 0.003 0.0001 0.0004 0.2 9.11 0.89 0.4 0.02 – – – – – – – – – – – – –
‘‘–’’ – not determined.
East Geological Institute (Vladivostok). The precisions of the analyses are 1‰ for d2H and 0.1‰ for d18O. The bubbling gas was sampled using the replacement method. The composition of the gas was analyzed by gas chromatography techniques using thermal conductivity detectors and molecular sieve columns with He and Ar as carrier gases for the determination of He, H2, N2, O2, and CH4. A Porapak Q column with He carrier gas was used for the separation of CO2. A combined CTR-3 Alltech column was used for the Ar analysis at room temperature with He as a carrier gas. Detection limits were 0.001 vol.% for He, H2 and N2, less than 0.001 vol.% for O2 and Ar, 0.001 vol.% for CO2. CH4 and CO2 gases isotopes ratios (13C/12C) were determined by isotope-ratio mass spectrometry MAT-253 using Trace-GC gas chromatograph at the Sapporo University (Japan). The precisions of the analyses are 0.1‰ for d13C and 1‰ for 2H. Tritium determinations were performed using electrolytic enrichment and subsequent measurement of counting rates; details of sample preparation for 3H analysis are described by Goriachev (1997). The standard deviation was 0.3–1.1 TU depending on the 3H concentration. 5. Results and discussion 5.1. Lithology Optical microscopy study of Mesozoic sandstones and siltstones was subsequently carried out. Core samples of the bedrock were sampled during the drilling in 1992. Sandstones are altered and
Fig. 3. Classification of studied water using Piper diagram.
Table 2 Components ratios of studied waters and seawater.
Average for seawaters Bay-head estuary Razdolnaya River Fresh groundwater (b. No. 1-Al) Mineral water (b. No. 2-E)
Na+/Cl
Ca2+/Mg2+
Ca2+/SO24
Cl /Br
0.55 0.57 9.14 1.13 15.1
0.3 0.48 1.98 3.19 0.96
0.15 0.35 2.6 1.72 37
287 347 – 230 356
presented by fine-grained and medium-grained types. Mineralogical composition: quartz (20%), plagioclase (40%), K-feldspar (10%), debris of tuffs (10%). The cement is muscovite and SiO2. Debris of tuffs is chloritized. Siltstones also altered, sometimes sulfidized. Mineralogical composition: quartz (30%), plagioclase (20%), muscovite and chlorite (50%). The cement is weathered and presented with hydromica–quartz, quartz– chlorite–hydromica, rarely with biotite. Zircon, sphene, leucoxene, anatase, tourmaline are accessory minerals. The bedrock lithological composition shows absence of organic matter in the upper fractured zone of Mesozoic rocks. 5.2. Water chemistry The chemical composition of studied waters is listed in Table 1 and on the Piper diagram, (Fig. 3), which demonstrates the proportions between the major water components of the area. Piper divided waters into three types. Surface and fresh groundwater lies on area of temporary hardness, and goes from rhyolite and basalts types of the rocks. Miocene sedimentary aquifer has complicated structure and heterogeneous water composition from fresh water characterized by Na–Ca–Mg–HCO3 (Na > 90% meq/l) type with low salinity (200 mg/L) and a high content of SiO2 (up to 50 mg/L) (borehole 1-Al) to Na–Cl type of waters with a TDS up to 14.0 g/L are distributed locally in form of lens (Rinkov, 1988). In terms of their chemical composition, the fresh Na–Ca–Mg–HC O3 type groundwater of borehole No. 1-Al can be roughly ascribed to the feed ground waters of the area (Fig. 3). Downward, in Mesozoic rocks alkali carbonated waters (HCO3– Na) is overspread (Fig. 3, borehole No. 2-E). Waters characterized by salinity of 2.5–6.0 g/L, HCO3 > 70% meq/l, Na > 95% meq/l, and temperature of 12.0–14.0 °C. These waters are enriched by F, Li, and B and have a low content of I. The ratios of major components (Table 2) in the waters different from those of the average composition of seawater. The obtained proportions indicate no influence
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of modern seawater, but sedimentation waters of marine origin exercise influence on groundwater. Third type is a bay-head estuary water which almost sea water. Monitoring of the waters from the boreholes No. 1-Al and 2-E during a complete annual cycle has revealed that both type of groundwater do not show any significant temporal variation in the chemical composition and do not have trend with atmospheric precipitations. Insignificant concentrations of chloride in the Mesozoic aquifer reflect the nonmarine character of the sediments, a condition different from that of the other geologically older basins (Dubinsky, 2014). The chemical signatures of the water demonstrate several geochemical processes. The main one, sulfate reduction, is a prerequisite reaction for the genesis of methane, is an attendant condition in its biogenesis, and enhances the enrichment of dissolved bicarbonate that in turn results in the depletion of calcium and magnesium. Bicarbonate is a product of the reduction, and with increased dissolved concentrations, calcite and dolomite precipitate because of reduced solubilities of calcium and magnesium. The Na–HCO3 and TDS-HCO3 correlations indicate that as Na content as TDS in groundwater directly depend on concentration HCO3 (r = 0,99). Ca–HCO3 relation shows good correlation (r = 0,8) but ingress of Ca at the 100 times less than Na (Table 1). Sulfate concentrations in the mineral water have a direct influence on the amount of barium found in the water because barite (barium sulfate) generally controls the solubility of barium in most natural waters (Hem, 1992). Barium concentrations in the water are high compared to other groundwater because of the low sulfate concentrations. During coalification and methanogenesis, water in contact with the coals is anoxic and reducing. Elements such as iron and manganese, which are soluble as reduced species (Fe2+ and Mn2+), have concentrations that are relatively high compared to surface water values as a result of the reducing environment. Low concentrations of calcium and magnesium, and particularly sulfate, typify the formation water associated with coalbed methane (Van Voast, 2003; Wheaton and Brown, 2005). The water temperature is 12–14 °C at a depth of 140 m of the given aquifer points to regional thermogradient. Late Neogenic volcanism was well presented at the study territory. Baranovsky Neogenic volcano is located 10 km to the North from the Razdolnoe Spa. Temperature measurements in the deep wells (1300 m and 2858 m) conducted during the drilling (1963, 1972) show that a geothermic step for sandstones is 15–24 m/1 °C (Voznyakovskaya and Shamin, 1993). The mass-balance calculations using Netpath software (Plummer et al., 1991) suggest that the chemical composition of the HCO3–Na waters is mainly controlled by albite dissolution. The saturation indexes (SI) obtained using AQUACHEM software (User’s Guide, 2005) indicate that the waters are undersaturated with respect to albite ( 3.2), anorthite ( 11.2), and chlorite ( 20.2); are in equilibrium with respect to calcite ( 0.3), chalcedony (0.2), quartz (0.7), siderite ( 0.02), and illite (0.19); and are oversaturated with respect to montmorillonite (1.0), kaolinite (1.5), and hematite (Fe2O3) (7.06). FeO (hematite) was also identified in the residue on 0.45-lm filter by X-ray phase analysis. The results of the thermodynamic calculations are well consistent with the mineralogical composition of the host rocks, whose study showed that feldspars are the most altered among the minerals of the sedimentary rocks of the area. Investigation of rare earth elements (REE) content in different types of waters became widespread in two last decades. They naturally occur in the environment, and are commonly used as environmental tracers for a range of geological and hydrological processes (Biddau et al., 2009; Choi et al., 2009; Dia et al., 2000; Johannesson et al., 1997; Möller et al., 2008; Tweed et al., 2006). REE-patterns of studied surface and mineral waters, and also
151
Fig. 4. North American Shale Composite normalized concentrations of REE in the studied groundwater from the Razdolnoe Spa.
Mesozoic rocks shows on Fig. 4. The flat curve of river waters commonly resembles the curve of the source rocks in the drainage basin (Elderfield et al., 1990). The curve of seawaters exhibits a negative Ce anomaly and progressive of the heavy REE, relative to the light REE (Piper and Bau, 2013). Elderfield et al. (1990), show that the river water have (Yb/Nd)SN ratio of 1, showing no relative fractionation with respect to shale, whereas that of seawater is 4.3, indicating an enrichment of HREE over LREE is taking place during water–rock interaction processes (Fig. 5). The patterns of distribution of rare-earth elements on surface, groundwater and host-rocks show that waters is connected with processes of diagenesis of marine sediments. According to Möller et al. (2008) concentrations of REE in the water indicate the recharge area for the initial water. Scatter plot of NASC normalized concentrations of Yb vs. Nd of the Razdolnaya River water and mineral water samples with data on Mesozoic rocks (Fig. 5) shows that a recharge zone for the fractured Mesozoic aquifer contains marine sediments. Regional hydrogeological data argue that during infiltration of the water to the fractured Mesozoic aquifer it might cross the Cenozoic marine sediments (Voznyakovskaya and Shamin, 1993).
Fig. 5. Scatter plot of NASC normalized concentrations of Yb vs. Nd of the Razdolnaya River water and mineral water samples with data on Mesozoic rocks. The data shows a linear trend with a correlation coefficient, r = 0.9.
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Table 3 Isotopic composition of oxygen and hydrogen of the studied waters. d18O‰ (VSMOW)
d2H‰ (VSMOW)
No.
Sampling locality, study object
Year of study
1 2
Sea water (Amursky Bay) Atmospheric precipitation in southern Primorye Fresh groundwater (catchment basin, hole No. 1-Al) Razdolnaya River
2007 2002
1.7 7.0
13 52
2008 2007
6.2 10.1
49 76
2007 2010 2002
11.2 11.6 11.85
88 82.5 86.6
2006 2007 2008 2008 2008
12.5 11.9 13.7 12.9 11.5
89 87 99 85.5 82.2
3 4 5 6 7
Mineral water HCO3–Na type, borehole 2-E
8 9 10 11 12
Note: Nos. 2 and 7 are taken from Chudaeva et al. (1999).
Fig. 6. Stable isotopes ratios in the Razdolnoe Spa basin groundwater.
5.3. Water isotopes The oxygen (d18O) and hydrogen (d2H) isotopic study of the ground and surface waters made it possible to determine their formation conditions. The obtained data are shown in Table 3 and Fig. 6. It is well seen in Fig. 6 that the isotopic composition of the marine and surface waters is enriched in heavy d18O isotope relative to the generally accepted line of meteoric waters. This is probably caused by several reasons: (1) evaporation accompanied by the removal of light isotope d16O) and enrichment in heavy isotope d18O; (2) the numerous oxygen and hydrogen isotope data collected by researchers of ground and surface waters of the southern Far East (Chudaeva, 2002) suggest that the regional line of the meteoric waters of Primorye is shifted toward a heavier oxygen composition relative to the global meteoric water line (GMWL). The examination of groundwater from coastal areas (Fig. 6, Table 3) revealed no interaction with modern marine waters. The mineral groundwater from the Razdolnoe Spa is isotopically distinct from modern meteoric waters as represented by the shallow groundwater and surface waters at the 1-Al and Razdolnaya
River (Fig. 6). There are two possible explanations: (1) these waters are modern recharge waters but are closer to the annual weighted average of precipitation for northern Primorye (Kharitonova et al., 2012). Na–HCO3 water was fed by meteoric waters via weakened fault zones in the northwestern part of the area, where Mesozoic rocks are exposed as remnants or insignificantly overlapped by Quaternary deposits or (2) these waters may represent older groundwater that were recharged under a different (colder) climatic regime. The fact that a groundwater from 140 m depth and high TDS in the Razdolnoe Spa is isotopically identical to modern recharge waters at the Razdolnaya River would support the second scenario. At the same time, the intricate hydrogeological conditions of the deposit, presence of confining layers and low water discharge attest to the complex feeding of the aquifer and, hence, wide drainage area. Tritium content in surface waters of the region varies from 4.7 TU to 29.3 TU, average 13 TU and correlates well with 3H concentrations in atmospheric precipitations (Kharitonova et al., 2012). Studied Na–HCO3 water sampled from depth of 10 m, contains 12.8 TU, very close to concentrations of tritium in surface waters of that area, is being formed in conditions of fast water recharge. At the same time water from the depth of 140 m shows 5.1 TU. Concentrations of tritium in mineral waters are definitely influenced by time and intensity of borehole exploitation: when large amounts of water are being taken, activation of outer areas of deposit occurs (cone of depression), i.e. a closed system becomes an opened one, into where waters with different concentrations of 3H start flowing. This hypothesis is clearly illustrated by data from being exploiting deposits of mineral groundwater spa of Primorye (Kharitonova et al., 2012). High-resolution tritium analyses show very low, but measurable levels of tritium in all of the confined aquifers located on the south-west coast of Primorye (Dubinsky, 2014). Because the age of the water in these aquifers is very old when compared to the half-life of tritium (12.35 years), there should be no tritium present within the confined aquifers. The tritium in these deep aquifers is either due to leakage from other aquifers or to contamination as a result of the exploitation (casing column problem). There is an insufficient evidence to distinguish between these alternatives.
5.4. The gas chemistry and carbon isotopes The free gas collected from the well consisted mostly of CH4 (62.7–68.3% by vol.), N2 (26.8–27.6% by vol.), CO2 (4.4–8.6% by vol.), with minor amounts of Ar (0.2% by vol.), O2 (0.2–1.0% by vol.) and very low H2 (0.001% by vol.) contents (Table 4). The relatively high He concentrations (0.1% by vol.) reflect that the study area is associated with extensional tectonics. The gas factor, i.e. the gas to water volume ratio, was estimated to be approximately 0.1–0.5. The total gas saturation was within 0.5–1.0 g/L (CH4) with the following partial pressures (bar): CH4 = 0.25, N2 = 0.11, CO2 = 0.03 and O2 = 0.008. High N2/Ar (130) shows the presence of non-atmospheric nitrogen derived from the organic matter of the host rocks. Low value of d13CCO2 and high value of d18OCO2 show that gases from the Razdolnoe Spa indicate carbonate reduction (Fig. 7a). This process cannot influence the chemical composition
Table 4 Chemical and isotopic composition of the associated gases of the Razdolnoe Spa (borehole No. 2-E). Hole No./date of analyzes
He (%)
H2 (%)
Ar (%)
N2 (%)
O2 (%)
CH4 (%)
CO2 (%)
2-E/2008 2-E/2013
0.1 0.1
0.001 0.001
0.23 0.27
26.8 28.5
0.19 0.22
68.3 65.5
4.43 5.41
d 13C(CH4)‰ (VPDB) 73.8 76.8
d D(CH4)‰ (V-SMOW) – 195.6
d 13C(CO2)‰ (VPDB) 19.4 17.1
d 18O(CO2)‰ (V-SMOW) +3.3 –
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153
Fig. 7. Naturally occurring methane isotopic composition of the Razdolnoe Spa associated gases (from the Whiticar (1999). White dots – values C-bearing gases from the Razdolnoe Spa (2-E borehole).
of Na–HCO3 water since oxygen isotopic ratios do not show isotopic exchange between oxygen of H2O and CO2 which could be explained by low amount of CO2-4.4–8.6% by vol. produced in the course of carbonate reduction. Carbon isotopic analysis of methane has become a popular technique in the exploration for oil and gas because it can be used to differentiate between thermogenic and microbial gas. Previous investigations of the methane origin in Primorye region has showed that the average isotopic composition of the methane in the Mesozoic deposits is between 29.2‰ and 36.0‰ PDB, and methane occurrences in Primorye are most abundant in the coal-bearing sequences and coal-bearing beds of sedimentary basins (Obzhirov et al., 2007). The genesis of associated gases of the Razdolnoe Spa was studied using the d13C and dD content (Table 4). A dD detection for CH4 from the mineral water of Razdolnoe was made for the first time. The obtained d13C(CH4) and dD (CH4) values definitely indicate the biogenic origin of methane (Fig. 7b). Thus the high methane content in the water is related to the biochemical processes and the presence of dispersed organic matter in the host rocks which could be Cenozoic marine sediments containing coalbed. Hence, within the occurrence, CH4 and CO2 are released by microbiological processes in the host rocks which break down organic matter. In spite of the numerous tectonic dislocations, gases are retained in the rocks owing to the overlaying water-bearing horizons and confining beds.
6. Conclusions The composition of the deep HCO3–Na mineral water of the Razdolnoe Spa reflects the geochemical and biogeochemical processes that occur over time in this territory and provides important clues to understanding of the geologic and hydrologic controls of the generation of gases. The investigations of the water and gases allow us to draw the following conclusions: – The oxygen (d18O) and hydrogen (d2H) isotopic study of the underground and surface water points to the common, meteoric origin of the studied water. No influence of modern seawater intrusions was detected. Water isotopic composition may comply with an older groundwater that was recharged under different (colder) climatic conditions. Concentrations of tritium in mineral waters are definitely influenced by time and intensity of borehole exploitation. Tritium in these deep aquifers is either due to a leakage from other aquifers or to a contamination as a result of the exploitation. There is an insufficient evidence to distinguish between these alternatives.
– The trend in the isotopic signature of the gases indicates that strata play an important role in the generation and storage of methane. A high methane and nitrogen content in the water is related to the microbiological processes and the presence of dispersed organic matter in the host rocks. The obtained d13C and dD values for methane definitely indicate its marine microbial origin. d13C of CO2 shows that gases from the Razdolnoe Spa have carbonate reduction genesis. Isotopic ratios between d18O(CO2) and d18O(H2O) show no isotopic exchange between oxygen of H2O and CO2. – Chemical characteristics of HCO3–Na mineral water are related to the transformation of organic matter. Microbial reduction of dissolved sulfate seems to drive the sequence of processes that modify the water quality. Bicarbonate is a product of the reduction, and with increased dissolved concentrations, calcite and dolomite precipitate because of reduced solubilities of calcium and magnesium. The cation exchange with clays may also deplete the dissolved calcium and magnesium. – Geological and hydrogeological data provide two possible explanations of mineral water origin: (I) the mineral water associated with methane and gases was developed in Cenozoic sedimentary rocks which contain organic matter. Water and gases crossflow to Mesozoic sedimentary rocks is conditioned by the block structure of the Mesozoic basin, regional groundwater flow and extensive tectonic dislocations; or (II) water and gases migrate from a deeper part of Mesozoic sediments which contain sustainable environment for water and gases formation.
Acknowledgments We are grateful to Dr. Blokhin for analyzing water samples for REE using ICP-MS at Far East Geological Institute, Russia. This work was supported by Grant of Russian Scientific Fund No. 14-17-00415. References Biddau, R., Bensimon, M., Cidu, R., Parriaux, A., 2009. Rare earth elements in groundwater from different Alpine aquifers. Chem. Erde – Geochem. 69 (4), 327–339. Choi, H.-S., Yun, S.-T., Koh, Y.-K., Mayer, B., Park, S.-S., Hutcheon, I., 2009. Geochemical behavior of rare earth elements during the evolution of CO2-rich groundwater: a study from the Kangwon district, South Korea. Chem. Geol. 262 (3–4), 318–327. Chudaeva, V.A., Chudaev, O.V., Chelnokov, A.N., Edmunds, M., Shand, P., 1999. Mineral waters of Primorye (chemical aspect). Dal’nauka, Vladivostok, 156 (in Russian).
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Chudaeva, V.A., 2002. Migration of chemical elements in the waters of the Far East. Dal’nauka, Vladivostok 10, 391 (in Russian). Dubinsky, A.P., 2014. Additional site exploration of South of Primorsky kray (1:200000). Hydrogeology Report Series of the Russian Hydrogeological Survey, TGF, Vladivostok. Dia, A., Gruau, G., Olivié-Lauquet, G., Riou, C., Molénat, J., Curmi, P., 2000. The distribution of rare earth elements in groundwaters: assessing the role of source-rock composition, redox changes and colloidal particles. Geochim. Cosmochim. Acta 64 (24), 4131–4148. Elderfield, H., Upstill-Goddard, R., Sholkovitz, E.R., 1990. Rare earth elements in rivers, estuaries, and coastal seas and their significance to the composition of ocean waters. Geochim. Cosmochim. Acta 54 (4), 971–991. Goriachev, V.A., 1997. Development and adaptation of the high sensitive gas proportion method of tritium measurement for oceanic purpose. Dissertation, Pacific Oceanic Institute, Vladivostok (in Russian). Hem, J.D., 1992. Study and interpretation of the chemical characteristics of natural water. U.S. Geological Survey Water Supply Paper 2254, 263 p. Johannesson, K.H., Stetzenbach, K.J., Hodge, V.F., 1997. Rare earth elements as geochemical tracers of regional groundwater mixing. Geochim. Cosmochim. Acta 61 (17), 3605–3618. Kharitonova, N.A., Chelnokov, G.A., Bragin, I.V., Vakh, E.A., 2012. Isotope composition of natural waters of the southern Far East, Russia. Pacific Geol. 31 (2), 75–86. Korobova, I.F., 1972. Geological structure and hydrocarbon potential of Borisovskaia area/Borisovskaia appraisal well No 1 report on 1963–1967 y., Irkutsk, 1972, pp. 257. Kuznetsov, Y.V., 1963. Geosciences results of oil and gas investigation for Suifun geosyncline belt of Primorye, Vladivostok, pp. 150. Möller, P., Rosenthal, E., Dulski, P., Geyer, S., 2008. Characterization of recharge areas by rare earth elements and stable isotopes of H2O. In: Hötzl, Heinz, Möller, Peter, Rosenthal, Eliahu (Eds.), The Water of the Jordan Valley Scarcity and
Deterioration of Groundwater and its Impact on the Regional Development. Springer, Berlin Heidelberg, pp. 123–148. Obzhirov, A.I., Gresov, A.I., Shakirov, R.B., et al., 2007. Methane occurrences and oil and gas potential of Primorsky Territory. Dal’nauka, Vladivostok (in Russian). Piper, D.Z., Bau, M., 2013. Normalized rare earth elements in water, sediments, and wine: identifying sources and environmental redox conditions. Am. J. Anal. Chem. 4, 69–83. Plummer, K.N., Prestemon, E.C., Parkurst, D.L., 1991. An interactive code (Netpath) for modeling net geochemical reactions along a flow path. US Geol. Surv. Water. Res. Inv., pp. 91–4078. Rinkov, V.S., 1988. Underground water of Far East. Hydrogeology Report Series of the Russian Hydrogeological Survey, TGF, Vladivostok. Tweed, S.O., Weaver, T.R., Cartwright, I., Schaefer, B., 2006. Behavior of rare earth elements in groundwater during flow and mixing in fractured rock aquifers: an example from the Dandenong Ranges, southeast Australia. Chem. Geol. 234 (3–4), 291–307. User’s Guide AQUACHEM: A Computer Program for Speciation, Reaction-Path, Advective Transport, and Inverse Geochemical Calculation, Waterloo, 2005. Voznyakovskaya, I.G., Shamin, A.I., 1993. Thermal waters reconnaissance on Razdolnaya River valley, thermal side 1989–1993 years. TGF Vladivostok, pp. 110. Van Voast, Wayne A., 2003. Geochemical signature of formation waters associated with coalbed methane. AAPG Bull. 87, 667–676. http://dx.doi.org/10.1306/ 10300201079. Wheaton, J.R., Brown, T.H., 2005, Predicting changes in ground-water quality associated with coalbed methane infiltration ponds: in western resources project final report-produced groundwater associated with coalbed natural gas production in the Powder River Basin. Wyoming State Geological Survey Report of Investigation No. 55. Whiticar, M., 1999. Carbon and hydrogen isotope systematic of bacterial formation and oxidation of methane. Chem. Geol. 161 (1–3), 291–314.
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Applied Geochemistry journal homepage: www.elsevier.com/locate/apgeochem
Geochemistry of mineral water and gases of the Razdolnoe Spa (Primorye, Far East of Russia) George Chelnokov ⇑, Natalya Kharitonova, Ivan Bragin, Oleg Chudaev Far East Geological Institute, Far East Branch of Russian Academy of Sciences, Laboratory of Hydrogeochemistry, 690022, Prospect 100-letya Vladivostoka 159, Vladivostok, Primorsky Kray, Russia
a r t i c l e
i n f o
Article history: Available online 9 May 2015 Editorial handling by M. Kersten
a b s t r a c t New isotopic and chemical data on the sodium bicarbonate water and associated gases from the Razdolnoe Spa located in the coastal zone of Primorsky Kray of the Russian Far East, together with previous stable isotope data (d18O, dD, d13C), allow elucidation of the origin and evolution of the groundwater and gases from the spa. The water is characterized by low temperature (12 °C), TDS – 2.5–6.0 g/L, high contents of B (5 mg/L) and F (4.5 mg/L) and low contents of Cl and SO4. Water isotopic composition indicates its essentially meteoric origin which may comply with an older groundwater that was recharged under different (colder) climatic conditions. Major components of bubbling gases are CH4 (68 vol%), N2 (28%) and CO2 (4%). The obtained values d13C and dD for CO2 and CH4 definitely indicate the marine microbial origin of methane. Thus the high methane content in the waters relates to the biochemical processes and presence of a dispersed organic matter in the host rocks. Based on the regional hydrogeology and the geological structure of the Razdolnoe Spa, Mesozoic fractured rocks containing Na–HCO3 mineral water and gases are reservoir rocks, a chemical composition of water and gases originates in different environmental conditions. Ó 2015 Elsevier Ltd. All rights reserved.
1. Introduction A wide variety of mineral groundwater types occur in the Primorsky Kray in the Far East of Russia and can be grouped into: (a) high pCO2 mineral waters; (b) thermal waters and (c) saline waters. The high pCO2 springs are situated in central and western Primorye closely associated with major structural lineaments (Chudaeva et al., 1999). Thermal water (<35 °C) is represented by two major groups in the East of Primorsky Kray. Saline waters are located in coastal zone of the south of Primorye region. The Razdolnoe Spa field is located about 4 km southwest of the Razdolnoe settlement in the valley of the Razdolnaya River (Fig. 1). During prospecting drilling for energetically useful thermal waters carried out in this area in 1989–1993, the HCO3–Na waters with a salinity of 2.5–6.0 g/L were discovered and the field was named Razdolnoe (Voznyakovskaya and Shamin, 1993). These mineral waters are bottled as drinking medicinal-table waters and are used for balneological treatment. The origin and conditions of cold mineral groundwater with the N2–CH4 gas composition have almost not been studied in the Far East of Russia. According to Korobova (1972), this type of waters ⇑ Corresponding author. Tel.: +7 9146624835. E-mail address: [email protected] (G. Chelnokov). http://dx.doi.org/10.1016/j.apgeochem.2015.05.001 0883-2927/Ó 2015 Elsevier Ltd. All rights reserved.
has been met during the exploration work on oil–gas in Primorye. The first attempt to elucidate the genesis of cold mineral waters in Primorye was made in 1995 in the framework of a joint Russian–British project (Chudaeva et al., 1999). The main goal of this paper is to investigate the geochemistry of the Razdolnoe Spa mineral water and associated gases. The genesis of groundwater and gases is discussed on the base of regional hydrogeological conditions, water and gas composition, water– rock interaction, d18O and dD of mineral and meteoric waters, and carbon isotopic composition in CO2 and CH4. 2. Geological setting The area of the Razdolnoe Spa is located in the junction zone of large geomorphologic structures: the West Primorye flatland with the Razdolnaya River valley, the easternmost tip of the East Manchurian upland (Borisovskoe plateau), and the western branches of Sikhote-Alin’ (Rinkov, 1988). Geological structure of area can be divided on two structural levels: lower-Mesozoic and upper-Cenozoic (Fig. 2). The Mesozoic rocks are the oldest formation in the area and compose the bottom and walls of the Pushkin depression. Jurassic, Triassic and Cretaceous rocks are mainly represented by terrigenous rocks (sandstones, siltstones). They do not outcrop within the area and were trapped during
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the drilling. The thickness of the Mesozoic rocks is more than 400 m. Cenozoic deposits with a sharp angle unconformity overlay the Mesozoic rocks. The Neogene sequence includes the UstDavydovka (N1ud) and Ust-Suifun (N1us) formations of the Miocene. The deposits of the Ust-Davydovka Formation are represented by sandstones, siltstones, and mudstones with thin lens of lignite. Sandstone is generally quite porous and has a good permeability. The sediments of the Ust-Suifun Formation are mainly gravel–pebble deposits with sandy joining material. The thickness of the Cenozoic deposits is no more than 100–120 m. Recent beds overlap all the older rocks and consist of loam, clay sand, sands, marine alluvium and gravel–pebble sediments from 6 to 20 m thick. Tectonically, the area is confined to the eastern wall of the Pushkin depression, which is bordered in the east by the Nizhnii-Suifun submeridional deep-seated fault traceable from the mouth of the Razdolnaya River to the north on 30 km. In addition, the western wall of the Razdolnaya River valley is cut by the Eastern Kedrovskii fault. The submeridional faults are complicated by a series of subsidiary faults; i.e., the study area is located in a complex tectonic environment. Tectonic processes affected as Mesozoic rocks also the Cenozoic rocks. The active geological processes in this area were presumably completed with extinction of the volcanic activity (Pliocene), which produced a large basaltic plateau to the NW of the studied area. 3. Hydrogeological conditions Hydrogeologically, the study area belongs to the central part of the southern Primorye artesian basin (Rinkov, 1988). The basin occupies an area of 5000 km2 from the Amursky Bay coast to middle Razdolnaya River flow. It is the Mezozoic depression filled up with Cenozoic terrigenous and marine sediments. The Neogen basaltic lava plains lie on the western and eastern margins of basin. The depression has a block structure and is confined by tectonic dislocations (Voznyakovskaya and Shamin, 1993). The regional
aquifer system is divided into two distinct water bearing units represented by Cenozoic sedimentary-rock aquifer and Mesozoic consolidated rock aquifer. The Cenozoic sedimentary-rock aquifer is usually comprised of poorly consolidated to unconsolidated sediments where water typically occurs in unconfined conditions. Distinguished for their adverse hydrogeological conditions, the porous-stratal water basins are predominantly composed of Palaeogenic and Neogenic rocks with sub-constituents such as sand, sandy clay, sandstone, siltstone, coal beds add silt. Unconfined waters lie in the river valleys and troughs at the depth of 2–91 m, flow rates of the wells range between 0.05 and 5.4 l/s. The groundwater has a wide range in the type and amount of dissolved chemical constituents. Most water having less than 600 ppm of dissolved solids is either calcium or sodium bicarbonate. Such water is used for the water supply of Vladivostok city. Water containing more than 10,000 ppm is either sodium chlorate or sodium-chlorate–bicarbonate and wide spread in coastal area. The origin of this type of water is connected with late Paleozoic transgression when sea level exceeded the modern over 10–12 m. The Mesozoic confine aquifer represents fractured sandstones, siltstones with thickness up to 800 m. A confined aquifer mostly occurs at depth intervals of 110–350 m, piezometric levels are 10–40 m below the ground surface, well water discharge range between 0.05 and 7.4 l/s. The groundwater signed to upper fractured zones and tectonic dislocations. The groundwater flow is dominantly fracture-controlled. A chemical composition of the groundwater of the Mesozoic aquifer is either fresh HCO3–Ca–Na or HCO3–Cl–Ca–Na (Kuznetsov, 1963). The regional recharge area in respect of the southern Primorye artesian basin is on the highlands – Shufanski Basaltic Plateau located on the west and east of the territory. The regional groundwater flow pattern shows overall NE trending flow lines. Most of the groundwater circulation is thought to take place within the Cenozoic aquifer and upper part of the Mesozoic aquifer. This however, does not indicate that there is no deep circulation or mixing of groundwater from the lower
Fig. 1. Location map showing study area.
G. Chelnokov et al. / Applied Geochemistry 59 (2015) 147–154
part of Mesozoic aquifer since regional hydrogeological conditions were studied only for depth up to 200 m (Voznyakovskaya and Shamin, 1993). Deep drilling data (Kuznetsov, 1963) show that fresh water with TDS of 0.4 g/L exists at a depth up to 1300 m. Other deep well (Korobova, 1972) shows that TDS rises up to 21 g/L and water has a HCO3–Cl–Na composition. Hydrogeology of the Razdolnoe Spa is ascribed based on data of third wells (2-E, 2-B and 1-Al) drilled within limits of study area. The basin is characterized by a complex hydrogeological structure and by groundwater of diverse geochemical composition. Well No. 1-Al (30 m deep) is located on recharge zone and discloses Pliocene volcanogenic aquifer (N2). Wells No. 2-E (314 m deep) and No. 2-B (500 m deep) are disclosed the following aquifers (from top to the bottom): (1) Quaternary alluvial sediments (aQIV); (2) Quaternary deltaic sediments (amQIV); (3) Miocene sedimentary aquifer consisting of the Ust-Suifun (N1us) and Ust-Davydovka (N1ud) Formations; (4) Mesozoic sediments (MZ). A cross-section demonstrating the hydrogeological conditions of the Razdolnoe Spa is shown on Fig. 2. Hydrogeological characteristics of major aquifers presented within the study area are showed below: (I) An upper, unconfined aquifer which is the nearest to the surface consists of upper quaternary-modern alluvial sediments-fine sands, pebble bed, and gravel, often with a
(II)
(III)
(IV)
(V)
149
sandy clay filler. Wide-spread throughout river valleys, this unit has thickness of 10–15 m and the maximum depth of water level in this aquifer is 3 m from the surface. In the Razdolnoe area, the water of this aquifer flows toward the Razdolnaya River and its feeders. An unconfined aquifer of quaternary marine deltaic sediments- sea mud, pebble bed, and gravel. Spread throughout Razdolnaya River valley over 30 km from the coast, has thickness of 10–20 m. Sediments were accumulated during the transgression. A confined Pliocene volcanogenic aquifer (N2) is restricted to the basaltic plateau occupying the northwestern and eastern parts of the area (Fig. 2). The regime of aquifer is inconstant and strongly depends on the atmospheric precipitation. Natural discharge goes to the adjacent and underlying water-bearing horizons. The maximum depth of the water level on watersheds is 100 m, and within depression areas is 2 m from the surface. Basaltic abundance of the water is very low and irregular. Wells discharge is about 2–5 l/s, the water is fresh, of sodium and calcium hydrocarbonate types. The Pliocene volcanogenic aquifer is characterized by well 1-Al (30 m deep) data. A Miocene sedimentary aquifer consisting of the Ust-Suifun (N1us) and Ust-Davydovka (N1ud) Formations; the groundwater has HCO3–Mg–Na–Ca composition and low salinity, except the area of Razdolnaya River Valley, where a saline groundwater of Cl–Na type with TDS (3–14 g/L) was locally disclosed during the drillings. Unfortunately, we presently have no opportunity to determine the water isotopic composition of the Miocene aquifer, as boreholes, which trapped it, was conserved. Mesozoic sediments. The deepest Mesozoic sedimentary aquifer spreads in Triassic, Jurassic and Cretaceous rocks, as they have similar lithology and represent a single hydraulic system. The aquifer is located at the depths of more than 100 m and has a very complex structure, where underground waters are confined to wide fracture zones and zones of tectonic disruptions. The groundwater is characterized by HCO3–Na composition, but mineralization of the aquifer varies from 2.5 to 14 g/L. Well No. 2-E in interval of depths 135– 280 m disclosed HCO3–Na water with TDS of 2.5–6.0 g/L and at depths of 500 m well No. 2-B revealed waters with TDS of 14 g/L. The variations of mineralization and wells discharge indicate the complexity and heterogeneity of the hydrogeochemical section of the study object.
4. Sampling and analysis
Fig. 2. Geological scheme and hydrogeological cross-section of the Razdolnoe Spa (from Voznyakovskaya and Shamin, 1993). (1) Upper Quaternary alluvial aquifer; (2) Quaternary deltaic sediments; (3) aquifer of Pliocene volcanogenic rocks (basalts); (4) Miocene sedimentary aquifer (pebbles, gravels, sands); (5) Mesozoic terrigenous-sedimentary aquifer (siltstones, sandstones); (6) area of Cl–Na type of water (TDS 5.4–14.0 g/L); (7) area of HCO3–Na type of water (TDS 2.5–6.0 g/L); (8) area of HCO3–Mg–Na–Ca type of water; (9) rock-fracture zone; (10) boreholes: number in the top, depth- in the bottom (m); (11) faults; (12) recharge area.
The mineral waters and gases of the Razdolnoe occurrence were studied in 2008–2014. Water samples were collected from boreholes, Razdolnaya River and its estuary. Groundwater samples were pumped from wells and collected in acid-washed, high-density polyethylene sample bottles. Before sampling, all water samples were filtered through 0.45 lm cellulose filters. Waters for cation analysis were acidified to pH < 2 with ultrapure HNO3. Water temperature, conductivity and pH were measured directly in the field. Major cations and anions were analyzed by ion chromatography. Carbonate species were titrated in the field with 0.1 N HCl. Trace element and rare earth elements (REE) concentrations in groundwater were determined by ICP-MS (Agilent 4500) analysis at the Analytical Center of Far East Geological Institute (Vladivostok, Russia). Analytical precision for the REEs, except for Ce and Pr, was better than 5% vs. RSD; for Ce and Pr, precision was 6% and 9% vs. RSD, respectively. Stable isotope compositions of waters (D/H and 18O/16O ratios) were determined by isotope-ratio mass spectrometry at the Analytical Center of Far
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Table 1 Representative chemical analyses of studied waters. Components
Units
Razdolnaya River
Boreholes No. 1-Al
No. 2-E
Depth T pH Eh TDS HCO3 Cl SO24 Na+ R+ Mg2+ Ca2+ Fetot Al Si Li As Ba I Br B F Mn La Ce Pr Nd Sm Eu Gd Tb Ho Er Tm Yb Lu
m °C
Surface 10 6.6 168 0.25 165 3.5 9.6 32 4.7 12.6 25.0 1.5 0.13 3.54 0.01 0.0009 0.02 – – – 0.1 0.01 1.12 2.02 0.19 0.69 0.12 0.025 0.074 0.019 0.023 0.061 0.010 0.057 0.012
20 10 6.53 290 0.115 74.5 11.5 7.9 13.0 3.0 4.25 13.56 0.1 0.25 43.6 0.001 0.001 0.006 0.00001 0.05 0.05 0.3 0.001 0.0048 0.002 0.001 0.0047 0.0011 0.021 0.0028 0.0005 0.0013 0.0021 0.0006 0.0021 0.0006
135 12 6.56 58 4.56 3252 89 0.4 1347 4.8 15.4 14.8 0.1 0.01 6.2 2.2 0.001 0.6 0.05 0.25 4.8 4.53 0.008 0.05 0.04 0.006 0.01 0.035 0.40 0.012 0.008 0.005 0.036 0.007 0.030 0.005
mV g/L mg/L
lg/L
Bay-head estuary waters Surface 23 6.8 + 7.31 143 3160 274 1787 63.3 199.8 95 0.06 0.009 0.8 0.003 0.0001 0.0004 0.2 9.11 0.89 0.4 0.02 – – – – – – – – – – – – –
‘‘–’’ – not determined.
East Geological Institute (Vladivostok). The precisions of the analyses are 1‰ for d2H and 0.1‰ for d18O. The bubbling gas was sampled using the replacement method. The composition of the gas was analyzed by gas chromatography techniques using thermal conductivity detectors and molecular sieve columns with He and Ar as carrier gases for the determination of He, H2, N2, O2, and CH4. A Porapak Q column with He carrier gas was used for the separation of CO2. A combined CTR-3 Alltech column was used for the Ar analysis at room temperature with He as a carrier gas. Detection limits were 0.001 vol.% for He, H2 and N2, less than 0.001 vol.% for O2 and Ar, 0.001 vol.% for CO2. CH4 and CO2 gases isotopes ratios (13C/12C) were determined by isotope-ratio mass spectrometry MAT-253 using Trace-GC gas chromatograph at the Sapporo University (Japan). The precisions of the analyses are 0.1‰ for d13C and 1‰ for 2H. Tritium determinations were performed using electrolytic enrichment and subsequent measurement of counting rates; details of sample preparation for 3H analysis are described by Goriachev (1997). The standard deviation was 0.3–1.1 TU depending on the 3H concentration. 5. Results and discussion 5.1. Lithology Optical microscopy study of Mesozoic sandstones and siltstones was subsequently carried out. Core samples of the bedrock were sampled during the drilling in 1992. Sandstones are altered and
Fig. 3. Classification of studied water using Piper diagram.
Table 2 Components ratios of studied waters and seawater.
Average for seawaters Bay-head estuary Razdolnaya River Fresh groundwater (b. No. 1-Al) Mineral water (b. No. 2-E)
Na+/Cl
Ca2+/Mg2+
Ca2+/SO24
Cl /Br
0.55 0.57 9.14 1.13 15.1
0.3 0.48 1.98 3.19 0.96
0.15 0.35 2.6 1.72 37
287 347 – 230 356
presented by fine-grained and medium-grained types. Mineralogical composition: quartz (20%), plagioclase (40%), K-feldspar (10%), debris of tuffs (10%). The cement is muscovite and SiO2. Debris of tuffs is chloritized. Siltstones also altered, sometimes sulfidized. Mineralogical composition: quartz (30%), plagioclase (20%), muscovite and chlorite (50%). The cement is weathered and presented with hydromica–quartz, quartz– chlorite–hydromica, rarely with biotite. Zircon, sphene, leucoxene, anatase, tourmaline are accessory minerals. The bedrock lithological composition shows absence of organic matter in the upper fractured zone of Mesozoic rocks. 5.2. Water chemistry The chemical composition of studied waters is listed in Table 1 and on the Piper diagram, (Fig. 3), which demonstrates the proportions between the major water components of the area. Piper divided waters into three types. Surface and fresh groundwater lies on area of temporary hardness, and goes from rhyolite and basalts types of the rocks. Miocene sedimentary aquifer has complicated structure and heterogeneous water composition from fresh water characterized by Na–Ca–Mg–HCO3 (Na > 90% meq/l) type with low salinity (200 mg/L) and a high content of SiO2 (up to 50 mg/L) (borehole 1-Al) to Na–Cl type of waters with a TDS up to 14.0 g/L are distributed locally in form of lens (Rinkov, 1988). In terms of their chemical composition, the fresh Na–Ca–Mg–HC O3 type groundwater of borehole No. 1-Al can be roughly ascribed to the feed ground waters of the area (Fig. 3). Downward, in Mesozoic rocks alkali carbonated waters (HCO3– Na) is overspread (Fig. 3, borehole No. 2-E). Waters characterized by salinity of 2.5–6.0 g/L, HCO3 > 70% meq/l, Na > 95% meq/l, and temperature of 12.0–14.0 °C. These waters are enriched by F, Li, and B and have a low content of I. The ratios of major components (Table 2) in the waters different from those of the average composition of seawater. The obtained proportions indicate no influence
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of modern seawater, but sedimentation waters of marine origin exercise influence on groundwater. Third type is a bay-head estuary water which almost sea water. Monitoring of the waters from the boreholes No. 1-Al and 2-E during a complete annual cycle has revealed that both type of groundwater do not show any significant temporal variation in the chemical composition and do not have trend with atmospheric precipitations. Insignificant concentrations of chloride in the Mesozoic aquifer reflect the nonmarine character of the sediments, a condition different from that of the other geologically older basins (Dubinsky, 2014). The chemical signatures of the water demonstrate several geochemical processes. The main one, sulfate reduction, is a prerequisite reaction for the genesis of methane, is an attendant condition in its biogenesis, and enhances the enrichment of dissolved bicarbonate that in turn results in the depletion of calcium and magnesium. Bicarbonate is a product of the reduction, and with increased dissolved concentrations, calcite and dolomite precipitate because of reduced solubilities of calcium and magnesium. The Na–HCO3 and TDS-HCO3 correlations indicate that as Na content as TDS in groundwater directly depend on concentration HCO3 (r = 0,99). Ca–HCO3 relation shows good correlation (r = 0,8) but ingress of Ca at the 100 times less than Na (Table 1). Sulfate concentrations in the mineral water have a direct influence on the amount of barium found in the water because barite (barium sulfate) generally controls the solubility of barium in most natural waters (Hem, 1992). Barium concentrations in the water are high compared to other groundwater because of the low sulfate concentrations. During coalification and methanogenesis, water in contact with the coals is anoxic and reducing. Elements such as iron and manganese, which are soluble as reduced species (Fe2+ and Mn2+), have concentrations that are relatively high compared to surface water values as a result of the reducing environment. Low concentrations of calcium and magnesium, and particularly sulfate, typify the formation water associated with coalbed methane (Van Voast, 2003; Wheaton and Brown, 2005). The water temperature is 12–14 °C at a depth of 140 m of the given aquifer points to regional thermogradient. Late Neogenic volcanism was well presented at the study territory. Baranovsky Neogenic volcano is located 10 km to the North from the Razdolnoe Spa. Temperature measurements in the deep wells (1300 m and 2858 m) conducted during the drilling (1963, 1972) show that a geothermic step for sandstones is 15–24 m/1 °C (Voznyakovskaya and Shamin, 1993). The mass-balance calculations using Netpath software (Plummer et al., 1991) suggest that the chemical composition of the HCO3–Na waters is mainly controlled by albite dissolution. The saturation indexes (SI) obtained using AQUACHEM software (User’s Guide, 2005) indicate that the waters are undersaturated with respect to albite ( 3.2), anorthite ( 11.2), and chlorite ( 20.2); are in equilibrium with respect to calcite ( 0.3), chalcedony (0.2), quartz (0.7), siderite ( 0.02), and illite (0.19); and are oversaturated with respect to montmorillonite (1.0), kaolinite (1.5), and hematite (Fe2O3) (7.06). FeO (hematite) was also identified in the residue on 0.45-lm filter by X-ray phase analysis. The results of the thermodynamic calculations are well consistent with the mineralogical composition of the host rocks, whose study showed that feldspars are the most altered among the minerals of the sedimentary rocks of the area. Investigation of rare earth elements (REE) content in different types of waters became widespread in two last decades. They naturally occur in the environment, and are commonly used as environmental tracers for a range of geological and hydrological processes (Biddau et al., 2009; Choi et al., 2009; Dia et al., 2000; Johannesson et al., 1997; Möller et al., 2008; Tweed et al., 2006). REE-patterns of studied surface and mineral waters, and also
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Fig. 4. North American Shale Composite normalized concentrations of REE in the studied groundwater from the Razdolnoe Spa.
Mesozoic rocks shows on Fig. 4. The flat curve of river waters commonly resembles the curve of the source rocks in the drainage basin (Elderfield et al., 1990). The curve of seawaters exhibits a negative Ce anomaly and progressive of the heavy REE, relative to the light REE (Piper and Bau, 2013). Elderfield et al. (1990), show that the river water have (Yb/Nd)SN ratio of 1, showing no relative fractionation with respect to shale, whereas that of seawater is 4.3, indicating an enrichment of HREE over LREE is taking place during water–rock interaction processes (Fig. 5). The patterns of distribution of rare-earth elements on surface, groundwater and host-rocks show that waters is connected with processes of diagenesis of marine sediments. According to Möller et al. (2008) concentrations of REE in the water indicate the recharge area for the initial water. Scatter plot of NASC normalized concentrations of Yb vs. Nd of the Razdolnaya River water and mineral water samples with data on Mesozoic rocks (Fig. 5) shows that a recharge zone for the fractured Mesozoic aquifer contains marine sediments. Regional hydrogeological data argue that during infiltration of the water to the fractured Mesozoic aquifer it might cross the Cenozoic marine sediments (Voznyakovskaya and Shamin, 1993).
Fig. 5. Scatter plot of NASC normalized concentrations of Yb vs. Nd of the Razdolnaya River water and mineral water samples with data on Mesozoic rocks. The data shows a linear trend with a correlation coefficient, r = 0.9.
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Table 3 Isotopic composition of oxygen and hydrogen of the studied waters. d18O‰ (VSMOW)
d2H‰ (VSMOW)
No.
Sampling locality, study object
Year of study
1 2
Sea water (Amursky Bay) Atmospheric precipitation in southern Primorye Fresh groundwater (catchment basin, hole No. 1-Al) Razdolnaya River
2007 2002
1.7 7.0
13 52
2008 2007
6.2 10.1
49 76
2007 2010 2002
11.2 11.6 11.85
88 82.5 86.6
2006 2007 2008 2008 2008
12.5 11.9 13.7 12.9 11.5
89 87 99 85.5 82.2
3 4 5 6 7
Mineral water HCO3–Na type, borehole 2-E
8 9 10 11 12
Note: Nos. 2 and 7 are taken from Chudaeva et al. (1999).
Fig. 6. Stable isotopes ratios in the Razdolnoe Spa basin groundwater.
5.3. Water isotopes The oxygen (d18O) and hydrogen (d2H) isotopic study of the ground and surface waters made it possible to determine their formation conditions. The obtained data are shown in Table 3 and Fig. 6. It is well seen in Fig. 6 that the isotopic composition of the marine and surface waters is enriched in heavy d18O isotope relative to the generally accepted line of meteoric waters. This is probably caused by several reasons: (1) evaporation accompanied by the removal of light isotope d16O) and enrichment in heavy isotope d18O; (2) the numerous oxygen and hydrogen isotope data collected by researchers of ground and surface waters of the southern Far East (Chudaeva, 2002) suggest that the regional line of the meteoric waters of Primorye is shifted toward a heavier oxygen composition relative to the global meteoric water line (GMWL). The examination of groundwater from coastal areas (Fig. 6, Table 3) revealed no interaction with modern marine waters. The mineral groundwater from the Razdolnoe Spa is isotopically distinct from modern meteoric waters as represented by the shallow groundwater and surface waters at the 1-Al and Razdolnaya
River (Fig. 6). There are two possible explanations: (1) these waters are modern recharge waters but are closer to the annual weighted average of precipitation for northern Primorye (Kharitonova et al., 2012). Na–HCO3 water was fed by meteoric waters via weakened fault zones in the northwestern part of the area, where Mesozoic rocks are exposed as remnants or insignificantly overlapped by Quaternary deposits or (2) these waters may represent older groundwater that were recharged under a different (colder) climatic regime. The fact that a groundwater from 140 m depth and high TDS in the Razdolnoe Spa is isotopically identical to modern recharge waters at the Razdolnaya River would support the second scenario. At the same time, the intricate hydrogeological conditions of the deposit, presence of confining layers and low water discharge attest to the complex feeding of the aquifer and, hence, wide drainage area. Tritium content in surface waters of the region varies from 4.7 TU to 29.3 TU, average 13 TU and correlates well with 3H concentrations in atmospheric precipitations (Kharitonova et al., 2012). Studied Na–HCO3 water sampled from depth of 10 m, contains 12.8 TU, very close to concentrations of tritium in surface waters of that area, is being formed in conditions of fast water recharge. At the same time water from the depth of 140 m shows 5.1 TU. Concentrations of tritium in mineral waters are definitely influenced by time and intensity of borehole exploitation: when large amounts of water are being taken, activation of outer areas of deposit occurs (cone of depression), i.e. a closed system becomes an opened one, into where waters with different concentrations of 3H start flowing. This hypothesis is clearly illustrated by data from being exploiting deposits of mineral groundwater spa of Primorye (Kharitonova et al., 2012). High-resolution tritium analyses show very low, but measurable levels of tritium in all of the confined aquifers located on the south-west coast of Primorye (Dubinsky, 2014). Because the age of the water in these aquifers is very old when compared to the half-life of tritium (12.35 years), there should be no tritium present within the confined aquifers. The tritium in these deep aquifers is either due to leakage from other aquifers or to contamination as a result of the exploitation (casing column problem). There is an insufficient evidence to distinguish between these alternatives.
5.4. The gas chemistry and carbon isotopes The free gas collected from the well consisted mostly of CH4 (62.7–68.3% by vol.), N2 (26.8–27.6% by vol.), CO2 (4.4–8.6% by vol.), with minor amounts of Ar (0.2% by vol.), O2 (0.2–1.0% by vol.) and very low H2 (0.001% by vol.) contents (Table 4). The relatively high He concentrations (0.1% by vol.) reflect that the study area is associated with extensional tectonics. The gas factor, i.e. the gas to water volume ratio, was estimated to be approximately 0.1–0.5. The total gas saturation was within 0.5–1.0 g/L (CH4) with the following partial pressures (bar): CH4 = 0.25, N2 = 0.11, CO2 = 0.03 and O2 = 0.008. High N2/Ar (130) shows the presence of non-atmospheric nitrogen derived from the organic matter of the host rocks. Low value of d13CCO2 and high value of d18OCO2 show that gases from the Razdolnoe Spa indicate carbonate reduction (Fig. 7a). This process cannot influence the chemical composition
Table 4 Chemical and isotopic composition of the associated gases of the Razdolnoe Spa (borehole No. 2-E). Hole No./date of analyzes
He (%)
H2 (%)
Ar (%)
N2 (%)
O2 (%)
CH4 (%)
CO2 (%)
2-E/2008 2-E/2013
0.1 0.1
0.001 0.001
0.23 0.27
26.8 28.5
0.19 0.22
68.3 65.5
4.43 5.41
d 13C(CH4)‰ (VPDB) 73.8 76.8
d D(CH4)‰ (V-SMOW) – 195.6
d 13C(CO2)‰ (VPDB) 19.4 17.1
d 18O(CO2)‰ (V-SMOW) +3.3 –
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Fig. 7. Naturally occurring methane isotopic composition of the Razdolnoe Spa associated gases (from the Whiticar (1999). White dots – values C-bearing gases from the Razdolnoe Spa (2-E borehole).
of Na–HCO3 water since oxygen isotopic ratios do not show isotopic exchange between oxygen of H2O and CO2 which could be explained by low amount of CO2-4.4–8.6% by vol. produced in the course of carbonate reduction. Carbon isotopic analysis of methane has become a popular technique in the exploration for oil and gas because it can be used to differentiate between thermogenic and microbial gas. Previous investigations of the methane origin in Primorye region has showed that the average isotopic composition of the methane in the Mesozoic deposits is between 29.2‰ and 36.0‰ PDB, and methane occurrences in Primorye are most abundant in the coal-bearing sequences and coal-bearing beds of sedimentary basins (Obzhirov et al., 2007). The genesis of associated gases of the Razdolnoe Spa was studied using the d13C and dD content (Table 4). A dD detection for CH4 from the mineral water of Razdolnoe was made for the first time. The obtained d13C(CH4) and dD (CH4) values definitely indicate the biogenic origin of methane (Fig. 7b). Thus the high methane content in the water is related to the biochemical processes and the presence of dispersed organic matter in the host rocks which could be Cenozoic marine sediments containing coalbed. Hence, within the occurrence, CH4 and CO2 are released by microbiological processes in the host rocks which break down organic matter. In spite of the numerous tectonic dislocations, gases are retained in the rocks owing to the overlaying water-bearing horizons and confining beds.
6. Conclusions The composition of the deep HCO3–Na mineral water of the Razdolnoe Spa reflects the geochemical and biogeochemical processes that occur over time in this territory and provides important clues to understanding of the geologic and hydrologic controls of the generation of gases. The investigations of the water and gases allow us to draw the following conclusions: – The oxygen (d18O) and hydrogen (d2H) isotopic study of the underground and surface water points to the common, meteoric origin of the studied water. No influence of modern seawater intrusions was detected. Water isotopic composition may comply with an older groundwater that was recharged under different (colder) climatic conditions. Concentrations of tritium in mineral waters are definitely influenced by time and intensity of borehole exploitation. Tritium in these deep aquifers is either due to a leakage from other aquifers or to a contamination as a result of the exploitation. There is an insufficient evidence to distinguish between these alternatives.
– The trend in the isotopic signature of the gases indicates that strata play an important role in the generation and storage of methane. A high methane and nitrogen content in the water is related to the microbiological processes and the presence of dispersed organic matter in the host rocks. The obtained d13C and dD values for methane definitely indicate its marine microbial origin. d13C of CO2 shows that gases from the Razdolnoe Spa have carbonate reduction genesis. Isotopic ratios between d18O(CO2) and d18O(H2O) show no isotopic exchange between oxygen of H2O and CO2. – Chemical characteristics of HCO3–Na mineral water are related to the transformation of organic matter. Microbial reduction of dissolved sulfate seems to drive the sequence of processes that modify the water quality. Bicarbonate is a product of the reduction, and with increased dissolved concentrations, calcite and dolomite precipitate because of reduced solubilities of calcium and magnesium. The cation exchange with clays may also deplete the dissolved calcium and magnesium. – Geological and hydrogeological data provide two possible explanations of mineral water origin: (I) the mineral water associated with methane and gases was developed in Cenozoic sedimentary rocks which contain organic matter. Water and gases crossflow to Mesozoic sedimentary rocks is conditioned by the block structure of the Mesozoic basin, regional groundwater flow and extensive tectonic dislocations; or (II) water and gases migrate from a deeper part of Mesozoic sediments which contain sustainable environment for water and gases formation.
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