Current status and management for the sustainable mineral water resources on the Far East of Russia

. The Far East of Russia has many manifestations of mineral waters with a wide range of chemical compositions. About 50 mineral water sources have been developed as spas and health resorts, and more than 25 produce bottled mineral water. The basis for resource assessment is data taken from about 150 mineral water fields and occurrences located all over the region. Data from different sources—natural springs and wells— has been summarized and analyzed. The details of the chemical composition of the different types of mineral waters and some geological aquifer peculiarities are described. The most widely used classification of mineral waters is presented. The present condition of these waters and the government standards laid down for their use are described. Examples of different mineral waters are given. Keywords : mineral waters, resources,


Introduction
In the Russian part of the Asia-Pacific region, significant reserves of groundwater of various composition and genesis are concentrated.Mineral water resources, and especially thermal water resources are abundant in the area.This is a result of the specific geological and tectonic conditions led to the origin of various chemical types of mineral waters.However, due to low population and poor infrastructure, no optimal results have been achieved that would enable the utilization of all of these water resources for useful purposes.The problems of providing the population of Asia with underground waters are the actual tasks of modern science.
The Russian part of the Far East -the extreme eastern territory of Russia, between Lake Baikal in Eastern Siberia and the Pacific Ocean.The Far Eastern Federal District is 6,215,900 square kilometres, 36.4% of the territory of Russia (Figure 1).The population of the region is 6,293,100 people (4.9% of the population of Russia) [1].The centre of the Far East is Vladivostok.The Far Eastern Federal District has land borders with the People's Republic of China, Mongolia and the Democratic People's Republic of Korea to the southwest.Now the region occupies a leading position in the country in geological prospecting and licensing.The main products of the mining industry of the Far Eastern region of Russia are fossil fuels (oil, gas, coal), precious metals (gold, silver, platinum) and precious stones (diamonds), nonferrous metals (tin, tungsten, lead, zinc) and nonmetallic minerals (boron, fluorite).
The uniqueness of the Far Eastern region in terms of the diversity of thermal and mineral waters attracting the attention both researchers and businessmen.Last decades, water demand has increased due to economic development and agricultural advancements.With increasing mineral groundwater use in the Far East of Russia, many quality-related problems have arisen as a result of natural and anthropogenic activities, and these issues must be considered when regarding community health.
The main aim of this paper is to show the mineral and thermal water potential of the Far East of Russia, their physical and chemical properties and the utilization.

Historical setting
The study of the hydrogeological conditions and chemical features of groundwaters of the Far East of Russia was conducted by various authors and groups of scientists as with a search goal to identify and study the hydrochemical anomalies in detail and to characterize the composition of different types of waters for different needs of the national economy.A significant contribution to the study of the mineral waters of the Far East was made by V.V. Averyev; V.I.Kononov; I.S. Lomonosov; G.S. Vertanian; E.V. Pinnecker; V.A. Kiryukhin; S.L. Shvartcev and many others.Generalizations of extensive hydrogeochemical works performed territorial hydrogeological expeditions and given in the volumes of the "Hydrogeology of the USSR" give a common presentation about various hydrochemical types of water.The heyday of hydrogeological studies came in the 60-70s.V.V. Ivanov (1960) gave an extensive review of the thermal waters of the Far East, patterns of their distribution, the main chemical composition.Particular attention was paid to the hydrothermal resources of Kamchatka and the Kuril Islands.Research G.I. Arsanova, G.F. Pilipenko, C.I. Naboko, G.S. Karpov, G.A. Golevoy, V.A. Kiryukhin and many others allowed to receive more detailed information and to reveal a number of patterns in the removal of a wide range of trace elements by hydrotherms.Later, the distribution and composition of the thermal waters of the Far East were reflected on the maps of the thermal waters of the USSR (Mavritsky, 1980).Information on the composition of the mineral waters of the Far East can be found in the several works [2][3][4][5][6][7][8][9][10].Some review of both chemical and balneological properties is given in the work "Mineral waters and peloids of the Far East" [11][12][13].

Groundwater resources and classification
Groundwater availability on the Far East of Russia is quite satisfactory.The major sources of groundwater are due to natural recharge from annual precipitation, streamflow, rivers, lakes etc.The territory is covered by a net of rivers (including Amur River) and tributaries that contribute to the formation of groundwaters.
Today in Far East of Russia approximately 50 manifestations of mineral waters are in use in spas and health resorts.Almost half of them also are used as bottled waters.With regard to geothermal resources of the Far East of Russia, of particular importance are those in the Kamchatka and Kuril islands.On other territories, the thermal waters are used mainly for balneological purposes, recreation and bottling.Here they are not used in agriculture, aquaculture, industry and technology.
Historically, the wide range of different types of mineral waters in Russia has led to the introduction of several mineral water classifications.The most widely used is the classification of Ivanov and Nevraev (Ivanov et al., 1964).This is based on the main balneological components and is generally satisfactory for classifying the principal types of mineral waters.Despite the fact that there are a lot of definitions of term mineral waters, the best one is short and simple.In respect of the mineral water, there are waters of specific physical and chemical properties which are effective for medical and balneological uses which are confirmed by a prolonged experience (Voronov, 2000).
Mineral waters of the Russian Far East are divided into three major groups: I -CO2-rich Na-HCO3 (Na-Cl-HCO3) waters; II -thermal alkaline waters and III -saline Na-Cl waters.
The cold CO2-rich mineral waters are the most widespread and frequently used groups of mineral waters in the Far East of Russia.The forecast resources of carbonate water only for the south of the Far East (Primorsky region) is more than 25000 m 3 /day.
The CO2-rich mineral waters have a low temperature (8-10 o C) and pH varies from 5.0 to 6.2.Total dissolved solids (TDS) varied widely from 0.4 to 6.3 g/l.The concentrations of alkali metals, SO4 and halogens are generally very low.The group is subdivided into HCO3 (on continent part of Far East) and HCO3-Cl waters (on Sakhalin island) depending on the dominant anions.
One of the best known and most interesting zones of carbonate waters occurs is south of the Far East of Russia (Primorsky and Khabarovsky regions) along with a Sikhote-Alin' ridge.Here more than 80 manifestations of bicarbonate waters, which include two biggest areas on the Far East: Shmakovka (2500 m 3 /day) and Mukhen (1000 m 3 /day) (Fig. 1), are located.The hydrogeology of this area is well known (Kharitonova et al., 2007;Chudaeva et al/, 1999;Chudaev, 2003).The high pCO2 waters associated with deep crustal fractures are present across a series of geological terrains with contrasting lithology and age (Shand et al, 2005).Mineral water is located in the upper hydrodynamic zone (<300 m) and their hydrogeochemical properties are largely dependent on CO2 gas content.The chemical composition of the waters varies greatly.There are six types of waters divided depending on the dominant cations, TDS and micro components content: 1. Primorsky; 2. Pokrovsky; 3. Lastochkinsky [5]; 4. Tursh-Su; 5. Darasunsky and 6.Shmakovsky (Chudaev et al., 2016).Many of the carbonate waters are bottled, most popular marks are from Shmakovka, Lastochka, Gornovodnoe and Mukhen areas.The Smakovka Spa Resorts are very popular with the population of the Russian Far East.
On Sakhalin Island the HCO3-Cl-Na CO2-rich mineral waters are represented by three major manifestations: Sinegorsky, Volchansky and Topol'noe.But the forecast resources of HCO3-Cl-Na waters on Sakhalin island are less than 200 m 3 /day.Mineral waters are used for spa treatment (Chelnokova, 2017), but in general, they are not actively developed.The mineral waters from Sinegorsky area using for Sinegorsk Spa and Resort and the Volchansky waters are not exploited (Chelnokov et al, 2018).The unique features of Sinegorsk CO2-rich waters that they contain up to 60 mg/l of arsenic (arsenic-rich high-pCO2 water).TDS changes significantly from 9.0 to 21.3 g/l.The pH changes from 6.3 to 9.2.The Na dominates as cation species ranging from 120 to 7000 mg/L.The concentrations of alkali metals, SO4, Si, Fe, Mn and trace elements are very high, mg/l: I -15, Ba -1.7, H3BO3 -3000, Br -17.5.Carbon dioxide (1.8-5.2 g/l) is the main component of the associated gases.
The thermal alkaline waters are another type of resources widespread on the Far East.Low-enthalpy thermal waters (24-92 o C) of HCO3-Na and HCO3-SO4-Na types with nitrogen as a dominant associated gas traditionally have great importance for recreation and balneology facilities.They have characterized relatively low mineralization (<0.5 g/l), with Na and HCO3 as the most common cation and anion and elevated concentration of silica (>50 mg/l of Si).All of them have alkaline pH (>8) and in most cases noticeable F content (0.8-3.9 mg/l).Other elements not exhibited elevated concentrations.Water circulation through crystalline rocks can lead to the formation of major hydrogeological complexes and locally to significant reservoirs of thermal waters.Waters have characterized with temperatures less than 100 o C (from 24 to 92 o C).Elevated Si content is explained by the more pronounced solubility of silicate minerals in alkaline thermal waters (Bragin et al., 2016).Waters are presented on Kamchatka, Okhotsk and Japan seashores (the Magadan, Primorsky and Khabarovsky regions) and the Jewish Autonomous Region.Occurrences are known at about 100 places in the Trans-Baikal region and are widely used by the local population.These waters are noted for their low mineralization and complex composition.Waters often contains radon as a balneological component (200-400 Bq/L).
Depending from the geological environment the chemical type of thermal waters changes from place to place.For example, waters from Kuldur and Talaia thermal areas have HCO3-Cl-Na or Cl-HCO3-Na types.In the regions with modern volcanic activities, geochemical features of thermal waters can change drastically.Thus on Kamchatka, thermal waters with nitrogen as a dominant associated gas (Paratunka geothermal area), belongs to SO4-Ca-Na type, have elevated mineralization (0.7-2.0 g/l) and pH from 5.9 to 9.2.
The third group of mineral waters is saline groundwater with methane and nitrogen main associated gases.On the Far East of Russia mineral waters with high salt concentration were found during prospect drilling for energetically useful thermal waters.By the geochemical characteristics waters divided into two groups: 1. Cl-Na or Cl-Na-Ca types with TDS vary from 4.5 to 50.0 g/l and and 2. Cl-HCO3-Na or HCO3-Na types with TDS vary from 0.7 to 1.8 g/l.It is deep-seated groundwaters locally spread within the seashore or in the sedimentary rocks of marine genesis.In parallel, main resources of this type of waters are discovered in Primorye Region, Sakhalin Island and Magadan.The forecast resources of saline Cl-Na waters are limited about 250 m 3 /day and they are not actively developed.Typically these waters are cold (T=10-14 o C), except Goriachie Kliuchi Spa (Daginskie) on Sakhalin island (T=+45 o C).Methane and nitrogen are the main components of the associated gases of this waters.It is mature groundwaters, characterized by higher concentrations of chloride, result from mixing between the Na-rich groundwater and saline groundwater at depth, associated with either modern seawater or connate (relict) seawater.Furthermore, the observed distribution of dissolved constituents in groundwater, such as I and B, may be linked to the complex geological history and may associate with old seawater incursion (Chelnokov et al., 2018).
Sakhalin island has immense resources of saline Cl-Na waters including those rich in bromine, iodine and boron.Such waters occur especially in the south part of the island: Sinegorsky, Amursky, Aniva (Ogonki), but one manifestation exist on the north -Goriachie Kliuchi (Daginskie).Leading examples include Goriachie Kliuchi (Daginskie) Spa and Sinegorsky Spa.They have been used for many years for medicinal purposes.The reserves of saline waters can be the sources of a variety of valuable industrial raw materials.The minimum required level for the medical purposes for the different halogens are 25 mg/l for bromine, 5 mg/l for iodine and 50 mg/l for boron.The waters do not always contain all these components together.For example, Sinegorsky wells contained 22 mg/l for bromine, 10 mg/l for iodine and 20 mg/l for boron; Goriachie Kliuchi: Br-9 mg/l, I-4 mg/l and B-24 mg/l; Aniva boreholes: Br-12 mg/l, I -2.5 mg/l and B-58 mg/l; Amurka well: Br-7 mg/l, I -6 mg/l and B-16 mg/l.
The large concentrations of iodine (3.6-10.2mg/l) in saline waters are explained by the high organic enrichment.As a result of diagenesis and consolidation, iodine is transferred from the sediment to the pore fluid (Chelnokov et al., 2018).In contrast with CO2-rich HCO3-Cl-Na type of mineral waters of Sinegorsky Spa Cl-Na type of waters do not contain arsenic.
The best known saline water manifestations in the Primorye Region is Rechica (Sukhodol Bay area).Hydrogeologically, the area is located in the central part of South Primorye province, Primorye composite artesian basin.Wells of up to 500 m deep drilled at the coastal zone in estuaries of Sukhodol River.Rechica wells revealed high calcium chloride sodium-calcium chloride mineralized water and brine water (20-110 g/l).Extrapolated reserves less than 10 m 3 /day.Waters are not utilized.
The saline mineral waters of Cl-HCO3-Na or HCO3-Na types with CH4-N2 as main associated gases are rare and the prospecting resources of this mineral waters no more than 20 m 3 /day.Such waters locally occur in Primorye (Razdolnoe spa), Amur Region (Konstantinovskaia).Razdolnoe Spa (Primorye) are bottled as drinking medicinal-table waters "Lotos" and are used for balneological treatment (Chelnokov et al. 2015).The prospected reserves are small, only 6 m 3 /day.Water is extracted from a depth of 300 m.The water has HCO3-Na type with mineralization of 4.8-5.3g/l, pH=7.8-8.0,contains elevated content of boron (H3BO3 -50-81 mg/l) and fluorine (4.7-5.2 mg/l).

Relevant Legislation
Underground mineral resources are owned by the State.The Ministry of Natural Resources and Environment of the Russian Federation (Minprirody of Russia) shall be a federal executive authority performing functions of public policy making and statutory regulation in the field of the study, use, renewal, and conservation of natural resources, including the surface and groundwaters.Questions of ownership, use and disposal of mineral resources are under the joint jurisdiction of the Russian Federation and the federal subjects of Russia.
The exploration and exploitation of groundwaters are regulated by the Underground Resources Low (No. 2395-1 from 21.02.1992).The Federal Water Resources Agency is a federal executive body performing the functions related to rendering State services and federal property management in the sphere of water resources.Subsoil areas of local importance -the extraction of groundwater to 500 m 3 /day, are under the jurisdiction of the relevant authorities of the constituent entities of the Russian Federation.
Obtaining concession licenses (from the Geology and Natural Resources Committee) for exploration and exploitation was regulated by the resolution of the Supreme Soviet of the Russian Federation No. 3314-1 from 15.07.1992.Only water wells for domestic use (drinking water supply, technological support or objects of agricultural) with flow rates below 100 m 3 /day, are excepted from this procedure.
The Water Code (No. 74-FZ from 03.06.2006) regulates the use and protection of water resources.All waters-surface and underground-belong to the state.Public water bodies can be used freely (for drinking, irrigation and other needs).For business, the right to use groundwater is subject of authorization.
Monitoring of the state of the environment is carried out in accordance with the Resolution of the Government of the Russian Federation "About the Establishment of the Unified State System of Environmental Monitoring" of 24 November 1993.Environmental problems arising from the extraction of mineral raw materials are handled by the following authorities: Ministry of Natural Resources of the Russian Federation; State control service in the sphere of nature management and environmental safety; State Environmental Protection Service; Federal Service of Russia for Hydrometeorology and Environmental Monitoring and other services (Arkhipova et al., 2018).

Conclusions
This study reviews recent groundwater conditions in the Far East of Russia, where mineral waters use has been increasing continually.The study area possesses almost all types of groundwater ranging from lightly mineralised water suitable for drinking to very highly mineralized waters of many types.As a result, hydrogeologists have had ample opportunity to work on the systematic classification of mineral waters.The main tasks in the field of investigation of mineral waters are preservation of water quality, protection from contamination and fundamental problems of origin and distribution.