Study of Indicator Properties of Chemical Elements , Corresponding to Geochemical Environment of Natural Mineral Water Formation

Studies show that unique hydro-chemical indicators that meet the spatial patterns of geochemical environments characterize each land area. The authors proposed a method to study the regularities in the chemical composition of natural mineral waters and identify the indicator elements that correspond geochemical peculiarities of their formation. The initial material of the study included the results of the water chemical analysis conducted on the mass spectrometer with inductively coupled plasma (ISP-MS) Elan 9000 DRC II (Perkin-Elmer, USA). Mineral waters were characterized by a set of qualitative and quantitative parameters: geochemistry of water migrants, element-by-element comparative analysis of the concentrations, areas of origin and the water extraction conditions. These parameters are linked in the summary table, from which a number of regularities were established. The following indicator elements are identified: Sr, Ba, Mn, Li, Br, B, I, Ge, Rb, corresponding to geochemical parameters of water formation environment.


Introduction
The chemical composition of groundwater, including mineral water, is a consequence of the interaction of geological rocks with underground hydrosphere, where water as a universal solvent is the main agent of water removal from mineral migrants (Perelman, 1982;Shvartsev, 1998).Specific hydrochemical indicators, acting as regional indicators of groundwater origin, characterize each land area.As our research shows, each of the natural mineral water is characterized by its 'fingerprint' of content and set of chemical elements, which act as 'geographic markers' for origin of water (Amelin et al., 2012).In addition to the practical significance, which is established in the falsification and geographical origin of natural mineral waters, study of chemical composition of water focuses on other tasks, one of which is reduced to the establishment of relationships between the chemical composition of natural mineral waters and geochemistry of their formation.
The purpose of this work is to study regularities in the chemical composition of natural mineral waters, and identify elements-indicators that meet the geochemical features of their formation.
The calibration solutions were prepared by diluting the appropriate standards.To review the analysis and identify mineral waters we used semiquantitative "TotalQuant" data collection mode, the advantage of which is in determination of the total isotope elemental composition of the sample in a relatively short measuring time (2-3 min).

Object of research
We investigated the following natural mineral waters: Narzan, Yessentuki number 17, Essentuki number 4, Rychal-Su, Perrier, Vitasnella, Livissima, Serebrany Sokol, Suzdalsky napitki, Lipetsky Byuvet.The initial materials of study were the results of a multi-element analysis and content of the major macro-ingredients (Table 1.2).The analysis was conducted on the data basis of FSBI "Federal Centre for Animal Health" in the framework of the identification of mineral waters, purchased in an open market, by geographical origin.The database was created based on waters of the relevant sources or wells.

Results and discussion
On the basis of a comprehensive approach the authors proposed a method to identify the indicator properties of some chemical elements that emphasize the geochemical characteristics of media formation of natural mineral waters.Mineral waters have been characterized by the following set of parameters: geochemistry of water migrants, element-wise comparative analysis of the concentration, areas of origin and water extraction conditions.The above set of parameters is configured in the summary table.

Geochemical properties of water migrants
The migration properties of most chemical elements are studied fully and are the criteria for geochemical classification,  (0,1)   1,2  1,7   2,9  3,1   5,2  4,9  3,3   5,6  4,8  3,8  3,0  4,6  7,  which makes it possible to trace the path of their introduction into the mineral water solutions (Kraynov et al., 2004).At the same time, water migration of such elements as W, Y, Rh, Te, La, Eu, Ce is poorly studied, especially as the concentration of these elements is less than 1mcg /L, along with elements such as Co, Pb, Tl , Th, Zr.

Element-wise comparative analysis of concentrations
In the analysis we used the most informative values: 1) the range of concentrations; 2) ratio of the maximum to the minimum concentrations (c max /c min , Table 3).
The value of cmax/cmin for elements Sr, Ba, Mn, Li, Br, B, I, Ge, Mo, Rb, Cs is measured in hundreds and thousands of times.Concentrations of Mo, Cu, Cs are less 5 mcg/L, which is negligible as compared with other elements.Lets express the value of element concentration in percentage and arrange mineral water in order to increase their concentration (Table 4).

Areas of mineral waters origin
Extraction of water under investigation is carried out both on platform and mountain areas: 1) Water from the platform area of the East European Plain (Serebrany sokol, Suzdalskiye napitki, Lipetsky Byuvet); 2) Water from mountain area of the Alpine region (Levissima, Perrier, Vitasnella) and the Caucasus (Narzan, Rychal-Su, Essentuki number 17, Essentuki number 4).

Water extraction conditions
Information about the method of mineral water extraction and temperature conditions is presented in Table 5.

The layout of summary table
To identify regularities, the set of parameters is configured in the table 6.
Qualitative parameters: 1) Horizontal line -number of microelements differentiated by properties in aqueous solutions (anions and cations) and by mobility; 2) Vertical line -number of mineral water, grouped on areas of origin -platform (P) or Mountain (G); 3) Method of production -source (Is) or well (Sk, depth); 4) Temperature mode -non-thermal (0), weakly thermal (t), thermal (T).
Quantitative parameters: 5) Values of concentrations of selected items in %, positions in the row; 6) Ranges of element concentrations (mcg/L) and cmax/cmin; 7) Content of macro-ingredients Cl -, SO4 2-, HCO3 -, Ca 2+ (mg/L) We set the following statements as the result of handling the sum of parameters in the table within the causal chain: 1. High concentrations of bromine, boron and iodine are characteristic of well waters of the Caucasus region, which indicates the presence of boron and iodine-bromine waters, confined to a negative geological structures -troughs of foothill areas.These structures accumulate brine (sodium chloride water) -the most favorable conditions for the accumulation of anions.High concentrations of bromine and boron in Lipetsky Byuvet are due to the inflow of deep brines from the area of stagnant water exchange in the overlying artesian basins.
2. Accumulation of germanium goes in sulfosalts formed under hydrothermal conditions in the surface, shallow, less medium depths that explains waters position relative to each other.First place is given to source of

Table 1 .
The results of the review analysis of natural mineral water (mcg/L, average value of three different batches of water).Note -*PO -the detection limit, **-not detected.

Table 2 .
The content of basic macro-ingredients of mineral water (mg/L, average value of three different batches of water).

Table 3 .
The concentration ranges and value c max /c min for elements in studied mineral waters.
100Table4.The distribution of mineral water by increase of concentration % in mineral water forRb, Sr, Ba, Mn, N, Br, B, I, Ge.

Table 5 .
The method of extraction and temperature mode of mineral water.

Table 6
. Summary of quantitative and qualitative parameters.