Biological sciences 7

HYDROCHEMICAL CONDITIONS OF WATER BODIES OF THE -CASPIAN BASIN Tulemisova G., Amangosova A., Abdinov R., Kabdrakhimova G., A. Orynbasarova Kh. Dosmukhamedov Atyrau state university, Atyrau, e-mail: [email protected]

The global environmental issues of technogenic pollution occur pressure on natural forms of the pathology of all living organisms and inevitably have an adversely аffect on them. In recent years, hydrobionts have become objects of study of the outdoor pollution level. Numerous publications, including reports of World Health Organiza- tion Expert Committees allow us to conclude that there is evidence to suggest about the rising aggressiveness of environment. One of the important aspects of such insufficiently controlled process is the contamination of the micro elementary nature. At the present stage, the ecological state of transboundary rivers is especially important. These rivers include the Ural River flowing through the territory of the Russian Federation and the RK, and flowing into the . The article presents the results of a study of the hydrochemical regime of the rivers of the Ural- Caspian basin in different periods of 2017. In the work for comparison, the data on the state of chemical indicators of drinking water in the region are characterized. In order to determine the state of the hydrochemical regime in the lower and upper reaches of the Ural River, the indicators of the River, the flow in the Aktyubinsk Oblast and the River, the flow of the river in the West region are given.

Keywords: The Ural-Caspian Basin, the Ural River, tributaries, the hydrochemical conditions, pollution, oil products

Environmental problems in the third larg- quality of fish populations has been decreas- est river in Europe, the Ural River Basin ing, that suggest a violation of their genetic have remained extremely tense. Meanwhile, pattern. There are troubling trends in the cur- there are 70 cities and settlements with total rent state of commercial stocks of sturgeons population of about 4.5 mln people. The total in the Caspian Sea. Over the past 10 years length of the river is 2428 km and its catch- fish catches have decreased by 10-fold in the ment area is 237 thous. km2. The length of Ural-Caspian basin. the river in the territory of Kazakhstan makes The areas for exploration and develop- 1084 km, including length within the bound- ment of hydrocarbons in the North-Eastern aries of West Kazakhstan Region – 761 km. Caspian Sea coincide with the areas for feed- The largest tributaries are the , Sakmara, ing and migration of sturgeons and other Ilek, Chagan Rivers. Below the Uralsk, there commercially valuable fish, the concentra- is no lateral in flow. The reduced river flow tion of foraging planktonic and benthic or- cause due to national water supplies and evap- ganisms. The large-scale development of oil oration of the extensive floodplain. The river and gas fields in the North-Eastern Caspian flow is formed at the top of the basin, mainly Sea is associated with environmental risk, as within the boundaries of Russian Federation the most intensive bioproduction processes (Kurmangaliyev R.M., 2008) [3]. occur in the peripheral (coastal and shelf) The Ural-Caspian Drainage Basin is lo- zones where the main biomass of marine flo- cated in the western part of the Republic of ra and fauna are concentrated [1, 2,7]. Kazakhstan and occupies the territory of The deterioration of the quality of the wa- four regions with a total area of 640,8 thous. ter condition due to external natural and an- sq.km, including Atyrau – 118,6 thous.km2, thropogenic factors and the continuing unsta- – 205,3 thous.km2 (except for the ter- ble state of marine biota, the technogenic load ritories of Ayteke Bi and regions), West will inevitably lead to ecosystem degradation Kazakhstan – 165,8 thous.km2, Mangystau – and irreparable damage the biota of the North- 151,3 thous.km2. On the whole almost 2 mln Eastern Caspian Sea. Study of chemical com- people live in this region. The main direction position of seawater and marine sediments is of economic activity is the oil and gas field fundamentalfor solving the problems involv- development, agriculture and fisheries. Inten- ing transformation and integrated use of water sification of agricultural and fish production bodies. Transitionalrunoff within the upper and largely depends on the regional water supply middle reaches of the river also contribute to (Onayev M.K., 2013) [6]. pollution [4, 8]. Preserving fish diversity in the Caspian Sea basin are one of the most pertinent is- Materials and methods of research sues: the commercially valuable fish catches During the current year, study was carried has been steadily decreasing, the low-value out based on the R & D Schedule on six rela- ichthyofauna has not been developed, the tively isolated water bodies of the Ural-Caspian

EUROPEAN JOURNAL OF NATURAL HISTORY № 1, 2018 8 Biological sciences

Basin: Ural River, its estuary, tributaries of Ilek Although, the pH level of drinking water in and Chagan River. February was within the limits of sanitary Collection of samples to assess hydro- standards. chemistry and toxicology was conducted Hydrocarbonates and carbonates were within expedition flights at 7 permanent ob- within established standards, although these servation stations: the Ural Rivers and their indicators have been decreased during winter– seashores. spring seasons (Table 1). The hydrochemical conditions of the Ural The salinity and the electrical conductiv- River in winter were estimated based on ob- ity (the EC) of the water bodies correspond to servations. Hydrochemical analysis included the values of the hydrochemical regime of the the following complex of parameters: pH, river (Tulemisova and others, 2017) [9]. The ORP, oxygen concentration, nitrite nitrogen high indicators in the winter and their reduc- content in water, permanganate oxidizabil- tion to the beginning of the flood period are ity, alkalinity, BOD5, water hardness, salinity, naturally occurring situation. Study of qualita- electrical conductivity, chlorides and sulfates. tive composition of pollutants was conducted Analyses were conducted according to the to determine the content of nitrites, boron, pe- most recognized hydrochemical methods (ST troleum products and easily oxidized organic ISO 9863-1-2008. Water quality. Determina- compounds. tion of alkalinity). The amount of nitrites of the toxic ox- Concentration of petroleum products in ides of nitrogen 1-3 times higher than the water and bottom sediments was measured by MPC values. There are extremely high con- the Fluorate 02-2M by fluorescent method in centrations of nitrites in spring before the accordance with the PND F14.1:2:4.35-95 and flood period. Their concentrations have PND F 16.1:2:21-98 (PND F, 98) [5]. increased during flood period, sometimes Boron concentration was also measured have maintained same limits. The content of by the Fluorate 02-2M by fluorescent method, nitrites varies within the MPC limits during without sample preservation. Permanganate winter (Table 1). oxidizability was determined according to the In this respect, the quality of the drinking method of oxidation of organic compounds water is much cleaner. The content of potas- with potassium permanganate in an acid me- sium permanganate oxidation compounds are dium. The concentration of oxygen and BOD5 much less during the winter than the spring were measured based on the dissolved oxygen period, which is typical for this water body content by an Anion-7051 oxygen meter within (Table 1). 5 days after sampling. The specific electrical This year boron content in the Ural River conductance (SEC) and the content of NaCl is much less than previous periods. However, ions, i.e. salinity, were also measured by the its contents increase during the flood period. Anion-7051 portable fluid analyzer. The water Petroleum products are always found in the pH and its oxidation-reduction potential (ORP) Ural River. In winter and early spring, con- were measured by an Anion-7051 portable flu- centration of petroleum products is lower id analyzer. than the MPC values, but their concentration have increased 1,1 times before the begin- Results of research and their discussion ning of flood period. Drinking water com- Study for the hydrochemical regimes of plies with the sanitation quality. Among all rivers of the Ural-Caspian basin are impor- the quality indicators nitrites appear to be tant for describing the ecological and toxi- constant all the periods. This suggests that cological state of the water body. This would nitrites have not been washed out during be especially relevant for the characteristics flood period, representing constant source of of the water bodies in different periods of the pollution. year. So it can be a useful way to identify the It is common knowledge that the primary nature of pollutants entering into the river pollutants enter the water bodies in the spring basin. Table 1 shows the data of the hydro- period. However, studies we have conducted chemical regime and the ecological state of over the last three years suggest that pollution the Ural River water and drinking water in appears to be constant, which increased only various seasons of 2017. It also contains the slightly for the flood period. indicators of flood period, winter and sum- In order to obtain the pollution sources of mer seasons. The pH levels of the samples the Ural River, water samples were collected are normally similar to magnitude. No spe- from the territory in the reservoir flows and its cial seasonal fluctuations were observed. tributaries (Table 2).

EUROPEAN JOURNAL OF NATURAL HISTORY № 1, 2018 Biological sciences 9 3 3 7* Table 1 Table 2 Table 0,05 0,0 90 0,460 0,0 26 0,131 0,0 21 0,107 0,0 30 0,150 0,018 0,019 0,027 0,0 5 0,05 0,288** 0,0371 0,0487 0,0152 0,0695 0,0495 0,0667 0,0350 0,0405 0,0318 0,0447 mg/dm ucts, mg/ dm Petroleum prod - 3 Petroleum products, 3 0,11 0,07 0,04 0,06 0,02 0,08 0,03 0,06 0,50 Boron, mg/ dm 0,50 0,07 0,18 0,06 0,25 0,10 0,19 0,20 0,43 0,15 0,24 Boron, mg/ dm 3 6,08 6,24 6,00 4,40 4,54 4,80 2,72 5,20 10-15 mg/dm oxidizability, Permanganate 3 3,5 6,20 2,88 4,32 3,05 4,80 1,60 1,84 3,20 3,28 - 10-15 mg/dm 311 652 333 335 350 362 426 675 EC, μS/cm 3 Permanganate oxidizability, Permanganate oxidizability, - 316,0 159,4 160,6 167,2 173,5 204,8 148,7 328,0 NаCI, Salinity, Salinity, mg/ dm - 912 924 278 675 964 EC, 1047 1405 1457 1320 1357 μS/cm - Еh, mV ORP, -0,037 -0,040 -0,041 -0,029 -0,042 -0,046 -0,022 -0,055 3 3 - 440,0 453,0 140,0 328,0 469,0 472,0 700,1 712,3 630,2 671,0 mg/ dm 0,35 0,12 0,15 0,10 0,20 0,16 0,05 0,25 0,08 Nitrites, mg/ dm Salinity, NаCI, Salinity, 3 - 5,2 3,1 3,2 3,0 3,2 5,9 3,6 3,3 -0,04 -0,05 -0,03 -0,04 -0,06 -0,06 -0,07 -0,08 -0,06 -0,07 ORP, Еh, mV 3,5-7,0 Hardness, mg•eq / dm 3 3 0,08 0,15 0,15 0,05 0,25 0,15 0,20 0,05 0,08 0,05 0,20 Nitrites, mg/ dm 5,9 4,0 3,1 3,7 4,3 5,5 3,1 3,25 3,5-5,0 3 Alkalinity, Alkalinity, mg•eq/ dm 6,1 6,3 6,5 4,50 4,80 6,70 6,74 6,84 7,03 7,10 рН 3,5-7,0 7,90 7,97 7,67 7,76 7,81 8,09 7,05 8,05 level Hardness, 6,5-8,5 Hydrochemical data of the rivers Ural-Caspian basin, May Hydrochemical regime data of the Ural River in different periods Hydrochemical regime data of the Ural River in different mg *eq/ dm 3 2,6 3,5 3,5 3,6 4,0 4,3 2,65 2,85 3,25 3,25 3,5-5,0 Alkalinity, Alkalinity, mg *eq/ dm 7,5 7,8 7,6 8,2 7,9 8,0 7,5 7,9 8,0 8,1 рН level 6,5-8,5 Indicators Indicators MPC Tap water Tap Ural River, June Ural River, Tap water Tap Ural River, April Ural River, Tap water Tap Ural River, March Ural River, Tap water Tap Ural River, February Ural River, Tap water Tap Ilek River, end of the village Georgiyevka 03.05.17 Georgiyevka village the of end River, Ilek Ural River, top of the city Uralsk, 04.05.17 Ural River, end of the city Uralsk, 04.05.17 Ural River, 04.05.17 Chagan River, Atyrau, University 05.05.17 Ural River, Ural River, January Ural River, Aktyubinsk, 03.05.17 IlekRiver, Tap water Tap Ural River, Atyrau, University 11.05.17 Ural River, MPC

EUROPEAN JOURNAL OF NATURAL HISTORY № 1, 2018 10 Biological sciences 3 Table 3 Table 0,01 0,05 0,06 0,30 0,05 0,05* 0,009 0,045 0,005 0,023 0,018 0,093 0,019 0,097 0,012 0,25** ucts, mg/ dm Petroleum prod - 3 0,06 0,00 0,07 0,05 0,09 0,08 0,07 0,50 0,760 Boron, mg/ dm 3 5,84 6,08 5,76 5,92 5,20 6,40 5,12 4,24 10-15 mg/dm Permang.oxid., - 303 367 358 368 379 374 377 391 EC, μS/cm 3 - 160,0 174,6 172,2 175,2 181,2 178,6 180,9 188,0 mg/dm Salinity, NаCI, Salinity, 3

2 О 6,0 6,30 7,87 7,86 7,15 6,98 8,52 9,91 mg/dm 3 0,15 0,12 0,13 0,13 0,14 0,12 0,13 0,05 0,08 Nitries, mg/ dm 3 4,0 4,0 3,3 3,2 3,5 3,5 3,80 3,5-7,0 Hardness, mg•eq/ dm 3 4,8 4,9 5,3 4,4 5,0 4,8 4,6 3,5-5,0 Alkalinity, Alkalinity, mg•eq/ dm mV ORP, Data on the hydrological-hydrochemical regime of Ural River by end flood period -0,011 -0,046 -0,049 -0,008 -0,015 -0,048 -0,019 +0,003 7,3 6,9 7,8 8,0 7,2 7,3 7,9 7,4 6,5-8,5 рН level – c oncentration of petroleum products for the 100 ml fixed sample; ** – concentration 500 sample.

N o t e : * Sampling site Bugorky Institute University Balykshy 7 station Lower Dambs of the canal Top water Tap MPC

EUROPEAN JOURNAL OF NATURAL HISTORY № 1, 2018 Biological sciences 11 3 Table 4 Table 0,05 0,008 0,039 0,049 0,223 0,0 28 0,131 0,040 0,181 0,0 35 0,161 0,096 0,035 0,030 ucts, mg/ dm Petroleum prod - 3 0,31 0,27 0,24 0,26 0,20 0,15 0,12 0,05 0,50 Boron, mg/ dm 3 4,80 4,77 4,10 4,00 5,84 8,00 4,50 3,78 10-15 dizability, mg/dm dizability, Permanganate oxi - - 718 808 908 EC, 1126 1126 1093 1083 1626 μS/cm 3 - 349,0 808,2 388,0 537,4 532,6 444,0 554,5 544,0 mg/ dm Salinity, NаCI, Salinity, - ORP, -0,046 -0,029 -0,037 -0,040 -0,041 -0,029 -0,042 -0,022 Еh, mV 3 0,20 0,08 0,15 0,14 0,16 0,14 0,08 0,10 0,08 Nitrites, mg/ dm 3 5,7 5,5 6,7 5,8 6,0 5,4 5,0 10,8 3,5-7,0 Hardness, mg *eq /dm 3 4,8 9,2 4,8 6,0 6,0 5,7 5,5 4,7 3,5-5,0 Alkalinity, Alkalinity, Hydrochemical data of rivers the Ural-Caspian basin, fall mg *eq/ dm 8,5 рН 8,00 8,20 8,20 8,00 8,00 6,50 7,50 level 6,5-8,5 Indicators Ilek River, Aktyubinsk, 09.10.17 Ilek River, Ilek River, Ilek end River, of the village Georgiyevka 09.10.17 top of the city Uralsk 10.10.17 Ural River, 10.10.17 Uralsk city the of end River, Ural 10.10.17 river a of River,beginning Chagan end of a river 10.10.17 Chagan River, Ural River, Atyrau, University 11.10.17 Ural River, Tap water Tap MPC

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Research has shown that the composition the upper reaches of the Ural River and the river of the Ural River, the Ilek River and its tribu- flows towards the territory of Kazakhstan. taries in the varies considerably. So that, there were high nitrite levels at the Ilek Conclusion River mouth – 4,5 MPC (Table 2), permanga- The Ural-Caspian basin is the most important nate oxidability – 6,08 mg/dm3 and petroleum area for the breeding of sturgeons and semi-ana- products – 1,9 MPC. Reduction for these in- dromous fish species and has the leading position dicators has determined in the Chagan River. in the commercial fishing industry in Kazakhstan. This suggests that no pollution were found in In recent years, there were significant chang- the territory of the West Kazakhstan Region. es over the entire basin affecting hydrobionts’ Although, the 2016 research [10] showed in- natural habitat. The anthropogenic impacts on creased concentration of petroleum products. coastal and marine ecosystems have increased An excess salt concentrations were found in the immeasurably. Due to the intensification of fish- Ural River, , along the University ery and violation of breeding and feeding pat- zone typically the Caspian Lowland. This area terns, their numbers have dramatically decreased. showed increase in concentration of nitrites – Of particular concern is the increasing amount of 2,4 MPC (Table 2). Other indicators in the Ural offshore oil and natural gas development. River were within established standards. Dur- In order to assess the current state of the ing this period drinking water complies with ecosystem functioning in the Ural-Caspian ba- the sanitation quality (Table 2). sin fisheries and predict its probable future be- By the end of flood period, the ecological havior, it is necessary to analyze the influence state of the Ural River was determined by the of multidirectional factors on the formation of collection of water samples along the different biological resources. In that context, the con- sections of lower reaches of the water bodies. tinuous monitoring of ecological status of the Water quality indicators such as pH, oxygen North-Eastern Caspian Sea and the Ural and and petroleum product levels describe the pres- Rivers is of the utmost importance. ence of pollution in the upper reaches of the Study of the hydrochemical regime compo- Ural River compared with the samples of the nents of the Ural River has shown that this year lower reaches (Table 3). The Lower Damba there were positive dynamics of parameter chang- section one of the most contaminated area – es of the state of the Ural-Caspian basin waters. 6.40 mg/dm3 (Table 3). References This area includes all the settlements, so 1. Amirgaliyev N.A. Ecological and Toxicological State there are household wastes (illegal dumping), of the Ural-Caspian Basin and Some of Its Research Priority // as well as extreme congestion of coastal vessels Proceedings of the International Scientific Conference “The Cur- along the river bank. By the end of the flood pe- rent State and Ways to Improve Research in the Caspian Basin”, Astrakhan, 2006, P.21-25. riod, the pollution inflow has slightly reduced. 2. Burlibayev M.Zh., Kurochkina L.Ya., Kashcheeva V.A, Er- The study of fall samples in the rivers of the okhova S.N., Ivaschenko A.A. The Ural River delta and adjacent territories along the coast of the Caspian Sea. Astana, 2007, P.264. Ural-Caspian basin showed a decreased rate of 3. Kurmangaliyev R.M. Ecological challenges of trans- pollution, compared with spring samples (Table 4). boundary watercourse of Ural River and ways for its resolvement / R.M. Kurmangaliyev // Gilim zhane bilim. 2008. No. 3, P.91-97. The Chagan River mouth is the only excep- 4. Leshan I.Yu., Khubitdinova A.F., Hydrochemical fea- tion, in that the high rate of permanganate oxi- tures of Ural River basin // Actual problems of the humanities dation equal to 8,00 ml/dm3, also the concen- and natural sciences, 2016., No.2-4 . P.11-13. 3 5. PND F 14.1:2:4. 128-98. Quantitative chemical analy- tration of petroleum products – 0,096 mg/dm sis of waters. Procedure for mea-surement of mass concentra- (1,9 MPC), compared to other stations. tion of petroleum products in samples of natural, drinking or waste water by fluorescence method with the Fluid Analyzer High levels of nitrite were found in the FLUORAT-02. In supersession of PND F 14.1:2:4.35-95; have Ilek River and are 2 – 4 greater than the MPC. been introduced in 2007-2018. M.: Lumeks, 2007. P. 24. There are also consistently high levels of nitrite 6. Onayev M.K . Use of water resources of the West Ka- zakhstan used in to land reclamation. // Science news of Kazakh- in the Ural River, Uralsk, although its concen- stan. 2013., Edition 3 (117). P.186-190. tration has significantly decreased compared 7. Ogar N.P. etc., Environmental monitoring of the North- Eastern Caspian Sea while development of oil fields. Almaty., to the flood period. In fall, the rates of miner- 2014. P.70-73. alization, salinity and the EC of the water body 8. Shimshikov B.Ye., Izbassarova A.K. Hydrochemical and toxicological characteristics of the state // KazNU Bulletin. Eco- have increased significantly (Table 4). It should logical series. 2014, No.2 (41). P.163-167. be noted that such event is a typical process nor 9. Tulemisova G.B., Abdinov R.Sh., Batyrbayeva G.U., the salinity has sharply increased both the Ural Kabdrakhimova G.Zh., Mustafina A. Zh. Current state of hydro- chemical regime of the rivers of the Ural-Caspian basin. // Pro- River and the squares of the North-Eastern Cas- ceedings of NAS RK. Chemistry and Technology Series. 2017, pian Sea. Summarizing the obtained results, it No. 1 (421), P.96-100. 10. Tulemisova G.B., Abdinov R.Sh., Kabdrakhimova G.Zh., should be noted that sources of pollution such Zhanetov T.B. Ecological conditions of the Ural River // KazNU as nitrites, petroleum products were found in Bulletin. Chemistry series. 2017., No. 2 (85), P. 18-24.

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