Aizen &Aizen, 2001
STREAM CHEMISTRY IN THE CENTRAL TIEN SHAN, KEKEMEREN RIVER BASIN Vladimir B. Aizen, Elena M. Aizen University of Idaho, Moscow, USA E-mail:
[email protected]
ABSTRACT To evaluate the regional variability and long-term changes in the solute content of surface waters in the central Tien Shan, we present data from ten stations collected for thirty years (1955 to 1985) from the head of second-order Kekemeren River, a tributary of the Narin River. Three altitudinal belts (i.e., high, middle and zone of transit) were revealed according to variability in the solute content of surface waters. At high altitudinal belt, maximum solute concentration was observed in May before intensive snow melt and flood peak; at other two belts the maximum occurred in April. The lowest solute concentration in stream water was observed at high-elevation alpine sites, ranging from 64.8 to 73.0 mg L-1. At lower elevational belts, the long-term average solute concentration was higher ranged from 131 to 257 mg L1 in April. Bicarbonate and calcium were the dominant ions in all three altitudinal belts, but relative composition of these ions decreased from high to lower elevational belts. During month of maximum solute concentration, at high elevational belt the long-term average solute concentration of bicarbonate composed 50% of total anionic charge, and Ca2+ accounted for 40% of total cationic charge; while at low zone of transit, bicarbonate composed 41% and Ca2+ accounted 34%. The maximum content of Mg2+ ions increased from 7% to 10% and SO42- from 3% to 8% from high to low altitudinal belt. The solute concentration of Na+ + K+ ions slightly increased with decreasing altitude from 3% to 6%. Phosphate concentration ranged from 0.015 to 0.005 mg phosphors L-1, iron from 0.12 to 0.005 mg Fe L-1 and silicon from 2.8 to 4.5 mg Si L-1. The pH values ranged from 7.6 at high altitudinal belt to 8.0 at low zone of transit, indicating neutral to slightly alkaline stream water. We associated the increased ionic concentration 14-19% of SO42-, 9-14% Ca2+ and 12-16% Na+ + K+ ions since 1971 with intensive agricultural development in the Fergana Valley, however this increasing is not statistically significant. Introduction Most records of the stream chemistry in the arid areas of Middle Asia concern the human impact on water quality (Chembarisov and Bachritdiov, 1989). In Middle Asia, where irrigation consumes more than 90% of total water use (Rubinova, 1991), the human impact on solute content of surface waters is generally associated with development of irrigation systems. Extensive development of irrigation systems and redistribution of surface runoff in the 1970s doubled the disolved-solid concentration in the Amu Darya (Kamalov et. al., 1977), Chu (Kann, 1978), Sir Dariya (Lobachev, 1980; Cicenko et al,
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1987), and Zeravshan (Videneeva and Belinson, 1990; Hoshimchodjaev and Kulmatov, 1992) rivers. Concentrations of Na+, SO42-, and Cl- increased. According to analyses, the Talas River at the Northern Tien Shan was only exception, where solute content shows no significant changes between 1935 and 1977 (Kann, 1978). Analyses of solute content in the Middle Asian lakes have been done by Snitnikov and Smirnova (1981) for the Chatir Kul Lake in the central Tien Shan; Nikitin (1987) for the main Middle Asian lakes and Gokhman et al. (1988) for the Issik Kul Lake. Coclusion Analyses of solute content at Middle Asian alpine watersheds considered melting waters from glaciers in Zailiyskiy (Vilesov and Shabanov, 1971; Fedulov, 1971), Zaalaiskii and ??? pskem (Kamalov, 1975) ranges. The TDS was found to be 60 mg L-1 in liquid precipitation, 46 mg L-1 in solid precipitation, between 72 and 140 mg L- 1 in seasonal snow pack and 94 mg L-1 in glacial ice. The large concentration of sulfate and nitrate ions in glacial ice was associated with the close location of major industrial cities. Observed ions of ammonium on some glaciers is also a result of industrial pollution (Vilesov and Shabanov, 1971; Fedulov, 1971, Kamalov, 1975). Kamalov (1975) found decreased solute concentration with increasing elevation in snow samples; this trend was attributed to decrease human impacts at higher elevations. This analysis revealed an increase with altitude of ionic concentration associated with aeolian dust. It was found also that, aeolian dust has less impact on ionic concentration of ice than on ionic concentration of seasonal snow pack; geological bed-rock ablation and glacier interaction with moraine is the main process caused solute content in melted ice samples. In the eastern Tien Shan, some observations of snow chemistry have been made by Tonnessen et al. (1991), Williams et al. (1992), Wake et al. (1994). In the eastern Tien Shan Williams et al. (1992) and Wake et al. (1994) also found high ionic concentration associated with aeolian dust. In spite of long-term observations of solute content beginning from 1955, little effort has been dedicated to analysis regional long-term changes in water quality components in headwaters of Tien Shan rivers. We present here an analysis of the main factors influenced on stream chemistry and information on long-term changes of solute content in surface waters at the head of Sir-Darya River, one of the largest Middle Asian rivers nourishing the Aral Sea. Study Region The Kekemeren River basin (Fig.1), located on the southern slope of the Kirgizskiy Alatoo, is typical of non-glacierized basins with seasonal snow cover. There is no forest in the basin, only bushes below 2800 m and meadows below the nival glacial zone. The nival glacial belt begins above 3500 m. Permafrost occurs above 3000 m. There are numerous spring fens at the low, flat belt of the basin. Hydro-geological map of the Kekemeren River basins is shown on the Fig.2. Below the confluence of West Karakol and Susamir rivers, the Kekemeren River is passing through the narrow valley with steep slopes formed by terrigenous deposits (Fig.1). The Kekemeren River basin is under western cyclonic impact all around the year, the majority of precipitation typically occurs in the summer (Aizen et al., 1997) (Fig.3). The Kekemeren River has about 60 tributaries, and is itself one of the northern tributaries of the Narin River, which, in turn, is the main tributary of Sir Darya River. The area of the Kekemeren River basin is 2410 km2. Altitudinal difference between the lowest and highest
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points in the basin is about 2440 m. The mean annual discharge in the Kekemeren River is 16.5 L s-1 km-2. Glacier runoff is not significant in the Susamir, West Karakol and Djumgol River basins with glacial area of less than 3% of total area. In this region, there is a transition (from lower to higher altitudes) from a zone with mainly rain nourishment, partially in the Djumgol basin, to a river zone supported by seasonal snowmelt. Kekemeren River runoff is formed from seasonal snowmelt and summer precipitation. Summer precipitation is mostly in the form of snow and mixed snow and rain because most of the area of the valley is above 3000 m, partially in West Karakol and Susamir River basins. Melt of summer snow between snowfalls creates the high level of rivers during June and July (Fig.4) when the main peak of runoff is observed after intensive melt of the seasonal snow pack. After summer, low discharge is nourished by ground water and is relatively steady throughout winter until the next spring. This river has a natural runoff regime; there are no artificial irrigation systems. There are no big industrial cities; several habitations with population from 1000 to 5000 people are mainly located in the Djumgol R. basin. However, to the west from the study area there is the wide Fergana Valley known as one of the largest agricultural regions in Central Asia. Data Collection and Methods Long-term monthly data of stream chemistry at ten stations and gages (Table 1) in the Kekemeren R. basin from 1955 to 1985 were obtained from State Water Cadastre, (1955 - 1985). We used data from April to September, when the chemical analyses were done, on mean monthly stream discharge (Reference Book of Climate USSR, 1988); pH and solute concentrations of the major ions (Ca2+, Mg2+, Na++K+, HCO3-, SO42-, Cl-, NO2-, NO3-); P, Fe, Si; and water temperature. At stream gages water discharge is measured through a cross profile of river by current-meter. Measurements of currents were done beginning at the 20cm from water surface and every 50cm. Discharge measurements were taken every 1m across the entire profile. Hydro-chemical samplings and analysis in streams at gages occurred at least one time per month. The pH electrode was calibrated with 7.0 and 10.0 buffers. Water samples filtered for chemical analysis are transferred in clean glass 100ml bottles to the Kirgiz Department of Hydro-Meteorology. Major soluble element content was determined by means of co-precipitation with thiooxine according to the methods (Tsirkunova et al., 1984; Vasilenko et al, 1985) of group concentration of major elements. The sediment was filtrated using a membrane filtration system “Sinpor” with a mean pore diameter of 0.4 microns. Germanium (lithium) detector with the resolution of 2.5 and 3.0 kev as gamma spectrometer was used for the laboratory analysis. Concentrations of major anions (Cl-, NO3-, SO42-) and major cations (Na+, NH4+, K+, Mg++, Ca++) were determined using a Dionex Model 2010 ion chromatograph with auto sampler. Five percent of samples will be run in duplicate in order to estimate precision of the analyses. Average solute content of main ions, P, Fe, Si and pH were calculated for each station. We calculated the ionic balance for each sample (in ueq/L) using the following equation: [Na++ K+] + [Ca2+] + [Mg2+] = [HCO3-] + [SO42-] +[NO3-] + [Cl-]
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Our analysis used spatial averaging within three altitudinal belts (high mountains, middle and flat-river transit illustrated in Table 1). The sum of the charges were within 5%. To monitor the long-term changes of solute content in stream chemistry we based on the most homogeneous data from the station of W. Karakol River, mouth, through a period from 1965 to 1985. We assessed changes in main ions Ca2+, Mg2+, Na++K+, HCO3-, SO42-, Cl-, NO2-, NO3-; P, Fe, Si; and pH by calculating a linear trend, standard errors, coefficients of determination, and F tests data from the station of W. Karakol River mouth. To pick up the anthropogenic component in the long-term ionic changes of stream water, , , we used two methods counting to flow adjust the solute concentration. The first method is based on the ratio between the river runoff for two periods with human impact and without it: = 2 – K1
(1)
where 2 is ionic concentration (Ca2+, Mg2+, Na++K+, SO42-, Cl-, NO2-, NO3-) for the period with intensive human impact; 1 is ionic concentration for the period without human impact; K is ration between average river runoff for the second and first periods. The second method (Maximova, 1982) assumes only natural variability in the bicarbonate ion (HCO3-). The criteria of human impact on stream chemistry is the ration (KHCO3- ) between ionic concentration of HCO3- and concentration of other ions in surface waters for the period without human impact: = 2 - (2-HCO3- / KHCO3-)
(2)
where 2 is ionic concentration (Ca2+, Mg2+, Na++K+, SO42-, Cl-, NO2-, NO3-) for the period with intensive human impact; 2-HCO3- is ionic concentration of HCO3- for the period with intensive human impact. To evaluate the human impact on solute content in stream chemistry, we compare data from the station of W. Karakol River, mouth, for two periods from 1965 to 1970 and from 1970 to 1985. The beginning of 70s is years of intensive development of irrigation systems in the Fergana Valley (Chembarisov and Bachritdiov, 1989). Results and Discussion Average solute content of surface waters at stations. Long-term average solute content of main ions shown in Fig.5 for the month of maximum solute concentration. The stream water has substantially uniform ion composition of bicarbonate and calcium. In the month of maximum solute content, the lowest solute concentration of stream water of 64 mg L-1 was observed at high alpine mountains (Tuya Ashu st.). Ions of HCO 3- compose 47% (from 45.8 to 53.1 mg -1) of anions and 3% of anions is associated with SO42-. On average, 40% of cations comprise ions of Ca2+ (from 12.4 to 13.9 mg L-1) in high mountain river streams. The relative content of Mg2+ ions is 6 -7 % (from 1.8 to 2.7 mg L-1).
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In the middle altitudinal belt (Karakol R., 5 km lower mouth W. Suek R.; Karakol R., mouth Irisu R.; Orto-Kugandi. Table 1), bicarbonate and calcium are still the dominant ions, but relative amount of these ions decreased (Fig. 5; Table 2). The relative amount of Mg2+ increased to 10 % and SO42- to 4% at Karakol, mouth Irisu R. Additional average 3 mg L-1 of Mg2+ and 4mg L-1 of SO42- ions are carried by ground waters circulated throughout the fractures in bedrock and inside the talus depositions, marlstone and mirabilites (Fig.2). Ground water from springs and bogs are characteristic of middle and low altitudinal belt. Absolute solute concentration also increased to 99 - 124 mg L-1 during maximum solute concentration (Fig.5). At middle altitudinal belt, Cl- ions observed in the stream water could be caused by evaporation from the water surface in abundant slow streaming bogs and dissolved halites spread at the area between the mouths of West Karakol and Djumgol rivers (Fig. 1). At the outlet from mountains on the flat terrain of valley, the surface stream waters are dipped and infiltrated into the alluvium. These waters nourish shallow alluvial aquifers. Intensive pinch of underground waters occurs around the confluence of West Karakol and Susamir rivers. The solute concentration of stream water there significantly increased up to 257 mg L-1 at the Djumgol station (Fig.5, Table 2) and is depended on the area of this transit belt at foothills. Bicarbonate and calcium are still the dominant ions similar to mountain belt chemistry; however light ions of Cl- ions increased up to 19.3 mg L-1 (5.1%) in the slow moving streams at flat terrain. The increase of SO 42- ions up to 38.7 mg L-1 (10%) at the Kekemeren R., 0.5km lower mouth Djumgol R. (Fig.5) could be caused by dissolved mirabilites (Fig.1) and by using of fertilization in the Djumgol basin. High sulphate concentration in stream chemistry could be associated with aeolian dust brought from the Fergana valley, where cotton production uses large amounts of fertilizer. Western air streams could deposit aeolian dust on the snow pack in Susamir valley during winter when soils of Fergana Valley are dry and not covered by snow. The predominant ion composition of bicarbonate and calcium in stream waters mainly reflects the composition of rocks formed by conglomerates (pudding rock), sandstone, marlstone, limestone, marbles, fluorite, granites, porphyries and diorites (Fig.2). Dissolution and combustion of the organic matter containing in overspread alluvial, alluvial fan deposits and shale outcrops also in the bicarbonate type of stream waters. The cations of Mg2+ is less spread than of Ca2+ and has formed mainly from marlstone contained MgCO3. Ions of HCO3-, Ca2+ and Mg2+ are dissolved by CO2. Low air temperature from 0.0 to 7.0 C (Table 2) and continuous contact with carbonate conglomerates (pudding rocks) during flow throughout the taluses and moraines are favorable for the dissolution of carbonates. The strong continental climate with large variations in air temperature at the high mountains causes the intensive weathering deposits and continuous accession of taluses by calcarenites. It is known (Posohov, 1975), there is more than 1% of CO2 in the air of weathering products while common atmospheric air contents only 0.03%. Sulphate ions are formed from dissolved mirabilites (Glauber’s salt) distributed at the West Karakol R. basin before its confluence with Djumgol R. (Fig.1). High sulphate concentration could be also associated with aeolian dust brought from the fertilized Fergana valley. The results on sulphate concentration in stream chemistry correspond to
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the tendency of high sulphate concentration observed in old dry snow sampled in Tien Shan (Kattelmann et al., 1995). Chloride ions are formed from dissolved halites spread at the area between the mouths of West Karakol and Djumgol rivers. Leaching of mirabilites and halites resulted in the distribution of sodium ions. The rocks are also formed by quartz, sandstone and shale contained silicon and iron ores. In stream water there is on average 2.8 -4.5 mg L-1 of Si, 0.05 -0.12 mg L-1 of Fe and 0.05 - 0.015 mg L-1 of P (Table 2). Average solute content of surface waters in altitudinal belts. Based on analyses of solute concentration and content of ionic components we revealed three altitudinal belts (Table 1): high, middle and transit. Long-term average content of ionic components (Fig.6, 7 and Table 2) and monthly solute concentration (Fig. 7) were calculated on the basis of averaging the data from stations located at three belts. High altitudinal belt is a region with the lowest solute content in stream waters ranged from 69 to 59 mg L -1 (Table 2) and uniform ion composition of hydrocarbon class and group of calcium. The region includes the heads of basins, source of rivers beginning from taluses and ancient moraines containing tuffs that deliver the main ions to the initial stream waters. There is extremely small content of Na+, and K+ of 1 mg L-1, phosphate of 0.015 mg P L-1, iron of 0.12 mg Fe L-1 and silicon of 3 mg Si L-1. Maximum solute concentration is observed on average in May there, before intensive snow melt and flood pick (Fig.4) while at the other two belts the maximum occurs in April (Fig.8), because snowmelt begins later and the ground is frozen in April at high altitudes. The minimum solute content in stream water observed on average in June at all three belts coincided with maximum river discharge. The inverse correspondence in solute concentration and river discharge indicate on the natural (i.e., without artificial impact) river runoff regime. In stream waters of the high altitudinal belt, monthly changes in solute concentration is associated mainly with changes of cations content (Fig.7). In April when soil is frozen at high altitudes, the relative content of Mg + increased up to 18% while content of Ca+ cations decreased to 30%. This result corresponds to Ivanov et al. (1972), Johannesen et al. (1977) and Skartvelt and Gjessing (1979) analyses that there is increased Mg+ component and decreased Ca+ component in melt waters flowing over the frozen ground than in waters flowing over melted soil. The stream waters at the middle altitudinal belt with solute content from 69 to 108 mg L-1 is also bicarbonate and calcium, but relative composition of these ions decreases and the absolute and relative compositions of Mg+ increases up to 10% and SO42- up to 7% (Fig. 6). At middle altitudinal belt, Cl- ions were observed in the stream water. Insignificant decrease of phosphate from 0.015 to 0.007 mg P L-1, iron from 0.12 to 0.05 mg Fe L-1 and silicon from 3 to 2.8 mg Si L-1 and increase of pH from 7.6 to 7.8 occurs relative to the high altitudinal belt (Table 2). Maximum solute content is observed in April, then solute content sharply decreases simultaneously with increased runoff (Fig.3). Minimum solute content is observed in June. From July to September solute content is constant (Fig.8). Monthly variations in solute concentration are associated with the changes in all anions and cations components (Fig. 7). At the third flat belt of mountain foothills, the transit water streams contain the maximum solute concentration ranging from 167 to 200 mg L-1 (Table 2, Fig. 6) Monthly variation in
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solute concentration is the same as at the middle altitudinal belt with maximum in April and minimum in June. Ions of NO3- observed at this belt (Fig. 7,8), but NO2-. Increased solute content (Table 2) up to 200 mg L-1, concentration of Ca+ up to 38 mg L-1, Na++ K+ up to 6 mg L-1, and NO3- up to 1 mg L-1 is the result of intensive ionic transmission from snow and interaction of water with plant residues, soils, ground water and geological bedrock (Fig.2). At zone of transit, on average, there are small changes in phosphate and iron. Silicon increased up to 4.5 mg Si L-1 and pH up to 8.1 (Table 2) indicating neutral to slightly alkaline stream water. Monthly changes in silicon and iron concentration correspond to monthly changes in general solute concentration, while variations in phosphate concentration has the inverse distribution, i.e., maximum solute concentration corresponds to minimum phosphate content and minimum river discharge (Table 2). Long term changes of ionic component content. At the W. Karakol R., mouth, located at the flat river transit belt, variability in the relative proportion of ionic constituents, solute content and pH is a function of changes in river runoff (Table 3) during both periods of maximum and minimum solute content. The increase of river runoff decreases the content of the most ionic components and solute content (Fig.9). For example, the anomalies of runoff at the W. Karakol River were more than 50 m3 s-1 in June of 1975 and involved decreasing most ionic components and solute concentration about 35 mg L-1 (Fig.9). The highest correlation with river runoff is typical for content of SO 42- anions amounted to 0.83, but concentration of Cl- anions does not correlate with river runoff. Concentration of NO3- ions and pH has positive correlation of 0.69 with river runoff (Table 3). The June deviations of ionic components exceeded the April ones (Fig.8) and the largest anomalies were associated with HCO3- and SO42- anions and reached to 20-25 mg L-1. At the flat river transit belt, we did not reveal statistically significant changes of both river runoff and solute content from 1965 to 1985 (Table 3, Fig.9). However, partition of anthropogenic component in changes of solute content from natural variability (Eqs.1,2) has resulted in increases up to 14-19% of SO42-, 12-16% of Na++K+ and 9-14% of Ca2+ ions for the period from 1970 to 1985 (Table 4). We assume the rise of ionic component is associated with aeolian dust carried from Fergana Valley. Content of Cl- and NO3- were not changed. Conclusion Seasonal, spatial and long-term variability of chemical characteristics in mountain river streams is presented. Analyses of solute concentration and content of ionic components revealed three altitudinal belts: high, middle and zone of transit. At high altitudinal belt, maximum solute concentration is observed in May before intensive snow melt and flood peak; at other two belts the maximum occurs in April, because snow melt begins early at lower altitudes. The minimum solute concentration in stream water is observed in June in all three belts, coinciding with maximum river discharge, diluting the solute concentration. Monthly variations in solute concentration are associated with both changes in anions and cations components. Variability in content of ionic components, solute concentration and pH is affected by river runoff during both periods of maximum and minimum solute concentration. Increases in river discharge decreases the content of most ionic components and solute concentration.
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The pH values ranged from 7.6 to 8.0, indicating neutral to slightly alkaline stream water. The current study analyses a natural variability in the solute content determined that the stream water has uniform ion composition of bicarbonate HCO3- and group of calcium reflecting the state of rocks. The lowest solute concentration of stream water of 64.5 mg L-1 was observed at high elevation alpine sample site and there is very small content of Na++ K+ of 1 mg L-1. The river streams also contain also phosphate, iron and silicon. The stream waters in the middle altitudinal belt with greater solute concentration than at high altitudinal region has also bicarbonate and Ca2+, but relative composition of these ions decreases, the absolute and relative composition of Mg+ and SO42- increases. Cl- ions are detected in surface-water samples collected from this belt. In the third flat belt of mountain foothills, the transit water streams notching through alluvium have the maximum solute concentration. Ions of NO3- were observed only at this belt. The inverse correspondence in solute concentration and river discharge indicate mainly on the natural (i.e., without artificial impact) river runoff and solute concentration regime. Statistical analyses did not reveal any significant changes of river runoff and its solute content for the period from 1965 to 1985 that assumes an absence of industrial impact on stream quality inside the Kekemeren River basin. However, separation of anthropogenic and natural variability resulted in increased concentration of SO2-, Ca2+ and Na+ + K+ ions since 1971 that is in accordance with results of snow sampled during 1990 in the study area (Kattelmann et al., 1995). We associated the increased ion concentration with intensive agricultural development of the adjusted Fergana Valley. Concentration of Cland NO3- were not changed. Acknowledgment: This work was supported by the EOS NASA grant NTW-2602. We appreciate valuable comments by Dr. D. David L. Nafts on draft of the manuscript
References Adishev, M.M. (Editor), 1987. Atlas of Kirgizskoi SSR, Moscow, 157 p. (in Russ.) Aizen, V.B., E. M. Aizen, J. Melack, 1997. Snow Distribution and Melt in Central Tien Shan, Susamir Valley. J. Arctic and Alpine Research, V. 29, No. 4, 403-413. Chembarisov, E.I. and B.A. Bachritdiov, 1989. Hydrochemistry of River and Drainage Waters of Middle Asia. Ukituvchi Publishing. Tashkent, 232 p. (in Russ.)
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Cicenko, K.V., N.N. Shuranova and I.A. Kann, 1987. Impact of irrigation on the interaction between surface and ground waters formed river and solute runoff at the middle reaches of Sir Darya R. Works of GGI, 316, Moscow, 48-71 (in Russ.) Fedulov, I.Ya., 1971. Chemistry of melted water from Chilik glaciers. In: Regime of Kazakhstan’s Glaciers. Alma Ata, 149-151 (in Russ.) Gokhman, V.V., V.G. Khodakov, E.A.Ilyina, and A.V. Gordeichik, 1988. On chemical discharge of rivers in the basin of Issik-Kul lake. Data of Glac. Stud., 63, Moscow, 142-145 (in Russ.) Hoshimchodjaev, M.M. and R.A. Kulmatov, 1992. Spacial distribution and migration of micro elements in streams of Zeravshan River. Works of SARNIIGMI, 142(223), Moscow, 100-115 (in Russ.) Ivanov, A.V., N.A.Vlasov, S.D.Zikov, N.A.Strazdina, and T.K.Vereshagin, 1972. About chemical composition of melted waters and snow in some regions of Eastern Siberia. Problems of Winter Studies, 4, 88-91 (in Russ.) Johannesen, M., T.Dale, E.T. Gjessing, A. Henriksen and R.F. Wright, 1977. Acid precipitation in Norway: the regional distribution of contaminants in snow and the chemical concentration process during snowmelt. IAHS-AISH Publ., 118, 116120. Kamalov, L.F., E.I. Chembarisov, G.N.Stepanov, 1977. Impact of soil-irrigation conditions in Amu Darya River Basin on its solute content and chemical composition. J. Hydrogeology of Noosphere, 2, 88-99 (in Russ.) Kamalov, L.F., 1975. Hydro-chemical characteristics of glaciers in the basin of Chirchik River. Works of SARNIIGMI, 27(108), 86-93 (in Russ.) Kann, I.A., 1978. Changes in solute content of river waters under the impact of irrigation exemplifying Chu and Talas rivers. Works of GGI, 251, 62-72, (in Russ.) Kattelmann, R., K. Elder, J.M. Melack, E.M. Aizen and V.B. Aizen, 1995. Initial survey of snow chemistry in the Tien Shan of Kirgizstan and Kazakhstan. IAHS Publ., 228, 318-321. Kira, T. (Editor), 1995. Proc. of Intern. Forum on ‘The Caspian, Aral and Dead Seas, Perspectives of Water Environment Management and Politics.’ UNEP, Osaka/Shiga, 146 p. Lobachev,G.N., 1980. Solute runoff of Sir Darya River in Fergana Valley. Works of SARNIIGMI, 77(158), 108-112 (in Russ.) Maximova, M.P., 1982. Criterions on diagnostic changes of ionic components in river waters under the anthropogenic impact. In. Proc. of Intern. Symposium on ‘Hydrochemistry of River Runoff SSSR’. Rostov na Donu, 144-145. (in Russ.) Posohov, E.V., 1975. General Hydrochemistry. Nedra, Leningrad, 208 p. (in Russ.) Reference Book of Climate USSR, Kirgiz SSR, 1988. Hydrometeo-Publishing, V. 18, 19, 31, 32, parts 1, 2, 4, Leningrad, 289 p. (in Russ.) Rubinova, F.E., 1991. Development of Anthropogenic Hydrology in the Middle Asia. Hydrometeo-Publishing. Moscow, 50 p. (in Russ.) Shnitnikov, A.V. and N.P. Smirnova (Eds), 1981. Climatology, Hydrology and Hydrophysics of Lakes in Central Tien Shan. Science. Leningrad. 244 p. (in Russ.) State Water Cadastre, the Main Hydrological Characteristics. Annual data about quality of surface waters Middle Asia. 4, 5; N.0-9; 1955 - 1985. (in Russ.)
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Skartvelt, A. and E.T. Gjessing, 1979. Chemical budgets and chemical quality of snow and runoff during spring snowmelt. J. Nord. Hydrol. 10, N2-3, 141-154. Tonnessen, K., K. Elder, R. Kattelmann and M. Williams, 1991. Seasonal snowpack dynamics and chemistry in the Sierra Nevada, California, USA and the Tien Shan, Xinjiang Province, China. Proc. of the Western Snow Conference, 59, 146-149. Tsirkunova, I.E., O.E.Veveris, M.V.Vrtsavs and V.F.Rone, 1984. NAA of natural waters. In: Monitoring of the Background Pollution of the Environment, 2, HydrometeoPublishing, Leningrad, 194-200. Vasilenko, V.N., I.M.Nazarov and Sh. D. Fridman, 1985. In: Monitoring of the Snow Cover Pollution. Hydrometeo-Publishing, Leningrad. Videneeva, E.M. and M.E. Belinson, 1990. Anthropogenic influence on hydrological and hydrochemical regime of Narin River. Works of SARNIIGMI, 133(214) Moscow, 35 - 42 (in Russ). Vilesov, E.N. and P.F. Shabanov, 1971. Chemical composition of melted water from glaciers in the basin of Malaya Almaatinka River. In: Regime of Kazakhstan’s Glaciers. Alma Ata, 136-142 (in Russ.) Wake, C.P., P.A.Mayewski and D.Qin, 1994. Modern eolian dust deposition in central Asia.Tellus, ISSN 0280-6509. Williams, M., K. Tonnessen, J.M. Melack and D. Yang, 1992. Sources and spatial variation of the chemical composition of snow in the Tien Shan, China. Ann. Glaciology, 16, 24-32.
Table 1. Volumes of water samples for chemical analysis Analysis oxidizing Fe ions NH4 NO3Si Color and transparency
Volume, ml 200 50 100 100 50 100
Analysis NO2HCO3SO42Clhardness Ca2+ and Mg2+
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Volume, ml 100 100 500 100 100 100
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Table 2. Brief description of determining the major soluble element content Content
Product of
NO2-, nitrites
SO2OH / C6H4 + HNO2 C6H4 + H2O \ \ NH2 N = NOH
SO2OH
Method
Color rose
Accuracy,% 3-5
Sensitiv ity 0.011 µEq L-1
Colorimetric
Colorimetric
rose
3 - 5
0.011
/
SO2OH
SO2OH / C6H4 + C10H7NH2 C6H4 + H2O \ \ N = NOH N = N – C10H6NH2 Renovation of nitrite with cadmium through /
NO3-,
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Aizen &Aizen, 2001 NO3- + H2O +2e- = NO2- + 2OH-
nitrates
µEq L-1
Cd0 – 2e = Cd2+ P, Phosphates Fe ions
Based on the formation of complex phosphorusmolybdenum acid: H7[P(Mo2O7)6]28H2O Fe+3 + 6CNS [Fe(CNS)6]3-
Colorimetric
blue
5 - 10
Colorimetric
red
5
Si, silicon
Based on the formation of complex colored acid: H8Si2(Mo2O7)6. Acid-based titration: HCO3- + H+ H2CO3 CO2 + H2O CO32- + 2H+ H2CO3 CO2 + H2O Titration by NA2B4O7: B4O72- + 2H+ +5H2O = 4H3BO3 1) titration by BaSO4 SO42- + Ba2+ = BaSO4 2) H N-N-C6H5 H / S N – N - C6H5 / \ / / N = N - C6 H 5 Pb + H – S Pb \ \ N = N - C6 H 5 N = N - C6H5 \ / S \ N-N-C6H5 H 1) titration AgNO3 Ag+ + Cl- = AgCl; CrO42- + 2Ag+ = Ag2CrO4 2) titration by Hg(NO3)2 and formation of HgCl2
Colorimetric
yellow
5
1) Amount of AgNO3; 2) Ratio between amount of Hg(NO3)2 and volume of sample
fulvous
1–2
violet
1 -2
Based on formation the steady alkaline complex of Ca ions with Na2H2C10H12O8N2 2H2O
Ratio between amount of Na2H2C10H12O8N2 2H2O and volume of sample
dark blue
1
20-30 µEq L-1
Based on feature of hydroxide Mg after interaction with C26H18O8N4S2Na2 to form the adsorption composite: Na2SO3N = NC6H4C = C – C6H4N = NSO3Na / C6H4OH C6H4OH Blazed photometry
Colorimetric (spectraphotometer, = 525nm)
From yellow to red
5
2 µEq L-1
-
HCO3 Hydrocarbon ions
SO42-, Sulphates
Cl-, Chlorides
Ca
2+
Mg2+
Na+ and K+
Determining of alkalinity
0.5
1) Weight of BaSO4;
1-2
0.003 mgP L-1 2.69 µEq L-1 0.1 mg Si L-1
2)Ratio between amount of Pb(NO3)2 and volume of sample
Emission spectral analysis
Table 3. Network of meteorological stations and stream gauges sampled stream chemistry in the Kekemeren River basin. n is station number on the Fig. 1; S is area of watershed; H is altitude; is latitude and is longitude. STATIONS
I belt: High mountains
Tuya Asu Ala Bel
n 2 1
S, km2 31 39
H, m 3225 3213
’, N 42 20 42 15
, E 73 40 78 03
II belt: Midlle altitude mountains
W. Karakol R., 5 km lower mouth W. Suek R. W. Karakol R., mouth Irisu R. Orto-Kugandi
3
324
2680
41 50
74 30
4 7
427 317
2200 2630
42 17 42 02
75 09 74 35
III belt: Flat river transit
Kekemeren R., 6km higher mouth W. Karakol R. W. Karakol R., mouth Kekemeren R., 1.8 km higher mouth Djumgol R.
5
2410
2100
42 09
74 00
6 9
1140 5160
1998 1843
42 12 41 52
74 04 74 20
BELTS
12
Aizen &Aizen, 2001 Djumgol R., Chaek Kekemeren, 0.5 km lower mouth Djumgol R.
8 10
2310 8250
1642 1819
41 55 41 51
74 31 74 21
Table 4. Long-term average (ave), maximum (max) and minimum (min) solute content; total ionic concentration (); month of maximum and minimum of solute content (m) (April, May, and June - IV,V,VI); average, maximum and minimum content of phosphate (P), silicon (Si) and iron (Fe) components; pH, and water temperature (TC) at altitudinal belts of the Kekemeren River basin: I is high mountains, II is middle altitude mountains, and III is flat river transit belts Belt I
ave
max
min
II
ave
max
min
III
ave
max
min
mg L-1 µEq / L % mg L-1 µEq / L % mg L-1 µEq / L % mg L-1 µEq / L % mg L-1 µEq / L % mg L-1 µEq / L % mg L-1 µEq / L % mg L-1 µEq / L
Ca 10 499 38 13 649 40 9 449 39 14 699 37 19 948 36 12 604 37 35 1747 37 38 1896
Mg 2 164 9 2 164 7 2 164 7 4 329 10 5 411 10 3 255 10 9 740 10 10 822
Na+K 1 35 4 1 35 3 1 35 4 1 35 3 2 69 4 1 35 3 2 69 3 6 207
HCO3 48 786 48 49 803 47 47 770 49 53 868 44 73 1196 45 47 770 44 113 1851 43 110 1802
SO4 2 42 2 3 62 3 1 21 1 5 104 4 7 146 4 4 83 4 14 291 5 24 500
% mg L-1 µEq / L %
34 33 1647 38
10 8,8 724 10
6 1,9 66 2
39 111 1818 45
8 10 208 4
Cl
2 56 2 2 56 1 2 56 2 3 85 1 10 28 2 3 1,4 39 1
NO3
64 1526
m
P 0.015
Si 3.0
Fe 0.12
69 1713
V
0.007
3.8
0.20
59.1 1439
VI
0.028
2.5
0.09
0.007
2.8
0.05
79 2091
1 16 0 1 16 0,3 0,7 11 0
108 2826
IV
0.003
3.5
0.08
69.2 1803
VI
0.009
2.2
0.03
0.005
4.5
0.06
177 4799 200 5525
IV
0.002
5.6
0.00
167 4513
VI
0.007
4.1
0.16
pH 7.6
TC 4.1
7.8
7.2
8.1
11
Table 5. Coefficient of correlation (r) between runoff and content of ionic components, linear trends (, µEq / L per yr.)of ionic component concentration in the W. Karakol River, mouth (1965 - 1985); their standard errors (, µEq / L), and 2 coefficient of determination (r ), F test ( p = .95, df = 1, - 2 = 19, where is number of years ) during April (IV) - month of maximum solute content and June (VI) - month of minimum solute content. m IV
VI
Runoff r , r2 F r ,yr.-1 r2 F
0.050 0.220 0.000 0.060 -0.340 0.920 0.010 0.140
pH 0.66 -0.001 0.006 0.002 0.042 0.62 -0.005 0.019 0.003 0.059
Ca -0.60 0.649 6.986 0.003 0.063 -0.67 0.349 0.140 0.000 0.003
Mg -0.44 -0.082 3.619 0.000 0.007 -0.24 0.164 0.044 0.000 0.002
Na+K -0.63 -0.552 4.972 0.005 0.100 -0.64 0.104 0.144 0.000 0.000
13
HCO3 -0.58 -0.016 6.011 0.000 0.000 -0.56 -0.033 0.367 0.000 0.000
SO4 -0.80 -0.104 9.369 0.000 0.002 -0.83 0.208 0.450 0.000 0.000
Cl 0.28 0.197 1.269 0.005 0.094 0.06 0.282 0.045 0.003 0.049
NO3 0.69 -0.081 0.758 0.002 0.045 0.68 0.032 0.047 0.000 0.001
-0.66 0.193 24.165 0.000 0.001 -0.73 0.162 0.895 0.000 0.000
Aizen &Aizen, 2001
Table 6. Evaluation of human impact on solute content in stream chemistry for the period from 1971 to 1985 in ionic concentration in the W. Karakol River, mouth calculated by two methods: the first one is considering river runoff and the second is based on ionic concentration of HCO3-. – is difference in ionic concentration for two periods, is ionic concentration of the main ions, K = Q71-85/Q65-70 is ratio in river runoff for two periods, (HCO3-) =71-85 – K65-70, mg L-1 =71-85 – K65-70,
Ca2+
Mg2+
Na++K+
SO2-
Cl-
NO3-
3.73
0.96
0.8
2.55
0.08
186.13
78.95
27.62
53.09
1.29
14 2.4 119,76 9 27.36 1365.26 27.54 1374.25
13 0.6 49,34 8 7.41 609.40 7.41 609.40
16 0.6 20,72 12 4.89 168.85 5.05 174.38
19 1.9 39,56 14 13.53 281.69 14.33 298.35
Runoff
µEq / L
/ ave 65-70, % (HCO3-), mg L-1 (HCO3-), µEq / L / ave 65-70, % ave 65-70, mg L-1 ave 65-70, µEq / L ave71-85, mg L-1 ave71-85, µEq / L
0.2 5,64 10 2.01 56.68 2.01 56.68
7 0 0 1.15 18.55 1.08 17.42
14.03 12.16
FIGURES Fig.1 Location map of the Susamir, West Karakol and Djumgol River basins Fig.2 Hydro-geological map of the Kekemeren River basins (after Adishev, 1987). Ground waters in: 1 is alluvial lower Quaternary Recent - shingle beds, sandy gravel rock; 2 is alluvial and alluvial fan deposits lower Quaternary Recent - boulder shingle beds, shingle beds; 3 is glacial middle/upper Quaternary - boulders, boulder loam, sands; 4 is upper Pliocene and lower Quaternary - compound interstratificated pudding rock, sandstone, sandy clay rock; 5 is undessected Neogene and Pliocene - compound inter-stratificated pudding rock, grit, sandstone, marlstone; 6 is Jurassic - sandstone, shist; 7 is lower Paleozoic, mainly terrigenous, effusive-sedimentary and effusive-metamorphic formations - sandstone, pudding rock, schist and shale, phyllite, quartzite, massive limestone, marbles; 8 is middle Paleozoic, mainly terrigenous, metamorphic, effusive formations - sandstone, pudding rock, grit, aleurolite, schist, phyllite, quartzite, infrequent limestone and marbles; 9 is Precambrian mainly metamorphic and effusive formations - gneiss, marbles, marbled limestones and sandstone; 10 ground water in the intrusive igneous rock - granites, granite-porphyries and quartz porphyries, granodiorites and diorites; 11 is aquifer fractures 12 are rivers 13 are lakes
14
Aizen &Aizen, 2001
Fig.3 Annual variation of long-term average precipitation in the altitudinal belts of Kekemeren River basin. (Reference book of climate USSR,1988; Central Asian Data Base - CADB). Fig.4 Annual variation of long-term average runoff in the altitudinal belts of Kekemeren River basin. (State Water Cadastre,1985; Central Asian Data Base - CADB). Fig.5. Long-term average absolute (mg L-1) and relative ionic composition (%) and solute concentration () during its maximum of stream water at three belts of the Kekemeren R. basin. Fig.6. Long-term monthly average absolute (mg L-1) and relative ionic composition (% equivalent) at three regions of the Kekemeren R. basin. Fig.7. Long-term monthly average solute concentration () during its maximum at three belts of the Kekemeren R. basin. Fig.8. Long-term anomalies of runoff (Q), pH, solute concentration () and absolute ionic composition () of stream water at W. Karakol R, mouth during maximum (April) and minimum (June) solute concentration .
Fig. 1
o
o
o
73 00' halite
iron ores
mirabilite
aluminium ores
fluorite
gold ores
o
baryte
I
K
G
R
S Z
I
I
1
r
a
K
R. a S
t
k u
l
o
e W 6
U
J
G
M
4281 m
R.
k
e
s
5
S
O 42 o 20'
S u s a m i r R.
R.
O
3 4
k
T
Y
Irisu R. m e
A
2
O t
75 00'
4420 m
L
A K
o
74 30'
clay
4224 m
42 20'
o
74 00'
73 30'
D
O
L
T
U R. 3384 m
A M o
N
I
D j
R
T
glaciers and rivers divides
O
Kekemeren R.
l S U S A MI R
10
BASIN
Hara Us-Nur Lake
K
A
W
canyon 73 o 30'
o
9
ground water abruption
5 stations and their numbers
g u m
8
O
bog
1 : 1 000 000 cm 73 o 00'
Y
7
S
42 00'
A
74 o 00'
15
74 o 30'
A
K
Aizen &Aizen, 2001
Fig. 2
73 o30'
73 o00'
74 o00'
74 o30'
75 o00'
P 42 o20'
PZ 2 42 o20'
PZ 1
PZ
PZ
ap Q III-IV
PZ 1 g QII
PZ
P ap QIII-IV
III
42 o00'
42 o00'
PZ
II
ap QII-IV
N II
III
PZ 2
PZ 2
73 o30'
73 o00' 1 a Q III
2
PZ 2
9
8
IV
74 o00'
ap QII-IV
P
3
g Q II
10 PZ
74 o30' 5
4
11
12
16
N
75 o00' J
6 13
7
PZ 1
Aizen &Aizen, 2001
Fig. 3 (a) P, mm 100
High and Midlle altitudinal belts
80 60 40 20 Flat, transit belt 0 Jan
Mar
May
July
Sep
Nov
(b) m
3
s
-1 FLAT RIVER TRANSIT BELT
250
Kekemeren, 1.8 km higher mouth Djumgol R.
200
Kekemeren, 0.5 km lower mouth Djumgol R.
150
Kekemeren, 6.0 km higher mouth W. Karakol R.
100
W. Karakol, mouth
50 0 Mar
MOUNTAIN BELT
Karakol, mouth Irisu R. May
Jul
Sep
Nov
17
Jan
Aizen &Aizen, 2001
Fig. 4 %
1562
Tuya Ashu
Eq / L
50
L
30 %
Ala Bel
1781
20
Eq / L
50
10
40
0
4224 m
30 20
+
-
2-
+ Ca 2+ Mg 2+ Na + K HCO3 SO4
Cl
-
Y
I
K+
-
-
2-
+ Ca 2+ Mg S2+ Na + K HCO3 SO4
Cl
NO 3
Z
I
G
I
K
10 0
A
2
R
T
Eq / L
O O
-
+ 2Ca 2+ Mg 2+ Na+ + K HCO3 SO4
Cl -
NO34281 m
3
O NO 3 t
Irisu R. K Karakol, mouth Irisu R.
4
m e
2584
Eq / L
50 k
1
S u s a m i r R. R.
3537
% Kekemeren, 6 km higher mouth W.Karakol R.
Eq / L e
50
40 s 30 20
5
40
U
G
M
J
0
6
20
Ca2+ Mg
+
+
Na + K
HCO3
2SO4
Cl -
40
NO3
30
7
20
0
+
Ca 2+ Mg 2+ Na + K
+
HCO3
2SO4
Cl -
10
NO -
3
0
S %
W.Karakol R., mouth, 4023
Eq / L
50
A M
Eq / L
50 2+
10
U
Orto Kugandi 3236
%
10
30
S
2646
Karakol, 5 km lower mouth W. Suek R.,
% 45 40 35 30 25 20 15 10 5 0
40
%
8
40
I
30
R
T
O O
20
0
+
-
2-
+ Ca 2+ Mg 2+ Na + K HCO3 SO4
Cl
-
10 % 40 35 30 25 20 15 10 5 0
5615
35 30 25
5 0
NO 3
Kekemeren, 1.8 km higher mouth Djumgol R.,
+
% Kekemeren, 0.5 km lower mouth Djumgol R.,
6858
40 30 20 +
-
2-
Cl -
NO 3
10 0
18
-
2-
+ Ca 2+ Mg 2+ Na + K HCO 3 SO4
Cl
Eq / L
50
+ Ca 2+ Mg 2+ Na + K HCO3 SO4
-
Eq / L
20 15 10
9
10
+
+
-
2-
+ Ca 2+ Mg 2+ Na + K HCO3 SO4
Cl -
2-
+ Ca 2+ Mg 2+ Na + K HCO3 SO4
Djumgol R., 6934
NO 3
Eq / L
-
NO 3
Cl -
NO 3
Aizen &Aizen, 2001
Fig. 5 HIGH MOUNTAINS, 1713 Eq / L
3%, 62 Eq / L 40%, 649 Eq / L
/L 47%, 803 Eq -1
Eq / L 3%, 35 Eq / L 7%, 169 MIDLLE ALTITUDE MOUNTAINS, 2826 Eq / L
4%, 146 Eq / L 1%, 56 Eq / L .
36%, 948 Eq / L
45%, 1196 Eq / L
HCO 3 2-
SO4 Cl NO3 Ca
2+
Mg2+
4%, 69 Eq / L FLAT RIVER TRANSIT,
3%, 282 Eq / L
10%, 411 Eq / L
5525 Eq / L
0.3%, 16 Eq / L( NO )3-
8%, 500 Eq / L
34%, 1896 Eq / L 39%, 1802 Eq / L -1
10%, 822 Eq / L 6%, 207 Eq / L
19
+
Na + K
+
Aizen &Aizen, 2001
Fig. 7
HIGH
Eq / L
anions
Eq / L
M O U N TA I N S cations
2000
2000
1500 1000
1000
500 0
M IDLLE
Eq / L
Eq / L
2000
2000
A L TI TU D E
M O U N TA I N S
HCO 3
% 50 40 30 20 10 0
1500 1000
1000
ions
% 50 40 30 20 10 0
500 0
2-
SO4 Cl NO3 Ca
2+
Mg2+ +
Na + K
F L A T R I V E R TR A N S I T
Eq / L
Eq / L
2000
2000
% 50 40 30 20 10 0
1500 1000
1000
500 0 Apr
May
Jun
Jul
Aug
Sep
Apr
May
Jun
Jul
Aug
20
Sep
Apr
May
Jun
Jul
Aug
Sep
+
Aizen &Aizen, 2001
Fig. 8 3
Q, m s
-1
60 50 40 30 20 10 0 -10 -20 -30 -40
Jun
Eq / L
Apr
pH
Apr
Jun
Apr
400 300 200 100 0.0 -100 -200 -300 -400 -500
160 80 0.0 -80 -160 -240 -320
Ca 2+ Eq / L Jun
400
Mg 2+ Eq / L
Apr
200 160 120 80 40 0.0 -40 -80 -120 -160 -200
300 200 100 0.0 -100 -200 -300 1969
1973
1977
1981
1985
1965
Apr
-
Cl Eq / L
2-
SO4 Eq / L
-
HCO 3 Eq / L
Jun
1.0 0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8
-540 -810 -1080
240
1965
Jun
1080 810 540 270 0 -270
Jun
Jun
56 42 28 14 0.0 -14 -28 -42 -56
Apr
+
Jun
Apr
NA + K Eq / L
Apr
+
Jun
210
Apr
140 70 0.0 -70 -140
1969
1973
1977
Y E A R S
21
1981
1985
-210 -280 1965
1969
1973
1977
1981
1985
