Variations in Different Compounds in Volga Water, Suspension, and Bottom Sediments in the Summer of 2009 I

Home , Sok (river), Unzha

See discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/226839859

Hydrocarbons in bottom sediments of the marginal ﬁlter of the Volga River

Article in Doklady Earth Sciences · January 2006 DOI: 10.1134/S1028334X06010247

CITATIONS READS 8 37

2 authors, including:

Inna Abramovna Nemirovskaya P.P. Shirshov Institute of Oceanology

167 PUBLICATIONS 465 CITATIONS

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Геолого-геохимические исследования природных и антропогенных процессов в воде, взвесях и донных осадках морских акваторий, в том числе в окраинных районах Мирового океана View project

All content following this page was uploaded by Inna Abramovna Nemirovskaya on 12 February 2016.

The user has requested enhancement of the downloaded file. 2 ISSN 00978078, Water Resources, 2012, Vol. 39, No. 5 pp. 533–545. © Pleiades Publishing, Ltd., 2012. 2 Original Russian Text © I.A. Nemirovskaya, 2012, published in Vodnye Resursy, 2012, Vol. 39, No. 5, pp. 496–509. WATER QUALITY AND PROTECTION: ENVIRONMENTAL ASPECTS

Variations in Different Compounds in Volga Water, Suspension, and Bottom Sediments in the Summer of 2009 I. A. Nemirovskaya Institute of Oceanology, Russian Academy of Sciences, Nakhimovskii prosp. 36, Moscow, 117851 Russia Email: [email protected] Received September 29, 2010

Abstract—Studies of water, suspension, and sediments of the Volga R. (from Konakovo Town to the delta) showed that at the confluence with tributaries, diffusion and dilution play the major role. Changes in conduc tivity, BOD5, pH, suspension, chlorophyll a, dissolved and organic carbon, lipids, and hydrocarbons take place mostly under the effect of natural processes. Typical features in the case of summer lowwater period are low chlorophyll a, suspension, and BOD5. The accumulation of pollutants takes place in bottom sedi ments because of an increase in the share of Corg, and hydrocarbons have a petroleum and pyrogenic compo sition.

Keywords: drainage basin, mixing zone, pollution, suspension, sediments, mineralization, BOD5, chloro phyll a, hydrocarbons. DOI: 10.1134/S0097807812030062

INTRODUCTION period. The tasks of the study were to examine the Volga drainage basin is the largest in Russia natural, main geochemical, hydrochemical, and hydrophysi industrial, and social complex. In this territory, cal processes in Volga watersheds; to study the mixing accounting for 8% of the area of European Russia, zones of the Volga and its tributaries (upstream of the 426 towns and cities are situated; 60 million lives, confluence, at the confluence, and at a site down including about 45 million of urban dwellers; 45% of stream of it where water mixing is complete); to ana industrial and 50% of agricultural production is pro lyze the distribution of major characteristics over flow duced. This is practically half of the country in terms depth; and to assess the environmental stat of the of population, industry, and agriculture. Volga. The expedition covered 3100 km and carried out 84 stations. The Volga basin has experienced much greater adverse impact of the accelerated, environmentally ill considered process of industrialization and urbaniza METHODS OF STUDIES tion in the 1930s–1940s, as well as in the period of cre ation of the powerful military industrial base of the Suspensions were isolated from surface water by Soviet Union [16]. The construction of the Volga nuclear filters (0.45 µm) under suction at 0.4 atm with chain of hydropower plants has transformed the main the aim to determine their concentrations (gravimet Russian waterway into a chain of huge reservoirs with ric) and composition (with the use of a scanning elec extremely slow flow velocity and intense development tion microscope at JSMU31 (Jeol, Japan) and by of eutrophication [4]. fiberglass filters GF/F (0.7–1.2 µm) for studying Subject to high anthropogenic load, the Volga basin organic compounds, including Corg, lipids, hydrocar has become most environmentally neglected in Russia bons (HC), chlorophyll (Chl a). Moreover, the con [18]. The discharge of pollutants into the Gorki and centration of suspension was determined from the Cheboksary reservoirs alone in 2000–2003 was 100– extinction of light in surface and deep waters with the 4000 thousand t/year [9]. use of a transparency meter PUMA, developed in From June 26 to July 24, 2009, an expedition was Oceanic Optics Laboratory, IO RAS [2]. Bottom sed carried out onboard Valaam 1 research vessel from iment (BS) samples were taken by a dredger and a Konakovo town to Astrakhan town and in Volga delta stratometer. branches (Fig. 1). The expedition was organized by The electric conductivity and temperature were Shirshov Institute of Oceanology RAS (IO) and Water determined by EKSPER0014 device with a sound, Problems Institute RAS (WPI RAS). The objective of which gives continuous information in surface sam the expedition was to carry out multidisciplinary stud ples and along the depth (down to 18 m). The coordi ies of Volga environment during summer lowwater nates of sample sites were determined with the help of

533 534 NEMIROVSKAYA

Kirov Perm Kostroma Yaroslavl Tver Ivanovo Izhevsk IoshkarOla Konakovo Vladimir Cheboksary Moskva Nizhni Novgorod Kazan a a am k K Ufa Ryazan O Tula Саранск Ul'yanovsk

Penza Orel Samara Tambov

Saratov

Volgograd

Astrakhan

Fig. 1. Schematic map of the expedition.

GPS navigator (Garmin) accurate to 4 m. The hydro as the difference between oxygen concentrations chemical determinations included pH (by potentio before and after the incubation. metric method), oxygen (iodometric method, titra Dissolved organic carbon (DOC) was determined tion), BOD5 (biochemical oxygen demand after five with a totalcarbon analyzer TOCVCh (Shumadzu, day incubation) [5]. The value of BOD5 was evaluated Japan). Particulate Corg (POC) and BS was deter

WATER RESOURCES Vol. 39 No. 5 2012 VARIATIONS IN DIFFERENT COMPOUNDS IN VOLGA WATER, SUSPENSION 535 mined by dry combustion method in AN7529 ana mS/cm lyzer (Russia) [14]; lipids and HCs were determined by IRspectrometry [19] in IRAffinity1 device (Shi 450 madzu, Japan); the concentration and composition of 400 polycyclic aromatic hydrocarbons (PAH) were deter 350 mined with the help of highefficiency liquid chroma 300 tography [19] with the help of Milikhrom02 device 250 (Ekonova, Russia); Chl a was determined by fluores 200 150 cent method with the help of Trilogy device (Turner, 100 USA). The methods are described in detail in [2, 14, 50 19, 26, 31, 34]. 0 500 1000 1500 2000 2500 km

RESULTS AND DISCUSSION Fig. 2. Variations in the electric conductivity of surface The collected data show that the electric conduc water in the Volga R. from Konakovo T. to Astrakhan C. tivity of surface Volga water gradually increased south ward down to Astrakhan (Fig. 2). This characteristic varied within 190–210 mS/cm. Downstream of Sura agreement with variations in other hydrochemical R. inflow, its values abruptly rose to 250 mS/cm and characteristics [5]. The electric conductivity in the further tended to increase down to the delta head. An Oka is 2.2 times higher than in the Volga because of the abrupt peak in electric conductivity was recorded at greater area of ploughlands and more powerful source Kama mouth, where its values were 50 mS/cm higher of mineral substances. Moreover, upstream of this site, than the background Volga values. The electric con Gorki Reservoir dam is situated, trapping mineral ductance increased to 300 mS/cm at Tolyatti, to 350 at matter runoff and discharging cold water from bottom Saratov, and to 400 at Kamyshin, and reached their horizons. Therefore, water temperature in the Oka is maximal value of 450 mS/cm at Astrakhan. Thus, the 0.9°С higher than in the Volga because the basin of the electric conductance increased more than twofold former lies further to the south. The length of the mix from the Upper Volga to its mouth. These data coin ing zone here reaches 10 km (Table 1). cide with the distribution of chloride concentration, Water temperature in the Kama near its confluence which varied from 6.3 mg/l in Upper Volga water to with the Volga is slightly (0.2°С) lower and its electric 31.6 mg/l in Astrakhan [5] because of variations in conductivity is 68 mS/cm2 higher than those in the subsoil water mineralization [18] and the input of aero Volga. The effect of Kama water in the Volga can be sols from arid regions of Russia. Because of this, in Volga seen within 18 km from their confluence. Water in the delta, where those conditions remained practically rivers of Bol’shoi Irgyz and Kamyshin also has higher invariable, the values varied within 440–445 mS/cm. mineralization than in the Volga, though to a lesser The temperature of surface Volga water along the extent than in the Oka and Kama. The water of the lat entire expedition route increased by more than 7°С. ter is 0.5 and 0.4°С lower than in the Kama, respectively. Clearly, the low temperatures are typical of the Upper The mixing zones are much shorter (1 and 2.7 km, Volga segment from Konakovo Town to Tutaev Town respectively). At the confluence of the Volga and (17–18°С). Further to Tolyatti, the temperature rose Kurdyum, complete water mixing and dilution took to 19–21°С. Downstream of Saratov HPP dam, the place immediately at the Kurdyum mouth because of temperature abruptly dropped by almost 3°С, seem its low flow. ingly because of water discharge from cold bottom The values of pH in surface water varied from 7.4 to horizons and because of a shorttime cooling. The 8.6. Lower values were recorded in the Upper Volga temperature increased near Saratov and reached its (7.4–7.6), while higher, in the Middle and Lower maximum (24.2°С) near Astrakhan. Volga (7.9–8.1). The maximal pH value was recorded The northern rivers of Unzha and Nemda, flowing in the Gorki Reservoir upstream of Tolyatti. After near one another, show lower electric conductivity and heavy rains, pH in this area dropped by 0.7. The effect temperature than the Volga itself. This is due to both of acid inputs could be seen at the mouths of the Oka the snowderived nourishment of those tributaries and Kamyshinka rivers, where pH dropped by 0.4 and (Table 1) and the lower anthropogenic load—lesser 0.5, respectively. Water alkalinity here varied within share of tilled areas on the banks and lesser urbaniza the range of 1.7–3.1 mgequiv/l, while that near Tolyatti, tion. The length of the mixing zone of those rivers is within 1.9–2.0 mgequiv/l. In other words, the buffer 5–6 km. Other tributaries located further downstream capacity of water was large enough to prevent their acidi along the Volga showed an inverse trend—water in the fication, which takes place at pH<6 [17]. tributaries was warmer and had higher mineralization. The concentrations of organic compounds were The maximal difference in terms of temperature and relatively low all along the expedition route. In partic electric conductivity was recorded at the confluence of ular, the distribution of BOD5 (a characteristic of the Volga and Oka (Table 1), a feature, which was in labile organic matter) in surface water suggested a

WATER RESOURCES Vol. 39 No. 5 2012 536 NEMIROVSKAYA

Table 1. Major characteristics of streams at the confluence sites of the Volga and Its Tributaries

Electric Mean an Temperature, °C Mixing Tributary Drainage Tributary conductivity, mS/cm Confluence site nual flow, zone length, km area, km2 nourishment m3/s length, km Volga Tributary Volga Tributary

Volga–Unzha 162 3780 60 Snowmelt 198 171 19.9 19.9 5 Volga–Nemda 426 27800 158 The same 198 186 19.9 19.3 6 Volga–Oka 1500 245 000 1200 The same 206 457 19.9 20.8 9.9 Volga–Kama 1805 507 000 3800 Snowmelt, 264 332 20.8 20.6 18 groundwater, rain Volga–Bol'shoi 675 24 000 23 Snowmelt 329 370 19.7 20.3 1 Irgyz Volga–Kurdyum 53 980 10 Rain, groundwa 330 331 20.4 20.5 0.2 ter Volga–Kamy 15 200 5 The same 352 360 23.1 23.5 2.7 shinka

slight pollution (Fig. 3). The mean BOD5 (3.3 mg/l) of Chl a in surface water was also rather low, not was slightly over the MAC for domestic water use exceeding 35 µg/l. The concentration of Chl a is a uni (2 mg/l), but less than the MAC for water bodies used versal characteristic of the abundance, metabolic activ for cultural–domestic needs (4 mg/l) [2]. The highest ity, and space and time dynamics of planktonic values were recorded in the Kuibyshev Reservoir algacenoses [15]. Notably, the concentration of suspen upstream of Kazan (6.7 mg/l) and in the Lower Volga sion in Volga delta branches varied within 1.5 to 30 mg/l near Verkhnee Lebyazh’e Village (6.8 km/l), i.e., in and that of Chl a varied from 6.5 to 22.8 µg/l [11]. areas not related with urban activities. Earlier (1995– The Secchi transparency of Volga water averaged 2000) the values of BOD5 reached 5 mg/l only at the 2.9 ± 1.1 m (n = 27), and that measured by transpar mouths of the Klyaz’ma and Kama rivers, while in ency meter reached 9 m–1 (on the average, 3.5 ± most cases they did not exceed 3 mg/l [18]. In the sur 2.9 m–1, n = 41) with a peak of 12.7 m–1 at Oka mouth. face water of the Kama Reservoir, the biological oxy The low values of light extinction factor are due to the gen demand varied within wide limits—from 0.5 to water dying by large amounts of humic acids, rather 4.0 mg/l [8]. In summer and autumn, the concentra than high suspension content [13]. Lower concentra tions were lower (9–1.4 mg/l). Therefore, the biologi tions of suspension (on the average, 2.7 mg/l) were cal oxygen demand is believed to be relatively low in all recorded in the area between the Gorki and Volgograd phases of water regime and all over the Kama Reser reservoirs. A clearwater zone began in this segment— voir [8]. the values of light extinction factor varied within inter DOC concentration in surface water varied within val 0.5–1.2 m–1. In most cases, the measured profiles 7–50 mg/l (Table 2). The highest concentrations were of light extinction were practically homogeneous recorded in Upper Volga, where between Konakovo down to the bed. The only exceptions were the water and Nizhniy Novgorod they averaged 26.8 mg/l (n = mixing zones of the Volga and its tributaries, where 11). In the Lower Volga DOC decreased on the average peaks were recorded at depths of 1–2.5 m. This is 2.8 times—to 9.53 mg/l (n = 14). This was most likely especially typical of the mouth areas of the Oka and due to the higher rate of decay of organic compounds Kamyshinka, which discharge large amounts of at higher temperature and to their lower input from the organic compounds into the Volga. less densely populated part of the Volga Basin. Further downstream of large cities, the concentra The concentration of suspension (Table 2) during tion of suspension did not increase; in particular, summer lowwater period was below MAC (10 mg/l) upstream and downstream of Nizhniy Novgorod, sus and much less than the mean concentrations for World pension concentration was 3.6 and 3.9 mg/l, respec rivers (460–500 mg/l) [12]. However, those data are tively; a peak of 12.7 mg/l was recorded at Oka mouth. close to the mass concentration of suspension at Chl a concentration in this area varied from 12 to Northern Dvina mouth, where, even during floods, it 33 µg/l, also with a peak at Oka mouth (Table 2). Sim varied from 1.9 to 32.8 mg/l [10]. The concentration ilar distributions of the concentrations of suspension

WATER RESOURCES Vol. 39 No. 5 2012 VARIATIONS IN DIFFERENT COMPOUNDS IN VOLGA WATER, SUSPENSION 537

mg/L 8

0 Ples Kama Marks Kazan Sok R. Uglich Tutaev Sura R. Samara Saratov Rybinsk Syzranki Myshkin Kalyazin Yur'evets Yaroslavl Primorsk Volzhskii Balakovo Gorodets Balakhna Klimovka Kostroma Novgorod Astrakhan Volgograd Kamyshin Khvalynsk Svetlyi Yar Cheboksary Chernyi Yar Rozhnovskii V. Lebyazh'e Zhigulevskaya Kuibyshevskoi

Fig. 3. Distribution of BOD5 in surface water. and Chl a were recorded at the confluence of other riv many biogenic particles consisting of freshwater algae ers with the Volga. Suspension concentration was (diatoms, individual pennate and centric cells and 2.6 mg/l at the mouth of the Kamyshinka and 1.6 and their colonies), as well as spores and pollen (Fig. 4). 1.0 mg/l upstream and downstream of this place, Phytoplankton cells were commonly few (Fig. 4a). respectively; the concentration of Chl a was 12 at the Among mineral particles, detrital grains with angular mouth and 1.6 and 8 mg/l upstream and downstream and angular–rounded shapes were found; globular of it, respectively. Although the suspended matter con accumulations (aggregates), consisting of fine scaly tains both mineral and biogenic particles and Chl a is formations; clay minerals and very fine mineral sus formed by biogenic compounds, a correlation was pension, which sometimes covered the entire filter found to exist between the distributions of suspension surface by a dense layer. Ash particles were detected in and Chl a (r = 0.75). The correlation between those samples near Yaroslavl and Tolyatti after heavy rains characteristics can be seen in space photos. In the (Fig. 4b). High concentrations of coarse mineral northern part of the Kuibyshev Reservoir, the concen grains and aggregates of clay particles were recorded trations of both suspension and Chl a was much near large cities: in Nizhniy Novgorod (Figs. 4c, 4d) greater than that in its southern part, which can be due and Volgograd. It is likely that flow velocity slowed to the effect of Kama water. It is worth mentioning that down here and aggregation of clay particles due to the concentrations of suspension and Chl a varied less Brownian motion was taking place. Moreover, those along the research vessel route than over the reservoir may be microaggregates of soils, which entered here area. This is due to variations in phytoplankton pro from the drainage basin. In addition to mineral parti duction in different parts of the reservoir. The biologi cles, diatoms, their colonies, and coccoliths were cal production of reservoirs forms as the result of inter detected here. Aggregates of clay particles and loose action between time and scale spatial dynamics of organic–mineral aggregates, consisting of biogenic phytoplankton at different scales, subject to the joint detritus and terrigenous grains, were also detected in effect of natural and anthropogenic factors. The geo river samples from the Oka and Kamyshinka rivers. graphic zonality in reservoir chain manifests itself in a decrease in phytoplankton abundance, an increase in The distribution of POC generally depended on its metabolic activity, and larger integral primary pro suspended matter concentration (susp) and Chl a in duction in Lower Volga reservoirs [15]. surface water: r(susp.–POC) = 0.51, r(Chl a–POC) = 0.57. Those relationships were violated at the inflow of Studying the suspension with the help of an elec tributaries into the main Volga channel. In particular, tronic scanning microscope has shown the presence of the mixing of Kama and Volga waters caused a 0.4 mg/l

WATER RESOURCES Vol. 39 No. 5 2012 538 NEMIROVSKAYA

Table 2. The concentrations of particulate matter and organic compounds in surface water along vessel route

Suspension DOC Chlorophyll Lipids AHC POC Site µg/l µg/l

Downstream of Konakovo 4.074 4.80 43.20 28.3 253 Upstream of Yaroslavl 2.089 50.07 1.83 40.50 26.3 310 Downstream of Yaroslavl 1.778 12.75 3.10 23.80 15.5 202 Nemda R. mouth 6.800 11.49 21.56 27.40 17.8 770 Downstream of Nemda R. mouth 6.933 12.02 16.50 12.80 8.3 464 Yur'evets 6.190 30.94 12.90 20.40 13.3 672 Upstream of Nizhniy Novgorod 3.600 49.11 12.05 15.70 10.2 340 Upstream of Kazan 1.867 9.824 2.18 29.90 19.4 148 Downstream of Kazan 1.233 9.588 4.49 19.70 12.8 91 Upstream of Kama mouth 3.800 9.858 2.59 42.20 27.4 280 Kama mouth 4.200 7.005 8.46 42.20 27.4 149 Downstream of Kama mouth 3.200 9.241 2.88 10.20 6.6 110 Upstream of Samara 1.444 16.06 3.43 14.40 9.4 282 Downstream of Samara 1.556 15.75 4.81 9.60 6.2 858 Bol'shoi Irgiz R. mouth 2.333 1.69 17.50 11.4 199 Downstream of Bol'shoi Irgiz R. mouth 2.311 2.31 18.70 12.2 191 Upstream of Saratov 1.200 13.03 6.62 29.10 18.9 223 Downstream of Saratov 1.267 7.087 4.80 11.70 7.6 78 Upstream of Kamyshinka R. 1.600 1.83 16.90 11.0 932 Kamyshinka mouth 2.578 3.10 32.30 21.0 727 Upstream of Volgograd 1.567 6.200 21.56 17.80 11.6 266 Downstream of Volgograd 1233 7.740 16.50 14.10 9.2 236 Lebyazh'e Settl. 9.600 12.90 45.30 29.4 437 Lower Volga 7.400 7.318 12.05 12.80 8.3 678 Narimanov Settl. 6.933 2.18 10.20 6.6 666 Upstream of Astrakhan 9.667 5.998 4.49 60.30 39.2 56 Downstream of Astrakhan 6.067 2.59 16.00 10.4 1022 Bakhtemir Branch 5.933 8.46 12.30 8.0 326 Ikryanoe Settl. 6.667 2.88 45.80 29.8 480 Nizhnee Ikryanoe Settl. 7.067 3.43 59.70 38.8 658 Oranzherei Settl 3.200 6.89 4.81 20.7 8.3 638

WATER RESOURCES Vol. 39 No. 5 2012 VARIATIONS IN DIFFERENT COMPOUNDS IN VOLGA WATER, SUSPENSION 539 increase in suspended matter concentration, while relation coefficients between the distributions of mois below this site, its concentration decreased by ture content (moist.), Corg, and AHC are lower: 0.6 mg/l. POC concentration increased almost twice r(moist–AHC) = 0.63: r(Corg–AHC) = 0.64. The at the mouth and decreased 2.5 times downstream of granulometric governing factor of AHC disappears in the mixing zone (Table 2). At the mouth of the Kamy the zone of avalanche sedimentation, in the mixing shinka, suspension concentration increased 1.6 times, zone of waters with different mineralization, and in and that of POC, 7.8 times. The tributaries seem to the areas receiving large amounts of petroleum prod discharge large amounts of organic compounds into ucts [19]. This may account for the 21.5fold increase the Volga. Suspension concentrations practically did in HC concentrations at stations bu and 21u at a not change near Samara City, while POC concentra change in Corg concentration by 2.7 time (Table 3). In tion increased three times. Such distribution of con silty sediments, HC share in Corg composition varied centrations of suspension and POC was determined by from 0.03 to 0.29% and that in sandy sediments, from the genesis of suspension and the ratios of mineral to 0.22 to 33.8%, reaching its maximum near a gascon organic compounds. The concentrations of aliphatic densate plant (Gandurinskii bank, st. 19u); in the hydrocarbons (AHC), which in many studies [6, 18, Kamyzyak Branch (st. 11u), it was 10.7% (Table 3). In 22] are identified with petroleum hydrocarbons (PH), modern BS, notwithstanding the higher AHC con in surface water in filtered suspension varied within centrations converted to dry mass, their share in Corg interval 6.2–39.2 µg/l (Table 2). Their mean concen composition was as little as 0.10–1.24%. tration (16.4 µg/l) corresponded to AHC background BS is assumed polluted when AHC concentration level in coastal water areas (16–20 µg/l) and slightly exceeds 10 µg/g for sandy and 100 µg/g for silty sedi differed from the concentrations in Volga delta in pre ments [3, 29, 33]. The obtained AHC concentrations in vious years (~18 µg/l) [18, 22]. Higher AHC concen Volga BS at stations 1, 8, 11, 15, 3u, and 23u (Table 3) are tration was recorded in Lower Volga water upstream of comparable with background concentrations. At low Astrakhan (39.2 µg/l) and near Novoe Ikryanoe AHC concentration, the alkane composition of BS (38.8 µg/l), i.e., the concentration did not rise after shows a uniform distribution of homologues (Fig. 5), large cities, as was the case with suspension. However, typical of oil HC. Such composition of alkanes is char those values are also below MAC for petroleum HCs acteristic of BS in Kamyshinka mouth (station 14) and (50 µg/l), a fact that may suggest an insignificant Volga delta (stations 3u, 7u, and 19u). Contrary to petroleum pollution. It is worth mentioning that AHC that, BS sample in front of Tolyatti, where AHC con concentrations in water in Volga mouth areas have centration is relatively high (107 µg/g, Table 3), terrig decreased in recent years relative to 1995–2004, and enous homologues dominated in alkane composition. their mean concentrations in water in rivers of the This is most likely due to the rapid decomposition of Volga basin and in delta branches varied within 10– petroleum compounds, especially, highmolecular 30 µg/l [22]. Oil films have been never seen along the (including even alkanes [19, 35, 36]), resulting in the expedition route. Earlier, higher AHC concentration accumulation of highmolecular odd AHC in sedi was recorded in waters of Volga–Kama chain of HPPs, ments. The share of film oil generally decreases with where it rose to 990 µg/l, while in most regions, it var the distance from major pollution sources, while that ied within 150–300 µg/l [18]. of other forms increases because of redistribution of AHC content of BS varied within a wide range (2– HC between migration forms, their concentration in 485 µg/g). Their concentration was much less in suspension, and, finally, in BS. Experiments showed coarse than in fine BS. The mean concentrations of that in a temperate zone in summer, a water body, even Corg and AHC were 0.73% and 27 µg/g for the entire heavily polluted with oil, can clear of it within one or data set, 0.96% and 10 µg/g for conventionally sandy two months [28]. On the other hand, when the input of BS, and 1.88% and 94% µg/g for silty sands, respec pollutants in a shallow water body is continuous the tively (Table 3). In the fine sediments of Volga delta sedimentation rate is higher than the rate of transfor branches (stations bu, 21u, 22u, and 24u), where the mation even in flowthrough water bodies [21]. That is share of fine aleurolite (fraction 0.05–0.01%) rose to why, the sediments at Kamyshinka mouth and in Volga 14–19%, the concentration of Corg increased to delta are polluted with petroleum HC. 1.192–1.348%, and that of AHC, to 44–54 µg/g The concentrations of PAH varied from 2 to (Table 3). 252 ng/g and did not exceeded 100 ng/g in most sam When the sorption processes play a leading role, a ples (Table 3). In this case, a high concentration was direct dependence can be seen to exist between BS also recorded in silty sediments. In areas with contin moisture content and the concentrations of Corg and uous input of pollutants, the lower concentration limit AHC in BS [19]. Indeed, in the area under consider of polyarenes is often above 100 and the upper is higher ation, a correlation exists between BS moisture and than 4000 ng/g [33]. PAH concentrations commonly Corg content (r = 0.96), because Corg concentration is increase in winter because of higher atmospheric pol mostly determined by the granulometric type of sedi lution [19, 25], since their main source is combustion ments. The value of correlation was exactly the same products. Therefore, notwithstanding the greater tol as that in BS sampled in 2003 and 2004 [21]. The cor erance of PAH to microorganisms as compared with

WATER RESOURCES Vol. 39 No. 5 2012 540 NEMIROVSKAYA

(а) (b) 1.8 µm 1.8 µm

Fig. 4. Material composition of filtered particulate matter collected (a) upstream of Yaroslavl: fibers with chitotrases; (b) down stream of Yaroslavl: combustion spheres; (c) upstream of Nizhni Novgorod: spores, fine mineral particles; (d) downstream of Nizhni Novgorod: many diatoms, a mineral is in the center. alkanes, model experiments show the decomposition tion in humusrich sediments in the course of their rate of benz(a)pyrene, the most carcinogenic pol diagenesis or during dehydration of steroids by micro yarene (BP), is 53 and 5.6% of the original amount per organisms [25, 29]. In water areas, where there is no hour [6]. All those processes result in that BP in PAH direct anthropogenic input, the share of PH in PAH is a minor component (Fig. 6). A dominating compo can reach 60% [35]. At N(naphthalene) /Ph ratios < 1, nent of PAH is pyrene (P), which accounts for 10 to there is direct oil input [33]. H is among the most 34% of the total. In areas with direct anthropogenic labile PAH. It rapidly decomposes in water; therefore, input, pericondensated polyarenes form in combus it was recorded only in individual stations. tion processes [25]. The low values of FL (fluoran Near Tolyatti, the concentration of PAH in BS thene) to P ratio (<1) indicate to the input of new mass increased against the background of decreasing pyrogenic PAH. As polyarenes decompose, the share Corg concentration. In the 1950s, PAH flux into the of more stable homologue FL increases. Moreover, the environment was maximal, since coal was used as fuel shares of phenanthrene (PH) and perylene (PL), [25]. Therefore, the concentration of polyarenes takes which have natural origin, are higher in BS. In rela place in the subsurface BS layers [36]. PL dominates in tively clear areas, PH forms during OM transforma the BS of the Oka and within BS mass near Tolyatti.

WATER RESOURCES Vol. 39 No. 5 2012 VARIATIONS IN DIFFERENT COMPOUNDS IN VOLGA WATER, SUSPENSION 541

Table 3. The concentrations of Corg and AHC in surface BS layer Sta Moisture HC, % Location Soil type Corg, % HC, µg/g PAH, ng/g tion content, % of Corg 1 Gorodets T. Gray silt 1.660 65.92 121.4 0.59 32 2 Upstream of Nizhni Novgorod Sand 0.029 19.95 6.7 1.85 Was not determined 3 Oka R. mouth '' 0.048 14.0 3.0 0.50 Was not determined 4 Donwsream of Cheboksary '' 0.009 4.9 4.36 Was not determined 5 Kama R. mouth Ñåðûé èë 1.690 50.9 46.8 0.28 33 6 Kama R. mouth The same 1.856 47.7 18.6 0.10 35 7 Kama and Volga water mixing '' 2.133 47.29 34.9 0.16 33 8Tolyatti roadstead '' 1.937 46.12 107.4 0.55 145 9 Downstream of Syzran Sand with shell 2.46 51.18 50.9 0.22 Was not determined 10 Volynsk T. roadstead Oxidized silt 1.789 49.5 71.3 0.40 Was not determined 11 Upstream of Bokakovo T. Brown fine sand 0.016 19.29 10.6 5.30 16 12 Bol'shoi Irgiz R. mouth The same 0.031 32.83 4.02 1.03 26 13 Upstream of Saratov C. '' 0.012 19.33 21.7 14.47 57 14 Upstream of Kamyshin T. Gray silt, red 1.789 49.5 71.3 0.40 85 from the top 15 Kamyshinka R. The same 3.899 50.24 485.4 1.24 178 16 Downstream of Volgograd C. Gray silt, red 0.136 16.55 2.40 0.14 13 from the top 17 Tsagan V. Sand with black 0.036 17.43 4.50 1.00 21 inclusions 3u Akhtuba R. (Dzhanai V.) Silty sand with 0.245 23.2 33.1 1.08 12 shell 7u Sarobelinskii Bank Silty sand 0.359 20.0 20.2 0.44 2 6u Zheltaya Branch (3 km from Black thin sludge 0.499 33.5 2.0 0.03 Was not determined Sarobelinskii Bank) 9u Belinskii Bank Dark silty sand 0.029 20.9 2.0 0.55 Was not determined (left from fairway) 11u Kamazyak Branch (Tabola) Fine bleached 0.012 18.7 16.1 10.71 Was not determined sand with shell detritus 12u Kamazyak Branch Sandy silt with 0.150 26.8 9.8 0.52 Was not determined (Verkhnekalinovskii V.) loam 14u Dug canal (challel) Fine washed sand 0.018 17.8 2.0 0.89 Was not determined 15u 3 km upstream of st. 14u, Dark silty sand 0.091 25.6 9.7 0.85 Was not determined in a branch 16u Old Volga Branch Fine washed sand 0.011 18.9 2.1 1.45 Was not determined (Chaganskii rift) 19u Gandurinskii Bank (5 km from Loam with fine 0.006 19.7 25.3 33.81 Was not determined the outlet into the sea), sand channel 20u Gandurinskii Bank Fine sand 0.155 28.1 19.0 1.00 29 (in the lagoon) 21u Gandurinskii Bank, Silty sand 1.348 54.5 43.0 0.26 29 in clear water 22u Bay left of st. 19 The same 1.192 44.1 28.1 0.19 252 23u Branch left of st. 19 Sand with loam 0.38 32.7 23.0 0.47 120 24u 7 km downstream of st. 19 Dark clay 0.81 35.4 29.2 0.29 24 (channel)

WATER RESOURCES Vol. 39 No. 5 2012 542 NEMIROVSKAYA

% (а) % 14 40 1 12 1 25 2 2 10 30 3 8 25 4 6 20 4 15 2 10 0 16 18 20 22 24 26 28 30 32 5 % Number of carbon atoms 0 NPHANFLPChrPLBP 18 (b) 16 3 14 4 Fig. 6. The composition of PAH in sediments: (1–4) sta 12 5 tions 7, 8, 22u, and 23u, respectively (the positions are 10 6 given in Table 3); N is naphthalene, PH is phenantreme, 8 AN is anthracene, FL is fluoranthene, P is pyrene, Chr is 6 chrysene, PL is perylene, BP is benz(a)pyrene. 4 2 0 production, a decrease was recorded in the volumes of 16 18 20 22 24 26 28 30 32 34 36 polluted wastewaters discharged into water bodies and Number of carbon atoms atmospheric emissions of gases from industrial plants. The summarized data on the major pollutants [18] Fig. 5. The composition of alkanes isolated from sedi show that the discharge of all their types in the Volga ments: (1–6) stations 8, 14, 3u, 7u, 19u, 21u, respectively basin has decreased (Table 4). In particular, by year (the positions are given in Table 3). 2000, the input has decreased 2.3 times for oil prod ucts, 1.5 times for phosphorus, 6.2 times for iron, The most likely source of PL is peat decomposition 3.2 times for chromium, and 1.7 times for zinc. The products transported by rivers [30]. The change in the result was that the environmental conditions of water reduction–oxidation conditions in sedimentation is and atmospheric air in the Volga basin somewhat reflected in the distribution of this polyarene in BS improved. The least was the decrease in the discharge mass [25, 32, 33]. of suspended matter (as little as 1.15 times); the con centration of suspension content was not found to Thus, summing up the results of the research, we increase downstream of cities. Oil fields were recorded can conclude that changes in the concentrations of the only at dams and near berths of cities (Kazan, Volgo examined compounds were governed by natural pro grad, etc.). The concentrations of not only AHC, but cesses all over the expedition route in the summer of also heavy metals decreased in surface waters. All 2009. The Volga flows almost along the meridian from along the expedition route, no rise of concentration the north to the south, i.e., in its more than 3 thousand above MAC was recorded for Al, Ni, Pb, and Zn. It is km course it successively crosses all natural zones of only in the upper reaches of rivers, that MAC for Fe European Russia (except for the Arctic one)—the and Mn were exceeded 1.52 times and those for Cu, coniferous and broadleaved taiga, forest steppe, 1.5–3 times [20]. Earlier, the values of MAC were steppe—and ends at the boundary of the desert zone. almost regularly exceeded for Cu and Mn and some Conversely, the annual runoff gradually decreases in times for Fe and Zn in the Ivankovo, Gorki, and the latitudinal direction in accordance with changes in Kuibyshev reservoirs, though no anomalously high climate dryness [1]. Since all rivers of the area receive concentrations were recorded [17]. In the lower mostly snowmelt nourishment, they show extremely reaches of the Volga, an increase in water mineraliza nonuniform runoff distribution within the year. At the tion was accompanied by Al, Ni, Zn and sometimes confluence of the Volga with its tributaries, diffusion Mn and Cd exceeding their MAC. However, the level and dilution play the main role. of concentration of some hazardous elements gener The distribution of pollutants was of local charac ally decreased relative to earlier determinations and, ter. In the Middle Volga, which receives the largest according to data in [17], this tendency still persists. tributaries of the Oka and Kama and experiences the On the other hand, the ecological situation cannot largest anthropogenic impact, the production pro be regarded as safe, because pollutants (oil and pyro cesses are suppressed and destruction ones are intensi genic HC) accumulated in sediments. The process of fied [15]. The comparison of major hydrochemical delta degradation, especially avandelta, which has characteristics also demonstrated the maximal differ become more rapid recently and which manifests itself ence between their current values from those mea in the increasing erosion of the outer delta margin sured before the 1990s [5]. During the abrupt drop of because of the construction of dams and levees [27],

WATER RESOURCES Vol. 39 No. 5 2012 VARIATIONS IN DIFFERENT COMPOUNDS IN VOLGA WATER, SUSPENSION 543

Table 4. Total masses of pollutants, t, discharged with wastewater into rivers and reservoirs of Volga basin (processed data given in [15])

Year Pollution type 1995 1996 1997 1998 1999 2000

Volume of polluted wastewaters* 12128.4 11502.2 11416.2 113.19.2 11200.2 11170.2 Discharges of organic matter

by BODtot 171956.8 157077.2 139509.1 124739.8 126231.6 128308.5 particulate matter 199793.0 192110.7 175465.7 182242.6 193516.3 174309.6 oil products 5829.7 4471.8 3968.0 2988.1 3213.9 2541.2 phenols 27.3 20.2 16.2 16.8 12.6 16.2 synthetic surfactants 1932.3 1812.9 1585.7 1454.5 1217.6 1054.6 sulfates 1224.7 1039.0 1085.2 953.4 887.2 852.9 chlorides 1895215 1500438 1463260 1451199 1660850 1744228 ammonium nitrogen 53820.2 49254.0 47570.2 42830.6 39855.6 39434.8 nitrites 4516.2 6961.6 4498.0 9775.4 4257.5 3906.5 nitrates 10645.5 117294.8 127087.4 126126.2 146499.6 133322.0 phosphorus 19790.8 14429.4 16113.8 15615.0 14864.7 12981.6 iron ions (total) 21912.7 14182.8 14970.8 7152.0 5186.0 3556.6 copper ions 139.3 117.7 125.3 82.1 72.4 58.7 chromium ions 172.0 140.3 157.0 100.5 107.3 53.4 zinc ions 463.4 431.6 414.9 335.9 336.5 280.7

Notes: * Million m3. could not but affect the concentrations and composi rivers of Nemda, Unzha, Oka, Kama, Bol’shoi Irgiz tion of pollutants in sediments. Therefore, unlike with the Volga, the major factor of variations in the water, which is more predisposed to seasonal varia mean solute concentrations along the river is the dilu tions, sediments serve as a natural accumulator of pol tion of Volga water by waters coming from tributaries. lutants [13]. HC concentrations in the BS of Volga In such cases, the greater water flow in the tributaries, delta have also dropped relative to the summer of the longer the mixing zone. 2003: AHC concentration decreased 5 times (from The mean BOD5 was 3.3 mg/l, which is higher than 150 to 30 µg/g), and that of Corg, 2 times (from 0.36 to 0.16%). This is due to the decay of oil HCs not only in the MAC for municipal–drinking water supply water mass, but also in the surface BS layer. The activ (2 mg/l), but lower than the MAC for water bodies of ity of oiloxidizing microorganisms reaches 57 ng/(l h) cultural–domestic water use (4 mg/l). The highest val during the hydrological winter and 80 ng/(l h) in sum ues were recorded in areas not related to urban activi mer [7]. ties and they seem to be caused by the decay of natural organic compounds produced by phytoplankton. Low concentrations of suspension in surface water CONCLUSIONS (3.5 ± 2.9 mg/l) are typical of summer lowwater The mineralization of Volga surface water increases period. No increase in the amount of suspension was from Konakovo Town to the delta from 190 to recorded after cities. Dominating in the composition 450 mS/cm. In the examined sites of confluence of the of suspension are natural biogenic and mineral forma

WATER RESOURCES Vol. 39 No. 5 2012 544 NEMIROVSKAYA

tions, ash particles were detected after a rain only near the Volga River and Its Reservoirs, Voda: Khimiya i Yaroslavl and Tolyatti. Ekologiya, 2010, no. 11, pp. 2–12. 2 The mean AHC concentrations in surface water 6. Izrael’, Yu.A., Tsyban’, A.V., Panov, G.V., et al., Cur (16.4 µg/l) corresponded to their background level in rent State of Marine Ecosystems in the Russian Feder coastal water areas and practically coincided with their ation, Meteorol. Gidrol., 1993, no. 9, pp. 6–21. 2 concentrations determined earlier [18]. In recent 7. Il’inskii, V.V. and Semenenko, M.N., Rasprostranenie i years, a decrease in the concentrations of oil HCs was aktivnost' uglevodorodookislyayushchikh bakterii v Kar recorded in Volga water. skom i Belom moryakh. Opyt sistemnykh okeanolog icheskikh issledovanii v Arktike (Occurrence and Activ The concentration of AHC in BS varied from 24 to ity of HydrocarbonOxidizing Bacteria in the Kara and 85 µg/g, and that of PAH varied from 2 to 252 mg/g. White Seas: Experience in Systems and Oceanological The accumulation of pollutants in BS leads to an Studies in the Arctic), Moscow: Nauch. mir, 2001. increase in the concentrations of oil and pyrogenic 8. Kitaev, A.B., Oxygen Regime of the Kama and Votkinsk highmolecular HCs in coarse sediments because of Reservoirs under Current Technogenic Load, Funda passive sorption. mental’nye Issledovaniya, 2009, no. 5, pp. 48–51. 2 9. Kochetkova, M.Yu., The Formation and Transforma ACKNOWLEDGMENTS tion of Water Quality in the Gorki and Cheboksary Res ervoirs, Extended Abstract of Cand. Sci. (Geogr.) Dis The author is grateful to the participants of the sertation, Moscow: Institute of Geography, RAS, 2009. expedition: V.A. Artem’ev, L.V. Demina, and 10. Kravchishina, M.D., Vzveshennoe veshchestvo Belogo N.G. Chernyavskii (IO RAS); A.V. Kotlyakov and morya i ego granulometricheskii sostav (Suspended Mat L.A. Khrustaleva (WPI RAS); D.A. Aibulatov (MSU) ter in the White Sea and Its Granulometric Composi for his help in sampling and data processing, as well as tion), Moscow: Nauch. mir, 2009. G.I. Sychkova and Z.M. Verkhovskaya (IO RAS) for 11. Kravchishina, M.D., Novigatskii, A.N., Politova, N.V., HC analyses; L.S. Shirokova (University of Tuluza, et al., Studying Water Suspension in Volga Delta during LMTG Laboratory) for the analysis of DOC; Spring Flood (May 2008), in Geologiya morei i okeanov V.F. Brekhovskikh (WPI RAS) for the presented sam (Geology of Seas and Oceans), Moscow: GEOS, 2009, ples of bottom sediments taken in Volga delta. vol. 3, pp. 307–312. 2 This study was supported by the Russian Founda 12. Lisitsyn, A.P., Fluxes of Suspended Matter and Pollu tion for Basic Research, project no. 110500456a; tion in the World Ocean and Methods of Global Moni Presidium RAS, program 21; grant of RF President, toring, in Vekhi krizisa (Stages of Crisis), Moscow: NSh 3714.2010.5); Project “Nanoparticles in Inner Nauka, 2004, issue 2, p. 133–193. and Outer Earth Envelopes.” 13. Lisitsyn, A.P., Processes in White Sea Drainage Basin: Preparation, Transportation, and Deposition of Sedi mentary Material, Matter Fluxes, the Concept of “Liv REFERENCES ing Watershed,” in Sistema Belogo morya T. 1 (White Sea System, Vol. 1), Moscow: Nauch. mir, 2010, 1. Abdurakhmanov, G.M., Karpyuk, M.I., Morozov,B.N., pp. 353–445. 2 and Puzachenko, Yu.G., Sovremennoe sostoyanie i fak tory, opredelyayushchie biologicheskoe i landshaftnoe 14. Lyutsarev, S.V., Determining Organic Carbon in raznoobrazie VolzhskoKaspiiskogo regiona Rossii (The Marine Bottom Sediments by Dry Ignition, Current State and the Factors that Govern the Biologi Okeanologiya, 1986, vol. 26, no. 4, pp. 704–708. 2 cal and Landscape Diversity of the Volga–Caspian 15. Mineeva, N.M., Results of Studying Plankton Primary Region of Russia), Moscow: Nauka, 2002. Production in Volga Reservoirs, Biologiya Vnutrennikh 2. Artem’ev, V.A., Taskaev, V.R., Burenkov, V.I., and Vod, 2007, no. 2, pp. 42–49. 2 Grigor’ev, A.V., Universal Portable Set for Measuring 16. Mnogoletnie dannye o rezhime i resursakh poverkhnost the Vertical Distribution of Light Extinction Factor, in nykh vod sushi (LongTerm Data on the Regime and Kompleksnye issledovaniya Mirovogo okeana: Proekt Resources of Continental Surface Water), Leningrad: “Meridian”. Ch. 1. Atlanticheskii okean (Multidisci Gidrometeoizdat, 1986, vol. 1, issue 23. plinary Studies of the World Ocean: “Meridian” 17. Moiseenko, T.I., Kudryavtseva, L.P., and Gashkina, N.A., Project, Part 1. Atlantic Ocean), Moscow: Nauka, Rasseyannye elementy v poverkhnostnykh vodakh sushi: 2 2008, pp. 165–172. tekhnofil’nost', bioakkumulyatsiya i ekotoksikologiya 3. Galimov, E.M., Kodina, L.A., and Stepanets, O.V., (Trace Elements in Continental Surface Waters: Tech Biogeochemistry and Problems of Pollution of Russian nophilic Properties, Bioaccumulation, and Ecotoxi Seas (Case Study of the Kara Sea), in Fundamental’nye cology), Moscow: Nauka, 2006. issledovaniya okeanov i more (Basic Studies of Oceans 18. Naidenko, V.V., Velikaya Volga na rubezhe tysyacheletii 2 and Seas), Moscow: Nauka, 2006, vol. 2, pp. 440–465. (The Great Volga at the Turn of the Millennium), Nizh 4. DanilovDanilyan, V.I., Losev, K.S., and Reif, I.E., niy Novgorod: Promgrafika, 2003. Pered glavnym vyzovom tsivilizatsii (Facing the Main 19. Nemirovskaya, I.A., Uglevodorody v okeane (snegled Challenge to Civilization), Moscow: InfraM, 2005. vodavzves'donnye osadki) (Hydrocarbons in the 5. Debol’skii, V.K., Grigor’ev, I.L., Komissarov, A.B., Ocean: Snow–Ice–Water–Suspension–Bottom Sedi et al., PresentDay Hydrochemical Characteristic of ments), Moscow: Nauch. mir, 2004.

WATER RESOURCES Vol. 39 No. 5 2012 VARIATIONS IN DIFFERENT COMPOUNDS IN VOLGA WATER, SUSPENSION 545

20. Nemirovskaya, I.A., Aibulatov, D.N., Artem’ev, V.A., at R/V Meduza and E/V Sevryuga (July–September 1996), et al., Multidisciplinary Studies of the Volga River in Okeanologiya, 1997, vol. 37, no. 4, pp. 624–627. 2 the Summer of 2009, in Geologiya morei i okeanov 28. Yanin, E.P., Organic Substances of Technogenic Origin (Geology of Seas and Oceans), Moscow: GEOS, 2009, in Urban River Waters, in Ekologicheskaya ekspertiza: 2 vol. 3, pp. 329–336. Obzornaya informatsiya (Environmental Expertise: 21. Nemirovskaya, I.A. and Brekhovskikh, V.F., Origin of Review Data), Moscow: VINITI, TsEP, 2004, part 4, Hydrocarbons in the Particulate Matter and Bottom pp. 42–64. 2 Sediments of the Northern Shelf of the Caspian Sea, 29. Bouloubassi, I. and Saliot, A., Investigation of Anthro 2 Okeanologiya, 2008, vol. 48, no. 1, pp. 48–58. pogenic and Natural Organic Inputs in Estuarine Sedi 22. Ostrovskaya, E.V., Nemirovskaya, I.A., ments Using Hydrocarbon Markers (NAN, LAB, Brekhovskikh, V.F., et al., Hydrocarbons in Water and PAH), Oceanol. Acta, 1993, vol. 16, no. 2, pp. 145–161. 2 Particulate Matter near Volga–Northern Caspian Sea 30. Fernandes, M.B. and Sicre, M.A., Polycyclic Aromatic Geochemical Barrier, Yug Rossii: Ekologiya, Razvitie, Hydrocarbons in the Arctic: Ob and Yenisei Estuaries 2 2009, no. 4, pp. 150–159. and Kara Sea Shelf, Estuarine, Coastal and Shelf Sci ence, 1999, vol. 48, pp. 725–737. 2 23. Ostrovskaya, E.V., Nemirovskaya, I.A., Brekhovskikh, V.F., and Kurapov, A.A., Effect of River–Sea Geochemical 31. Jeffrey, S.W., and Humphrey, G.F., New Spectropho Barrier on the Oil Pollution of Bottom Sediments in the tometry Equations for Determining Chlorophylls A, B, Zone of Development of OilandGas Deposits in the Cj and C2 in Higher Plants, Algae and Natural Phy 1 Northern Caspian Sea, Zashchita Okruzhayushchei Sredy toplankton, Biochem. and Physiol. Pflanz, 1975, 2 2 v Neftegazovom Komplekse, 2009, no. 9, pp. 34–42. vol. 167, no. 2, pp. 191–194. 32. Page, D.S., Boehm, P.D., Douglas, G.S., et al., Pyro 3 24. Perechen’ rybokhozyaistvennykh normativov: predel’no genic Polycyclic Aromatic Hydrocarbons in Sediment dopustimykh kontsentratsii (PDK) i orientirovochno Human Activity: a Case Study in Prince William 4 bezopasnykh urovnei vozdeistviya (OBUV) vrednykh Sound, Mar. Pol. Bul., 1999, vol. 38, no. 4, pp. 247– 2 veshchestv dlya vodnykh ob"ektov, imeyushchikh 260. rybokhozyaistvennoe znachenie (List of FisheryRelated Standards: Maximal Allowable Concentrations (MAC) 33. Tolosa, I., Mora, S., and Sheikholeslami, M.R., et al., and Safe Reference Levels of Impact (SRLI) of Haz Aliphatic and Aromatic Hydrocarbons in Coastal Cas ardous Substances for Water Bodies of Fishery Signifi pian Sea Sediments, Mar. Pol. Bul., 2004, vol. 48, cance), Moscow: VNIRO, 1999. nos. 12, pp. 44–60. 2 34. UNESCO. Protocols for the Joint Global Ocean Flux 25. Rovinskii, F.Ya., Teplitskaya, T.A., and Alekseeva, T.A., Study (JGOFS) Core Measurements, IOC/SCOR Manual Fonovyi monitoring politsiklicheskikh aromaticheskikh and Guides, Paris: UNESCO Publ., 1994, no. 29, uglevodorodov (Background Monitoring of Polycyclic pp. 128–134. 2 Aromatic Hydrocarbons), Leningrad: Gidrometeoiz dat, 1988. 35. Wang, Z., and Fingas, M.F., Development of Oil Hydrocarbon Fingerprinting and Identification Tech 26. Rukovodstvo po metodam analiza morskikh vod. RD niques, Mar. Pol. Bul., 2003, vol. 47, no. 3, pp. 423– 2 52.10. 24392 (Guide on Methods of Seawater Analy 452. sis. RD 52.10. 24392), Oradovskii, S.G, Ed., St. 36. Wu, Y., Zhang, I.G., Tiezhu, M., and Bin, L., Occur Petersburg: Gidrometeoizdat, 1993. rence of NAlkanes and Polycyclic Aromatic Hydro 27. Sapozhnikov, V.F., Multidisciplinary Ecosystem Stud carbons in the Core Sediments of Yellow Sea, Mar. ies of the Northern Caspian Sea Chem., 2001, vol. 76, nos. 12, pp. 1–15. 2

SPELL: 1. Zashchita, 2. pp, 3. predel’no, 4. vrednykh

WATER RESOURCES Vol. 39 No. 5 2012

View publication stats