CHEMICAL COMPOSITION OF SURFACE WATERS OF PRIMORYE
Common information Envirionmental conditions of the territory Tumen river area Khanka Lake
Surface waters are the most sensitive part of environment which cumulate results of all processes taken place in the catchment and transmit their to the seas. Geologists, geochemists, oceanologists and biologists pay attention to the composition of dissolved and suspended matters from the continent because it helps to understand mordent and ancient sediment processes, inputting nutrients and pollutants to the sea as well as environmental conditions of the territory which can lead to genetic changes in the biological objects.
Primorye is administrative territory bordering the Sea of Japan. The territory is characterized by humid climate with annual meteoric precipitation about 1000 mm as rain and snow. This is mountain region composed of volcanic and sedimentary rocks of different ages. Some mining activity has taken place in this area.
Primorye is lesser contaminated region compared with central Russia, but in the southern part of the territory the pollution problems are quite serious. Efforts for the clean-up of water are unsatisfactory and contamination by municipal wastes, fertilizers and pesticides in agricultural regions, heavy metals from the mining industry and other sources take place.
Surface waters of Primorye were studied
in order to evaluate their compositions from different views because
there is transition zone from continent to the Pacific ocean where
erosion processes and inputs this material from catchments to the sea are
combined. There was combined data obtained during a number of years in
the field expeditions
Two main directions of this study are focused on the rivers water discharge composition and material input to the Sea of Japan on the one side as well as the environmental conditions of Primorye territory on another. Two areas (Tumen river and Khanka Lake) was studying in more detail due to special interest to it at the present time.
The total western catchment of the
Sea of Japan is about 120 thousand sq. km. It stretches along
the Sea of Japan with river catchments mostly of 2-4 thousand square
kilometers. Composition of the river input to the Sea of Japan was
studied using hydrological information and published chemical data
as well as original studies (Fig.1-1).
The total discharge of river material is about 4.3 million tons per year
composed as 2.7 million tons of dissolved matters including different groups
(Fig.1-2) and 1.6
million tons of suspended solids. The main discharge of dissolved material
as well as suspended solids is connected with warm mounhts of year (April-October).
The complex study of river material composition was made for about 20 rivers
of the catchment of the Sea of Japan (Fig.1-3)
It was found that in the western drainage area of the Sea of Japan two zones may be distinctive with some differences of drainage rocks. In the northern part (Eastern Sikhote-Alin) predominant volcanic rocks, in the southern part (catchments of Amur and Ussury Bays) - more sedimentary deposits.
After calculation an increasing of suspended matters and dissolved materials discharge per unit catchment area was found in the southern part but total component discharge is higher in the northern part. The extend of weathering is greater to the south: kaolinite and smectite minerals were only found in those area as well as finer size suspended and bottom material (Chudaeva, 1979; Chudaeva, Chudaev, 1982).
Concentrations of Corg in suspensions of western Russia catchment area of Japan Sea are 2.1 - 10.2 % from concentrations of suspended matters. Opposite correlation was found between organic matters concentrations and suspended sediments (Fig.1-6). In the southern zone concentrations of Corg (%) lesser compared with Western Sikhote- Alin. Because of higher suspended contents and concentrations of the total Corg (mg/l), discharge of Corg (mg/sq. km) in the southern zone is higher (Chudaeva,1980).
Concentrations of S in suspensions
are 102 - 103
It seems that the main form of S in suspensions is organic one because
S concentration is higher then in main rock minerals and some correlation
between Corg sus and
Ssus was found (Fig.1-7).
In the total discharge of S to the Sea of Japan only 2.8 % bring as Ssus and main part as SO4 form.
There are some distinction in concentrations
of the base elements in the southern and northern zones.
Discharge of Nasus from northern and southern zones are about 10 and 25% from total (suspended and dissolved) concentrations respectively, Ca - 4 and 13%; Mg - 8 and 28%. Relation of Sidiss and Sisus for rivers of the northern zone is 0.85, but for rivers of the southern zone - 0.19 because of big distinction in suspension concentration in river waters.
The differences are clearly shown in the suspended solids. From the Eastern Sikhote-Alin to the catchment of the Amur and Ussury Bays an increase in suspended concentrations of Fe, Mn, Cr takes place with corresponding decrease of Zn, Cu, Ni, Pb, which are specific metals for ore minerals of the Eastern Sikhote-Alin (in spit of higher pollution in southern part which gives rising of concentrations).
Detailed study of heavy metals was made for the material inputs to the Sea of Japan. Heavy metals are natural constituents of rocks, solids, and sediments. Since the beginning industrial revolution, however, man-induced changes have altered both the quantities and the manner by which many metals are now being incorporated in sediments. Locally, metals may be present in concentrations that are potentially toxic to organisms. This presumes that a significant quantity of a given metal can be released back into water column or can be metabolized by the biota.
Dissolved metal concentrations was
found not so high because there is low river waters mineralization. No
clear differences in two part of the Japan Sea catchmant was distinct.
First of all elevating of concentrations was resulted from water pollution.
Suspended solids are characterized by higher concentrations of Zn, Cu,
Ni, Pb, and Cd, caused by metallogenic features of the region.
Special procedures have been used to predict potential mobility of any metal by partitions the total content into: (1) an exchangeable phase, (2) organic-sulfide phase, (3) easily reducible phase, (4) moderate reducible phase, and (5) residual phase (Chudaeva et al.,1982).
Results, which were obtained with described procedures are next: More then half of Fe (61%) in the river particulate material is in mobile phase (1-4) not related to the mineral lattice. Phase Fe(1) is about 4% of total contents. The organic phase of suspended iron results in about 6 %. In total discharge of Fe (dissolved and suspended) prevailed solid one and in southern part it combined with finer material.
The prevailed part (80 %) of Mnsus in the Japan sea catchment rivers exists as a mobile phase, not associated with mineral lattice. About 46 % of total suspended Mn content is an easily extracted phase(1). It is likely to assume that an essential part of Mn in suspended sediments can be subjected to desorption while the rivers and sea waters are mixed. In the southern area, discharge of Mndoss and Mnsus increases. Mnsus prevailed in Mn input to the sea is more connected with 0.01 - 0.001 mm particles in the southern zone, but in northern zone - 0.01 - 0.1 mm size material.
The mobile, easily extracted phase (46%) takes place in migration of Znsus. The organic phase of Znsus makes up 21%. The total mobile phase of Znsus is about 80%. Evidently a considerable part of mobile form of Znsus is caused by the high concentrations of Zndiss in the river waters of the region. In the northern zone 59% of Zntotal inputs to the sea as Zndiss. In the southern zone it is only 32%.
The mobile Cu phases (1-4) make up 83%. In common, Cusus is equal distributed between all described chemical phases. Discharge of Cu to the sea is more connected with suspensions. In the southern zone , discharge of Cutotal per unit catchment area prevails over it in the northern zone.
The half of Nisus is related to the mineral lattice. The distribution of Nisus in mobile phase is (1) -13%; (2) -7%; (3) -10%; and (4) -22%. The river inputs of Ni to the sea is predominantly in suspensions.
Cr up to 57% migrates as a form not connected with lattice and more then half of it related to phase (4). The organic form of Cr makes up 16.8%. The form of Cr associated with Fe, Mn hydroxides reaches 8.8%. Discharge of Crsus is higher in southern part of region. Discharge of Crsus is higher in southern part of region.
Almost 80% of Pb exists as mobile phases. The easily extracted form (1) amount to 22.9% and the form Pb precipitated by Fe and Mn hydroxides is equal to 33.1%. In the migration of the suspended lead, the organic phase results in 14.6%. On the hole, phases (1) and (2) increase in the northern area. Discharge of Pbsus is connected with 0.001 - 0.01 mm particles in the southern part and with 0.01 - 0.1 mm size in the northern part.
Concentration of Cd in river suspensions of the northern part is up to 3-9 ppm. Mobile form of Cd is about 70-90% of total Cd in suspensions.
So from this previous studies was found that nature of mobile forms are different for different phases. For example, Crsusp has lowest mobil level and its mobile phase is more connected with crystalline hydroxides which can be more difficult derived from suspension to solution. Zn is accumulated in surface layers of suspended solids and may be more easily extracted in water column. Cusus is more connected with organic matters which is more stable form and this is why Cu is more stable compared with Zn.
Investigations provided later with a little different procedure for partitioned analyses of Co, Zn, Ni, Cu, Cr, Ba, and V in other group of river sediment showed that only vanadium has a consistency in its metal incorporation over a wide range of environmental conditions.
Distribution of elements concentrations in size-fractions of river suspended solids is different but their input to the sea is more similar and is connected first of all with the main size-fractions (Fig.1-5).
Envirionmental conditions of the territory
The most part of the Primorye territory do not belong to the Japan Sea catchment but the Amur river basin which input material to the Okhotsk Sea. In order to understand environmental conditions on the Primorye territory studying of some other rivers was lead. For the central part of Primorye suspended metal concentrations connected with sulfide mineral sources is less then in the Eastern Sikhote-Alin.
Using the data obtained in the field trips and some published data of the Hydrological Survey of Russia as well as extrapolation to similar territory (Chudaeva,1994), the extend of contamination of Primorye surface waters was defined (Fig.2-1) The degree of pollution was considered for each area based upon the background values for surrounding fresh waters as well as the legally permitted concentrations for certain elements. The northern part of Primorye together with all upland areas and thinly populated places of the south do not contain any serious pollution (first degree) (photo 5-7). The greater part of the territory of southern Primorye is moderately contaminated: an increase in concentrations of one or more components above the background of surrounding fresh waters was found (second degree). In some places municipal or factory wastes input a lot of contaminating components to the surface waters (third degree). These areas mainly connected with the towns (Vladivostok, Ussuriysk, Partizansk, Dalnerechensk, Lesozavodsk, Spassk, Dalnegorsk), as well as mining activity elsewhere. The type of chemical impact on the waters was studied for Rudnaya river, the most contaminated stream in the Eastern Sikhote-Alin. Here the mines and factories contribute some wastes to the Rudnaya river that made significant changes in concentrations of the main chemical components. The ratios and amounts of the major ions also differ considerably to the natural background. The changes in the levels and forms of heavy metals in the Rudnaya river were also observed (Arzhanova et al,1995). Main control on the decrease on concentrations of heavy metals is dilution with water from clean tributaries. There rather high concentrations of heavy metals both in solutions and suspensions (Fig.2-2). The role of mobile forms of metals in the Rudnaya river is greater then in others of the Eastern Sikhote-Alin (Fig.2-3). Metals in mining suspensions also entered the river sediments as detrital minerals (Voroshilova, Ylpatyevsky, 1976) and possibly also as dissolved and particulate mobile forms of metals which are transported to the sea. Towards the mouth of the river the mobile forms correlation becomes similar to the other rivers but the concentrations are higher and a large amount of this metals reach the Sea of Japan as dissolved and suspended (mainly 0.01-0.1 size fraction) forms. Fortunately this is not a large river (catchment =1140 sq. km) and it contributes to the Sea of Japan not more then 1% of total water discharge from the Eastern Sikhote-Alin.
Razdolnaya river is the biggest river of Japan Sea catchment in south part of Primorye. If in upper part of the catchment it is not so contaminated, Ussuriisk city is located in central part inputs a lot of the chemical elements.
In the central part of Primorye Bolshaya Ussurka river was special investigated. Most part of the catchment is low populated and quite beauty but some mining activity takes place in the territory, mainly on the Dalnaya river catchment, tributary of B.Ussurka. It was found that there concentrations of heavy metals (dissolved and suspended) are lower then in the Japan Sea catchment rivers but in some sections (Melnichnoe, Vostok) concentrations may be elevated. Because of little discharge of Dalnaya river, inputs of 227.4 t/y Fe, 13.9 t/y Mn 38.3 t/yZn, 15.5 t/y Cu, 3.3 t/y Ni 0.36 t/y Pb, 0.79 t/y Cd, and 0.36 t/yCr in dissolved form as well as 2830 t/y Fe, 59.5 t/y Mn, 13.4 t/y Zn, 4.8 t/y Cu, 2.76 t/y Ni, 1.05t/y Co, 4.63 t/y Pb, 0.12 t/y Cd, and 0.36 t/y Cr in suspended form rough calculated for mine drainage waters is visible for tributary of B.Ussurka.
Tumen river area
The chemical composition of the surface and ground waters in the Russian territory close located to the Tumen river is the subject of special interest because the cross-border of three countries (Russia, Korea and China) is there, and the territory is planned under active development. In the discussed material all existing data obtained some years ago are used. Now they are quite important to be a base level in the estimation of the water chemical changes in nears future.
The data on chemical composition of the Tumen river are not substantial. Single data shows that the river water is HCO3-Ca with TDS less then 200 mg/l.
We collected data for the surface waters of the S-E slope of the Chornii mountains of the Russian territory. Because the N-W slope of these mountains locates in the Chinese territory, and is a part of the catchment of the Tumen river, we can extrapolate our data on this part of the catchment.
The main features of the surface waters
in the studied territory are: low salt concentrations, high O2,
low organic matter contents (2-12 mg/l), HCO3-Ca composition
and pH of about 7.
Calculation of average composition and monthly discharge of the main ions with surface waters showed main salt discharge from May until October (more than 80%) (Fig.3-4, 3-5). It is close to the water discharge distribution (Fig.3-6).
Studies of dissolved and suspended heavy metals in the surface waters gave us a knowledge of lesser levels of Fe,Mn,Cu,Zn,Ni,Pb,Cd concentrations in the surface waters compared with some other parts of Primorye.
forms of the distribution of heavy metals in the suspended solids of the
rivers was investigated using successively stronger reagents.
The main form of suspended Fe is crystallized oxides and residual
stable form (Fig.3-7). Mn more often is connected
with an easily mobile phase, but other forms take visible place, too
(Fig.3-8). Suspended Zn migrates mostly as an
easily extracted form (Fig.3-9). For Cu all discussed
forms are important in the process of migration (Fig.3-10).
Ni and Cr are more associated with stable, residual forms. Pb is actually more connected with Fe and Mn hydroxides in the suspensions but other discussed forms maybe present, too.
territory as a total is not actively polluted in its surface waters
if compared with some other places of Primorye.
Khanka lake was studied in detail (photo
8 ). Its catchment area is 15,400 km2
and water square is 4070 km2.
This is rather shallow lake with a maximum depth of 5-6 m. Five rivers
and several little streams provide inputs to the Lake and one river discharges
to the large Amur river basin. Lake Khanka is a boundary lake with China
but the most part of it catchment and water surface is within Russian
Group of problems arose with unsatisfactory using of agricultural lands around the Lake (Fig.4-1), Some waters pollution problems are connected with pesticides, sometimes heavy metals, phenols, and petroleum products (Chudaeva, 1996). Maximum pesticide contamination (sum of chlorinated hydrocarbons: DDT, DDE, DDD, lindane) was indicated in fore streams: Spassovka, Bolshie Usachi, Vtoroi Erik, and Kazachii Erik (up to 0.5-1 ug/l) (Fig.4-2). Concentrations of 0.1-0.5 ug/l ware found in most part of the lake with more then 0.5 ug/l close to the mouth of Spsssovka river. Pesticide contamination was connected with agriculture and mainly with rice fields.
The water runs over the surface and carries away exposed topsoil and nutrients (Fig.4-3,4-4). In all rivers of the catchment and in the lake components of fertilizers was found and an increase of P(PO4) in some rivers and Lake had occurred. During field studies it was found that dissolved and suspended concentrations of P in the lake, as a rule, were higher then in streams. Only in two rivers, Bolshie Usach and Spassovka, total (dissolved and suspended) concentrations of P were higher then in the lake: >2g/l. Relatively high concentrations of N were found in all rivers of the catchment and in the lake water. The main form was N-NH4 up to 3-5 time higher then Russian admitted level (0.39 mg/l). In the rivers of Bolshie Usachi and Spassovka, concentrations of nutrients (N, Corg) were sometimes much higher. Calculation of input of N and P in the lake and discharge from the lake through the Sungach river shows the largest part of nutrients stain in the lake. The high concentrations of nutrients usually cause eutrofication of reservoirs. It is possible that high concentrations of suspended sediments is the factor controlling eutrofication of Khanka lake. However in the recent years increase in green algae populations has been observed more then ones.
Another kind of the chemical contamination is connected with heavy metals. There are some natural reason for heave metal fluctuations in concentrations and in form of migrations. However, part of the heavy metals comes to the lake from industrial and municipal wastes of Spassk city and municipal wastes of the villages. In the lake water total (dissolved and suspended) concentrations of heavy metals were found to be higher then in the rivers. It means that accumulation of heavy metals takes place in the lake. The Hydrological Survey that led to monitoring of some chemical components in the water sometimes recorded pollution of Spassovka river by phelols and petroleum products as well as other chemicals. Last years due to the economic difficulties industrial activity was down and the ecological situation in the Khanka Lake area became to improve.
Some data obtained for the Primorye surface waters together with colleagues from the British Geological Survey during INTAS project and from South Alabama University show results been closely related to the scheme described above (Fig.2-1).
Arzhanova V.S., Chudaeva V.A., Ylpatyevsky P.V. The relationships
of the natural and pollution-originated constituents in the discharge of
the Rudnaya river, Sea of Japan catchment, Russia. //Proc. Symp. Water-Rock
Interaction-8 (Ed. Kharaka Y.K., Chudaev O.V.). Rotterdam.:Balkema. 1995.
Chudaeva V.A. Material characteristic of river discharge of west part of Japan sea basin //Geochemistry and mineralogy of sedimentary complexes of Far East. Vladivostok.:DVNC. 1979. P.151-171(in Russian).
Chudaeva V.A. Organic matters in rivers suspensions // Geochemistry and petrochemistry of sedimentary complexes of Far East. Vladivostok.: DVNC. 1980. P.129-135(in Russian).
Chudaeva V.A.,Gordeev V.V., Fomina L.S. Forms of elements in rivers suspensions of Japan Sea catchment. // Geochemistry. 1982. No 4.P. 585-596 (in Russian).
Chudaeva V.A., Chudaev O.V. Some features of river solid material of the SW Primorye. // Sedimentary and quaternary morpholitogeneses of the Far East. Vladivostok.:DVNC. 1982. P.118-130 (in Russian).
Chudaeva V.A. Metal contamination of surface waters of Primorye // Mineralogical magazine. 1994. V.58A. P.169-170.
Chudaeva V.A. Some ecological problem of the Khanka Lake in the Russian Far East //Environmental pollution. 1996.V.1.P.373-380.
Voroshilova Z.G., Ylpatyevsky P.V. Role of tecnogeneses in distribution of minerals in bottom sediments // Geochemistry of hypergenesic zone and people technical activity. Vladivostok.:DVNC.1976. P.57-64(in Russian).
VALENTINA CHUDAEVA, Pacific Institute of Geography Far East Branch Russian Academy of Sciance