ХИМИЯ НА МОРЕТО on the Recent Dynamics of Some Chemical
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13 Трудове на Института по океанология Том 3. Варна, 2001 Българска академия на науките ХИМИЯ НА МОРЕТО On the recent dynamics of some chemical parameters along the Bulgarian sector of the Danube River Alexander Stoyanov, Galina Shtereva, Anton Krastev, Ognyana Hristova, Lidia Mihova, Ilia Shterev Institute of Oceanology, Bulgarian Academy of Sciences, Varna, Bulgaria Along the main factors influencing The main contributors of pollution are: negatively the Black Sea ecosystem the industry (72.0 %), agriculture (10.2 %) and Danube river could be considered the key transport (3.7 %) - Fig. 1. The industry is one contributor with its annual flow of about 200 of the main consumer of water, over 93.0 % - 202 km3 draining an area of about 817 000 of the total amount is used for the km2, e.g. exceeding almost twice the surface manufacture. Typically high water consuming area of Black Sea itself. The indirect branches are: the energetic (86.5 %) and the “Bulgarian share” in the pollution of Black chemical, petroleum and rubber industry (4.5 Sea originated from a catchment area of 49 %). Among the other branches of the national 600 km2, e.g. 6 % of the total Black Sea economy agriculture utilizes about 5.8 % of watershed with an annual flow of 1.8 km3 per the total amount of the water used (including year. 4.4 % for irrigation). The building industry, More important among the Bulgarian forestry, transport and communication have Danube tributaries are the following river an insignificant share in water consuming. valleys: Lom, Ogosta, Iskar, Vit, Ossam, From the total amount of the discharged Yantra and Russenski Lom. Smaller, shorter waste waters into the main Danube river and of low water flow are the rivers: tributaries the industrial waste effluent Topolovetz, Voinishka, Vitbol, Archar, accounts for more than 78.2 %, the transport - Skomlia, Tzibritza, Suhodolia, Topchijska, 4.8 %, the municipality industry - 11.8 %, the Senkovetz, Karagiol and Suha. agriculture - 4.8 % and the building industry - The Bulgarian part of the Danube river 1.0 % respectively (K r a s t e v, watershed covers 42 912.6 km2, e.g. K r a s t e v a, S t o y a n o v, 1995). accounting for about 38.69 % of the country From all the drained waste waters 98.7 % area. The population inhabiting the Danube are not treated. The different industry river catchment area has increased in number branches account for about 93.7 % of the from 3 003 506 in 1934 to 3 766 298 people total untreated waste waters discharged into in 1992. The density of the population was the Danubian tributaries, ranked in the highest in 1985 - 3 969 604 inhabitants, e.g. following order: energetic, electricity and 44.35 % from the total population of the heat production - 87.5 %, chemical and country (Y e a r B o o k.., 1991). petroleum industry - 4.2 % and food industry - This region is characteristic with a variety 0.6 % (Fig. 2). of industrial and economic activities. Both the agriculture and forestry are 14 14.1% 3.7% 10.2% Industry Agriculture Transport Others 72.0% Fig. 1. Main contributors of pollution Energetic, electricity and heat 5.8% 1.9% 4.2% 0.6% production Chemical and petroleum industry Food industry Agriculture and forestry Others 87.5% Fig. 2. Untreated waste waters discharged into the Danubian tributaries along the Bulgarian sector responsible for about 5.8 %. Of the total waters by the food industrial plants (27.5 % pollutants discharged into the Danube river of the total). The negative effects of this drainage basin (1 564 000 kg per day) 78.2 % industry is best expressed over the river Vit are industrial contribution of the chemical and waters in its middle and lower course in petroleum industry in particular (13.4 %). particular - accounting for over 86.3 % of the The discharge from the latter is highest into pollution. The cellulose - paper making the rivers: Ogosta -28.5 %, Russenski Lom - industry accounts for about 4.5 % of the total 27.0 %, Ossam - 15.9 % and Iskar - 12.1 %. pollution of the river waters. The influence is The industrial plants responsible for the strongest upon the Iskar river (24.0 % of its highest pollution are: the oil industrial plants total pollution) and upon the Ossam river - in Pleven and Russe towns, the poliamide 17.6 %. The leather furrier industry together fabric plant in Vidin, the chemical firm with the bootware manufacture are another “Himko” in Vratza, the chemical plants in serious pollution source of the Danube river Sofia (Ravno pole), “Sviloza” in Svishtov, the drainage basin, accounting for about 4.2 % of pharmaceutics plant (antibiotics) in Razgrad, all total pollutants. The impact of this the chemical firm “Latex” in Bialla and the industry is strongest on the Yantra river and chemical industry plants in Silistra. its tributary Rossitza. The textile industry Of all wastes, especially the solid ones, accounts for 1.1 % of the total waste water the greatest share is discharged into the river discharge to the Iskar river and for about 7.1 15 % to the Ogosta river. The wood - processing POC, nutrients ( P 3− , N − , N − , industry in Troyan, Belli and Cherni Ossam PO4 NO2 NO3 discharges its waste waters into the Ossam N + and Si ), metals ( Fe and Mn ), total river accounting for about 6.3 % of the NH 4 overall pollution of the river (K r a s t e v, suspended matter in the Danube river at K r a s t e v a, S t o y a n o v, 1995). station Silistra on monthly to weekly The comparison between the data periods sampling frequency. All parameters are 1975-1980 and 1981-90 shows that the analyzed by standard methods (L u r e, 1973, nutrien content in all the rivers increases P o t a p o v a, 1980) during the second period. This increasing is The variability of dissolved oxygen is considerable in the river Iskar, Ossam, Yantra closely related to the temperature changes and Russenski Lom under the influence of the (Fig. 3), only the cases of oversaturation agriculture, industrial and municipal waters respond to Chl. a maxima (S t o y a n o v et (Table 1). al., 1997). Its values are in the range from The total input of nutrients from the 5.51 to 14.38 ml/l. The maximum in March is Bulgarian watershed into Danube river for the considerably higher than absolute maximum period 1992 - 1993 is following: 7 720.10 (10.36 ml/l) for long-term monitoring 1950- tons 1985 (R o z h d e s t v e n s k y, 1991). per year of N + , 25 505.38 tons per year of The nutrients dynamic follows the hydro- NH 4 meteorological features of the period with significantly higher concentrations in winter. N − and 2 476.96 tons per year of P 3− . NO3 PO4 The minimum values are during the summer period closely related to the increase in The results reveal that N + totally NH 4 temperature, the decrease of water level and increase of biological uptake. decreases in all rivers. Decreasing of N − NO3 During our studies the maximum of phosphate phosphorus (0.09 mg/l) was and P 3− is established in the most of the PO4 established in December and the absolute rivers and that could be related both to the minimum (0.02 mg/l) - in August. Relatively high concentrations of phosphates were reduction in the capacity of the industrial established in February and March (Fig. 4). production and to some new waste waters This is due to the extensive rainfall during the treatment plants putting into operation. long winter period. Therefore, the minimum The scientific study of the Danube river is shifted to August instead of May-June by water chemistry and its influence on the R o z h d e s t v e n s k y (1991). Black Sea chemistry was conducted by The maximum nitrite nitrogen Institute of Oceanology since 1950 at st. concentration during the 1975-80 period at Russe (R o z h d e s t v e n s k y, 1962, Silistra is 20 µg/l at high level of the river in 1979, 1985, 1986, 1991, 1998). May-June, and the minimum is 11 µg/l - at The aim of our investigations is to assess low level in August (T s a n k o v, the current status were conducted during the P e c h i n o v, 1990).The absolute maximum period July 1995 - June 1996 on the base of of N − during our study is 83 µg/l in April. determination of the main chemical NO2 parameters: dissolved oxygen, alkalinity, The absolute minimum 1 µg/l is registered in Table 1. Average data of nutrient content in the rivers from Bulgarian watershed River NH4 ,mg/l NH4 ,mg/l NO3,mg/l NO3,mg/l PO4 ,mg/l PO4 ,mg/l 1975-90 1992-93 1975-90 1992-93 1975-90 1992-93 Ogosta 6.00 2.80 11.70 6.77 0.23 0.15 Iskar 1.38 0.89 13.00 4.89 0.38 0.28 Vit 4.23 2.60 3.29 4.01 0.65 0.68 Ossam 0.98 0.87 7.63 5.32 0.42 0.19 Yantra 1.70 1.05 4.06 4.56 0.41 0.72 Rus.Lom 9.30 1.96 22.06 3.09 1.69 1.71 16 October.