Assessment of Organic Pollutants in Sediments from Maritsa River Basin (Bulgaria) V.M
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Bulgarian Chemical Communications, Volume 49, Special Issue G (pp.231 –236) 2017 Assessment of organic pollutants in sediments from Maritsa River basin (Bulgaria) V.M. Genina1,2*, G.M. Gecheva1, I.G. Velcheva1, M.I. Marinov3 1 University of Plovdiv, Faculty of Biology, 24 Tsar Asen Str., Plovdiv 4000, Bulgaria 2 Executive Environmental Agency, branch Plovdiv, 1 Perushtitsa Str., Plovdiv 4000, Bulgaria 3 East Aegean River Basin Directorate Plovdiv, 35 Yanko Sakazov Str., Plovdiv 4000, Bulgaria Received November 13, 2016; Revised January 5, 2017 Sediments were sampled from 5 sites from the Maritsa River basin in the period 2013-2014 with the aim to assess effects of the anthropogenic pressure caused by the pesticides production and by the intensive agriculture. Sites were located in the middle part of the Maritsa River basin (near Plovdiv city) and the watersheds of Chepelarska and Stryama rivers. Methods for analysis of certain priority substances and specific pollutants were applied in order to establish trends in the accumulation in sediments, as required by the Directive 2000/60/EC and Directive 2008/105/EC. The reported data for organic pollutants are the first for the studied river basin. Key words: sediments, Maritsa River, PCBs, OCPs, PAHs INTRODUCTION mixtures for a wide range of applications from the 1930s onwards [2,]. However, after their toxicity The Maritsa is the largest river on the Balkan became recognized, PCBs were progressively Peninsula; it is the biggest river in terms of discharge banned in most developed countries during the volume and the third longest river in Bulgaria. It 1980s [4]. Due to their large-scale production, emerges from springs in the Rila mountain range and extensive use and environmental persistence, these its basin is a cross-border watershed for Bulgaria, compounds have accumulated in many ecosystems Greece and Turkey. The number of the tributaries of all over the world; in aquatic environments they are Maritsa River is about 100. The most significant trapped in sediments. PCB contamination continues among them are the rivers Chepinska, Topolnitsa, to be a problem as compounds can be transferred Luda Yana, Vacha, Chepelarska, Stryama, Sazliyka, from the sediment to the lower trophic levels of an Arda, Tundzha, Ergene. ecosystem through microbial and bottom-feeder Sediments are by far less variable in time, but uptake. much more heterogeneous than waters. Determining Organochlorine pesticides (OCPs) have been organic compounds in river sediments enables the widely used in the past, but because of their high identification of the contaminant origin in local persistency in environment and accumulation in the regions. Polychlorinated biphenyls (РСВs) are toxic food chain, they can still arouse topical concerns chemicals, which precipitate in soil and water. They about human health. are mixtures of synthetic and organic chemical Polyaromatic hydrocarbons (PAHs) are a large substances which share similar chemical structure. group of organic substances with two or more РСВs had been derived for their very high flash benzene cores. They are characterized by low points and were widely deployed as fire- solubility in water, but high solubility in fats. The extinguishing agents, electrical insulators and polycyclic aromatic hydrocarbons are produced plasticizers mainly in electrical apparatuses. Most mainly by incomplete combustion of coal and diesel often they are introduced into the environment fuel. There are several hundred PAHs. These through defective equipment, illegal discharge, compounds are absorbed by organisms mainly scavenge oil from electrical equipment, as well as through the respiratory system, but may also be hazardous waste. They are a family of 209 synthetic assimilated together with water and food. The most molecules composed of a biphenyl nucleus with thorough study of the carcinogenic effect is that of chlorine at any, or all, of the 10 available sites [1]. inhaled benzo[a]pyrene (BaP), essential source of The ortho-, meta- and para positions are important in which is tobacco smoke. determining the chemical properties of PCB, such as The aim of the research was to identify the extent high dielectric constants, nonflammability, of accumulation of organic pollutants in “sediment” hydrophobic quality and chemical stability. The matrix in selected river valleys and monitoring usefulness of these properties led PCBs to be used in stations along the Maritsa River basin. The study for * To whom all correspondence should be sent. E-mail: [email protected] © 2017 Bulgarian Academy of Sciences, Union of Chemists in Bulgaria 231 V.M. Genina et al.: “Assessment of organic pollutants in sediments from Maritsa River basin (Bulgaria)” the first time provided information about the organic anthropogenic pressure from point and diffuse pollutants and could be a basis for initial sources of organic pollutants, the typological examination of the level of pollution in the surveyed characteristics of the rivers, the composition of the water bodies and identification of the sources of bottom substrate (pebbles, gravel, sand, slime, clay), anthropogenic pressure. The selection of indicators the hydrological characteristics (water runoff, water (priority substances and specific pollutants) provides level) and accessibility for sampling. The geographic particular guidelines for planning future monitoring characteristics of the monitoring stations (watershed, for assessment of their chemical and ecological river, location, geographic coordinates) were status. The data from the analysis conducted may be specified below. used for the purpose of monitoring the tendencies in Stryama river, the village of Slatina (42.6902; the pollution of water bodies in terms of the 24.56917) has been selected as a potential reference examined indicators. site for national type R5 Semi-mountain rivers in EXPERIMENTAL Ecoregion 7, slightly influenced by anthropogenic pressure and limited impact on the quality elements: The monitoring of sediments was accomplished extensive agriculture and forestry in the vicinity of in accordance with Guidance document No. 25 on the monitoring station; low pressure from domestic chemical monitoring of sediment and biota to the discharges in the catchment area of the site (the town common implementation strategy for the Water of Klissura); limited automobile traffic; good Framework Directive (WFD) 2000/60/ЕC. chemical and good to high ecological status The research was conducted at 5 monitoring identified as a reference point for type R5 in the stations located in the Maritsa River basin and two RBMP of East Aegean River Basin district. of its major tributaries – Chepelarska River and Substratum was consisted mainly by pebbles, gravel Stryama River (Fig 1). The selection of the stations and sand, and organic slime where the current is was made in compliance with the key criteria and the sluggish. Moderate to significant water runoff, best practices of the strategy for sampling of moderate to high current velocity, water level was sediments specified in Guidance document No. 7 [5] 0.2-0.4 m. of the WFD. Thus, stations were selected upon a preliminary analysis of the information about the Fig. 1. Map of the studied region. Stryama river, the village of Manole (42.1871; lowland rivers in Ecoregion 7, located in a region 24.91314) – type R13 Small and medium-sized with settlements in the catchment area of the of 232 V.M. Genina et al.: “Assessment of organic pollutants in sediments from Maritsa River basin (Bulgaria)” monitoring station; intensive agriculture; cumulative before the dam near the village of Manole, sand; pressure from small settlements (<2000 p.e.); significant water runoff, low velocity of the current, automobile traffic; good chemical and moderate water level: 1.0-3.0 m. ecological status; substrate – mostly sand and at Samples were collected from their upper layer, places where the current is sluggish – organic slime. which indicates the actual materials deposited and Moderate to significant water runoff, moderate to the actual extent of pollution. Furthermore, the low current velocity, water level was 0.3-0.6 m. sediment topmost layer forms the habitat of the Mouth of Chepelarska river, Kemera bridge benthic organisms, which are part of the biological area (42.1457; 24.87722) – type R5 Semi-intensive quality elements for the assessment of the status of rivers in Ecoregion 7, a site of significant water bodies. The sediments are composed of anthropogenic pressure from industrial plants particles varying from very fine clay (< 2 µm) to producing pesticides and metals (Agria AD, KCM larger pebbles and stones with a size of several mm. AD); discharge of untreated waste water from large Their surface is often covered with organic settlements (Assenovgrad >1000 p.e.); intensive substances which have the effect of binding element agriculture; automobile traffic; poor chemical status for many pollutants and other compounds. The (metals) and poor ecological status; substrate – smaller the particle is, the greater the relative surface mostly gravel and sand, and where the current is area is, which means that the majority of monitored sluggish – organic slime. Moderate to significant substances are contained in the fine fractions of the water runoff, moderate to low current velocity, water sediments, which are the main source of nutrients for level: 0.3-0.5 m. the biota. The size of the particle is one of the most Maritsa river upstream of Plovdiv city important factors, which controls