MIGRATION OF HEAVY METALS IN THE WATER S. S. MILOVANOVI]*, M. T. NENADOVI]**, S. ERAKOVI]*** J. GRBOVI] NOVAKOVI]**** and M. A. LJE[EVI]***** * INN Vinča, Laboratory for Material Sciences, Belgrade, Serbia, msneza@vin.bg.ac.yu ** INN Vinča, Atomic Physics Laboratory, Belgrade, Serbia, milosn@vin.bg.ac.yu * **INN Vinča, Laboratory for Material Sciences, Belgrade, Serbia, sanjicae@gmail.com **** INN Vinča, Laboratory for Material Sciencs , Belgrade, Serbia, jasnag@vin.bg.ac.yu *****Institute of Environmental Research and GIS, Belgrade, Serbia ABSTRACT During the last decades, environment has been strongly exposed to the effect of different harmful pollutants, especially from the atmosphere. Harmful substances from the air, in addition to the direct effect on forest trees is depositing in the soil, and have an adverse effect on soil chemistry and pedogenetic processes. The problem is more pronounced in aqueous ecosistems. The aim of this study was to investigate the migration of heavy metals (lead, mercury and cadmium) in the atmospheric water. The results obtained in Serbia show some characteristic properties regarding the accumulation and migration of heavy metals in the water and enable pollutant localization. It can be noticed that Pb concentrations are within the “maximal acceptable concentrations”. By the comparison of the study heavy metal concentrations with the average contents in the European water, it can be concluded that most samples have lower concentrations of heavy metals. Keywords: atmospheric pollutants, environment. water, migration, heavy metals, Introduction There are 35 metals that concern us because of occupational or residential exposure; 23 of these are the heavy elements or "heavy metals": antimony, arsenic, bismuth, cadmium, cerium, chromium, cobalt, copper, gallium, gold, iron, lead, manganese, mercury, nickel, platinum, silver, tellurium, thallium, tin, uranium, vanadium, and zinc [1]. Interestingly, small amounts of these elements are common in our environment and diet and are actually necessary for good health, but large amounts of any of them may cause acute or chronic toxicity. Heavy metal toxicity can result in damaged or reduced mental and central nervous function, lower energy levels, and damage to blood composition, lungs, kidneys, liver, and other vital organs. Long-term exposure may result in slowly progressing physical, muscular, and neurological degenerative processes that mimic Alzheimer's disease, 125 Parkinson's disease, muscular dystrophy, and multiple sclerosis. Allergies are not uncommon and repeated long-term contact with some metals or their compounds may even cause cancer [2]. For some heavy metals, toxic levels can be just above the background concentrations naturally found in nature. Therefore, it is important for us to inform ourselves about the heavy metals and to take protective measures against excessive exposure. In most parts of the United States, heavy metal toxicity is an uncommon medical condition; however, it is a clinically significant condition when it does occur. If unrecognized or inappropriately treated, toxicity can result in significant illness and reduced quality of life [3]. For persons who suspect that they or someone in their household might have heavy metal toxicity, testing is essential. Appropriate conventional and natural medical procedures may need to be pursued [4]. Environmental and health risks in Serbia Fig. 1. Changes in imission of heavy metals in Serbia (Sources: Republic Hydrometeorologicl Service of Serbia) In Fig 1 the imission of heavy metals in various cities in Serbia has been reported. As one can see there is significant immsion of lead, arsenic as well as nickel and cadmium in industrial zones and surrounding of Pančevo Mladenovac and Niš. Lead in the environment arises from both natural and anthropogenic sources. Exposure can occur through drinking water, food, air, soil and dust from old paint containing lead. In the gene- ral non-smoking, adult population the major exposure pathway is from food and water. For infants up to 4 or 5 months of age, air, milk formulae and water are the significant sources. Lead is among the most recycled non-ferrous metals and its secondary production has therefore grown steadily in spite of declining lead prices. Its physical and chemical properties are applied in the manufacturing, construction and chemical industries. It is easily shaped and is malleable and ductile. There are eight broad categories of use: batteries, petrol additives (no longer allowed in the EU), rolled and extruded products, alloys, pigments and compounds, cable sheathing, shot and ammunition. In humans exposure to lead can result in a wide range of biological effects depending on the level and duration of exposure. Various effects occur over a broad range of doses, with the developing fetus and infant being more sensitive than the adult. High levels of exposure may result in toxic biochemical effects in humans which in turn cause problems in the 126 synthesis of hemoglobin, effects on the kidneys, gastrointestinal tract, joints and reproductive system, and acute or chronic damage to the nervous system. Lead poisoning, which is so severe to cause evident illness, is now very rare indeed. At intermediate concentrations, however, there is persuasive evidence that lead can have small, subtle, subclinical effects, particularly on neuropsychological developments in children. Some studies suggest that there may be a loss of up to 2 IQ points for a rise in blood lead levels from 10 to 20µg/dl in young children. Lead accounts for most of the cases of pediatric heavy metal poisoning [5]. It is a very soft metal and was used in pipes, drains, and soldering materials for many years. Considering situation in Serbia lead concentration levels in 2006 were slightly decreased almost in all monitoring stations except for the high value measured in Belgrade. Analysis of meteorological data showed road dust transport by outgoing SE-ESE wind from the old city of Belgrade (H s =100–250 m) as a possible Pb source at the chosen site, which was located in the park. A comparative measurement of Pb deposition on linden leaves was carried out in the vegetation period (1 April–31 October) of 1997 and 2006. The Pb distribution on leaves differed in the two growing seasons, while the sum of Pb deposition rates on the downward and upward oriented petri dishes remained practically equal. The Pb accumulation on linden leaves was higher in 2006 for several reasons, but mostly as there was intensive soil supply by rain water as ‘yellow’ rain was reported during the night 15/16 April, on 16 and 17 April 2006. A Pb concentration of 312 ng mL-1 with a total precipitation of 12.6 mm was found in the weekly wet sample of 13–20 April. (Fig 2,3) Dry deposition rates of 17 and 84 μg m-2d-1 for Cd and Pb, respectively, were measured on the upward facing dishes two weeks later (27 April–4 May). The synoptic analysis confirmed the development of the Saharan cyclogenesis and its influence on the Balkan Peninsula in the period of 14 to 17 April 2006. In this region the impact of dustfall originating from the Saharan storm was evident either during wet deposition or through resuspension processes. Taking into account cadmium one can say following facts: Cadmium is produced as an inevitable by-product of zinc (or occasionally lead) refining, since these metals occur naturally within the raw ore. However, once collected the cadmium is relatively easy to recycle. The most significant use of cadmium is in nickel/cadmium batteries, as rechargeable or secondary power sources exhibiting high output, long life, low maintenance and high tolerance to physical and electrical stress. Cadmium coatings provide good corrosion resistance, particularly in high stress environments such as marine and aerospace applications where high safety or reliability is required; the coating is preferentially corroded if damaged. Other uses of cadmium are as pigments, stabilizers for PVC, in alloys and electronic compounds. Cadmium is also present as an impurity in several products, including phosphate fertilizers, detergents and refined petroleum products. Cadmium derives its toxicological properties from its chemical similarity to zinc an essential micronutrient for plants, animals and humans. Cadmium is biopersistent and, once absorbed by an organism, remains resident for many years (over decades for humans) although it is eventually excreted. In the general, for non-smoking population the major exposure pathway is through food, via the addition of cadmium to agricultural soil from various sources (atmospheric deposition and fertiliser application). ambient air and drinking water. In humans, long-term exposure is associated with renal dysfunction. High exposure can direct 127 to obstructive lung disease and has been linked to lung cancer, although data concerning the latter are difficult to interpret due to compounding factors. Fig 2. Changes in imission of lead in Serbia Fig 3. Changes in imission of lead in Belgrade between 1997 and 2006. Cadmium may also produce bone defects (osteomalacia, osteoporosis) in humans and animals. In addition, the metal can be linked to increased blood pressure and effects on the myocardium in animals although most human data do not support these findings. As one can see in Fig 4. the significant increase of Cd concentration in Belgrade and surrounding was noticed in 2000. Summary Taking into account the facts written below The average daily intake of Cd for humans is estimated as 0.15µg from air and 1µg from water. Smoking a packet of 20 cigarettes can lead to the inhalation of around 2-4µg of cadmium, but levels may vary widely. Average daily lead intake for adults is estimated at 1.6µg from air, 20µg from drinking water and 28µg from food. For the majority of people however, dietary Fig. 4. Changes in imission of lead in lead exposure is well below the provisional Belgrade Between 1997 and 2006 tolerable weekly intake recommended by the UN Food and Agriculture Organisation and the World Health Organization. And based on the results of heavy metal content in water in Serbia, it can be concluded that Pb concentrations are within the “maximal acceptable concentrations”. By 128 the comparison of the study heavy metal concentrations with the average contents in the European water, it can be concluded that most samples have lower concentrations of heavy metals. The study results are the initial base for the study of the present state of heavy metal and microelement contents in the atmospheric water in Serbia. Further study should be undertaken in the aim of identifying the role of heavy metals in a series of reactions and processes leading to the change of the natural (original) water properties. References [1] Glanze, W.D. Mosby Medical Encyclopedia, Revised Edition 1996. 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