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I. Kisić et. al The Origin of Arsenic in Soils and Groundwater of the Pannonian Part of... ISSN 1848-0071 628.11+546.19=111 Recieved: 2017-03-13 Accepted: 2017-05-26 Professional Paper THE ORIGIN OF ARSENIC IN SOILS AND GROUNDWATER OF THE PANNONIAN PART OF CROATIA IVICA KISIĆ, JASNA NEMČIĆ-JUREC¹, FERDO BAŠIĆ², ŽELJKA ZGORELEC University of Zagreb Faculty of Agriculture, Zagreb, Croatia ¹Public Health Institute of Koprivnica-Križevci county, Koprivnica, Croatia ²Croatian Academy of Sciences and Arts, Zagreb, Croatia e-mail: [email protected] The paper was presented at 4th International Symposium on Environmental Management - Towards Circular Economy, December 7th – 9th 2016, Zagreb, Croatia Arsenic content in surface layer (0-25 cm) varies from 0.9 mg/kg soil to almost implausible 490 mg/kg. The reason for the highest content in hydromorphic soils should probably be sought in recent history. It is less probable that the reason for the increased arsenic content in hydromorphic soils is the geological origin of rocks in river valleys. It is more probable that the reason for the increased arsenic content is river flooding and changes in river flows in the recent past. Based on 208 groundwater samples from 12 locations of Koprivnica-križevci county during 2009-2012, the range of arsenic concentration from <0.1 µg/l to 25.4 µg/l was determined. The concentrations are, generally, very low (<0.1-6.9 µg/l) on the most of locations. The values in Vratno and Kolarec locations indicate an increase in arsenic concentration above the permitted values. Groundwater that is rich with arsenic is result of the natural mineral weathering of rocks. Key words: origin of arsenic, soil, groundwater. Podrijetlo arsena u tlu i podzemnim vodama panonskog dijela Hrvatske. Sadržaj arsena u površinskom sloju tla (0-25 cm) varira od 0,9 mg/kg do skoro nevjerojatnih 490 mg/kg tla. Razlog za najviši sadržaj u hidromorfnim tlima vjerojatno treba tražiti u novijoj povijesti. Manje je vjerojatno kako je razlog povećanog sadržaja arsena u hidromorfnim tlima geološko podrijetlo stijena u riječnim dolinama. Vjerojatniji razlog povećanog sadržaja arsena su poplave rijeke i promjene u riječnim tokovima u nedavnoj prošlosti. Na temelju 208 uzoraka podzemnih voda, iz 12 lokacija Koprivničko-križevačke županije u razdoblju od 2009. do 2012. godine, određen je raspon koncentracije arsena od <0,1 μg/l do 25,4 μg/l. Koncentracije su općenito vrlo niske (<0,1-6,9 μg/l) na većini lokacija. Vrijednosti na lokacijama Vratno i Kolarec pokazuju porast koncentracije arsena iznad dopuštenih vrijednosti. Podzemne vode bogate arsenom rezultat su prirodnog mineralnog trošenja stijena. Ključne riječi: podrijetlo arsena, tlo, podzemne vode. INTRODUCTION Arsenic is a chalcophile trace Arsenic in soil binds to Al and Fe element, 53rd most abundant element in the hydroxides, clay fractions and organic Earth’s crust. Arsenic is found in the matter, as well as calcium and phosphorus following oxidation states: As3-, As0, As3+, compounds [1]. Kabata-Pendias [2] states As5+, while As0 and As3+ are found under that a smaller part of arsenic is mobile in soil - reducing conditions. The ionic forms AsO2 , while the most part of it is strongly bound to 3- 2- 2- AsO4 , HAsO4 , H2AsO3 are predominant sesquioxide and is unavailable to plants. in soil and they are also the most mobile, but Because of its toxicity and distribution in the arsenic can also be found as As3+ and As5+. environment, arsenic affects human health The Holistic Approach to Environment 8(2018)1, 23-36 Page 23 I. Kisić et. al The Origin of Arsenic in Soils and Groundwater of the Pannonian Part of... and nowadays it is one of the recurring factors including pH, redox potential and themes of global thinking and action aimed presence of ligands. The rate of arsenate at protecting the environment. Arsenic adsorption decreases as pH and silicic acid occurs as a component of more than 200 concentration increased. Large minerals in the values ranging from a few concentrations of phosphate, bicarbonate, promilles to a few percent. In 60% of cases it silicate or organic matter can enhance appears in the form of arsenate, 20% in the desorption of arsenic [10, 11]. form of sulphide ores and sulfosalts, and the Hence, it is very important to evaluate rest is in the form of arsenic, arsenite, arsenic concentration and influence of oxides, silicates and elemental arsenic. naturally present ligands on the absorption of Smedley and Kinniburgh [3] state that the arsenic on surfaces with variable charge and content of arsenic in igneous rocks is 1 to 15 to determine the level of contamination [10, mg/kg, while volcanic rocks have a 12, 11]. Well-known groundwater areas that somewhat higher content of arsenic. In have high concentrations of arsenic have sedimentary rocks the content of arsenic been found in different countries around the ranges from 5 to 10 mg/kg. Metamorphic world [11]. Natural problem areas of rocks that are formed by weathering of groundwater with arsenic tend to be found in igneous and sedimentary rocks contain two types of environment: in inland or in arsenic at a concentration of 5 mg/kg. strongly reducing aquifers often derived Kabata-Pendias and Pendias [4], as well as from alluvium [11]. Contamination of Geochemical atlas [5], state that the content groundwater with naturally present inorganic of arsenic in natural soil ranges from 0.1 to arsenic was determined in some areas [13]. 40 mg/kg soil. Bissen and Frimmel [6] report Prolonged drinking of such water risks the that natural sources of arsenic contamination development of diseases; therefore, the include volcanic activity, dissolution of important preventive is to assess the minerals that contain arsenic and, in recent concentration of arsenic in water [14]. years more frequent, forest fires. Based on Contamination of groundwater with the previous studies, it has been estimated arsenic has been evidenced in the Pannonian that the volcanic eruptions emitted 17,150 part of Croatia. Hydro-chemical results tons of arsenic into the atmosphere, and 27 suggest that the occurrence of arsenic in the tons into the oceans [7]. groundwater depends on the local Arsenic and its compounds are geological, hydrogeological and mobile in the environment. Weathering of geochemical characteristics of the aquifer rocks converts arsenic sulfides, or other [15]. A health risk assessment model was compounds, to arsenic trioxide which enters applied to calculate cumulative exposure to by dissolution into rain or groundwater [8]. arsenic, because toxic and carcinogenic risks In addition to the normal levels of arsenic in are a result of drinking groundwater soil or water, people could be exposed to contaminated with arsenic in the Pannonian higher levels in several ways, as is the case part of Croatia [16]. in areas containing unusually high natural The basic aim of this paper is to try to levels of arsenic in rocks which can lead to determine the reasons for the increase in unusually high levels of arsenic in soil or arsenic content at certain locations in the water. People living in an area like this could Pannonian part of Croatia. Using the data take in elevated amounts of arsenic in collected so far, a more detailed and drinking water [9]. The potential toxicity and systematic investigation of soil and availability of arsenic in the soil, water and groundwater contamination by arsenic will in the environment is dependent on several be conducted. The aim of this research is: The Holistic Approach to Environment 8(2018)1, 23-36 Page 24 I. Kisić et. al The Origin of Arsenic in Soils and Groundwater of the Pannonian Part of... 1. To determine the types of soil in the 4. To determine the total arsenic study area and different land use of concentration in groundwater sources soils; at locations of north-western Croatia, 2. To determine the content of arsenic in Koprivnica-križevci county (part in particular soil types and land use; of Pannonia); 3. To expose the assumption about the To estimate the origin of arsenic in origin of arsenic in particular soil groundwater. types, based on collected and systematized data; MATERIALS AND METHODS This study integrates the results of to ensure unobstructed extraction of determining chemical parameters of 1088 hydrocarbons, a borehole working area was soil samples and the content of arsenic in made (land-use conversion was carried out) 961 samples. Soil samples were collected at within which mining works were various locations in the Pannonian region of implemented. Outside of this area, soils have Croatia (Figure 1. A) in the period from continued to be used in agriculture or 1989 to 2015. Composite soil sampling was forestry. These enclosures, in accordance carried out according to land use: forestry with the number of wells from which land, agricultural land and industrial land use hydrocarbons were extracted, ranged from – technosols. Regarding the agricultural and 750 m2 to 1500 m2. forestry soils, the following are represented When the extraction of hydrocarbons in the research: Arenosols, Cambisols and was completed, there was no need for Luvisols (automorphic), and Fluvisols, borehole working areas. Upon completion of Luvisols, Gleysols and Stagnosols the rehabilitation, the borehole working area (hydromorphic) [17, 18]. The industrial is restored to its original purpose (agriculture usage (Technosols) represents a borehole or forestry) or it is converted into working area of oil or gas wells. It is a soil construction land. which has been used for decades as the area Soil samples were taken from the from which hydrocarbons are extracted. remediate drilling area and the surrounding When the oil/gas field has been discovered soil, which borders the borehole region. decades ago, their original intention use was Methods used to determine the studied abandoned - agriculture or forestry.

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