2016 | 69/2 | 245–253 | 9 Figs. | 3 Tabs. | www.geologia-croatica Journal of the Croatian Geological Survey and the Croatian Geological Society

­The use of factor analysis to distinguish the influence of parent material, mining and agriculture on groundwater composition in the Strumica valley, Macedonia Ivan Boev1, Ajka Šorša2, Biljana Kovačević3, Saša Mitrev3 and Blažo Boev1

1 „Goce Delčev“ University Štip, Faculty of Natural and Technical Sciences, Bul. Krste Misirkov, 10-A, P.O. Box 210, 2,000, Štip, Republic of Macedonia; ([email protected], [email protected]) 2 Croatian Geological Survey, Department of Geology, Sachsova 2, 10,000, Zagreb, Croatia; (corresponding author: [email protected]) 3 ”Goce Delčev” University Štip, Faculty of Agricultures, Bul. Krste Misirikov, 10-A, P.O. Box 210, 2,000 Štip, Republic of Macedonia; ([email protected], [email protected]) doi: 10.4154/gc.2016.19

Abstract Article history: Determination of groundwater chemistry in the Strumica valley was essential given its widespread Manuscript received March 01, 2016 use for irrigation in the agricultural industry. 224 samples were collected form boreholes forming Revised manuscript accepted May 31, 2016 the dataset for the study. The groundwater chemical composition was examined for selected - Available online June 28, 2016 analytes: As, Sr, Mn, Ni, Cu, Zn, Mo, Ba, Pb, Na, Mg, Al, K, Ca, Ti, Li, Cr, Fe, U, CaCO3, Cl , - + 2- 3- NO3 , NH4 , SO4 and PO4 . The source and internal correlations of the analytes were subjec­ ted to multivariate statistical analyses (factor analyses), which yielded 7 factors. Geochemical maps of these factors were generated using the kriging method. The groundwater chemistry was

predominantly controlled by the geology with some anthropogenic influence due to agriculture and mining, affecting the concentrations and spatial distribution of arsenic, phosphates, sul- phates, nitrates and some metals (copper, iron, chromium, lead, nickel, zinc). Mining of copper/ - Keywords: groundwater, chemistry, factor gold (molybdenum) in the region of Ilovica increased the concentration of Al, Cu, Pb, Cr, NO3 , 3- analyses, Strumica, Macedonia Ni, Zn, Na, K, Li and PO4 in groundwater, but only at a local level.

1. INTRODUCTION 2. STUDY AREA Influences on the chemistry of groundwater are numerous. Apart The Republic of Macedonia is located in southern Europe, in the from the geological setting and hydrogeological characteristics, central part of the Balkans, at latitude of approximately 42o north groundwater quality can be impacted by anthropogenic influen­ and longitude of 22o east (Fig. 1), and covers a geographic area ces. Increased population growth rates, intensive agriculture and mining could significantly change the groundwater geochemistry. The groundwater investigation in Macedonia as part of the pro­ ject „Hydrogeological survey of Groundwater in Macedonia” was one of the newest projects in this area of research (JOVANOVSKI, 2009). In addition, numerous studies were also performed in Macedonia and the Strumica valley, including a systematic hy­ drogeological investigation in Macedonia, performed as part of the framework of the hydrogeological map of SFR Yugoslavia, 1:500 000 (IVKOVIĆ et al., 1983). MICEVSKI et al. (2005) stu­ died the hydro geothermal potential of the Strumica valley. A wa­ter quali­ty assessment was undertaken of the water resources in the Strumica river basin (POPOVSKA & GESHOVSKA, 2014), and the chemical element composition of water samples from the river Vardar (Republic of Macedonia and Greece) and its major tributa­ries was also studied (ILIĆ POPOV et al., 2014). Some hydroche­mical data were determined in the groundwaters of the Pelagonia valley (MIRČOVSKI et al., 2015). More recently, the con­centration of macro-, micro-, trace and ultratrace elements in some natural waters from eastern and south-eastern Macedonia were reviewed by ŠIJAKOVA-IVANOVA & AMBARKOVA (2015). Groundwater in the Strumica valley was used mainly in the irrigation system and to a considerably lesser degree as drinking water. The main goal of this investigation was to establish any correlations between various analytes, define their sources (geo­ genic and anthropogenic), present their spatial distribution and investigate the influence of the Ilovica mining area on ground­ water composition in the region using multivariate statistics (fac­ tor analyses). Figure 1. Study area. Geologia Croatica Figure 2. Serbo the in mountain Ogražden tween two parallel faults, one to the north along the border of the valley. The valley is a tectonic graben formed in the Pliocene be The largest part of the investigated area is located in the Strumica AND PEDOLOGICAL CHARACTERISTICS 3.HYDROGEOLOGICAL GEOLOGICAL, north metres (JOVANOVSKI, 2009), and prevailingmilli 547 approximately winds is are from rainfall the average annual The 2007). to 40 °Cbetween summer varies in temperature The coldwetwinters. and summers dry and warm by characterized climate, Mediterranean temperate a valley has Strumica The represented. being Mediterranean to continental from zones, climatic different with variable is donia’sclimate valley and to basin the the gravitates drainage Black Sea. Mace­ the through flows river Strumica The inhabitants. 45,000 with the biggestnear The border nia, with Bulgaria. city is Strumica, 19.1%areas, plains and 1.9% water. surface of25,713 km 246 The Strumica valley is locatedThe Strumica the in south east of Macedo - west and south A geological map of the investigated area (RAKIKEVIK et al., 1978, 1980; MICEVSKI et al., 2005.) 2 , of which 79% is composed of hills/mountainous ofhills/mountainous ofcomposed which79%, is - east. - Macedonian massif and the the and massif Macedonian - 20 (CARTER, °C winter in

­ ­ ­ over 3,100 (CARTER, hectares 2007). extends Ilovica in 2014).mine (molybdenum)copper/gold The area investigated the of east et (RAKIKEVIK al., the 1978, to 1980; POPOVSKA located & Ilovica GESHOVSKA, in tantly and Poderiš,Kalugerica in basin but mostmica drainage impor tigated area: around Strumica, Kukliš, Veljuša; the northern Stru posed that the depth of the basin varies from 700 – 1,200 m. sediments. tufaceous and sup geophysicalofbasis (2005), al.data, the MICEVSKIonet sands gravel, clay, sandy iments: The Strumica valley is predominantly covered by Quaternary sed and the Pliocene epoch is represented by clays, sands and gravels. andesitesandconglomerates dacitessandstones,sediments, and The Tertiary rocks are comprised of Upper Eocene volcanogenic sic) is represented by diabase, granite, granodiorite and rhyolites. youngerPalaeozoic rockswerenot found.Mesozoic The (Juras ­morphites and magmatites prevailed in the older Palaeozoic. The metamorphites, represented by various gneisses and schists. Meta­ 2005; Fig. 2). The oldest rocks are Precambrian high Vardaret al., zone 1978, (RAKIKEVIK 1980; MICEVSKI et al., the in Belasicaof bordermountain alongthe south, the to other The metal occurrences are numerous throughout the inves the throughout numerous are occurrences metal The Geologia Croatica 69/2 Croatica Geologia - temperature temperature ­ ­ ­ ­ ­ ­ Geologia Croatica

­ ­ ­ ­ ­ ­ ­ ­ ­ ­ ­ 2 247 ­cular . - 2) 2) was used in the 3 - 4 37 - 2). The mg/lTitanium standard ± 2 (998 2). ICP for μg/l. U was calibrated in the range of 1 – 10 μg/l μg/l.10 – 1 calibrated was U in theof range

- was stochiometrically determined from the value determinedvalue stochiometricallythe from was - μg/l. and For Sr the Ba (tot) calibration(tot) range 3

37 4 - Qualitative and quantitative determination of trace elements elements trace determinationof quantitative and Qualitative Determinationnitratesundertaken was colorimet theof by PO The Ammonium ions were determined by the colorimetric Sulphatеs Sulphatеs were determined by the colorimetric method us bias ranged from 1% – 10% and precision, expressed as intermeas expressed precision, and 10% – 1% from ranged bias elements. analysed the all for 10% than better was precision diate processing Data 4.2. The analytical data screenedwere in order to carry univariout Analyti analyses. statistical analysis) (factor multivariate and ate cal results falling the below detection limit ROLLINSON, (DL; were calculated to 1993) half of the DL value for the parti a normal The datageochemical element. follow generally never that essential is it analyses factor carryingout for but distribution, method using the spectrophotometer typeUV 6715, JENWAY ml 25 transferred a was to treatedsample the of ml 20 Here, Vis. sodium Potassium tartrate(25%), of ml 1 Then flask. volumetric 1 ml 1 NaOH ml(7.5%), Nessler’s reagent minu­ and 30 afterdistilled read was water absorbance The mark. the to up add were tes at a nm.of 420 wavelength The apparatus was calibrated in calibration five levels in the concentration rangeof 5 – 30 mg/l Flukamg/l, 4 ± mg/l (1000 IC ammonium standardthe for using 1974b). analytical)(EPA, (ICP spectrometry mass plasma coupled inductively by made was using – anCX MS), apparatus. Agilend 7500 Calibration the of apparatus for the total cation and anion content of the elements range concentration the in was Pb and As Cu, Ni, Mn, Cr, Ti, Li, from 1 – 10 cal a К and Na (tot), Mg (tot), Ca for μg/land 100 – 10 from was ibration range from – μg/l5,000 1,000 was used. Multi element standard solutions (Periodic table mix Fluka) 1 92091, for ICP, the of calibration For elements. these of calibration for used were se 7500 standard solution Agilent an Mo of state oxidation total ries Tuning PA 2 mg/l) (100 7697 (CAS: 10 – 1 of range using an Agilent standard solution 7500 Series Tuning 1 PA (5 mg/l) (7697 in range thecalibration (tot) Ti of calibration mg/l)used was for used was mg/l) (1,000 ICP standardfor chloride A μg/l. 10 – 1 of μg/l. – 5,000 in The1,000 the range of (tot) Cl calibration of for ing a spectrophotometer (JENWAY 6715, UV Vis) according to UV Vis) 6715, ing a spectrophotometer (JENWAY For this purpose,the (1978). method EPA 375.4 20 ml concen BaCl ml 1 flask. Then, volumetric mltransferred was 25 HCl), trated a sample to ml 1.25 + g/L (60 NaCl ml 1 alcohol, glycol ml 1 g/l) and distilled water was (150 added up to the mark. Absorb ance was read after 30 minutes nm. 420 at of a Thewavelength concen the in levels calibration apparatuscalibratedfive in was – mg/l0.5 tration using range 0.1 a of sulphates standard IC for mg/l mg/l, 4 ± Fluka analytical). (1000 ric method using the same spectrophotometer transferreddirectly was type concentratedsample The Vis. UV JENWAY 6715, into a 2 ml cuvette and the absorbance was read at wavelengths cali­ five in calibrated apparatus was The nm. 275 and nm 220 of standNitrate the mg/lusing 5 – 1 from range a in levels bration (DALMACIJA mg/l(Flukaanalytical) 4 mg/l± 1000 IC, for ard 2006). AGBABA, & in the waters with the assumption dissolved P that all is the P of in phosphate forms. P was determined by inductively coupled plasma mass spectrometry apparatus (ICP – MS), type Agilend CX. Calibration the of 7500 apparatus P for is in range from 10 μg/l. are asμg/lexpressedResults 100 PO – ­ ­ ­ ­ ­ - ­ - na nuous ­nuous (Pure 3 -Macedonian disconti Štip, within two complex cultiva - west west from Strumica - and west (POPOVSKA, 2014, . For that purpose, 20 ml of of ml purpose,20 that For . - east from Ilovica settlement settlement Ilovica from east 3 - east, the Strumica valley in the middle and - . land use categories. Land use of the the of use Land categories. use land non-irrigated arable land IVANOVA & AMBARKOVA, 2015). AMBARKOVA, & IVANOVA - , 2016). The largest part was the uninvestigation of , 2016). (Pure trace, Sigma) for determination of nitrates and am nitratesand determination of for (Puretrace,Sigma) 4 covered a smaller part of the area. The sample points Alkalinity is determined according to the EPA Method 305.1 305.1 Method EPA the to according determined is Alkalinity Land use was observed at Corine Land Cover 2006 (DIS Fluvisols cover the flood plain surface of the Strumica river. Strumica the river. of surface plain flood the cover Fluvisols Macedonia is divided into four catchments: the Vardar, Stru Vardar, the catchments: four into divided is Macedonia nge are transferred­nge for titration flask ml Erlenmeyer to 250 a SO 2 ora wine white (pale yellow). of until colour the HCl M with0.01 (1974a) and expressed as mg/l CaCO mg/l as expressed and (1974a) the sample, 30 ml distilled water and several drops of methyl H testedand ºС +4 refrigerator in at a stored were Samples monia. 2007). within(JOHNSTON, days two of each sample was filtered (MN 640 m de Ø125, No. 43 (white each of 43 was sample filtered No. (MN Ø125, 640m de One partribbon)). ml) (500 was treated with 1 ml HNO trace, Sigma) for qualitative and quantitative determination of sulphates and trace elements, 300 ml was treated with 0.6 ml Protection at the Agriculture faculty, determine to were used UGD Unfiltered hours. and untreated samples alkalinitywithin an hourafter The restarrival laboratory. the at bottles which were washed out several times with water from the from water with times several out washed were which bottles Samples air. exclude to order in top the filling to before borehole transferredwere to the Laboratory and EnvironmentalPlant for Groundwater samples were collected from 224 boreholes over the the over boreholes 224 from collected were samples Groundwater minu­ 10 for out pumped was borehole the from Water area. field tes by electrical pump. Samples were stored in 1 l sterile glass 4. MATERIALS AND METHODSAND 4.MATERIALS analysis and Sampling 4.1. urban fabric, inland marshes, natural grasslands and vine yards the for except categories, use land all distributedare over grasslandstural COMAP dertaken on patterns tion city at Cambisol and 2 samples north samples 2 and Cambisol at city Regosol. and Leptosol at River terrace sediments (MAKSOIL, 2016; Fig. 2.). The sampling sampling The 2.). Fig. 2016; (MAKSOIL, sediments terrace River points were predominantly located at the Fluvisol, about 10% were in urban areas, only 6 samples north city at Humic Calcaric Regosol, 2 samples south from Bansko (ŠIJAKOVA Upper and Proluvium the on developed were soils alluvial These spectively. spectively. An assessment based on the geochemistry of some natural waters in Macedonia including five samples fromStrumica the valley showed satisfactory levels of water quality made lakes) were classified into five classes (Official classes Gazette of five classified into were made lakes) to Strumicabelongs the qualityinbasin Water 1999). RM18/99, re water, irrigationpolluted and for water i.e. IV, IIIand classes catchment basin was established in 1953 with 23 piezometric but since wells, 2000 only two themof been have in use. Water quality is regulatedGazette the of „Law by waters” (Official on man- naturaland (rivers, surfacewaters the and 1998), 4/98, RM effort was made in the Strumica valley of building hydro meliora­ hydro building of valley Strumica the in made was effort depths to wells of number a digging involved which systems tion between15 to 250 m. Groundwater monitoring in the Strumica part of the Vardar zone to the south use its and area this in groundwater of importance The 3). 2, figs. special a (1983), al. et IVKOVIĆ to According history. long a has mica, Crni Drim and Južna basins. TheMorava catchment area of the Strumica river comprises part of the Serbo massif to the north Boev et al.: The use of factordistinguish analysisof to influence the use material, parent Theagriculture mining and of groundwateral.: on et compositionBoev ... Geologia Croatica >1) which explains 70.0 % of the variance. A more eigenvalues detailed overwith (those retained were factors 7 The torization. fac for adequate were data the that 0.001showed< sphericity the groundwater.in analyte ofcentration a particular con the of variability great the conclusively indicated data the of werenotable statistics descriptivehigher. means The the that siderable. Comparing the mean and median values, it can be seen Table 1. reveals that the range for most analytes proved to be con 5. RESULTS AND DISCUSSION could data be evaluated. geochemical factorized the of influences anthropogenic and/or the lowest to the highest values. As a result, thefrom transition different smooth a geogenic gain to percentiles) two (oneforclass classes 50 into classified were maps factor the on scores factor factor score values were generated usingthe on the kriging based method. maps The geochemical the analyses, variogram After ArcGIS software GIS in maps geochemical generating for used and database the using IBM SPSSperformed software. was analysis Statistical factors. the of explanation facilitate to ings were rotated by Varimax rotation with Kaiser Normalization 1960). 1 werethan selected (KAISER, factor load retained The eigenvalues The greater for factorizing. adequacy data estimate to used were Sphericityof test Bartlett’s and (KMO) test Olkin derstanding and to simplify the interpretation. The Kaiser hidden correlations in the in dataset order to a acquire un better possible detect and variables observed the reduce to performed was data (FA) the analysis ofFactor2008). al., et (REIMANN logwere data the Therefore, all variables are & close FILZMOSER, 2000). to it (REIMANN Table 1. 248 PO SO NH NO Cl CaCO U (mg/l) Fe (mg/l) Cr (mg/l) Li (mg/l) Ti (mg/l) Ca (mg/l) K (mg/l) Ba (mg/l) Mo (mg/l) Zn (mg/l) Cu (mg/l) Ni (mg/l) Mn (mg/l) Al (mg/l) Mg (mg/l) Na (mg/l) Pb (mg/l) Sr (mg/l) As (mg/l) Element/Ion - (mg/l) 4 4 4 3 2- 3- + - (mg/l) (mg/l) (mg/l) (mg/l) 3 The values of the KMO test of 0.722 and Bartlett’s test of test Bartlett’s 0.722 ofand test KMO the of values The The calculated factor scores were stored as a new variable in (mg/l) Descriptive statistics of the contents of analyses in the groundwater samples (n=224). TM using its Geostatistical Analyst extension. extension. Analyst Geostatistical its using 197.19 213.56 154.76 443.32 252.53 Mean 23.73 21.85 36.54 47.76 11.63 12.62 28.04 17.61 48.88 20.68 0.51 0.96 2.99 0.79 6.05 9.96 7.18 0.89 1.38 3.38 - transformed to base 10 logarithms 10 base logarithms to transformed Median 193.62 123.16 166.28 188.32 15.86 22.18 70.35 37.97 22.60 13.95 0.16 0.07 2.86 0.67 0.48 2.62 5.48 5.32 9.07 6.10 0.49 8.52 1.05 2.62 1.91 - Meyer Standard Deviation ­ ­ ­ ­ ­ ­ - 138.91 364.61 136.27 155.35 625.84 206.78 44.01 35.66 52.23 38.34 33.74 21.62 12.44 21.01 25.38 38.41 1.05 4.63 8.91 0.92 9.74 4.94 1.55 1.70 2.67 vial parent material and use of pesticides, fertilizers, sludge of use and and material parent pesticides,vial fertilizers, of of Fluvisol village the as permeability Podareš.allu and The Strumica river from the rich metal occurrences around areas such of part from the the couldarsenic northern be partly transported ing from the Serbo As in groundwater was due to weathering and leaching As from the pitovo (Tab. 3; Figs. 2 & 3). Bosilovo, An elevated concentration of Sučevo, arsenic Monos and Turnovo, Borievo Radovo, Robovo, Murtino, at Ednokućevo, tributaries Štučka and Turija the of mouth the at and river Strumica the of part lower the in ( (0.80), As were Fe(0.74),1 factor for0.5 (0.68),than Mn SO Table 2. the sense factor lowerloadings 0.3 than could be ignored. that In factor. individual an about explanation additional some only give loadings lower factor 0.5,since than greater loadings factor have impacts biggest The loading. factor its of value the increasing the by increases factor the to analyte particular a of viewis givenabout Tables factors the in 3. 2.and influence The 7 6 5 4 3 2 1 Factor - 0.61), Ba (0.58) and PO - rich minerals of magmatic and metamorphic rocks originat rocks metamorphic and of magmatic minerals rich The association of analytes within the factor loadings greater The eigenvalue and explained variance of retained factors. 3160.71 1034.49 1369.10 3600.25 1244.18 284.30 300.25 610.11 915.04 405.41 353.76 208.96 127.42 165.65 209.51 Range 55.86 95.34 86.00 95.83 36.38 16.28 21.45 21.28 Eigenvalue 7.80 6.04 1.56 1.87 1.99 2.39 2.79 3.42 3.47 - Macedonian Macedonian massif and the Vardar zone. The 4 3 - (0.54). The factor scores were highest Variance (%) Minimum 11.2 13.7 13.9 6.2 7.5 8.0 9.6 0.00 0.25 0.03 0.14 4.19 0.03 0.14 5.00 0.00 0.40 1.98 5.77 0.68 0.46 0.31 0.33 0.06 0.55 0.52 2.31 0.10 0.31 0.01 0.09 0.08 Geologia Croatica 69/2 Croatica Geologia Cumulative variance (%) Maximum 3165.71 1036.47 1371.41 3600.27 1244.27 300.50 284.44 614.30 915.07 411.18 354.44 209.43 127.97 166.17 209.59 70.0 63.7 56.3 48.3 38.8 27.6 13.9 55.89 95.49 86.40 96.14 36.71 16.35 21.55 21.58 7.80 6.04 4 2 ­ ­ ­ -

Geologia Croatica ­ ­ ­ ­ ­ est 249 ion EN - w - 3 P 4 - Macedo

- ast – south south e - (0.69), Mo (0.69), Ba (0.62), (0.54), U - and U. The lack of these elements indicate elements these of lack The U. and - (0.45) (Tab. 3; Fig. 4). A large proportion the4). of Fig. 3; (Tab. (0.45) - 2 4 ENDIAS & MUKHERJEE, 2007; KABATA MUKHERJEE,2007; & ENDIAS P - . - The lowest factor scores were recorded in Ban the areas factor were scores of The lowest There were also highrelatively negative factor loadings of The geochemical behaviour of other analytes in this factor The spatial distribution of factor scores of factor 2 is divided is 2 factor of scores factor of distribution spatial The 2 4 analytes have their origingeological in the rocks of the Vardar zone and the Quaternary proluvium of the upper river terrace, that in the geological background there are small amounts of Na, Na, of amounts small are there background geological the in that uranium minerals soluble or chlorides present. Mg or Ca two more analytesCl more two pogenic origin. pogenic was The and close. Fe colloidal Mn oxides are important in the sorption other colloidal substances and ions, such as PO assumptions suggest that part of the arsenic content is of anthro of is content arsenicthe partof that suggest assumptions (mainly connected to that zone and partly to the Serbo the to partly and zone that to connected (mainly (KABATA separationby lines running north north which passed through Murtino Strumica Towards (Fig. 4). city were located the highest factor scores values while the smallest was This area. investigated the of part opposite the at were values clearly connected with the geology near (RAKIKEVIK zone Vardar et al., the 1978, of metamorphites and magmatite The 1980). Strumica city inand beyond the Strumicaare composed valley, of rocks which when weathered release to the environment and Mg including; loadings, factor highest the with ions groundwater, (0.80), Ca Ti (0.75), Cl (0.69), (0.46) and SO (0.46) DIAS & PENDIAS, 2001). Ba is associatedDIAS & with PENDIAS, K 2001). in the mag adsorbed easily is duringand mobilizesweathering rocks, matic onto Mn and Fe oxides. The Barium ion is mobile in solutions without sulphates as by the revealed factor negative loadings of SO nian Several metal massif),occurrences 2). (Fig. were recorded sko and Banica. The low values were also on the upper flow part flow upper the on also were values low The Banica. and sko of the Strumica river, north of the confluenceof theJazga and area. inandIlovica rivers the Turija ­ 7 0.28 0.09 0.02 0.11 0.04 0.20 0.22 0.20 0.11 0.01 0.09 0.12 0.19 0.15 0.02 0.81 0.41 0.57 –0.05 –0.07 –0.14 –0.05 –0.21 –0.07 –0.00 6 0.06 0.09 0.00 0.27 0.13 0.06 0.18 0.03 0.04 0.14 0.21 0.26 0.07 0.47 0.76 0.74 –0.19 –0.06 –0.09 –0.04 –0.04 – –0.36 –0.16 –0.20 –0.02 – 5 0.15 0.02 0.11 0.07 0.26 0.03 0.14 0.06 0.13 0.19 0.11 0.05 0.20 0.35 0.32 0.06 0.54 0.73 0.56 –0.29 –0.04 –0.08 – –0.20 –0.28 –0.42 4 0.02 0.24 0.21 0.05 0.07 0.06 0.23 0.04 0.20 0.21 0.10 0.05 0.19 0.11 0.43 0.94 0.93 –0.05 –0.01 –0.15 – –0.15 –0.26 –0.13 –0.07 –0.10 ENDIAS & PENDIAS (2001), in ENDIAS & PENDIAS (2001), Factor loading Factor P - 3 0.11 0.20 0.11 0.04 0.10 0.11 0.21 0.13 0.30 0.24 0.06 0.10 0.05 0.26 0.51 0.49 0.78 0.67 0.79 , 2016). , – –0.26 – – –0.17 –0.14 –0.04 –0.35 –0.08 2 0.2 0.20 0.11 0.01 0.09 0.09 0.07 0.05 0.06 0.06 0.17 0.14 0.05 0.02 0.45 0.69 0.62 0.46 0.80 0.75 0.69 0.54 –0.01 –0.05 –0.07 – DISCOMAP 1 0.17 0.12 0.14 0.06 0.08 0.00 0.12 0.00 0.06 0.20 0.68 0.80 0.74 0.54 0.48 0.58 –0.09 –0.16 –0.16 –0.14 –0.21 –0.41 –0.14 –0.40 –0.61 Spatial distribution of factor scores of Factor 1. Factor of scores factor of distribution Spatial Rotated factor matrix of the factors. the of matrix factor Rotated , 2016; 2016; , According According to KABATA 3 – + 3– 2– 3 4 4 4 – Cr CaCO Mn SO Analyte As Fe Sr NO Na K Cu Ni Zn Li PO Pb Mo U Al Mg Cl Ca Ti Ba NH Figure 3. 3. Figure SOIL downwards out leaches arsenicsediments, and soils drained well arsenicirrigationwith Additionally, horizons. soil lower the into These groundwater. the to again As recycles groundwater loaded manure in the intensive agricultural production increased concentrationthe of arsenic in both soil and groundwater (MAK Table 3. 3. Table Boev et al.: The use of factordistinguish analysisof to influence the use material, parent Theagriculture mining and of groundwateral.: on et compositionBoev ... Geologia Croatica Figure 5. (0.51) and Ni (0.49) in factor 3 were recorded in the north lower, the with lowest of the areas in Ilovica and Bansko. presence of sulphates which reduce the mobility of barium. region SO Strumica the of et al., rhyolites 1978, (RAKIKEVIK 1980). the The factor loadings of Ba and in uranium including Figure 4. 250 4 2 The high factor scores of Al (0.79), Al ofscores factor high (0.78), The Cu (0.67),Pb Cr In the south - were almost the same; they are balanced as a result ofresult athe as balanced same;are they the were almost Spatial distribution of factor scores of Factor 3. Spatial distribution of factor scores of Factor 2. - eastern eastern part of the study area, factor scores were - western western the Ilovica region, due to the mining of copper/gold(molybdeof mining the to due region, Ilovica the 1980). The highest factor score of this factor was, as expected, in et especially in al., Kalugerica and 1978,Poderiš (RAKIKEVIK and uranium magnetite in the region Strumica and north, farther of copper, chromium, some iron, with occurrences metal linked score on a line from Piperovo – Prosenikovo – couldStrumica be factor high The lower5).(Fig. were scores factor zone, middle south and - eastern parts of the investigated area, whereas in the the in whereas area, investigated the of parts eastern Geologia Croatica 69/2 Croatica Geologia ­ Geologia Croatica ­ ­ 251 (0.73), Ni (0.56) (0.56) Ni (0.73), - 3 The factor loadings of factors 5 were; NO factorswere; 5 Theloadingsfactor of et al., 1978, 1980; Fig. 2). The lowest factor values were registered registered as aremarble, which were good sources Ca of and Sr (RAKIKEVIKvalues factor lowest The 2). Fig. 1980; 1978, al., et Bansko. and Kukliš, inareasthe Svidovica of and Zn Higher(0.54). factor scores were noted in the areas of Banica – Strumica, Ilovica, Bosilovo, Monospitovo and 7). Apart(Fig. dovica Svi from the composition, evident geological agriculand miningIlovica increasedinby were loadings factor

3 zinc (copper) and gold occurrences. The occurrences. gold and (copper) zinc - Spatial distribution of factor scores of Factor 5. Factor of scores factor of distribution Spatial Spatial distribution of factor scores of Factor 4. Factor of scores factor of distribution Spatial Factor 4 was characterized by high factor loadings of CaCO of loadings factor high by characterized was 4 Factor Strumica and Dobrejci (Fig 6). This part of the Vardar zone is definedby ofthe presence magmatites andmetamorphites such (0.94) and Sr (0.93) andand in low Sr (0.94) Mnthe (0.93) (0.43) region of Banica, Figure 7. 7. Figure to this (Fig. 2). thisto (Fig. num) and numerous lead numerous and num) geo­ the and reservoir geothermal a as known well is area Bansko backgroundlogical the of and Ilovica Bansko region is relevant Figure 6. 6. Figure Boev et al.: The use of factordistinguish analysisof to influence the use material, parent Theagriculture mining and of groundwateral.: on et compositionBoev ... Geologia Croatica Figure 9. Weathered Mo tends to make strong metal. complexes this of with behaviour organic geochemical mat the of result a is 5 factor production.negativeA of loading factor Mo sivein agricultural from oftwo types aone origin, natural and another due to inten area of and the Banica Strumica settlements also probably stems DISCOMAP, 2016). 1978,al.,et 1980; Fig.2; (RAKIKEVIK locations other in ture Figure 8. 252 A nitrate (NO nitrate A Spatial distribution of factor scores of Factor 7. Spatial distribution of factor scores of Factor 6. 3 - ) in factor 5 with a high factor value in the the in value factor high a with 5 factor in ) ­ ­ 6. Factor loadings are high for Na (0.76), K (0.74) and Zn ( ovo – Debila and ofeast Bansko. environment et al.,(SALMINEN alkaline 2005). the in mobile more is molybdenum as reason is the opposite behaviour of Mo compared to most metals, ter which reduce its mobility and entry into groundwater. Another Figure 8. presents the distribution of factor scores of factor scores of factor distribution the presents 8. Figure The lowest factor scores were noted in two regions Prosenik Geologia Croatica 69/2 Croatica Geologia - 0.47). ­ Geologia Croatica - ­ ­ ­ ­ - ­ ­ ­ ­ ­ ­ ­ 253 Basic Basic 1972), 1972), - 921125 - 94 94 [ - 1 - - – in Macedo in – 29 April 2005. April 29 - 9768.1000127. - Basic Basic Geological Map of SFRY eastern Macedonia.– Geologia Mace­ Geologia Macedonia.– eastern 94 94 [ - - 324c897e3ba7&enrichSource=Y292ZXJQYWdlOzI Eplanation for hydrogeological map of SFR Yugosla SFR of map hydrogeological for Eplanation - – in Macedonian].– Geološki zavod, Skopje (1969 Skopje zavod, Geološki Macedonian].– in – ttps://www.researchgate.net/publication/282612958_Hy h 928d - Verlag Berlin Heidelberg, 561 p. 561 Heidelberg, Berlin Verlag - 4e89 - T., PETERSELL, V., PLANT, J.A., REEDER, S., SALPETEUR, SALPETEUR, S., REEDER, J.A., PLANT, V., PETERSELL, T., ttp://www.maksoil.ukim.mk/masis/ (22.2.2016). ttp://www.maksoil.ukim.mk/masis/ - – in Croatian].– Savezni geološki zavod, Beograd. zavod, geološki Savezni Croatian].– in – h 970d - IVANOVA, T. & AMBARKOVA, V. (2015): Geochemical assessment of assessment Geochemical (2015): V. AMBARKOVA, & T. IVANOVA, - PENDIAS, A. & MUKHERJEE, A.B. (2007): Trace A. elements A.B. from Trace & (2007): soil PENDIAS, to MUKHERJEE, PENDIAS, A. & PENDIAS, H. (2001): Trace elements in soils and plants.– plants.– and soils in elements Trace (2001): H. PENDIAS, & A. PENDIAS, 1:500000 - - 5. , , - (2005): Geochemical Atlas of Europe, Part 1, Background Information, Atlas Metho­ of Part Europe, 1, Information, Background Geochemical (2005): p. 526 Espoo, Finland, of Survey Geological Maps.– and dology south and eastern from waters natural some 5–14. 1, 29, donica, of the Strumica Valley with a Special Review of the Bansko Locality.– Proceed Locality.– Bansko the of Review a Special with Valley Strumica the of 24 Turkey, Antalya, Congress, Geothermal World ings valley, Pelagonia the of part Bitola’s the in waters ground the for data drochemical 15–24. 1, 29, Macedonica, Geologica Macedonia.– of Republic 4/98. No. Skopje, 18/99. No. Skopje, Water.– of sification Drainage & Irrigation Basin.– River Strumica in Resources Water of Assessment doi:10.4172/2168 127. p. 3, Engineering, Systems karta SFRJ 1:100000, list Strumica K34 sheet Strumica 1:100000, Beograd. zavod, geološki Savezni K34 za list Strumica Tumač SFRJ 1:100000. karta geološka Osnovna sheet Strumica the of Geology 1:100000, SFRY of Map Geological p. 69 Beograd, zavod, geološki Savezni Skopje, zavod, Geološki nian].– geo of treatment statistical the for Consequences myth. a of death geochemistry: 1001–1014. 39, Geology, Environmental data.– environmental and chemical p. 362 Ltd., Sons, & Wiley John Explained.– Analysis Data p. 352 England, Limited, UK Group Longman tation.– HALAMIĆ, V., GREGORAUSKIENE, A., GILUCIS, M., DURIS, W., VOS, DE LIS, J., LOCU G., KLEIN, P., JORDAN, G., KLAVER, J., P., HEITZMANN, S.Å., OLSSON, P.J., A., O’CONNOR, K., MAZREKU, J., MARSINA, TURA, R. OTTESEN, I., SANDSTRÖM, H., SIEWERS, U., A. 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POPOVSKI, E., MICEVSKI, - - ­ , ­ ­ ­ ­ ­ ­ ­ - 3 Qual ) may may ) - 3 4 (0.57) and U (0.41) (0.41) U and (0.57) matematički fakultet, De fakultet, matematički - - 3 4 and Ni and negative in factorandand Ni negative - 3 22.2.2016). ( . - 3 – Prirodno in Serbian].– 4 east of the city of Strumica. The analytes - ttp://discomap.eea.europa.eu/map/EEABasicviewer/?webmap=b h 5cbf63906584ef2ac5d29d627faf923 5cbf63906584ef2ac5d29d627faf923 Project, Macedonia on behalf of Euromax Resources Limited.– Report for NI 43 NI for Report Limited.– Resources Euromax of behalf on Macedonia Project, Canada. Ontario, Toronto, Associates, Oak Broad 101, of water drinking ity control Sad. Novi hemiju, za partmant Besides arsenic, nitrate, metals, some andBesides some phosphates The clear regional geological background was observed in The Ilovica region is home to porphyry copper/gold (molyb porphyrycopper/gold to home is region Ilovica The A possible explanation for the large variations in factor The last factor with an eigenvalue >1 was factor 7. The fac factor was 7. >1 The last factor with an eigenvalue DISCOMAP (2016): (2016): DISCOMAP DALMACIJA, B. & AGBABA, J. (eds.) (2006): Kontrola kvaliteta vode za piće [ piće za vode kvaliteta Kontrola (2006): (eds.) J. AGBABA, & B. DALMACIJA, Strumica valley was of a more local nature. local more a Strumicaof was valley REFERENCES report on the copper gold G.S. Technical on resources (2007): the CARTER, Ilovitza including Cu, Pb, Cr, Ni, Zn, Li have an anthropogenicoriginanas have Li Zn, Ni, Cr, Pb, Cu, including mining. and/or production agriculture intensive of consequence a The influenceof mining in Ilovica on the groundwater in the especially intensive agricultural production. Further research is requiredthis on subject. high factor loading of As in factor 1 could be linked to the ele inobserved The arsenicgroundwater. in of concentration vated back geogenic attributedpredominantlythe was to As of crease ground and to a lesser degree due to anthropogenic influences, factors 1, 2, factors3 and partly1, in factors The 4 andlast two 5. factors 6 and 7 were affected by more local geological variations. The mica valley was predominantly influencedby the and geology, only some minor additional anthropogeniccorded. effects were re which explained 70.0 % of the variance in the data. Factors 1, 2, variancethedata. 1, the in Factors of % explained70.0 which and 6.2% 7.5 8.0, 9.6, 11.2, 13.7, and6 explained7 5, 4, 13.9, 3, Strugroundwaterin chemistry Theof variance,respectively. of Ni, Zn, Na, K, Li and PO and K, Li Zn, Na, Ni, CONCLUSION 6. >1 eigenvalues withfactors 7 yielded analysisPerforming factor This was one of the highest factor scores in the area of Ilovica in Ilovica of area the in scores factor highest the of one This was four factors 5, 6, (3, and 7). The elevated factor loadings in the area were noted by a number of analytes: Al, Cu, NO Pb, Cr, groundwater (RAKIKEVIK et al., 1978, 1980; CARTER, 2007). 2007). CARTER, 1980; 1978, (RAKIKEVIKgroundwater al., et the high Additionally, concentration of a number of the studied analytes was increased in groundwater mining. to intensive due be be contributed fertilizers to the due use of andseptic pesticides, manure. systemssmallamountsand of denum) ore which increased the concentration of metals in the scores for this scores for factor throughout the is investigated due to some (PO phosphates addition, In phenomena. geological local tor loadings in this factor were Li (0.81), PO (0.81), Li were factor this in loadings tor 9). Fig. 3; (Tab. were observed in the areas of Dobrejci, east of Petralinci and Bosilovo and south in origin. geogenic were The factor scores were highest in the zone east of Bansko and inand Bansko of east zone the inhighest were scores factor The the Ilovica areas. Zinc had a positive factor loading in factor 5 was correlatedit where with NO scores factor lowest The K. and Na with correlated was it where 6 Boev et al.: The use of factordistinguish analysisof to influence the use material, parent Theagriculture mining and of groundwateral.: on et compositionBoev ...