Occurrence of Vivianite in Alluvial Quaternary Sediments in the Area Of

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2017 | 70/1 | 41–52 | 7 Figs. | 2 Tabs. | www.geologia-croatica.hr Journal of the Croatian Geological Survey and the Croatian Geological Society

Occurrence of vivianite in alluvial Quaternary sediments in the area of Sesvete (Zagreb, Croatia) Anita Grizelj1, Koraljka Bakrač1, Marija Horvat1, Radovan Avanić1 and Ivan Hećimović2

1 Croatian Geological Survey, Sachsova 2, 10 000 Zagreb, Croatia; ([email protected]) 2 Anina 29, 10 000 Zagreb, Croatia doi: 10.4154/gc.2017.01

Abstract Article history: Boreholes Badel-1 and Badel-2, located in Sesvete near Zagreb, were drilled through 71.50 and Manuscript received August 09, 2016 84.40 m of Quaternary sediments, respectively. Within these sediments, the occurrence of earthy Revised manuscript accepted November 17, 2016 aggregate and 1-2 mm nodules of the deep blue coloured mineral vivianite was observed. Inter- Available online February 20, 2017 pretation of the depositional environment, provenance of the sediments and vivianite occurrence was based on sedimentological, mineralogical and palynological analyses. Three different facies within the alluvial environments were interpreted: 1) gravels and sands typical of alluvial environments 2) structureless beds of silts and clays deposited in oxbow lakes, marshes and floodplains

3) chaotic sediments deposited in the upper part of the alluvial fan.

Macroscopically, an earthy aggregate is essentially an occurrence of flattened vivianite crystals grouped in clusters. The studied sediments are the product of intensive weathering of different types of rocks from Medvednica Mt. with a prevalence of green-schists. Rocks from Medved- 2+ Keywords: vivianite, Quaternary sediments, nica Mt. as the source of ferrous iron (Fe ) and phosphorus (P), and reductive depositional en- alluvial, informal Bistra Formation, Zagreb, Croatia vironments can indicate conditions for genesis of vivianite.

1. INTRODUCTION observed (Figs. 3, 4A). Vivianite (Fe3(PO4)2 x 8H2O) is a ferrous Quaternary sediments from the Zagreb area were studied in iron phosphate mineral which forms in waterlogged soils and many aspects during the last century (e.g. GORJANOVIĆ- aquatic sediments (BERNER, 1981; BERMANEC, 1999; 2+ KRAMBERGER, 1907; CRNKOVIĆ & BUŠIĆ, 1970; ŠIMUNIĆ ROTHE et al., 2014, 2016). It is probably the most stable Fe or- & BASCH, 1975; ŠIMUNIĆ et al., 1988; VELIĆ & DURN, 1993; thophosphate mineral in sedimentary environments and in natu- ŠIKIĆ, 1995; VELIĆ et al., 1995; VELIĆ et al., 1999), but they are ral systems, stable under pH conditions from 6 to 9 (NRIAGU, ide color shown most completely on the Basic Geological Map of SFRY, 1972). The precipitation of vivianite often occurs directly from 1:100.000, sheet Ivanić Grad (BASCH, 1983a, 1983b). Pleistocene the pore water which contains high concentrations of ferrous iron 2+ deposits are represented by aeolian and aquatic-aeolian sedi- (Fe ) and soluble reactive P which is found in anoxic non-sulfidic ments while in the Holocene, deposits are dominated by alluvial environments (NRIAGU, 1972; RODEN & EDMONDS, 1997). and subordinately by deluvial-proluvial sediments. Marsh sedi- The aim of this article is to determine the sedimentological ments are less abundant. Similar distinctions of these sediments and mineralogical characteristics of alluvial Quaternary sedi- are applied on the Geological Map of the Republic of Croatia ments in the area of Zagreb where vivianite occurs. 1:300.000 (2009). Similar sediments are described by AVANIĆ et al. (2006) 2. GEOLOGICAL SETTINGS from the outcrop near Vojnić (Fig. 1A), and consist of silts, clays, The North Croatian Basin is the south-western part of the Pan- gravels and sands which were deposited in an alluvial environ- nonian Basin System (PBS) (PAVELIĆ, 2001) which comprises ment and belong to the informal Bistra Formation. The chrono- the biggest part of the Central Paratethys realm (HARZHAUSER stratigraphic position of this formation is still under debate due to & PILER, 2007). Medvednica Mt., is a neighboring mountain to the lack of absolute dating evidence. AVANIĆ et al. (2006) sug- the study area (Fig. 2), and represents one of the inselbergs in the gest that the Bistra Formation spans a Pliocene-Pleistocene age. PBS which exposes Palaeozoic-Mesozoic rocks deformed during During mapping for the Basic Geological Map of the Repub- Cretaceous-Palaeogene times and surrounded by Miocene sedi- lic of Croatia at 1:50.000 scale, two boreholes: Badel-1 (45°82'64''N; ments (TOMLJENOVIĆ et al., 2008). Tectonically, it is located 16°09'98''E) at 71.50 m deep and Badel-2 (45°82'67''N; 16°10'09''E) in the Zagorje-Mid-Transdanubian shear Zone (ZMTDZ) seg- at 84.40 m were studied in the area of the former „Badel” factory ment of the Sava Zone. This part of the Sava Zone is the area of in Sesvete (Fig. 1). On this map, Quaternary sediments are sub- the connection between the Southern-Eastern Alps, Tisia block divided on the basis of their lithology. In the Pleistocene, silts, of the PBS and the Inter nal Dinarides (PAMIĆ & TOMLJENOVIĆ, clays, sands and gravels of the informal Bistra Formation (BS) 1998; HERAK, 1999; HAAS et al., 2000; HAAS & KOVÁCS, are dominant while in the Holocene-Pleistocene, sands and gra- 2001; PAMIĆ 2002, 2003). vels of the second terrace (t2) are present. The Holocene is repre- The core of Medvednica Mt. is composed mostly of a variety sented by (a) silts and clays of marsh environments and (b) sands, of metamorphic rocks such as metapelites, metapsammites, slate- silts and gravels of alluvial environments. Within the investigated phyllites, slates, quartzites, marbles, blueschists, greenschists of sediments of the boreholes, the deep blue mineral vivianite was Palaeozoic age and more rarely of Mesozoic age (BELAK et al., Geologia Croatica Badel-2 (Bad-2,45°82′ cherts and, occasionally, pyroclastic and magmatic rocks also oc also rocks magmatic and occasionally, pyroclastic and, cherts radiolarian rocks, sedimentary clastic different Mesozoic the 1983b; ŠIKIĆ Cre et al., Upper 1979; for common Mesozoic rocks are and limestones dolomites ŠIKIĆ, (BASCH, except 1995). Subordinately, relationships and which taceous Tertiary sediments The are most transgressive. tectonic in during generally are rocks & VENEC LUGOVIĆ, 2009). and non-metamorphic Metamorphic (SLOMt. Medvednica at exposed mélange ophiolite langinian Va Late to Callovian Early the in crust oceanic of fragments abundant most the represent dykes by dolerite intersected lly occasiona rocks extrusive 2008). Mafic al., et TOMLJENOVIĆ 2006; al., et LUGOVIĆ 1998; TIBLJAŠ, & BELAK 1995, Figure 1. 42 A)

Location mapand, B) Lithostratigraphic geological mapoftheSesvete area withlocations ofboreholes Badel-1(Bad-1, 45°82 67′′ N; 16°10′ 09′′ E) indicated. - - - - - by tectonic thinning of the crust and isostatic subsidence, while while subsidence, isostatic and of crust the thinning by tectonic developmentcharacterized ofwas basin phase syn-rift Miocene ment of the PBS took place in two The Early phases. and Middle (HORVÁTH & ROYDEN, 1981; ROYDEN, 1988). The develop complex rocks shallow of by acomparatively basement rated sepa (sub-basins) depressions deep different-sized of number a Plate belts mountain (Fig. pine, and Dinaric Carpathian European 2) and includes the of Al the by subduction surrounded is (Apulian)ItPlate. and African the beneath collision continental to due 1999; al., et HALAMIĆ 1995; BABIĆ &LUGOVIĆ, al., et 2002; SLOVENEC 2012). 2008, GORIČAN, & (HALAMIĆ curred The formation ofThe formation the PBS in the Early commenced Miocene Geologia Croatica 70/1 ′ 64′′ N; 16°09′ 98′′ E) and E) and - - - Geologia Croatica ------43 ). Analyses were performed by deterperformedAnalyses were by ). -3 ; δ=2.84 gcm 3 Preparation for qualitative and quantitative mineralogical Grainsize analyses performedwere using combinationa of Preparation of coarser sand and fine gravel samples included samples fine gravel andcoarser sandPreparation of sepa vivanitewere individualXRPDanalysis,grains of For SEM-EDS analysiscarriedwas SEM-EDS theJEOLMulti-Puron out sificationof sediments. analyses the light of and heavy mineral fraction silty of and sandy samples included the carbonate following: fraction dissolution mm0.09–0.045 the separation acid,of hydrochloric cold 4% with mineral fraction fromthe sandy and siltysediments using sieves, separation the heavy of and light mineral fraction using bromo (CHBr form sieving and aerometricandsieving nomenclature methods.Theaccording to was used the for clas (1973) andTREFETHEN KONTA (1950) mination of 300-400 grainsmethod according to MANGE & MAURER (1992). per sample using the ribbon counting separation mm 2.80 mm, mm sieves and by 0.90 1.25 fraction. rated using a stereomicroscoperateda usingXRPDneedle. patterns and were equipped X`Pert) (typeverticalPhilipsgoniometer a on recorded with a Cu-tube using the following experimental conditions: 45 40 mA, kV, PIXcel detector,PW 3018/00 primary beam diver and continuous º2θ/s). gence scan 1/4° 0.02 (step pose scanning microscopeperformed at accelerating (JSM-35).20keV potential and 90-mA Morphologic filament analysesspectromeenergydispersivecurrent. by analysesCompositional were try (EDS) utilized a liquid nitrogen cooled INCAx-act Oxford Instruments detector with the microscope operating at 20-keV - - - - 3 The evolution of Neogene sedimentation on Medvednica Mt. sedimentationMt. Medvednica Neogene on of evolution The samples).

ed Palaeozoic-Mesozoic crystallinePalaeozoic-Mesozoic edDuring basement.Mio the Pannonian Basin System (PBS) and its surroundings with the locations of the study-area marked in red. Based on http://maps-for-free.com/. marked in red. of the study-area with the locations (PBS) and its surroundings Basin System 2. Pannonian Figure 3. METHODS thicknessthe measurement of following: the included work Field of the deposit, defining the typeof contacts between intervals, determining the type of sediments and sampling for grain-size analysismineralogical-petrologicalsamples), (14 and palynolo (14 cene, various types clasticof sediment and limestones were de posited in different marine, brackish and freshwater environments depending on the PBS development. Pliocene and Quaternary sediments silts, consist clays, sands of and gravels which were environments.fluvial andfreshwaterswamps lakes,indeposited gical analysis. Mineralogical-petrological analysis included the microscopefollowing: analysis unconsolidated of sedimentary rocks (16 samples), X-ray powderanalysis diffractionof vivianite (1 sample) and measurement (XRPD), of CaCO SEM-EDS was described in detail by PAVELIĆ et al., 2003; AVANIĆ et al., al., et AVANIĆ 2003; et al., et ŠIKIĆ describedwasPAVELIĆ detailin by 2017; al., et GRIZELJ 2003; 2006; BASCH, GRIZELJ, & 1983a, 1983b; ĆORIĆ,KOVAČIĆ et al., 2009;VRSALJKOet 1999; VRSALJKO, HERAK,1995; ŠIKIĆ, 1979; 1977; 2006;al., According al., 2006; toBRLEK the et aforementionedal., 2016. authors, Early Miocene sediments unconformably overlie tecto ROYDEN, 1981; ROYDEN et al., 1983; ROYDEN, 1988, 1988, ROYDEN, 1983; al., et ROYDEN the Middle and Upper Miocene post-rift phase was marked by 1981; subsidence caused by cooling & of the lithosphere (HORVÁTH ROYDEN, 2001). PAVELIĆ, nis Grizelj et al.: Occurrence of vivianite in alluvial Quaternary sediments in thearea of Sesvete (Zagreb, Croatia) Geologia Croatica Figure clasticsediments from 3.Adetailedgeological boreholes column ofQuaternary Badel-1andBadel-2. 44 Geologia Croatica 70/1 Geologia Croatica ------45 high high is not 2- concentrations and S 2+ The associated sands are interpretedassociatedaresandsThe

m in size, grouped into clusters (Fig. 4C). The occurrence m Thegrain size,clast-supported naturepoor itsthegravel, of boreholes Badel-1 boreholes andBadel-1 Drilled Badel-2 (Figs. 3, 1, 4A). deposits structure b) sands, and gravels a) three into facies: grouped are less chaotic beds silts sediments. and and of clays, c) 4.1.1. Gravels and sands facies4.1.1. Gravels and sands form decimetre to metre thick lenses and inter beds structurless which overlie silts beds and clays with an ero interbeds,someclast-supported Inboundary.gravels lower sional fining fine-grained upwards, from sandy of and tendency the show gravel in part the lower to silty sands and clayey in the upper part. rarely, very or sandsiltysand, sorted gravelly matrixpoorly The is silts. arePebbles mostly 0.2 to 2 cm in diameter. Sands form in lenseschangingthickor intointerbedsm terbeds 6 to of from0.5 gravels.They are fine to coarse-grained, poorly sorted, hori and earthyaggregates blue sand, gravelly theWithinbedded. zontally and 1-2 mm size nodules of oxidizes vivianite were observeddemonstratedTheirpresencewasXRPD and by 4A). and 3 (Figs. EDS analyses (Fig. 4B and Macroscopically, 4D). earthy aggre essentiallyis occurrencegatean flattened of vivianite crystals up to 6 oxidation-reductionsedimentsreactionslinkedintovivianite is of (ROTHE et It al., appears2016). when pore waters have suffi highciently orthophospate and Fe present in high amounts 2015). ROTHE et al., (NRIAGU, 1972; sorting and the boundary, erosional lower together indicate sedimentconcentration and depositionflows in streamchannels 1984). STEEL,(NEMEC & as having been deposited from sheetflows (NEMEC & KA ------was measured using the 3 , specific gravity 2.0). The residue The specific , gravity 2.0). 2 ), hydrochloric acid (HCl, 15%), and hydrofluoric and 15%), (HCl, acid hydrochloric ), 7 O 2 P 4 Vivianite from sample Bad-1/14.60-15.20 m; A) photo showing a mineral aggregate in sediment, B) XRPD pattern of the separated material (Viv material of the separated B) XRPD pattern in sediment, – vivian- aggregate a mineral showing photo sample Bad-1/14.60-15.20 m; A) from Vivianite Standard palynological processing techniques (FAEGRI & All analyses were made at the Croatian Geological Survey Collins calcimeter. were usedIVERSEN, MOOREto extract et 1989; al., 1991) the organic matter. The samplesphate (Na weretreated with sodium pyrophos 4. RESULTS AND DISCUSSION 4. RESULTS cone oil for palynomorph identificationfor was car oil analysis.Pollen cone transmitted BH-2 microscopeOlympusatlightunder an out ried immersion) magnifications (oil andx600 x1000 x400, combined interferencethewith contrast.to order inusedFluorescence was distinguish reworked palynomorphs. Photos were taken using a Moticam 2300. Palynologicalcollection the Croatian of Geological Survey. residues and slides are stored in the (Croatia, Zagreb). was sieved at 10 µm mesh. using Microscope a nylon at 10 was slides were sieved prepared using glycerin palynofacies for analysis, and with sili tological determinationtological the boreholes, mineralogical of investi gation of vivianite and definitionof a stratigraphic affiliation of the deposits based on palynological analyses. A detailed geolo gical column the of investigated boreholes is shown in Figure 3. Vivianite was found at depths m in upsediments to 15.20 the of 4.1. Description and interpretation of facies Geological investigations consisted petrographic of and sedimen ite, Qtz – quartz,ite, C) crystalsD) EDS spectrum image – flattened SEM Ms – muscovite), to 6 mm length, analysis. up of elemental potential and 90-mA current. CaCO Figure 4. Figure Grizelj et al.: Occurrence of vivianite in alluvial Quaternary sediments in thearea of Sesvete (Zagreb, Croatia) acid (HF, 40%), to acid 40%), remove (HF, the minerals,clay carbonates and si lica, respectively, followed by separation by lica, the followed organic of respectively, residue by means Zinc of chloride (ZnCl Geologia Croatica on their CaCO their on (Tab. 1). are These poorly sediments to very poorly Based sorted. brown to brown colours. Zircon appears as colourless, rounde colourless, as appears Zircon colours. brown to brown dark in pleochroism, strong with crystals hypidiomorphic rarely allotriomorphic, of form the in B)occurs 5 (Fig. type) (Dravite (Tab. 1). Tourmaline samples some in present are brookite and pyroxene chloritoid, titanite, while samples, all almost in present are 5) (Fig. kyanite and amphiboles rutile, zircon Tourmaline, yellow yellowpale colours. in dark to noticeable pleochroism, with grains as allotriomorphic appears Staurolite grains. regular (Fig.and staurolite 5 D). as pale occurs ir pink-coloured, Garnet (Tab.(Fig. B-E) HMF 5 the in garnet are 1) minerals significant A-E).Other 5 (Fig. colour green yellowish to yellow pale with pleochroism, expressed weakly with grains allotriomorphic as most 24 from samples, to ranging 95 % (Tab. 1). Epidote appears in dominant (epidote,clinozoisite) zoisite, are group epidote the from minerals the HMF the in minerals translucent the Among ofbiotite. amount small a 1/25.00Bad-2/62.00 contain and m m Bad- Samples abundant. less is chlorite while limonite), and (magnetite minerals opaque followedby samples, all in (HMF) small very a in Bad-2/12.40 of spicules. sponge amount present asmall mcontain is (Tab.Bad-1/4.30and 1). m Muscovite Samples samples all %. almost 12 in to 2 quantity from varies K-feldspars of amount The abundant. less are tuffs and quartzite Chert, abundant. most the are schists metamorphic low-grade them, rare. The amount of varies from rock 2 fragments to 54 %. Among are extinction homogeneous with grains while prevail tinction ex low undulatory with Grains 87%. to 40 from varies content its and LMF the in mineral common most the is Quartz (LMF). light and fraction the from light by mineral Samples grains are dominated heavy the of analyses from the offractions sandy-silty fraction modal mineral samples (Fig. of results the shows 1. Table 4.2. Contentofheavyandlightminerals 1993). &POSTMA, (NEMEC material unconsolidated deposited ofpreviously destabilization sudden ofa outcome the or to 1984), fan, STEEL, alluvial a proximal to which may point teristicscharac These particles. clay-sized to gravel coarse from of sizes, the deposits poorly and a sorting, disorganization, wide range internal of grain by characterized indicate are They uneven. is plane bedding lower The a debris clays.and silts structureless on deposited are sediments Chaotic flow (NEMEC sediments chaotic 4.1.3. of Facies & roscopically visible. The CaCO depths down to 15 m as a short zone linear or dots which are mac at sediments the in present sporadically is of vivianite aggregate 3).Earthy (Fig. aggregate vivianite earthy and coal fauna, and or the facies of of chaotic They fragments sediments. contain flora beds of silts Structureless and clays overlie gravel and sand facies clays and silts of beds structureless of 4.1.2. Facies frequent 1996, 2000). (MIALL, environments Such luvial flow. waning a by of al typical are gravel and of sand changes lateral and vertical deposition suggests lenses sandy 1999). ZANCI, 46 Vojnić( nearby described sediments Pliocene-Pleistocene to similar marshes, oxbow and in lakes deposited be could sediments these facies, alluvial coarse-grained with association In plain. flood the on suspension from deposited were they that clays suggests and silts of size grain (Tab.1). The silts sandy calcareous and silts clayey sandy calcareous silts, silts, clayey calcareous silts, Translucent minerals prevail in the heavy mineral fraction fraction mineral heavy the in prevail minerals Translucent AVANIĆ al., et 2006). 3 content and grain size they are classified as clayey clayey as classified are they size grain and content The sandy matrix, upwards fining tendencyand 3 content varies content from 3.3varies to 47.3 %

3). 3). d - - - - -

Table 1. Modal composition of the heavy and light mineral fractions of the sample from boreholes Badel-1 (Bad-1) and Badel-2 (Bad-2) determined by polarizing microscope. Op – opaque minerals, Bt – Biotite, Chl – chlorite, THM- – Trans lucent heavy minerals, Tur – tourmaline, Zrn – zircon, Rt – rutile, Am – amphibole, Px – pyroxene, Ep-Zo-Czo – epidote, zoisite, clinozoisite, Grt – garnet, Ky – kyanite, St – Staurolite, Ttn – titanite, Brk – brookite, Clo – Chloritoid,- Oth. – Oth er minerals, Qtz – quartz, Kfs – K-feldspar, S – rock fragments (schists, chert, and quartzite), Ms – muscovite, Sp – sponge spicules, + – traces (<1%), * 3– (wt. CaCO %) analysed by Collins calcimeter.

% HEAVY MINERALS (%) TRANSLUCENT HEAVY MINERALS (%) LIGHT MINERALS (%) CaCO3 HEAVY SAMPLE SAMPLE DESCRIPTION Ep-Zo- (wt. %)* MINERAL Op Bt Chl THM Tur Zr Rt Amp Px Grt Ky St Ttn Brk Cld Oth. Qtz Kfs S Ms Sp FRACTION Czo Bad-1/4.30 m silt 3.3 Prep. 31 6 63 2 2 6 6 24 41 3 12 + 2 87 3 2 8 + Bad-1/8.00 m Clayey silt 4.2 2.1 29 + 71 1 4 1 + 89 3 + 1 2 72 10 17 1 Bad-1/9.00 m Silty gravelly sand 4.2 3.8 23 + 77 + 2 6 81 5 + 1 + + 1 62 4 33 1 Bad-1/25.00 m Calcareous clayey silt 27.6 Prep. 25 + 1 72 3 1 5 3 61 11 2 10 2 + 2 82 6 8 4 Bad-1/39.40 m Gravelly silty sand 3.3 7.7 7 93 5 2 1 + 81 7 + 3 1 86 4 10 + Bad-1/47.40 m Calcareous clayey silt 18.4 4.3 7 1 92 1 + 1 93 4 + 1 + 1 73 2 24 + Bad-1/55.40 m Gravelly silty sand 7.5 18.4 8 92 1 1 + 97 + + 70 6 24 + Bad-1/71.00 m Calcareous sandy clayey silt 11.3 8.0 6 + 94 1 + + 1 89 3 + 3 + 1 74 7 19 + Geologia Croatica 70/1 Bad-2/4.00 m Calcareous sandy silt 32.1 0.8 32 68 2 2 7 1 + 36 36 4 9 + + 2 76 7 17 Bad-2/12.40 m Clayey silt 8.0 1.6 24 1 75 3 1 1 6 64 16 + 6 + 2 67 6 27 + + Bad-2/ 21.00 m Calcareous silty sandy gravel 47.3 4.2 13 + 87 1 + 1 2 86 5 1 2 + 1 62 11 17 Bad-2/44.50 m Calcareous gravelly sand 21.1 8.4 5 4 91 1 1 3 94 1 + + 40 6 54 + Bad-2/62.00 m Calcareous silty gravelly sand 17.8 8.1 9 + 91 1 + 1 91 5 + 1 1 76 7 17 + Bad-2/84.00 m Calcareous clayey silt 12.2 8.2 4 96 + + 2 95 1 + 1 + 75 12 13 + Geologia Croatica - - - - 47 mon are various varieties of quartzite (synmetamorphic quartz (synmetamorphic quartzite of varieties various are mon mainly) (Figs. 6 A, ParticlesB). of black metapelites and me tapsammites are less abundant. Micrite to microsparite carbonate particlesarerare.alsoThese carbonate particles differ fromcar bonate particles found at deeper and their levels origin possible limestonesfrom Cretaceous(?) correlatedto be likely very could the area. Sample Bad-1/15.00 m The sample Bad-1/15.00 m of the sand and sandy to gravelly fracgravelly to sandy and sand the of m Bad-1/15.00 sample The tions dominantly metapelites consist black of and metapsam - -

and sandy-gravelly fraction (1.25–2.80 mm) Sample Bad-1/9.00 m In the sand and sandy to gravelly fractions the investigated of m particlessample Bad-1/9.00 of the rocks from greenschist fa prevail.cies They are represented metabasic by rocks richin the epidote-actinolite-plagioclase mineral assemblage. More com 4.3. Analyses of the sandy fraction (0.90–1.25 mm) 4.3. grains, very rarely as idiomorphic, prismatic grains (Fig. 5 A). Amphiboles are pale green to brownish green prismatic crystals with expressed prismatic cleavage. Photomicrographs of the Heavy mineral fraction: A, B, C) off; fraction: of the HeavyD, E) sample Bad-1/47.40 m, analyser mineral off; A, B, sample Bad-1/39.40 m, analyser F) sample Bad- 5. Photomicrographs Figure Table 1. in the same as are abbreviations Mineral off. 2/62.00 m, analyser Grizelj et al.: Occurrence of vivianite in alluvial Quaternary sediments in thearea of Sesvete (Zagreb, Croatia) Geologia Croatica rocks, which are also present on sedimentary clastic Medvednica different and magmatic pyroclastics, cherts, Mt. (ŠIKIĆ et al., radiolarian limestones, dolomites, phyllites, slates, metadiabases, metagabbros, schists, chloritoid and Amphibolite Formation. tra Badel-1from Bis Badel-2and boreholes well as informal the as rocks clastic for material of source main the were rocks These (metapelites, meta marbles, metasediments metatuffites). arenites, by overlain of metabasites Mt. consists ofslopes Medvednica the (2006) the greenschist facies common rocks of Medvednica Mt. According to most LUGOVIĆ whichthe et al. and cropsstructure base the outforms rock onmetamorphic thezoic southern gest that the source rocks were from the Medvednica Mt. Palaeo sug samples the of mm) 2.80 – 1.25 fraction sandy-gravelly and gioclase needles. and pla epidote, actinolite facies contain were They discovered. greenschist the to belonging afew fragments rock Only particles. goethite two contains sample of investigated the fraction sand The common. so not are marble) or fragments limestone lized by recrystal (represented particles carbonate and matter organic the without metasandstones and Sandstones C). 6 (Figs. quartz) (synmetamorphic present is particles quartz of amount large a or as (?)mined graphite meta-anthracite Figs. 6 C, D. In addition, deter be could they of metamorphism degree their on pending de microscopically) and and macroscopicallyvisible (which is particles of these component main the is matter Organic mites. seeinthetext). 1/15.00 m(detaileddescription Figure 6.Photomicrographs ofthesandandsandyto gravelly aggregates fraction of theinvestigated Bad-1/9.00m; C,D)samples: A,B)Sample Bad- Sample 48 The The composition of the HMF, (sandy 0.90 fraction – 1.25 mm ------preservation of the grains is medium to good, i.e. some grains’ grains’ some i.e. good, to medium is grains the of preservation of degree The counted. were palynomorphs promising became material when and environment the check to was intention first the because wasn’tmeasured concentration pollen fortunately, Badel-1/9.70 m because there wasn’t enough organic residue. Un mi palynomorphs. Quaternary with clayand together silt in observed are deposits interglacial eroded from nomorphs & 1980),BIRKS, (BIRKS environments when paly redeposited ments (mainly Miocene). Such redeposition is common in glacial of older of sedi redeposition consequence the is palynomorphs and size of gularity the organic clasts. ofdamage Mechanical the an structure, the on based transport relatively and short nents, compo organic terrestrial of input fluvial pronounced a dicates in that residue organic total the in phytoclasts of structured the of samples the is analyzed the absolute characteristic dominance main The components. organic less or more containing clay) and silt (i.e. samples, fine-grained the from taken were depth) 18.40m at Badel-2 from one and depth, 59.00m and m 58.20 9.70at Badel-1 m, from (three analysis pollen for samples Four 4.4. Palynology Bistra Formation. Bistra informal the to rocks parent as amount a minor in contributed 1977; 1979, ŠIKIĆ, 1995; BASCH, 1983a, 1983b; 2006) HERAK, nimum of 200 palynomorphs couldn’t be reached only in in only reached be couldn’t palynomorphs 200 of nimum All samples contain palynomorphs (Tab. 2; Fig. 7). A

Geologia Croatica 70/1 ------Geologia Croatica

------49 is in the is one and al Mougeo decrease (GROTE, Zygnema (22%) are an an are (22%) are an indica Pinus the optimum is Mougeotia Sphagnum , and redeposited Spirogyra -type (10%), Quercus and Mougeotia Larix Sigmopollis Sigmopollis ) were determined,were ) indica -type fern increases (13%). -type fern increases (13%). Spirogyra Zygnema Polypodium Polypodium Spirogyra, Polysphaeridium completely disappear, completely conifer In Badel-2 only one sample was analyzed from 18.40 m deep. m 18.40 analyzedfromwas sample one only Badel-2 In According to the classification,Köppen’s theclimate was Sigmopollis in the pore waters The(NRIAGU, presence 1972). of limo , dominate, in acidic lakes (TURNER GRAHAM 1995; et al., 2+ (10%), Graminae,(10%), Cyperaceae pollen, Quaternary deposits indicates eutrophic a shallow water body sedimentsfluvial (MEsuppliedperiods which warmpluvial with 15–20°C, and for most species of Such high1968). 14–22°C temperatures(HOSHAW, are easily reached in shallow water exposed to direct solar radiation, at least during the warm season A GEEL,(VAN pH 1978). value of of inferredzygosporesthewasfrom 7.0–8.0 DEANIC, 2006, VAN GEEL et al., 1989, WOROBIEC, 2014). In 2014). WOROBIEC, 1989, al., et GEEL VAN DEANIC,2006, the Zygnemataceae, zygospore formation occurs mostly during the spring season in clean, oxygen-rich, shallow fresh water (VAN GEEL, The 1976). optimal temperature for Spores1977). of the planktonic algae nite and magnetite in the HMF of sandy and silty fractions,siltyFe-Mn and sandy HMFof themagnetite inand nite of phases,contenthigh Fe sourceof concretionssedimentsina as phosphorus (P) in stream sediments of some creeks from Med andreducing conditions, as 2012), al., et (GALOVIĆ vednica Mt. seen from the gray sediments colour of and palynomorphs the of investigated samples the were prerequisites some of vivianite for formation. A variety factors of are primary of importance and may affect vivianite formation as such as well, redox conditions, deg (52%) while the share of (52%) Redeposited dinocysts confirm(2%) erosionof theolder sedi- partupperfromthe m Badel-1/9.70 Sample Miocene). (i.e. ments the coreof contains a very small amount organic of a residue of mixed composition. Sporomorphs are rare with only 52 speci 4.5. Origin of vivianite The occurrence of vivianite in sediments of the informal Bistra Formation is not a ubiquitous occurrence and it is not indicative for these deposits according to field investigations duringgeolo 2000). Spores of the Spores planktonic 2000). of algae sporefern (56%), conifer mens: gical mapping. the One most of important factors vivianite of for mation is a sufficiently high concentrationof orthophospate and Fe dinoflagellate ( cysts ting open vegetation, erosion and deposition on the floodplain. Similar vegetation was also growing around Lake Bled during Dryasthe Younger (ANDRIČ et al, 2009). It is also dominated by conifer pollenand (43%) Cyperaceae is significant. the but proportion algae (8%) The occurof (23%) rence of zygospores of of zygospores of rence indicator of meso-oligotrophic streamslower to calm water en alga The 1989). al., et GEEL vironments (VAN tia m 1996). et al., Badel-1/9.70 sample of most likely humid boreal deposition (Df) during the depositionm m and and dryBadel-2/18.40 of m, Badel-1/59.00 samples Badel-1/58.20 during (Dw) boreal & FILIPČIĆ, 2003). (ŠEGOTA of the mostof common freshwater algae, and is common from arc tic to tropical areas, in lakes, springs and streams, and in even occasional ponds, whereZygnemataceae,especially 1926). (TRANSEAU, season it appears as the first alga after the rainy gae tor of the slowly-moving shallow eutrophicto mesotrophic fresh 1989). et GEEL al., water VAN environment 1980, et al., (PALS Due to vegetational succession, boreal mires alter to heathland. genus moss the m Badel-1/58.20 sample the In

------Pi 4 7 3 3 7 B(%) Carya 18.4m Badel-2 1 0 1 0 24 1 1 A 13 24 11 83 23 12 25 3 5 1 6 6 6 B(%) 59.0m Badel-1 13 0 1 6 2 3 1 6 2 7 2 3 1 A 11 21 22 7 6 5 7 2 B(%) -type Polypodium and (6%) 58.2m Badel-1 1 0 1 0 6 2 8 4 2 1 A -type is among the most resis 15 13 the most abundant (68%), and

10 10 26 13 22 B(%) 9.7m Pinus, Badel-1 25 42 3 4 1 2 1 2 1 6 2 14 2 8 5 2 1 2 4 2 4 1 7 2 5 2 4 1 2 9 4 A 52 100 204 100 339 100 359 100 10 1919 11 37 106 52 225 66 153 43 Polypodium (2%) spores (2%) that prevailed in the acidified (pH Sphagnum The oldest sample from the core Badel-1 at 59.00 m is domi is m 59.00 at Badel-1 corefrom the sample oldest The (6%) were brought in the depositional environment in wind brought the depositional by were (6%) sample: palynomorphs: total palynomorphs sum total Quercus Graminae Larix Dinocyst Mougeotia Tilletia Asteraceae Pteridium Polypodium unknown Zygnema Spirogyra Cichoriaceae Cyperaceae Picea Lycopodium Sphagnum Caryophyllaceae Mimosaceae Sigmopollis Bisaccites gen et sp indet. Bisaccites Pinus Table 2. Distribution of palynomorphs. Table Grizelj et al.: Occurrence of vivianite in alluvial Quaternary sediments in thearea of Sesvete (Zagreb, Croatia) structure and sculpture are partially destroyed making more pre cise determination impossible.poor in species. The The plant communitytant sporomorphs to corrosion, containing is the most sporopollenin relatively samplescommon in is it thereforeand 1984), 1964, (HAVINGA, that are scarce in palynomorphs. Tertiary relicts (e.g. whose pollen is very resistant), except redeposited forms, were observed,not which could indicate that the samples are probably glacial, indicatesvegetationFrigophile Pleistoceneage. theyoungera of particular to deposits (ŠERCELJ, uniformquite the is flora stage cold the period.Since cold classify to difficult is it 1979) and/or stadial, in the case when they are not linked to the previ ous warmer or following period. nated conifer by pollen. 3-4) mires belonging to the boreal floralelement. Boreal mires a moderatelyfavour and cold humid climate, so when the ice started after to melt the last in Age Ice Europe, 10000 years ago, area. covered a huge it weather Wetter and higher com sea levels cea or streams. Less abundant is fern moss bined to raise groundwater tables everywhere, so that large mires (RAEYMAEKERS,basinsand drained lowlands poorly in arose Columns A – Number of identified palynomorphs of identified per samples A – Number Columns of palynomorphs per samples B – Percentages Columns Geologia Croatica systems, an increased nutrient supply led to accelerated eutrophi accelerated to led supply appea the and conditions redox and oxygen in change a cation, nutrient increased an systems, (Fig. freshwater 3).many in could be that curres reason Another abovesilts water permeability the in horizons which oc vivianite such is influence hardlypossible. One ofthe reasons is low clayey samples analyzed the of 2015,case al., 2016),the et ROTHE in al., 1999; et (GOSLAR settings sedimentary influenced nically detected. be cannot sample/sediment the in present of vivianite amount small avery that possibility ally, the is there Addition not occur. will vivianite not present, are factors tioned (ROTHE et al., 2016). It is obvious that if some of the above men des and silicate and clays, pH release, orthophosphate temperature (oxyhydr)oxi Fe(III) remaining by potential resorption position, com community microbial matter, of organic potential radation Figure 7. 50 P) Phytoclasts andBadel-1/59.00m:R) Badel-1/9.70 m: Although vivianite has been detected in many anthropoge many in detected been has vivianite Although Photomicrograph ofdetermined palynomorphs: G) Pinus, H) Polypodium-Type, I) , T) Sphagnum andPinus, S)Picea, T) , J) Cyperaceae, Asteraceae,Polysphaeridium, J) K) L)

Badel-2/18.40 m:A Polypodium-Type, U)Sigmopollis. ------) vironment: en alluvial in deposited facies three into grouped Badel-2 were and Badel-1 boreholes from sediments Quaternary Analysed 5. CONCLUSION al., et 2016). (ROTHE sediments the within of years thousands for many persist can vivianite that demonstrates layers sediment deep in vivianite of presence The data). (unpublished depth m 44.80 at factory „DIOKI” the near borehole another in recorded were nodules vivianite of Zagreb, area the In deposition. its supply during sulphur and production matter vels, organic le nutrient of ranges low with sediments pre-industrial in only present cases some in is (2015), al. et vivianite ROTHE to ding 2016).al., et (ROTHE Accor sediments ofthe capacity binding rance of S of rance Pinus , B)Cyperaceae, Asteraceae, C) Graminae, D) E) 2- Quercus; in the water column, indicating a loss of Fe and P and Feof loss a indicating column, water the in Scale Bar=10µmexceptScale onP)=50µm. Badel-1/58.20 m:M) Picea, N) Pinus, O) Geologia Croatica 70/1 Zygnema Polypodium-Type, , F) Spirogyra - - - ; Geologia Croatica

------51 – in Complex

– in Croatian].– Geochemical atlas

– in Croatian].– Zbornik ra Geological Map of the Republic of Geological Map of the Republic of VAN GEEL, B., ��CKA, B., SZERO-SZERO B., B., ��CKA, ��CKA, B., B., GEEL, GEEL, VAN VAN

Dali je gora bila Zagrebačka odleđena i

Was the Zagreb Mt. thawed and how the Zagreb Mt. thawed and how the Zagreb the Zagreb Was – in Croatian].– Targa, Zagreb, 264 p. Targa, – in Croatian].– The Dinaridic-Alpine connection – as seen from Hun from seen as – connection Dinaridic-Alpine The Revised Middle Miocene datum for initial marine flo marine initial for datum Miocene Middle Revised

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IAS Meeting of Sedimentology.Opatija, Sedimentology.Opatija, of Meeting IAS nd structureless beds of silts and clays deposited in oxbow lakes, marshes and on floodplains chaotic sediments deposited in the upper part the allu of vial fan. Field Trip Guidebook, 167–172. Trip Field in the NE Dinarides: Dating, internal structure and geotectonic implications.– Eclogae geologicae Helvetiae, 95, 263–275. 1) gravel andgravel sand deposits typical 1) alluvial of environments 2) 3) drobiologia, 631, 121–141. clay ceramic Gaj Ivošević (2006): B. KRUK, & D. TIBLJAŠ, LJ., HEĆIMOVIĆ, G. DURN, & D. TIBLJAŠ, I., VLAHOVIĆ, In: Vojnić.– of vicinity the in deposit 39–47. Guidebook, Trip Field Opatija, Conference, Clay Mid-European 3rd (eds.): Medvednica Mt. of facies Miocene Upper and Midle The (2003): I. GALOVIĆ, K., (Northern Croatia).– In: VLAHOVIĆ, I. & TIŠLJAR, J. (eds.): Evolution of Depositional Environments from Paleozoik to the Quarternary in the 22 Basin, Pannonian Karst the and Dinarides proxy Lateglacial palaeoenvironmental record from Lake Bled, Slovenia.– Hy M.C., MARTINČIČ, A., MARINOVA, E. A., M.C., & MARINOVA, MARTINČIČ, A. BRANCELJ, (2009): Below the first two facies at a depth up to 15.20 m earthy m ag 15.20 to up depth a at facies first thetwo Below Deposition theof sediments based on the samples analysed BABIĆ, LJ., HOCHULI, P.A. & ZUPANIČ, J. (2002): & ZUPANIČ, BABIĆ, LJ., HOCHULI, P.A. AVANIĆ, R., BAKRAČ, K., L., M., A., GRIZELJ, ŠIMIĆ-STANKOVIĆ, WACHA, AVANIĆ, BAKRAČ, D., VRSALJKO, M., MIKNIĆ, D., PAVELIĆ, M., KOVAČIĆ, R., AVANIĆ, ANDRIČ, M., MASSAFERRO, J., EICHER, AMMANN, U., B., LEUENBERGER, Grizelj et al.: Occurrence of vivianite in alluvial Quaternary sediments in thearea of Sesvete (Zagreb, Croatia) ACKNOWLEDGEMENT This study was supportedand by the Ministry of Science, Education 181-1811096-1093 No. ProjectCroatia, of Sports,Republic and the Croatian Science Foundation Project No. are4425. We very thankful to Branko HLEVNJAKMining, Geology and Petroleum Engineering) (University for access to the (Cro BELAKMirko of to sediments.thanks Zagreb,go Special alsoborehole Faculty of REFERENCES gregates and nodules vivianite of were determined. analySEM 6 flattenedto crystalclusters up revealed ses occurrence is associated with the presence limonite, of magnetite and Fe-Mn concretions in sediments as a source phases, Fe of a high content phosphorus of in(P) the stream sediments some of creeks from Medvednica and reducing Mt., conditions as sug gested the by palynomorphs the investigated of samples. palynology sedimentsfor (from both underlying and overlying those with vivianite) most probably occurred in a marshy envi ronment m; m) m; (Badel-2/18.40 Badel-1/58.20 Badel-1/59.00 with periodic fluvial inputof terrestrial organic components, as aswell on sandbanks and meadows wet on a floodplain According m). to the Köppen classification,(Badel-1/9.70 based of on palynology, the climate was most deposition likely humid boreal during (Df) (Dw) boreal during dry m depositionm, and of samplesBadel-1/59.00 m Badel-1/58.20 Badel-2/18.40 and m. the sample Badel-1/9.70 ma the originof the on discussionthe for Survey) Geological atian terial and for Dariodiscussion HRUŠEVAR on vegetation cover. 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