Croatian Diatomites and Their Possible Application As a Natural Insecticide

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2017 | 70/1 | 27–39 | 4 Figs. | 6 Tabs. | www.geologia-croatica.hr Journal of the Croatian Geological Survey and the Croatian Geological Society

Croatian diatomites and their possible application as a natural insecticide Ines Galović1, Josip Halamić1, Anita Grizelj1, Vlatka Rozman2, Anita Liška2, Zlatko Korunić3, Pavo Lucić2 and Renata Baličević2

1 Croatian Geological Survey, Department of Geology, Sachsova 2, 10000 Zagreb, Croatia; ([email protected]) 2 University of Josip Juraj Strossmayer in Osijek, Faculty of Agriculture in Osijek, Vladimira Preloga 1, 31000 Osijek, Croatia 3 Diatom Research and Consulting Inc., 14 Tidefal Dr. Toronto, ON, MW 1J2, Canada doi:10.4154/gc.2017.04

Abstract Article history: In recent decades, there has been an increase in the use of diatomaceous earth (DE) as a natu- Manuscript received November 17, 2016 ral insecticide because of its low mammalian toxicity, worker safety, low risk of food residues and Revised manuscript accepted February 24, 2017 the occurrence of resistant insect populations associated with the use of chemical insecticides. Available online February 28, 2017 Therefore there is potential for research into known but previously undescribed Croatian mid- Miocene marine diatomites from the perspective of their potential as proper DE that could be mixed with plant extracts as a new formulation for grain storage protection. The marine diatomites belong to the Paratethyan near shore environment, deposited in the upwelling zone during a mid-Miocene temperate climate. Palaeontological, mineral and geochemical analyses were done on ten promising marly sediments from 26 outcrops and one borehole from the North Cro- atian Basin. The most important ingredient of diatomaceous sediments is silica (biogenic opal-A and SiO2 bound in other silicate minerals including quartz, clay minerals, micas, etc.). The amorphous silica content of the tested Croatian diatomites is relatively low ( 50%) in comparison with the Celatom® MN 51 standard (medium to high efficient DE) (73.6%), nevertheless they show in some part even slightly better efficacy against insects. It seems that the enhanced content of smectite in diatomaceous sediments also influences increased absorption of DE. Based on palaeontological results, the most efficient diatomites from the Podsusedsko Dolje and Markuševec (Medvednica Mt.) consist of the mid-sized planktonic Coscinodiscus group of species where Thalassionema nitzschioides dominate and is positively correlated with their absorption. The usage of Boströms’ standard formula for getting opal-A from geochemical data was abandoned because of negative results and the modified Murdmaas’ formula for hemipelagic sediments was Keywords: diatomite, palaeontology, mineralogy, applied. Preliminary results on the aforementioned diatomite (as inert dusts) show good efficacy geochemistry, natural insecticide, mid-Miocene, against tested insects Sitophilus oryzae (LINNAEUS), Tribolium castaneum (HERBST) and Croatia Rhyzopertha dominica (FABRICIUS).

1. INTRODUCTION chlorinated hydrocarbons, Bacilus thuringiensis, botanicals and Diatomite is a porous, lightweight, siliceous sedimentary rock chemicals (SUBRAMANYAM & HAGSTRUM, 1995; KLJAJIĆ mainly composed of diatom skeletons formed in marine to fresh- & PERIĆ, 2005). Since only a physical method of controlling in- water environments of mid to high latitudes and contains >30% sects is involved in DE, genetic resistance is generally unlikely amorphous opaline silica (SiO ·nH O). Commercial diatomite according to EBELING (1971). However, a potential tolerance or 2 2 even resistance should be considered when choosing DE for re- contains >60% of biogenic silica (BSi). Mostly high-grade diato- placing existing grain protectants (KORUNIĆ, 1998; RIGAUX mite (>80% BSi) is used as diatomaceous earth (DE), crushed et al., 2001; FIELDS, 2003; VAYIAS et al., 2008). and oven-dried inert dust with a minor content of calcium car- The efficacy of DE against insects depends on the different bonate, volcanic glass and terrigenous particles (HARWOOD, properties of the diatom particles, including physical and morpho- 2010). Sediments that contains <30% of diatoms belongs to the logical characteristics of diatoms, rather than on its origin. The tripolite. physical property of diatomite is in its specific gravity (density) Biogenic silica is non toxic to mammals and has been regis- of diatom frustules (skeletons), which is about half that of water. tered in many countries as a food additive. DE is known as a po- The perforations (pores and striae) and open structure of diatom tentially useful grain protectant because it is safe to use, does not frustules renders diatomite a considerably lower density (0.12– affect grain end-use quality, provides long-term protection and 0.25 g/cm3) and high porosity (75–85%), able to absorb and hold is comparable in cost to other methods of grain protection up to 3.5 times its own weight in liquid i.e. in this case wax. Well- (KORUNIĆ, 2013). Ideally, active DE should have a high BSi known diatoms with pores (areolas) have the physical ability to content with a uniform particle size (less than 10 microns), a high absorb wax (lipids) from the insects’ epicuticle, causing its dehy- oil sorption capacity, a large active surface, and very little clay dration and death (EBELING, 1971; KORUNIĆ, 1998), according and other impurities (KORUNIĆ, 1998). Lately, there are nume to high absorbency which speeds up the incorporation of oil. rous reports from around the world on the widespread resistance The earliest known Croatian diatomites are from the Pod- of several stored-product insects to grain protectants from the susedsko Dolje outcrops (Medvednica Mt.), and can be described groups of synthetic pyrethroids, organophosphates, carbonates, as diatomaceous tripolite (outcrops J1-J4: PANTOCSEK, 1903 Geologia Croatica belong to the south-western marginal part of the Pannonian Basin the of North Croatian Basinsediments (NCB) and (Sarmatian) Hrvatsko Zagorje Basin (HZB), mid-Miocene investigated The GEOLOGICAL2. SETTING usage for as DE the agriculture in protection of stored products. sults of Croatian diatomites are presented here with their potential (Fig. 1). The palaeontological, mineralogical and geochemical re Mt. Žumberak at Slavoniaone and in two region, Banovina the research six more outcrops of diatomite have been discovered in ducted from con 2014 DIACROMIXPEST – insecticides“ conventional thetic, replaceto syn botanicals and dusts formulationsoninert based insecticide natural new of „Development project (HRZZ) tion 2006). not known for the Sarmatian (GALOVIĆ & BAJRAKTAREVIĆ, tions on the Podsusedsko Dolje outcrops, where 23 were hitherto seven more diatom taxa were during those determined investiga nica, Žumberak (Jur diatomite) were discovered in Hrvatsko Zagorje (CR), at Medved 2000 to 2004, a few more outcrops from of1:50.000 diatomaceous tripolite (i.e.Map Geological Basic Croatian the for gations KRAMBERGER (1908) (1957). and JURILJ the During investi GORJANOVIĆby used was diatomite of terminology applied marly sediments by many of the aforementioned authors. The first forlaminated Croatia in (Fig.used 1). term, broad Tripolitea is B2 (outcrops Zagorje vatsko RAK PD 1981;outcrops RAKTAREVIĆ, and JURILJ, 1957; outcrop B1: KOCHANSKY 1984); Figure 1. 28 Our investigations ofOur part the are Croatian Science Founda TAREVIĆ, 2006), and Lopatice and Gornja Šemnica in Hr  – Basic Geological Map of Republic of Croatia 1:50.000 from 2000 to 2009; Locations of investigated diatomites in Croatia, Pannonian Basin System based on http://maps-for-free.com: - 2016 (ROZMAN et al., 2015). Throughout this - 1 and Jur - - 2) and Požeška gora Mts. Seventy B3: BAJRAKTAREVIĆ, 1984) BAJRAKTAREVIĆ, B3: - MA: GALOVIĆ & BAJ & GALOVIĆ MA: - DEVIDÉ & BAJ ------acteristic of acteristic the early post the end of the Sarmatian) and less sediment input, which is char compression(due and at cooling lithosphere to deepening basin ofthe consequence probablyais thickness small aSuch ments. VIĆ et al., 1986) clastic limestones, and volcanicwith rare frag consist of marly sediments of the tripolite type (BAJRAKTA tian deposits is relatively small (50 to 150 m), they predominantly & BAJRAKTAREVIĆ, 2006). The total thickness of the Sarma siliceous microplankton (JURILJ, 1957; HAJÓS, 1986;1998; GALOKOVÁČ et al., 2001), and corroborated by investigations of also existed, as shown by the last Miocene transgression (RÖGL, the connections with and the Indo Mediterranean (GALOVIĆ,oscillations seasonal with 2001). Sarmatian, the In more moderate becomes Sarmatian the during climate the nian, enced by climate changes. From in period the the Bade warmer and fauna and their endemism. was This all more strongly influ flora to changes in fa resulting salinity, in decrease further voured influence terrestrial stronger a isolation; by followed was the connection with the other marine areas further weakened, and integration of the Paratethys. At of the beginning the Sarmatian, sea level dropped, causing the ofbeginning the isolation and dis and rupted re-established until the end of the Badenian when the 1988; RÖGL, 1996). These connections have been repeatedly dis Boreal terranean, and Indo tectonic events, sea-level changes regional and by connections controlled with was the MediParatethys Central the of evolution The Mountains. rounded by and Carpathian the Alps, Dinarides pean plate collision (HORVÁTH & ROYDEN, 1981).Euro and African PBS the of isresult a sur as Miocene early the velop in de to began region intracontinental 2003)1).(Fig. al., This et. Paratethys)(PBS)(Central(PAVELIĆ, System 2001; PAVE  – this investigations with explanations in the text. - - rifting phase (PAVELIĆrifting et al., 2003). PacificOceans (STEININGER etal.,  – J1-J4 (1903 to 1957) and B1-B3 (1981 to Geologia Croatica 70/1 Croatica Geologia - Pacific realms VIĆ RE LIĆ ------ Geologia Croatica 29 The parts of the geological outcrops from Medvednica Mt. where the most effective Croatian diatomite and tripolite were found. were tripolite and diatomite Croatian effective most the where Mt. Medvednica from outcrops geological the of parts The Figure 2. 2. Figure I. Galović et al.: Croatian theirdiatomitespossible and al.: Galović applicationI. et naturalinsecticide a as Geologia Croatica (LM) (LM) analyses. Siliceous microfossil slides for SEM preparations (H peroxide hydrogen 30% concentrated with treated and beaker a placedin cm 1 Approximately applied. is Survey cal method preparation used by the The Croatian standard Geologi 3.2. Palaeontology vednica Mt. (Fig. 2)asdiatomite. were affirmed gical, mineral and geochemical analyses) only samples(palaeonto properties physico-chemicalfrom Med preliminary their on smaller particles in the second year of the with research project.efficacy Based testing for μm <45 diameter a to milled but ples, (LIŠKA et al., 2015). Sample PDK ofis mixture all five PD sam MR-10B (mm laminated marl) and examined as natural pesticide marlslaminated from the same horizont), MR10 (siltic marl) and MA analyses: further for selected were and efficacy insecticidal ing tive Celatom efficacy by comparingthem with standard mediumto high effec ca. 10 kg) were taken for testing onpreliminary their insecticidal (D)(ROZMAN et al., 2016) (Fig.1) from the Dolje borehole at Podsusedsko Dolje were also examinedMali Deanovići (MD) and Vukičevići (VU) in Banovina. Samples (PR),(SU),Šušnjar Čuntički Prnjavor (MR),(BA), Martinovići (MA) and Podsusedsko Dolje (PD) at Medvednica Mt. atand ŽumberakBačuga Mt., Crkovec (CR) in Hrvatsko Zagorje, Markuševec Baničevac (BN) and Opatovac (OP) in Slavonia, Jurjevčani (JU) investigation: forfurther twelveselectedwere Croatia, in mites seasonality. Among 26 well outcrops known Sarmatian of diato of result a as laminated mostly are They cm. 48 approx. small, (Fig. varieties 2). ofare sampled the diatomites thicknesses The their and clay silt, varve, diatomite, marls, laminated tripolite, The representative sediments for diatom analyses belong to marl, 3.1. Field research with laboratory tests 3. MATERIALS AND METHODS deposits nian sandstone intercalations, crop with out limestones in and a marls narrow calcite-rich of zone consisting alongsediments the Bade Sarmatian Mts., Samobor and Žumberak the of region the For marlydue depositsof to the predominated, deepening the basin. laminated later whereas down, laid were limestones and nites, et al.,lated (VRSALJKO 2005; VRSALJKO, 1997). accumu sandstones and marls laminated to thin-bedded ment, of ingression advanced and the deepening depositional environ of environments (VRSALJKO, 1999). reduced salinity Through in accumulating deposits, Sarmatian clastic for regions source welling zone (GALOVIĆ & BAJRAKTAREVIĆ, 2006). up ofthe characteristic sediments marine shore mid-Sarmatian known Croatian diatomites from Medvednica Mt.2010). belongWellal., to near et ROJHT 2007; al., et SCHÜTZ 2006; al., et (ŘEHÁKOVÁ, 1977; HAJÓS, 1986; HORVAT, 2004; ROETZELage from Slovenia, Austria, Czech, Slovakia, Hungary and Serbia depositsof Miocene marine alsoParatethys diatomitesare from of Miocene age (DOLLEY & MOYLE, 2003). Nevertheless, otherposit that outcrops near Lompoc in California is a marine deposit posits are in lacustrine origin, although the largest producing de de 2016), exploitedcommerciallyearth most diatomaceous the 30 - In the the In of the parts Individual al., et OGG Ma; (23 Miocene the of beginning the Since 4, PD - 1, PDK, D NCB 2 ® O , ( MN 51. After testing, ten samples showed promis 2 VRSALJKO ) to oxidize organic matter for light microscope microscope lightfor matter organic oxidize to ) Sarmatian shallow-water gravels, biocalcare gravels, shallow-water Sarmatian - 01 and D NCB , 2003). - 02B, JU were uplifted and thus became became thus and were uplifted . In total, 57 In samples (each of - 1, OP 3 of the sediment is is sediment the of - 4 and OP - 4A (less lo ------ insoluble rock residue and the < 2 µm offraction samples. Some X 3.3. Mineralogy metry). sym (bilateral Pennales and symmetry) (radial Centrales ders: gov/ij/). ments were made using free ImageJ software (https://imagej.nih. (1978)GERSONDE & HORVAT and (2004).measure Diatom or their representative parts are counted according to SCHRADER tion (VILIČIĆ, 2003; HORVAT, 2004). Only wholemagnifica x 500 under valvesdiatomalongof transects genera diatom valves 300 for undertaken were methods Quantitative quality. DE of determination for the essential are analyses morphometric their Smear slides using awere BH2 Olympusexamined LM. were coated with gold and studied with a JEOL JSM slide preparation for both LM and SEM analysis. The specimens were in used slides techniques smear SEM and preparation stub Standard disaggregation. improve to 15seconds approximately water. Some of the samples were treated in an ultrasonic bath distilled for with rinsed then are sediments The components. clay remove to pyrophosphate sodium of 10% and carbonate move also include with treatment 20 % of concentrated HCl acid to re some Cr and Ba minerals and oxides of Al, Fe, Hf, Mn, Sn, TaSn, Mn, Fe, Hf, Al, ofoxides and minerals Ba and Cr some was dissolved in HCl. This preparation method is only forpartial in heated were split HNO g 0.25 The samples. g 15 on performed (ICP spectrometry mass emission plasma coupled etry/inductively PANalytical Axios material is cast in a platinum mold. Fused discs were analysed on molten The tetraborate. a a platinum–gold crucible lithium with the loss on ignition (LOI).sample in treated The was fused then determine to (Vancouver, heated ofwassample g 5 Canada).A Zn, and Zr in laboratories of the Bureau Veritas Commodities Ltd Ni,Pb, Sr, Cu, V Ba, elements as sometrace joroxides and selected samples were also analysed by XRF methods for the ma all composition mineralogical their of understanding Forbetter 3.4. Geochemistry 2003). RockJock the using made were gence 1/4 º, and continuous (0.02scan º2Θ/s). 45 kV, 40 mA, PW 3018/00 PIXcel detector, beam primary diverwere:conditions Experimental used. Croatia)was (Zagreb,vey X‘Pert) with equipped a at Cu tube the Croatian Geological Sur 4 ofml methanol a in McCrone mill. (zincite)standard were carefully weighed and ground with about et al., 1984). For quantitative analyses samples with 10% internal (STARKEY550 ºC and ºC 400 to heating glycoltreatment, ter tion of samples and onaf oriented mounts ofmaterial, dried air SON, 1956). Clay wereon minerals the determined < 2 µm frac (1 molacetate dm ammonium an with other minerals. Carbonate fractions were dissolved by acetic acid with peaks overlappingdiffraction eliminate to dissolved be to samples largecontained amounts of that had carbonate minerals - ray powder diffraction (XRPD) was recorded on bulk samples, Determined diatoms are traditionally divided into two or two into divided traditionally are diatoms Determined with together species diatom of diversity and Composition The inductivelyThe coupled plasma atomic emission spectrom samples of residue insoluble the of analyses Quantitative For XRPD analysis a Philips vertical X - AES AES / ICP 3 -HClO 4 - HF to fuming and taken to dryness. The residue The dryness. to taken and fuming to HF - MS) methods for measuring trace elements were mAX . ® ® computer program (EBERL, (EBERL, program computer -3 ) buffer of pH 5 (JACKof5 pHbuffer ) - ray goniometer (type Geologia Croatica 70/1 Croatica Geologia - 35CF SEM. 2 O 5 ------, Geologia Croatica 31

– – – – – – – – – – 50 28 63 42 30 15 26 14 40 23 28 20 20 40 38 46 36 63 28 32 31 9–45 8–35 8–12 29–34 16–18 11–28 34–54 20–35 25–60 20–62 10–16 32–44 28–43 18–21 68–72 39–80 14–30 12–31 20–50 10–40 12–20 12–40 12–29 34–65 19– 37 19– 54–117 ≥40–75 size (μm) size

5 7 6 + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + 27 PDK

5 6 + + + + + + + + + + + + + + + 16 JU-1

+ + + + + + + + + + + + 25 17 MA-4

8 + + + + + + + + + + + + + + + + + + + + + + + 22 D-02B

+ + + + + + + + + + + + + + + + + + + + 59 D-01

6 + + + + + + + + + + + + + + + + PD-1 spp., spp., Liradiscus spp, spp, Chaetoceros spp., Melosira, Paralia, Stephanopyxis, Thalassiosira) Stephanopyxis, Paralia, Melosira,

GRUNOW JURILJ JURILJ Hyalodiscus,

(BREB.) HENDEY (BREB.) (Bacteriastrum (Bacteriastrum ANDREWS JURILJ JURILJ

JURILJ JURILJ GRUNOW cellulosus HAJÓS tenellus EHRENBERG maior KRASSKE KRASSKE EHRENBERG spp.) SCHRADER PANTOCSEK PANTOCSEK PANTOCSEK GRUNOW (BOYER) SMITH (BOYER) sussedana sussedana var. var. EHRENBERG HAJÓS var. var. SCHMIDT PANTOCSEK EHRENBERG CLEVE & GRUNOW & CLEVE PANTOCSEK GRUNOW) HASLE & FRYXELL & HASLE GRUNOW) EHRENBERG (EHRENBERG) EHRENBERG (EHRENBERG) var. var. (GRUNOW) PERAGALLO (GRUNOW) (SMITH) SHESHUKOVA-PORETZSKAYA & GLEZER & SHESHUKOVA-PORETZSKAYA (SMITH) biggiba HAJÓS (PANTOCSEK) ANDREWS (PANTOCSEK) var. PANTOCSEK PANTOCSEK (Coscinodiscus, EHRENBERG) GRUNOW EHRENBERG) (KÜTZING) GRUNOW (KÜTZING) AGARDH (GREVILLE) RALFS (GREVILLE) EHRENBERG (BRIGHTW.) GRUNOW (BRIGHTW.) fossilis PANTOCSEK (EHRENBERG) lanceolata lanceolata (GRUNOW) ANDREWS & STOELZEL & ANDREWS (GRUNOW) EHRENBERG (ROPER) HASLE & SIMS & HASLE (ROPER) PANTOCSEK SMITH (GREVILLE) GRUNOW (GREVILLE) Periptera var. var. GRUNOW JURILJ JURILJ HAJÓS var. var. var. JURILJ JURILJ (EHRENBERG) CLEVE (EHRENBERG) group group polymorphus polymorphus sarmatica sarmatica quadrata spp. spp. spp., spp., JURILJ JURILJ cf. sp. (SCHUMANN) CLEVE (SCHUMANN) cf. cf. GREGORY fa. fa. Diatom distribution with their morphometrics. Legend: + scattered (< 5 %), rare (5–9 %), low abundance (10–15%), abundant (16–35%), high abundance abundance high (16–35%), abundant (10–15%), abundance low %), (5–9 rare 5 (< %), + scattered Legend: morphometrics. their with distribution Diatom sp. sp. Delphineis surirella surirella Delphineis angustatum Dimeregramma Cocconeis scutellum scutellum Cocconeis lorenziana Cymatosira angustata Delphineis C. evolvens evolvens C. fluminensis Cocconeis quarnerensis C. Cocconeis Cocconeis conciata conciata Cocconeis disculus C. distans C. Caloneis boryana boryana Caloneis moniligera Climacosphenia andesitica Cocconeis canaliculata C. Ardisonia fulgens fulgens Ardisonia biddulphiana Biddulphia Biddulphia Achnanthes saeptata saeptata Achnanthes Achnanthes binodis Amphora costata Amphora Achnanthes baldjiki baldjiki Achnanthes brevipes Achnanthes rara Achnanthes Xantiopyxis balearicum Triceratium laetum T. Pennales Stephanopyxis turris turris Stephanopyxis ( leptopus Thalassiosira cysts siliceous and spores resting Perissonoë trigona trigona Perissonoë westii Pseudopodosira oligocaenica Rhizosolenia stellaris Stellarima Melosira dickiei dickiei Melosira Melosira sulcata Paralia Coscinodiscus sarmaticus sarmaticus Coscinodiscus Hemiaulus laevis Hyalodiscus scoticus Hyalodiscus Coscinodiscus radiatus radiatus Coscinodiscus ( rothii Coscinodiscus rugulosus Coscinodiscus Coscinodiscus miocaenicus miocaenicus Coscinodiscus obscurus Coscinodiscus iridis oculus Coscinodiscus perforatus Coscinodiscus Coscinodiscus apiculatus Coscinodiscus curvatulus Coscinodiscus doljensis Coscinodiscus Anaulus minutus Anaulus simplex Anaulus brunii Asteromphalus Coscinodiscus Actinocyclus octanarius Actinocyclus octanarius Actinocyclus senarius Actinoptychus Diatom/sample Centrales Table 1. 1. Table fragments. in species – (>50%) species dominant (36–50%), I. Galović et al.: Croatian theirdiatomitespossible and al.: Galović applicationI. et naturalinsecticide a as Geologia Croatica Table 1. 32 Thalassiotrix longissima Thalassionema nitzschioides Synedra tabulata Synedra fulgens Synedra crystallina Surirella subfastuosa Staurosirella pinnata Staurosirella leptostauron Rhopalodia gibberula Rhaphoneis rhombica Rh. nitida Rh. cocconeiformis Rh. amphiceros Rhaphoneis amphiceros Rhabdonema hamuliferum Planothidium quarnerensis Plagiogramma staurophorum Plagiogramma bipunctatum Plagiogramma biharense Opephora marina Opephora gemmata Nitzschia Nitzschia frustulum Nitzschia doljensis Navicula Navicula latissima Mastogloia M. splendida Mastogloia sarmatica Mastogloia lacustris Mastogloia binotata ( Lyrella hennedyi Hantzschia virgata G. stricta Grammatophora stricta G. oceanica Fragilaria construens G. oceanica Grammatophora oceanica Grammatophora robusta Grammatophora miocaenica Grammatophora macilenta Grammatophora insignis Grammatophora angulosa Fragilaria brevistriata Eunotia Epithemia zebra Epithemia adnata Encyonema Diploneis Diploneis smithii Diploneis subovalis Diploneis splendida Diploneis ovalis Diploneis fusca Diploneis crabro Diploneis coffaeiformis Diploneis bombus Di. minus Di. minor Dimeregramma distans Dimerogramma boryanum Centrales Diatom/sample cf. var. spp. continued spp. (GREGORY) RALFS var. sp. (GREGORY) GRUNOW tenella sp. var. var. sp. biharensis (GREGORY) CLEVE neglectum (GREGORY) CLEVE oceanica macilenta var. (GREVILLE) W.SMITH (BRÉBISSON) CLEVE (W.SMITH)STICKLE & MANN var. (EHRENBERG) EHRENBERG (BRÉBISSON) CLEVE var. (GRUNOW) HUSTEDT (GREGORY) PETIT (KÜTZING) BRÉBISSON EHRENBERG PANTOCSEK var. (SCHMIDT) HANNA & GRANT (ROPER) GRUNOW var. CLEVE (KÜTZING) GRUNOW rhombica var. saxonica (GRUNOW) GRUNOW fa. PANTOCSEK obtusa (EHRENBERG) WILLIAMS & ROUND (EHRENBERG) GRUNOW GRUNOW) CLEVE GRUNOW (EHRENBERG) MÜLLER JURILJ (GRUNOW) ANDREWS quadrata fossilis (SCHMIDT) CLEVE EHRENBERG minor GREGORY porosa EHRENBERG CLEVE & GRUNOW EHRENBERG JURILJ EHRENBERG GRUNOW EHRENBERG PANTOCSEK (EHRENBERG) WILLIAMS & ROUND (SM.) GRUNOW EHRENBERG EHRENBERG (GRUNOW) WITKOWSKI,LANGE-BERTALOT & METZELIN PANTOCSEK KITTON SMITH (GRUNOW) GRUNOW PANTOCSEK HAJÓS GRUNOW HAJÓS (KÜTZING) GRUNOW JURILJ PANTOCSEK (GREGORY) HEIBERG JURILJ JURILJ PD-1 69 + + + + + + + + + + + + + + + 8

D-01 32 + + + + + + + + + +

D-02B 74 + + + + + + + + + + + + +

MA-4 60 + + + + + + + + +

JU-1 30 12 + + + + + + + + + + + + + + + + + + + + + + 9

Geologia Croatica 70/1 Croatica Geologia PDK + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + 8

size (μm) 33–139 do 172 10–26 17–32 20–30 25–45 50–66 22–40 37–93 40–60 25–80 28–32 30–50 43–57 22–45 12–17 9–15 34 22 34 34 20 15 17 40 18 35 64 69 38 40 28 46 34 51 39 8 – – – – – – – – – – – – – – – – – – – – – – – – –

Geologia Croatica

- - - - - 50 4, 4, 33 - 4 4 is and - * * 2 + 34 64 . neglec . MR-10B EHREN ). The LD The ). var

90 required to kill to required

nitzschoides

* * 1 2 3 + 25 69 and LD and MR-10 50 50 (SCHMIDT) HANNA (SCHMIDT) * * 1 1 6 1 Chaetoceros didymus + 81 10 Thalassionema OP-4A (GREGORY) RALFS (GREGORY) (GREGORY) GRUNOW. Approxi (GREGORY) GRUNOW. on the right from the sample D-02B. sample the from right the on group, * * 1 1 7 2 + + 73 16 OP-4 Rh. nitida Rhaphoneis cocconeiformis Rhaphoneis group with resting spores and siliceous cysts. Based Based cysts. siliceous and spores resting with group values were calculated by Probit analysis using IBM 02B), Fig. 3. The 3. dominantFig. species 02B), in sample MA - 90 Coscinodiscus curvatulus curvatulus Coscinodiscus Dimerogramma minus Dimerogramma Coscinodiscus * * 1 2 18 40 28 11 JU-1 Diatom distribution with their sizes is given in to1. Table JURILJ, PDK, PDK, D Insecticidal efficacy was estimated as lethal doses lethal as estimated was efficacy Insecticidal (LD population tested the of 90% and 50% and LD 2013). Statistics(IBMCorp. Released, SPSS 4.RESULTS Palaeontology 4.1. In total, in samples from Medvednica and Žumberak Mts, 111 determined diatom species were with fourteen variants and two forms. Among them, four species had not been previously dis covered in Podsusedsko Dolje: BERG, tum & GRANT and mately 90% of the diatom species are less than 50 μm in size, while larger specimens are mostly broken (GALOVIĆ et2015). al., natu potential a as diatomite of character physical the emphasise ral pesticide. The most abundant species in the samples belong to the Chaetoceros (tripo diatomite prospective most the results, palaeontological on (MA Mt. Medvednica from be would use commercial for lite) on the left an an left the on - - - A S. * 2 4 ** 33 11 50 - D-02B D-02B * 5 + ** 44 10 41 41 3 D-01 3 O 2 O 2 Thalassionema nitzschioides nitzschioides Thalassionema * * * 2 3 + 19 30 34 12 12 PDK PDK (total) – 3∙Al 2 (total) – 2.7∙Al 2 * * 1 5 ** 47 28 19 AES and Perkin Elmer Elan 6000/9000 MA-4 - 10B, (Tab. 5). Therefore Murdmaas’ modi Murdmaas’ Therefore 5). (Tab. 10B, - , 100 grams of clean soft wheat of differentva of wheat soft gramsclean of 100 , Opal-A= SiO Opal-A= SiO gas evolved into the LECO CS230 analyzer a when into CS230 the LECO gas evolved 2 21 days old were addedwere Inertintodays old each jar. 21 dusts were - SEM images of partially crushed diatom diatom crushed partially of images SEM S.oryzae Quantitative mineral composition of samples (in wt. %) obtained by XRD analysis using RockJock® computer program (EBERL, 2003). (EBERL, program computer RockJock® using analysis XRD by obtained %) wt. (in samples of composition mineral Quantitative , , 7 We tested and abandoned this formula because of a negative negative a of because formula this abandoned and tested We From the last century, the Boströms’ standard formula (BOS formula standard Boströms’ the century, last the From Kaolinite Clay minerals Clay Smectite Chlorite Illit/muscovite Aragonite Feldspar Pyrite Calcite Quartz Opal-A Opal-C MINERALS Table 2. 2. Table (<1%) traces – + (1–20%), subordinate – * (20–40%), abundant – ** treatments were conducted in 4 repetitions. dark. Bioassay in was and RHkept % ±5 65 °C, 28±2 at conditions controlled under rieties (approx. 13% m.c.) was mixed with a determined quantitya with mixed was m.c.) 13% (approx. rieties of each dust in glass jars of 200 mL. Fifty unsexed adults of oryzae tested in 3 or 4 different doses, depending on inert dust, and all 3.5. Insecticidal efficacy Insecticidal 3.5. In order to test insecticidal efficacyof inert dusts against rice weevil, from hemipelagic sediments fromused:hemipelagic was result for sample MR sample for result fiedformula (MURDMAA et al.,1980)for extracting opal TRÖM at al., 1972) for estimating biogenic silica from geochemi from silica biogenic estimating for 1972) al., at TRÖM data cal used: was ing the CO withperchloricacid. leached is split preparedsample and Zr. Additionally, volatization during fumingSPECTRO by may done result were inanalyses The Sb. and S As, of loss some CIRIOS VISION ICP Inorganic ICP-MS. carbon was determined by directly measur I. Galović et al.: Croatian theirdiatomitespossible and al.: Galović applicationI. et naturalinsecticide a as Figure 3. 3. Figure Geologia Croatica Pb Celatom® Diatomaceous Earth Functional Additive Standard Celatom® MN 51: Zr Se Li Sc Ta Nb Y Sn Ce W Ba La V Bi Sb Cd Sr Th U As Co Ni Zn Pb Cu Mo Element Sample/ Table 4. Some samplesof smaller amounts contain feldspar and pyrite. siosira leptopus include diatoms dominant bigger but mostly fragmented of species smaller nitzschioides Thalassionema *** ** * Additive Celatom Table 3. 34 samples contain quartz (SiO quartz contain samples 4.04 balite)at at approximately 4 Å (Fig. 4) and opal centred a peak single broad amorphous) produces near ordered, amounts of mineral opal-C in some samples). Opal-A (highly dis clay minerals and opaline silica (biogenic opal-A with very small (calcite aragonite),and/orminerals carbonate are samples ofall analysed rock samples is given in Table 2. The main components the of residues insoluble the of composition mineralogical The 4.2. Mineralogy Celatom® MR-10B MR-10 OP-4A OP-4 JU-1 D-02B D-01 PDK M Element Sample/

A-4

Measured trace elements: Ba, Cu, Ni, Pb, SO Standard DE In %

15 mg/kg, As

Major and trace elements content measured by XRF method (in %) in Croatian diatomites and major elements in Celatom® Diatomaceous Earth Functional Trace element content in Croatian diatomites (mg/kg).

MN 51** MA-4 24.4 5 40 12 6 19 2.4 1.4 275 104 0.5 0.8 75 46.8 39 0.5 54 24 1.8 518 8 8 15 21 113 19.4

= - ®

17.4 3 23 5 4 13 1.0 <0.5 340 64 <0.1 6.2 33 32.9 49 0.3 21 12 0.9 3405 3 10 7 6 81 6.9

20 mg/kg. PDK 4.06 Å (JONES & SEGNIT,1971).& (JONESanalysed Å 4.06 All SiO MN 51 standard.

, 73.60 16.22 14.21 3.96 7.37 61.91 18.65 55.58 21.26 47.71*

Coscinodiscus stellatis Coscinodiscus

2 Coscinodiscus curvatulus, C. doljensis doljensis C. curvatulus, Coscinodiscus

20.2 4 8 5 35 14 1.6 1.2 183 75 0.3 0.8 65 41.5 6 7 16 34 0.4 35 17 1.3 427 6 89 14.7 D-01

7.80 5.44 4.73 1.31 2.32 5.31 3.15 6.83 4.51 8.81 2 O Coscinodiscus oculus iridis oculus Coscinodiscus D-02B 3

14.4 3 7 4 29 9 1.3 0.8 168 81 0.2 4.5 63 4 5 8 82.9 26 0.3 23 12 1.7 549 4 81 11.8

Thalassiosira leptopus 2 in an assemblage with abundant abundant with assemblage an in

) ranging in content from 1 from content in ranging )

Fe 1.80 2.05 1.57 0.40 0.97 2.20 1.34 2.85 1.98 3.85 2 3 JU-1 O 2.2 2 3 2 6 14 0.7 0.5 336 43 0.1 0.8 2 10 5 27 5 21.3 22 0.2 15 8 0.6 3438 31 5.6 , Sr, V

2 - O CaO 5.60 36.90 37.15 49.26 44.72 6.13 38.10 5.59 36.29 9.63 C (well 5 OP-4 2.3 3 3 2 10 2 5 12 0.8 0.4 176 23 0.2 1.1 8 5 23 9 24.6 8 0.1 17 2.2 6405 35 10.8 , Zn, and Zr. and

Paralia sulcata MgO OP-4A 0.30 1.42 1.89 0.24 0.34 1.13 0.49 1.30 0.67 0.92 - 0.8 3 2 1 7 1 2 9 0.6 0.2 170 17 0.1 0.3 6 0.05 14 5 6 0.05 9 0.4 13 31.0 5161 4.3 ordered α

MR-10 . In the PDK Na 98.7 11 6 3 7 3 11 25 1.1 0.6 632 51 0.2 2.9 36 48 10 5 22 20 4.1 133 0.2 37.9 1745 10.4 SUM other oxides 0.16 0.24 0.39 0.48 0.19 0.21 0.25 0.47 0.37

Thalas O

cri MR-10B

- 8.0 4 7 4 8 3 5 30 1.3 0.6 679 60 0.2 1.6 8 52 12 6 25 24 2.0 62 0.2 31.4 1653 12.9 5%. sto and . 0.92 0.83 0.09 0.19 0.82 0.44 1.05 0.59 1.43 K 2 O - -

MnO respectively). In comparison to the standard sample (Celatomsample standard the to comparison respectively).In holeDoljePodsusedsko (D relatively small (< 47.71%) except for the samples from the bore 3.96 to 61.91%. The contentmeasured of SiO in Table 3. The concentration of total silica in samples varies from The results of geochemical analysis for major elements are shown 4.3. Geochemistry MN 51)MN majoritythe of samples analysed have contenta high of and the variation is a composite of all the errors inherent in any in inherent compositeaerrors is of the variation all the and minerals have a wide range of Clay variations groups. in chemical mineral compositionclay different within considerably varies ofratio SiO samples. different The in quantities different present in theyare but phases, mineral same the contain samples the of most that cene pelitic sediments from the Croatian part of the PBS revealed et al.cording to GRIZELJ (2007; 2017) analyses of XRPD Mio 3.5 2.7.from to varies and clayconstant, silty and almost is Ac SiO the that assumption the on based are calculations of types (Tab.These 5). formulas maas’ Murd and Boströms’ by calculationsof results than silica opal ples obtained by XRPD analyses (Tab. 2.) gave larger amounts of compositionofsam mineralogical of the analyses Quantitative (Tab. of opal-Aamounts quartz 2).lesseror and greater contain of results showedThe analyses XRPD all analysed samplesthat 5. DISCUSSION ficacyin issamples seen D (RW), vil Results among our samples of inert dust efficacy againstrice wee 4.4. Insecticidal efficacy on common stored pests to contentthe higher of connected are organic matter. trations of especially uranium, in sample MR-10 from Banovina, ofconcentrations creased Ni (>50 mg/kg). The elevated concen samples MR-10 and MR-10B from Banovina region also have in Medvednica Mt. (Tab. 4). The MA samplessample in from Medvednica Mt.determined is and sample, standard of earth diatomaceous for mg/kg 15of value recommended the exceed of Pb(19.4concentration elsewhere. highest The whichmg/kg), form than Mt. Medvednica from samples in higher are Cu and is given in Table 4. It is thatsignificantthe concentrations of Mo valueshigh of LOI (>18.60%). in results samples the in component carbonate of content high (Tab.3). MgO The of content 35%)high relatively(> and CaO 0.07 0.07 0.02 0.005 0.02 0.04 0.04 0.03 0.07

The measured The contentmeasured of elementstrace of nine DE samples TiO 2.30 0.23 0.24 0.07 0.12 0.27 0.16 0.31 0.25 0.41 2 S. oryzae S.

2 /Al P – 0.07 0.08 0.11 0.007 0.06 0.10 0.21 0.11 0.10 2

2 O O 5

can vary within one clay mineral group and and group oneclay mineral within vary can are shown in Table shownin are ef6., highest wherethe 5.50 35.04 36.53 42.78 41.31 18.60 35.22 22.52 33.33 23.44 LOI

- - SUM*** oftrace elements 01, D 01D and 2 /Al - 02B and MA 2 – 0.728 1.541 1.105 1.345 2.326 1.048 2.442 0.002 2.218 O

- 3 02B;55.58 61.91% and % ratio in terrigenous clay terrigenous in ratio

2 Geologia Croatica 70/1 Croatica Geologia in most samples is - 4. 96.90 99.25 99.08 99.74 99.24 98.97 98.95 98.97 99.51 98.96 SUM

- 4 from from 4 TOT/C – 9.93 10.42 11.61 10.76 5.83 10.07 8.56 – 9.65

------

Geologia Croatica 35 values (95% (95% values 90 MN 51 against against 51 MN ® LD90* /LD 50 334.1 (86.64-399.00) (86.64-399.00) 334.1 606.7 (575.90-648.08) (575.90-648.08) 606.7 (436.21-487.52) 458.7 (763.36-944.09) 831.1 (699.14-813.40) 744.4 (668.39-816.94) 726.4 447.2 (419.88-481.90) (419.88-481.90) 447.2 (240.55-422.56) 359.6 954.1 (847.50-1159.46) (847.50-1159.46) 954.1 (750.76-1161.96) 867.7 Lethal doses (ppm) doses Lethal LD50* 300 ppm=83.5% ppm=83.5% 300 300 ppm=82.5% ppm=82.5% 300 156.5 (62.28-213.26) (62.28-213.26) 156.5 351.4 (324.22-373.43) (324.22-373.43) 351.4 (183.05-266.05) 232.2 (646.91-778.77) 693.3 (564.40-623.79) 588.6 (346.71-460.50) 421.5 (517.44-555.17) 534.8 (314.80-391.50) 362.8 (L.) adults after 7 days of exposure with LD with exposure of days 7 after adults (L.) MN 51 51 MN Efficacy of 9 Croatian inert dusts and standard Celatom standard and dusts inert Croatian 9 of Efficacy ®

JU-1 JU-1 MA-4 MR-10 MR-10B OP-4 OP-4A PD-1 Celatom Inert dust dust Inert D-01 D-02B Table 6. 6. Table *LC50 and LD90 expressed as parts per million (ppm), Confidence limits (CL) are given in given are (CL) limits Confidence (ppm), million per parts as expressed LD90 and *LC50 parentheses Sitophilus oryzae oryzae Sitophilus limits). fiducial MR-10B

1.53 5.44 –0.10 16.32 14.69 16.22 MR-10

4.73 0.02 1.44 14.21 14.19 12.77 OP-4A

3.96 3.93 1.31 3.54 0.03 0.42 OP-4

7.37 2.32 6.96 6.26 0.41 1.11 JU-1

3.15 9.45 8.50 9.20 18.65 10.15 D-02B D-02B on collected samples in content ) 2

5.31 61.91 15.93 14.34 45.98 47.57 D-01 6.83 55.58 20.49 18.44 35.09 37.14 according to standard Boströms’ formula (BOSTRÖM (BOSTRÖM formula Boströms’ standard to according are from Table 3. Table from are B

according to modified Murdmaas’ formula (MURDMAA (MURDMAA formula Murdmaas’ modified to according O PDK 2 M M 9.08 4.51 7.73 21.26 13.53 12.18

and Al and 2 2 MA-4 8.81 23.92 47.71 26.43 23.79 21.28 XRPD pattern of bulk sample D-02B, and insoluble rock residue of sample MA-4. sample of residue rock insoluble and D-02B, sample bulk of pattern XRPD

Content of Opal-A of Content 3 B M O 3 According to the geochemical analyses there is a significant a is there analyses geochemical the to According 2 O 3 2 2 O 2 Opal-A Opal-A Al 3∙Al 2.5∙Al Element/ mineral SiO variation in the total silica (SiO silica total the in variation analytic analysis: operator, instrument, method, beneficiation, 1989). WEAVER POLLARD,1973; and sampling(WEAWER Table 5. 5. Table Opal-A and 1972) al., at SiO 1980). al., et Figure 4. 4. Figure I. Galović et al.: Croatian theirdiatomitespossible and al.: Galović applicationI. et naturalinsecticide a as Geologia Croatica commercial usage as DE (Tab. 2, Fig. 4). As a BSi component, component, BSi a Fig.(Tab.4). As DE 2, as usage commercial amount of opal D samplesD in lysed samples compared to sample Celatom there. The content of arsenic (As) is significantly lowerin allana lead might be a result of the weathering of the galenite ore deposit while the concentrations in all other samples are lower. Enhanced MA sample the solely in exceedsvalueslimit therelative Celatomto toxiclead(Pb) ofamountareThe arsenicandof importance. Pb Among the trace elements, only the concentrations of potentially Celatom contentin their than smalleris mites TiO+ MnO in the sample (Tab. 2). The sum of all other oxides (Na Mt. probably originates from the chlorite mineral group occurring tion of iron registered in the sample MA vi from the Medvednica Mt. as well as in the sample MR-10BFe3). The (Bano detectedsmectitewhichthe (Tab.itsadsorption increased and 2 elevated(Al content of alumina Celatom on the amount of the clay component in the sample. In relation to mite in association with calcite. The content of depends alumina content which is probably due to CaO the the originally precipitated dolowith associated samples most in is content MgO The higher contents of CaO compared to the standard sample (Tab. 3). preliminary testing. All samples exceptefficacy insecticidal in showed promising they whyD-01 reason a be and D-02B have much JU, OP and MR have enhanced CaO (36.90 (1995) calcium oxide also has some insecticidal activity. Samples bonate component (CaO) content. According to FIELDS & MUIR pleslowest the with of concentration silica have car highest the depends on the amount of biogenic silica greatly (KORUNIĆ, insects product stored against DEsofeffect 2013). insecticidal Sam 3.96 from ranges 7.37% to concentration The SiO more depleted diatomite. ≤7.37%)ofordinary instead whywetripolite advocateiswhich SiOof content est ples from the Medvednica and Žumberak Mts. (Tab. 3). The low samples isBanovina from lower the in sam that registered than of concentration The silica the area. in marine ato more coastal belongs Žumberak from 2006), whilethat BAJRAKTAREVIĆ, & (GALOVIĆ blooming seasonal with climate temperate the of zone upwelling the to belong Mt. Medvednica from tomites is in accordance with their origin where the most prospective dia from the tance Podsusedsko Dolje site is only 25 today.km This Medvednica Mt. (mean = 48.63%) considering that the direct dis which is significantly lowerthan the average silicacontent onthe the SiO position and phase crystalline of the mineral. This also applies to com the modify that processes tectonic and diagenesis as well logy of the depth and its as variations the during mid-Sarmatian, geomorpho marine the of result the likely most are diatomites investigated the of content silica the in variations marked rally ple PDK and samples D atPodsusedsko the Dolje sam the from site, wheredistance the 4, and 61.91% sample D the Medvednica Mt. (21.26% sample PDK, 47.71%, sample MA 36 - na) in comparison to Celatom 02B have smaller amounts of quartz (4 quartz of amounts smaller have 02B The highest efficacy againstthe rice weevil, 2 content (18.65%) at the Jurjevčani site Mt.), (Žumberak ® MN 51 only one analysed sample, MA The 2 O 2 + P + 3 - in comparison content is slightly higher in all analysed samples analysed all in higher slightly is content 01,D - SiO A (41 2 O 2 2 is found in the samples from Slavonia (OP:Slavonia from samples the in found is - 5 concentrations in those analysed samples are 02B and MA 02B and ) in the analysedthesamples in ) of Croatiandiato - 50%), as BSi, which make them suitable for - - 02B) (Tab. 3). This is particularly evident 01 and D - 4 (19.4Mt.,4 Medvednica from mg/kg) with the standard Celatom ® 2 O - MN 51.MN The highest concentra - 02B is about a kilometre. Late 3 4 (Tab.4 6). Samples D ),which isprobablyof apart - 4 from the Medvednica - - ® 49.26%) which could ® 5 %) and maximum maximum and %) 5 MN 51MN (Tab. 4). MN 51 MN (15 mg/kg) ® S. oryzae MN 51(Tab. MN 3). - 4, has a slightly 2 (Tab.3). The 2 O, K ® MN show - 01 and 2 O + - 51. ed ------ - abundant, bigger species (65 nitzschioides Thalassionema is classified as carcinogenic to humans by the International International the by Agency humans for Research to on Cancer (IARC, 1997). DEs carcinogenic registered as as classified is shown to be carcinogenic if inhaled. In addition, crystalline silica BELL, 2004). Micro CAMP & LYNNE 1996;al., 1991; et al., CADY et FLÖRKE (SiO quartz microcrystalline to line biogenic silica (opal iceous deposits undergo mineralogical changes from non-crystal process of diagenesis. It is well known that diagenesisduring thesil in calcinations by modified partially are samples These 5). agreement with the results of Murdmaas’ modified formula(Tab. of sponge spicules was noticed only in samples of OP, which is in 2). Based on the palaeontological results, the sporadic appearance Slavonia OP sample MR-10B did not contain opaline silica. Two samples from Sample MR-10 from Banovina region has only 3 % opal-A, insects while the of (JACKSON suffocation & or WEBLEY, desiccation 1994), whichinternal increases in efficacy as well.resulting samplesmay damagethedigestive or breathingorgan, alsotract silicoflagellatesNevertheless,noticeablein spicules andsponge doljensis sized (<45 μm) mid of consist diatomites efficient most the that show metrics morpho diatom on results The higher. be would activity cidal of and if ofit pores isand distribution striae greater, the insecti size and number the ofphysicalmoderegarding own action, its According to ZIAEE et al. differences of mortality rates with the standard Celatom tively against of 61.50% and 99%, respectively, and 25.50% and 34.0%, respec ment) showed in sample MA dominica against 1) 2015) of samples (MA sampleterised MA oftent opal sample as DE like MA rugulosus cus Coscinodiscus doljensis, Coscinodiscus sarmaticus and with their smaller representatives ( discus perforatus radiatus scinodiscus oculus iridis Sitophilus oryzae with oil sorption of 1.20 were equally effective against rice MA weevil dusts ert other with DEs 1.13oilwith from sorption to 1.96 ml/g dust. In fective against 50S with oil sorption of 3.23 ml/g dust was significantly more ef (2016)FIELDS KORUNIĆ & Sipernat byaerogel silica ducted con experiment the effectivemore In desiccants. are lipidsand for the capacity sorption havehigher a available surfaces active cacy against insects. According to KORUNIĆ et al. (2016), larger effi on effect great haveal.,2015)a mayphenomena these and et PRASANTHA (ROHITHA insects treated the of clesurface can particles effectively adsorb epicuticular lipids from the cuti DE shapes. round and cylindrical of diatoms to relation in ticle cu cover insect better shapes body linear and flattened discoid, KORUNIĆ(1998), with with agreement diatoms in that is This lassionema nitzschioides , ) with numerous smaller pores, and lancet shaped shaped lancet and pores, smaller numerous with ) Coscinodiscus stellatis (FAB.) the highest efficacy (7 and 14 days after treat and after (FAB.)days (7 efficacy 14 highest the Tribolium castaneum Tribolium - - A (28%)A (5%) of amount small aquartz and charac 4 and OP - , R. dominica R. 4 with oil sorption of 1.23 and Celatom 1.23and of sorption oil with 4 Paralia sulcata Sitophilus granarius Coscinodiscus (LINNAEUS) and granary weevil, var. - - 4 (Tab. 2). In previous et(LIŠKA testing al., crystalline silica minerals (quartz) have been - - cellulosus - 4, MR 4A contain small amounts of opal 4 (Fig. 3, Tab. 1). The relatively high con - , A) to microcrystalline opal (opal that make up its active(Fig. surface 3). Thalassiosira leptopus

. In addition, there were no statistical statistical nowere there addition, In . (2013) each diatom species could have - - 80 μm) of - 4, reaching 10, MR ( dominate in the assemblage with with assemblage the in dominate ), giving better ),efficacy better giving of D Coscinodiscus curvatulus Coscinodiscus curvatulus ), which are mostly fragmented, , Coscinodiscus rothii (HERBST) and and (HERBST) 2 (ILAS t l, 1985; al., et (WILLIAMS ) (LINNAEUS) in comparison - 10B, OP Coscinodiscus curvatulus, Coscinodiscus T. castaneum Geologia Croatica 70/1 Croatica Geologia - 4, OP , Coscinodiscus Coscinodiscus Rhyzopertha Rhyzopertha , S. granarius - Coscinodis 4A and PD group , mortality mortality Coscino ® ® - MN MN 51. C (Tab. MN 51 MN - and and CT/C) -

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BLAŠKOVIĆ, Z., BAJRAKTAREVIĆ, for in methods control insect grain stored Physical (1995): J. BANKS, & P. FIELDS, BAZHAL, I.G., VORONA, L.G., LESHCHENKO, & A.V. PEREVERZEVA, I.N.

, , - ------ 4 4 ® - - ca ca 2+ 4= - sized mites mites - , Ca , + . Unfor . Celatom , Na , mg/kg. The mg/kg.

+ MN 51 MN Thalassionema Thalassionema ® ® , together with inert with together , 36.29) in correlation in 36.29) - Celatom and takingaccount andinto 5%) which makes them suit them makes which 5%) S. oryzae S. - 5 %. Concerning insecticidal insecticidal Concerning %. 5 - 4, PDK). Based on palaeontolog on Based PDK). 4, - S. oryzaeS. group of species where where species of group (5.60) probably also increased efficacy. Ca efficacy. increased also probably (5.60) 4 and smaller fraction of PDK show no diffe no show PDK of fraction smaller and 4 - 4 (28%) and PDK (12%), but in combination with combination in but (12%), PDK and (28%) 4 MN 51 MN - dominate correlatedwhich is positively with their ® ® Coscinodiscus 02) have the highest have amorphous (41 component silica 02) (WEAVER, 1989). Interlayer cations are hydrated and hydrated are cations Interlayer 1989). (WEAVER, - 2+ the allowed maximum Pb concentration is 15 is concentration Pb maximum allowed the Celatom 01, D 01, ca ca in relation to the standard DE. Diatomites from borehole - other natural compounds, with other insecticide effects, to pro insecticidal level. higher) even same(or the vide effects against the rice weevil, weevil, rice the against effects the small thicknesses of all prospective Croatian diatomite lay some inertmixingwith duststhese of possibility the is there ers, 19.4. mg/kg, Tab. 4). According to the standard sample sample standard the to According 4). Tab. mg/kg, 19.4. 51 MN 1 is samples the in quartz of content rences of mortality rates with the standard standard the diato with rates Croatian mortality of prospective rences all of thicknesses small the tunately, and higherlead inthe of content slightly 48 cm) MA (approx. (MA DE as usage classical inadequatefor them make sample (II) ions are known to improve flow rate inmodified diatomite para mentioned all of because Probably 1975). al., (BAZHAL et MA diatomite meters increased content of smectite gives even slightly better absorp (9.63 CaO of level higher The property. tion with planktonic planktonic nitzschioides sili amorphous of concentrations smaller much Even absorption. MA sample in on stored products insect rice weevil weevil rice insect products stored on (MA Mt. Medvednica from dust of DEmid consists resultsical analysed the efficient most (D (4 quartz of amounts small and efficacy 50%) highest the exhibit They DE. as usage commercial for able Sarmatian diatomites from Medvednica Mt. have different physi different have Mt. Medvednica from diatomites Sarmatian cal properties and efficacyon grainstore insects. The analysed Croatian diatomites have significantlylower concentrationof sili ristic for smectite (SLOVENEC & BERMANEC, & 2003). (SLOVENEC smectite risticfor CONCLUSION 6. meq/100 g) and will readily adsorb cations such as H as such cations adsorb readily will and g) meq/100 Mg and resultingreplaceable, in the swelling and charactedehydration 1972; BANKS & FIELDS, 1995; SUBRAMANYAM & ROESLI, ROESLI, & SUBRAMANYAM 1995; FIELDS, & BANKS 1972; 2000) that also influenced better adsorptionshere. In almost all has It mineral. clay dominant the is smectite samples analysed the (60–130 capacity exchange base large a structure, with layer 2:1 a (28%) and PDK (12%), in combination with the increased content content increased the with combination in (12%), PDK and (28%) also are Clays properties. absorption better even gives smectite of known as inert dusts like DEs (MACELJSKI & KORUNIĆ, high content of carbonate minerals (calcite and aragonite), and a and aragonite), and carbonate minerals of (calcite highcontent smaller and De amountquartz2). (Tab. of opal-A (12%), (3%) MA samples in silica amorphous of concentrations lower spite ance with their origin in the upwelling zone and with seasonal during Sarmatian,changes the growth limitedinthat theirrapid the bloomingBAJRAKTAREVIĆ, 2006). Nevertheless, period sample PDK has a (JURILJ, 1957; GALOVIĆ & with the fact that smaller are µm) particles signifi of DEs (<45 cantly moreaccord in effectiveis this but thanusual, than smaller larger mostly are particles Species (KORUNIĆ et 2011). al. opal-C were contained in samples PDK and D-01 (Tab. 2). Sam 2). (Tab. D-01 and PDK containedsamples in were opal-C ple PDK appeared to have the best outcome on withRW inert agreementin is This days. after5 even microns 25 than less dust insecticides generally less have than 6% of quartz, like use all anathe or mask, dust proper a of use the However, samples. lysed of low crystalline silica DE can protect against this health risk of amountssmall Very 2000). ALLEN, & (DESMARCHELIER I. 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