The Geochemical Atlas of Croatia revealed differences in the spatial distribution of geochemical elements between the Croatian Dinaric coastal region and the Pannonian Basin. In the Pannonian Basin, 1,254 topsoil samples (0-25 cm) were analysed for 27 elements and pH values. This geodynamic unit is characterised by the variability of geological, pedological and land-use-related characteristics. To analyse the geochemical properties of soil above different lithological units, soil types and land use and land cover classes, a discriminant function analysis was performed using the compositional data. The study shows significant geochemical and ecological patterns, with the first two discriminant functions explaining a major proportion of the variability: in the GEOLOGY model, DF1 explains 33.31% and DF2 17.97%; in the SOIL model, DF1 explains 51.59% and DF2 20.22%; in the CLC model DF1 explains 59.85% and DF2 30.30%. The geological model distinguishes between the Quaternary sediments and the older lithological units and highlights alkaline and acidic soil conditions. The soil model shows the effects of fluvial and alluvial deposits, agricultural practices and the underlying geology on soil composition and emphasises the enrichment of essential nutrients and heavy metals in the soils. The land use and land cover model illustrates the anthropogenic influence on agricultural soils and the susceptibility of wetlands to heavy metal accumulation. The results obtained illustrate the complex interaction between geology, the topsoil layer, as well as land use and land cover, providing awareness for environmental management and monitoring, and the need for further geochemical studies of the soils in the Pannonian Basin.

Topsoil geochemistry maps of the city of Sisak were compared with historical maps to explain the geochemistry of the topsoil. Historically, three periods of Sisak's development can be distinguished: 1) the Celtic and Roman period; 2) the Medieval period, and 3) the industrial era during the 20th century. Comparison of the geochemical maps with the historical maps reveals 1) the accumulation of elements in the soil and their preservation over 2,000 years; 2) the influence of infrastructural interventions on the geochemical composition of the topsoil and 3) the high rate of accumulation of potentially toxic elements in the topsoil due to rapid industrialisation on purely arable land.

Hectometric blocks of Middle Triassic mafic pyroclastic rocks, represented by volcanic agglomerates/breccias and lapilli tuffs, form part of the ophiolitic mélange of Mt. Medvednica, situated in the southwestern segment of the Zagorje-Mid-Transdanubian Zone. These rocks share petrochemical characteristics with pyroclastic derivatives of alkali, within-plate basaltic lavas of Mts. Medvednica, Samoborska Gora, and Kalnik, indicating the occurrence of explosive events preceding the dominant effusive submarine volcanism during the Middle Triassic (Illyrian-Fassanian?) stages. The formation of these pre-ophiolitic pyroclastics is associated with an intracontinental rift setting and reflects melts derived from an OIB-type enriched mantle plume source. These pyroclastics represent uncontaminated melts that erupted through a highly thinned continental crust. In geodynamic terms, the formation of pyroclastites occurred during the Late Anisian-Early Ladinian along the continental margin of Palaeotethys through the proto back-arc rifting of continental lithosphere (Adria Plate), leading to the formation of the Maliak/Balkan Neotethys Rift, in the emerging northwestern segment of Neotethys. The investigated pyroclastic rocks of Mt. Medvednica document the extension in an evolved intracontinental rift basin, which immediately preceded the generation of the initial Neotethyan oceanic lithosphere during the Upper Triassic.

Within the framework of the pan-European project “URban GEochemistry (URGE) in Europe – Soil, children, health”, pedological and geochemical investigations of the soils of the city of Sisak and its adjacent surroundings were carried out, and three urban and two rural soil profiles were examined. The mineralogical composition and concentration of selected potentially toxic elements (PTEs) Cr, Cu, Ni, Pb and Zn in the soil were determined. The Community Reference Bureau of Reference (BCR) sequential extraction procedure (SEP) of these PTEs was undertaken and the potential risk to human health and the environment was assessed. The concentrations of Cr and Ni are generally similar in urban and rural soil profiles, while the concentrations of Cu, Pb and Zn in soil horizons/layers are higher in urban profiles. The extracted fractions of PTEs gave the following general distribution: in urban soil profiles residual (RES) > reducible (ORG) or oxidisable (FEMN) > exchangeable (CARB), except for Cu where ORG > RES > FEMN > CARB, while in rural soil profiles RES > FEMN or ORG > CARB, except for Pb where FEMN > RES or ORG > CARB. The differences between soils in urban and rural profiles depend mainly on the historical land use, i.e. on the duration and intensity of anthropogenic influences on the soil and, to a lesser extent, on the geogenic origin of the parent material and the pedogenic processes. The studied elements in the urban soil profiles are predominantly of anthropogenic origin, indicating a possible influence of the ancient settlements of Segestica and Siscia and of heavy industry in the 20th century. The anthropogenic influences on the rural profiles are low and geogenic influences dominate. Risks to the environment were assessed in the soil profiles based on PTE concentrations in the CARB fraction and the sum of the CARB, ORG and FEMN fractions from BCR SEP. All calculated risks to human health and the environment were rated as no-risk, very low risk and low risk.

Stream sediment is widely used as a medium in geochemical surveys. This study examined major element chemical composition of stream sediment produced by weathering in lithologically diverse terrain. Such sediment represents mixed sediment, therefore, the aim was to interpret its provenance and model the transitions within its major element composition. The particular interest was to link major element composition, mineral composition and the sediment source rocks. In order to interpret the sediment origin principal component analysis was employed and representative samples with highest and lowest scores were analysed for mineral composition. Scores also suggested four lithology-based groups of stream sediment samples. Transitions between groups were described with linear models for compositional data. Despite the ambiguity, links between major element composition, mineral composition and provenance were established. Besides sorting out sources of mixed sediment and minerals which control the transitions, this study contributes to general understanding of the Psunj Mt. geology, while the results can be used in geochemical surveys in areas of a similar geological setting.

This work aims to unveil the origin, geodynamic significance, and diagenetic history of pyroclastites and associated chert documented within the Upper Anisian volcano-sedimentary succession of the Ivanscica Mt. in Central Europe. An abundance of pyroclastic material points to polyphase volcanic activity and deep-water sedimentation along the rim of an oceanic realm. Radiolarian-based dating revealed Illyrian age of chert intercalated with pyroclastites. The latter are largely vitro-crystalloclastic and were emplaced as airborne tuff. The crystalloclasts of sanidine, plagioclase, altered pyroxene, and amphibole are principal tuff constituents merged in the altered glassy matrix consisted of palagonite, clay minerals, and calcite. Variations in alteration assemblages reflect an extensive in situ eogenesis in an open hydrologic system that gradually evolved toward a restricted fluid percolation environment. Mineralogy, chemistry, and occurrence of andesitic tuff clearly denote an explosive volcanic activity formed at the top of suprasubduction zone. Such scenario presumes a complex genesis outlined in following steps: (a) partial melting and dehydration of down-going Palaeotethyan slab which gave rise to the subduction-related magmatism {LILE, Th, and LREE [(La/Lu)(cn) = 6.51-9.42] enrichment; negative anomalies of Nb-Ta, P, and Ti [e.g., (Nb/La)(n) = 0.31-0.44]}; (b) magma contamination via interaction with continental crust during magma uplift along tectonically weakened zones of upper crust [positive Pb spikes, negative epsilon(Nd) (-4.18 to -4.44), and Sm-147/Nd-144 <= 0.113175]. This is in favour of geodynamic evolution that hypothesizes the existence of an active, ensialic, and mature volcanic arc developed along the southern active continental margins of Euramerica (Laurussia) during Late Anisian subduction of Palaeotethyan lithosphere.

An insecticidal efficacy of two newly developed grain protectant formulations were assessed against lesser grain borer Rhyzopertha dominica (Fabricius) (Coleoptera: Bostrichidae) on wheat and corn after 6 months period of. Tested formulations, marked as F1H and F2H, based on inert dust, laurel leaves, lavender essential oil, corn oil, silica gel (both F1H and F2H) and pyrethrin (only F2H) were tested at six doses (from 100 ppm to 600 ppm) depending on formulation and type of grain. The appropriate weights of each formulation, were added seperately to plastic containers containing 10 kg of wheat or corn. An initial population of 200 adults of R. dominica were added into each container and left under natural environmental conditions for up to 6 months. A commercial diatomaceous earth (DE) insecticide, Celatom® Mn 51, was used for the comparison of the results, in addition to the untreated control. After six months, both formulations showed higher insecticidal effect than DE Mn 51 in corn and in wheat. Furthermore, the initial population of R. dominica, introduced in wheat was suppressed almost completely, with only 0.7%-5.3% live adults found, depending on formulations and dose. The order of efficacy was F1H>F2H>DE Mn 51. Similar suppression of the initial population was recorded in corn, where F2H was slightly more effective than F1H with 2.0%-10.6% and 4.1%-9.5% live adults found, respectively. At the same time, in the treatments with DE Mn 51 there were 4.7%-74.7% and 33.4%-56.1% live adults in wheat and corn, respectively.

Modelling of topsoil geochemical data using discriminant function analysis, along with a set of corresponding geochemical maps, portray a legacy of environmental contamination in the city of Sisak. Based on centred log-ratio (clr) transformed compositional data from topsoil samples collected on Kupa-Odra and Sava River floodplain sediments and loess, underlying the Sisak urban area, and regrouped according to their land use characteristics (urban, industrial and agricultural areas), a few element clusters emerged accounting for discrimination between the defined groups. The most prominent feature of the lithological model, as suggested by the first discriminant function, is the carbonate group (Mg, Ca, Sr) versus anthropogenic sourced elements/transitionmetals (e.g., Sn, Zn, Ba, Mn, Pb, U, Ag, Cr, V) dichotomy separating soil developed on floodplain sediments of Sava and Kupa-Odra Rivers from those evolved on loess. The major attribute of the land use model, according to the main discriminant function, is differentiation between urban/industrial and rural (agricultural) samples based on contrast provided by the carbonate component and other anthropogenic sourced element clusters (predominantly alkaline and concentrated over the loess substrate), in contrast to fertiliser trace and transition element clusters (predominantly acid and disseminated over Kupa-Odra and Sava River floodplain sediments). In both cases, the second discriminant function provides additional information on the secondary level, i.e., in the lithology model the Kupa-Odra sediment group is distinguished from other lithological groupings owing to its predominantly transition element signature. In the land use model, urban soil samples are separated from industrial ones based on the characteristic Na-Sr-Ca-pH(KCl) element association (urban waste) against a typical 'industrial' element signature (Zn-Cd-Mn-Pb-Mo).

Geochemical investigation of topsoil from a mixed industrial and residential area in the southern part of the city of Sisak was carried out in order to determine the concentration, spatial distribution, metal-bearing phases and sources of Ba, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V, W and Zn by applying inductively coupled plasma mass spectrometry (ICP-MS) and scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS). The uncontrolled industrial development in a very short period of only 50 years, beginning in the 1930s and ending in the 1980s, has left a legacy of serious contamination of topsoil. The concentrations of studied elements in topsoil in the industrial zone were generally elevated and at some locations much higher compared to the rest of the Sisak area. Morphologies and chemical composition of metal-bearing particles in the heavy mineral fraction of three selected soil samples were studied using SEM/EDS. According to the results of the SEM/EDS analysis, the sources of studied elements could be ascribed predominantly to anthropogenic input from steelworks, recycling of steel scrap, ferroalloys production and to a lesser extent to the pedological processes in the soil and parent material. It is concluded that the SEM/EDS results provide significant information about the sources and apportionment of anthropogenic induced contamination in soil, and assist in the interpretation of conventional analytical results.

Proceedings contains articles presented at Conference divided into sections: open lecture (1), chemical analysis and synthesis (3), chemical and biochemical engineering (8), food technology and biotechnology (8), medical chemistry and pharmacy (3), environmental protection (11) and meeting of young chemists (2).

A soil geochemical survey of the city of Sisak, Croatia, and its surroundings was done to determine the concentration, spatial distribution and sources of the elements in the soil. Factor analysis indicates 8 factors describe the geochemical variations in the topsoil: 4 anthropogenic, 2 geogenic and 2 mixed ones. The main influence in the urban and rural soils was parent material and anthropogenic inputs in the old part of the city, along roads and railways, and in the industrial areas. The results indicate that soils are a very good media for accumulating trace elements in urban and industrial areas.

Laboratory bioassay was carried out to study the insecticidal effect of 9 Croatian inert dusts against Sitophilus oryzae (L.) and to test their influence on bulk density of treated wheat. In order to compare effectiveness of Croatian inert dust samples, a standard USA diatomaceous earth (DE) Celatom® Mn 51, registered as an insecticide for stored-products protection, was used. Wheat kernels with approximately 13% moisture content were treated with inert dusts at doses 300, 400, 500 and 600 ppm and mortality of S. oryzae adults was assessed after 7 and 14 days and progeny after 49 days. The most effective Croatian inert dust samples were D-02B, D-01 and MA-4 with the LD90 values of 359.6, 447.2 and 458.7 ppm, respectively. In addition, effective dose that reduced F1 progeny in half was lower in regard to the other tested samples including the standard DE Mn 51, with the ED50 values 71.9, 54.6 and 137.6 ppm, respectively. According to the XRF analytical results, the highest amount of biogenic silica (BSi) was found in samples D-02B, D-01 and MA-4 (45.98, 35.09 and 21.28%, respectively). Paleontological data analysis confirmed diatoms species in only 5 samples of Croatian inert dusts (D-01, D-02B, PD-1, MA-4 and JU-1). All tested inert dusts affected reduction in bulk density of treated wheat at the LD90 concentrations, from 4.4 (D-02B) to 5.6 (JU-1) kg hL-1. More effective inert dusts at lower doses equally reduced bulk density as less effective inert dusts at much higher doses.

In recent decades, there has been an increase in the use of diatomaceous earth (DE) as a natural insecticide because of its low mammalian toxicity, worker safety, low risk of food residues and the occurrence of resistant insect populations associated with the use of chemical insecticides.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 Croatian Basin.The most important ingredient of diatomaceous sediments is silica (biogenic opal-A and SiO 2 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 applied.Preliminary results on the aforementioned diatomite (as inert dusts) show good efficacy against tested insects Sitophilus oryzae (LINNAEUS), Tribolium castaneum (HERBST) and Rhyzopertha dominica (FABRICIUS).

Over 4000 agricultural and grazing land soil samples were collected for the "Geochemical Mapping of Agricultural and Grazing Land Soil of Europe" (GEMAS) project carried out by the EuroGeoSurveys Geochemistry Expert Group. The samples were collected in 33 European countries, covering 5.6 million km(2) at a density of 1 sample site per 2500 km2. All samples were analysed by ICP-MS following an aqua regia extraction. The European median Cd concentration is 0.182 mg/kg in agricultural soil and 0.197 mg/kg in grazing land soil (including eastern Ukraine). The Cd map demonstrates the existence of two different geochemical background regimes in northern and southern Europe, separated by the southern limit of the Quaternary glaciation. Cadmium shows two times higher background concentrations in the older and more weathered southern European soil than in northern European soil.The spatial distribution patterns of Cd in the collected soil samples are mainly governed by geology (parent material and mineralisation), as well as weathering, soil formation and climate since the last glaciation period. Locally, in several areas, the natural anomaly pattern is overprinted by anthropogenic emissions from former mining, ore processing and related metal industries. Some Cd anomalies can be attributed to urbanisation and the use of fertilisers. A comparison of the raw data Cd concentration map with its clr-transformed counterpart and selected single element ratio maps demonstrates that substantial additional information about sources and processes governing the distribution of Cd in agricultural soil at the European scale can be obtained. Results of a PCA, carried out following the classical approach (standardised) versus a PCA based on the statistically acceptable approach, using clr-transformed data, are quite comparable. (C) 2016 Elsevier B.V. All rights reserved.

Over 4000 soil samples were collected for the "Geochemical Mapping of Agricultural and Grazing Land Soil of Europe" (GEMAS) project carried out by the EuroGeoSurveys Geochemistry Expert Group. Cadmium concentrations are reported for the <2 mm fraction of soil samples from regularly ploughed fields (agricultural soil, Ap, 0-20 cm, N = 2218) and grazing land soil (Gr, 0-10 cm, N = 2127). The samples were collected in 33 European countries, covering 5.6 million km(2) at a sample density of 1 sample each per 2500 km(2) and were analysed in an aqua regia extraction followed by an ICP-MS finish. The median Cd value is 0.181 mg/kg for the Ap and 0.202 mg/kg for the Gr soil samples. The data allow a directly comparable country-specific regional exposure and risk characterisation for all EU countries covered. Direct risks of Cd for terrestrial organisms are only predicted for a few isolated sample sites: 2.3% of the Ap and 4.5% of the Gr sites, respectively. (C) 2016 Elsevier Ltd. All rights reserved.

Cilj ovog preglednog rada je prikazati tijek napredovanja na istraživackom projektu Hrvatske zaklade za znanost pod naslovom „Razvoj formulacija novih prirodnih insekticida na osnovi inertnih prasiva i botanickih insekticida i njihovih kombinacija kao zamjena za sintetske konvencionalne insekticide“ - DIACROMIXPEST IP-11-2013-5570. Na proslogodisnjem seminaru „DDD i ZUPP“, 2015. godine u Moscenickoj Dragi održano je predstavljanje ovog istraživackog projekta gdje su sudionici seminara upoznati s novim istraživanjima prirodnih insekticida koja se provode u Hrvatskoj. Ovim projektom unazad dvije godine istražuju se i razvijaju prirodne formulacije insekticida s ciljem primjene u zastiti uskladistenih poljoprivrednih proizvoda, a uz manje modifikacije i u javnom zdravstvu, komunalnoj higijeni, zastiti biljaka u vegetaciji, veterini te prehrambenoj industriji. Istraživanja razvoja formulacija baziraju se na novoj tehnologiji mijesanja i najprihvatljivijoj kombinaciji prirodnih hrvatskih supstancija razlicitog mehanizma djelovanja na insekte, kao sto su inertna prasiva i biljni ekstrakti. Zbog sinergije fizikalnog i kemijskog mehanizma djelovanja ocekuje se povisena djelotvornost na insekte u odnosu kada su iste supstancije primijenjene same. Pretpostavka je da bi ovako složeni mehanizam djelovanja usporio mogucu pojavu rezistencije, a s obzirom da su sve supstancije u formulacijama prirodnog podrijetla ne bi trebala postojati zabrinutost o stetnim ostatcima insekticida u obrađenoj robi, na povrsinama i u prostoru. U ovom projektu istraživacki tim cine znanstvenici iz Diatom Research and Consulting Inc. iz Kanade (dr. sc. Zlatko Korunic), Hrvatskog geoloskog instituta (prof. dr. sc. Josip Halamic i dr. sc. Ines Galovic), te Poljoprivrednog fakulteta u Osijeku kao nositelja projekta (prof. dr. sc. Vlatka Rozman, prof. dr. sc. Renata Balicevic, doc. dr. sc. Anita Liska, i Pavo Lucic, mag. ing. agr.).