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Natural (40K, 226Ra, 232Th, 238U) and anthropogenic (137Cs) radionuclides in consolidated sedimentary rocks (limestones s.l. and marls) and unconsolidated sediments (stream sediments and soils) of the Kaštela Bay (Adriatic Sea, Croatia) coastal area were studied. Kaštela Bay is a typical karstic environment and it is under strong anthropogenic influence due to industrialisation and urbanization. Relationships between radionuclides, their behaviour in different types of samples and possible influencing factors were studied. Radionuclides were also studied in relation to selected metals (Al, K, Ca, Fe, Ti, Mn, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Pb, and As) and distribution in limestones s.l., marls, stream sediments and soils. Radionuclides’ massic activities were determined by gamma-spectrometry and metals mass fractions were measured by EDXRF technique. Relationships were studied using statistical tools (principal component analysis, factor analysis). It was found that stream sediments were more similar to source rocks (limestones s.l. and marl) than to soils in terms of natural radionuclides’ activities. 40K and 232Th in consolidated rocks were preferentially bound to alumosilicates and associated with the majority of studied metals. However, this was not the case with 226Ra and 238U, which did not show any preferences regarding binding to mineral components or associating with metals. On the other hand, all four natural radionuclides presented the same behaviour in unconsolidated sediments, i.e. they were all preferentially bound to alumosilicates and associated with the majority of metals. 137Cs did not associate with any of the metals or other radionuclides in sediments. The statistical approach applied in this study revealed differences in radionuclides’ relationships and behaviour in a karstic environment and implied possible influencing processes or factors. This approach can be applied in other types of environments as well to study preferential radionuclides’ binding to certain mineral components that influences radionuclides’ mobility and transport to other environmental compartments.

Objective / Purpose: The objective of this study was efficacy assessment of Bioapifit® wound care ointment consisted of honey, Cera flava, glycerin, the oil macerates of astringent and soothing herbs combined with three essential oils for the treatment of venous ulcers. Materials and methods : 50 patients with total 112 venous ulcers with the total surface area of 572.5 cm 2 were treated 60 days (twice a day) with Bioapifit® wound care ointment applied on conventionally cleaned wound and covered with bandage during the whole course of the study. The healing process was assessed by Venous Clinical Severity Score (VCSS) tool twice a month. Results: At baseline the mean value and standard deviation of the VCSS score was 25.03 ± 4.37 and 25.53 ± 3.36 for females and males, respectively. The surface area ranged from 1.6 to 28.1 cm 2 for females and from 1.60 to 29.20 cm 2 for males. The mean value and standard deviation of the total VCSS score following the treatment decreased to 6.26 ± 4.0 and 6.47 ± 3.9 for females and males, respectively. Total number of active ulcers decreased from 112 to 17 and the total surface area of all ulcers from 572.5 cm 2 to 7.6 cm 2 . No side-effects were observed during the course of the study. Conclusion / Discussion: Two months application of Bioapifit® wound care ointment resulted in complete closure of 84.8% of the ulcers and reduction in their surface area for 98.7% with the mean healing time of 37.2 days.

This study proposes the application of the comet assay for the evaluation of DNA damage from frozen human whole blood samples that could be readily used in human biomonitoring and epidemiological studies. It was done on simply frozen whole blood samples collected from male volunteers (N = 60) aliquoted in small volumes and stored at −80 °C without the addition of cryopreservatives for a period of 5 years. To test the applicability of the alkaline comet assay for the evaluation of DNA damage in frozen whole blood, samples were quickly thawed at 37 °C and immediately embedded in an agarose matrix followed by an alkaline comet assay procedure. We concluded that the whole blood freezing and prolonged storage do not severely affect comet assay values, although background values were higher compared to our historical control data from the fresh whole blood. Even the influence of the variables tested, such as age, body mass index, smoking habit and alcohol consumption were in agreement with our previous data using fresh blood. The obtained results suggest that the comet assay could be applied to frozen blood samples, if properly stored, even for decades, which would certainly facilitate large-scale human biomonitoring and long-term epidemiological studies.

Objective/Purpose: The purpose of this work was the assessment of the clinical efficacyand safety of Bioapigyn® vaginal ointment for pelvic muscle tonus compared topelvic floor muscle training in alleviating the symptoms of stress, urge andmixed urinary incontinence and vulvo-vaginal disorders in child-bearing andmenopausal & postmenopausal women. Materialsand Methods: The experimental group consisted of 66 women was treated 28days with Bioapigyn® ointment for pelvic muscle tonus (2.5 mL/day). The controlgroup also consisted of 66 participantswas subjected to pelvic floor muscle training during 28 days (five times aday). ICIQ-UI SF score, the residual urine volume, perineometry, the totalscore of vulvo-vaginal symptoms and vaginal pH were determined before and afterthe treatment or training. Results:Following the treatment with Bioapigyn® ointment ICIQ-UI-SF score decreased54.9%, perineometry parameters increased between 31.5 and 34.3%, residual urine decreased for 76.9% and vaginal pH for 14.2%. All the symptoms ofvulvo-vaginal disorders disappeared completely in all participants. The controlgroup showed no changes in vaginal pH or the improvement concerning thevulvo-vaginal complaints. ICIQ- UI-SF score decreased for 4.3%, residual urinevolume for 9.1% while perineometry parameters increased between 4.3 and 8.3%. Conclusion/Discussion: Bioapigyn®vaginal ointment for pelvic muscle tonus alleviate the symptoms of incontinenceby tightening and firming of the smooth muscles of the pelvic floor thanks tothe ingredients with smooth muscles contraction/relaxation and astringentproperties. Low pH, high osmolarity, viscosity, greasiness and coating effectof the ointment eradicated vulvo-vaginal complaints.

Using alkaline comet assay, DNA damage tail length (TL) and tail intensity (TI) parameters were compared between fresh whole blood and 1-year frozen small volume whole blood in EDTA at -80 °C without cryo-preservation. The studied group consisted of 25 volunteers with different health conditions who served as their own controls for frozen blood results. Without the purification step after thawing, the results and the usefulness of this protocol for future/retrospective (including re-analysations of putative outliers) studies were analysed. Medical surveillance and blood sampling were done at Merkur University Hospital Zagreb. No significant differences between fresh and frozen blood samples in terms of the mean TL values (mean ± SD: 29.03 ± 12.26 vs. 25.36 ± 6.97, respectively) and the mean TI values (9.19 ± 10.37 vs. 10.17 ± 8.55, respectively), and highly damaged cell percentage were determined among 25 volunteers. Median TI frozen samples values of entire group were within the allowed 10-11% (8.24). At the individual levels, no correlation between fresh and frozen whole blood samples was observed in 11 volunteers who suffered from diabetes mellitus type 2. Strong correlation between fresh/frozen samples was seen for TL (r = 0.64, p 0.015) and TI (r = 0.71, p 0.005) in nondiabetic subgroup. Overall, the results demonstrated the usefulness of the 1-year frozen blood without induction of heavily damaged DNA. Due to the different DNA damage behaviour connected with different health conditions, future studies should involve more volunteers, oxidative DNA damage comet assay measurements, the inclusion of a washing step after thawing and inclusion of disease/antioxidant biomarkers.

Cilj ovog rada je izdvajanje cinka iz elektropećne prašine postupkom alkalne ekstrakcije pomoću jake natrijeve lužine te korištenje visokog neutralizacijskog/koagulacijskog učinka preostalog alkalnog krutog ostatka za obradu kiselih industrijskih otpadnih voda. Ispitana je i mogućnost regeneracije otpadnog mulja postupkom alkalne ekstrakcije cinka te primjene preostalog krutog ostatka za obradu kiselih otpadnih voda. U tu svrhu je korišteno sedam kompozitnih uzoraka elektropećne prašine iz Siskačke čeličane s udjelom cinka u rasponu od 5,71% do 28,18%. Alkalnom ekstrakcijom izdvojeno je između 62,4 i 84,6% cinka a sastav eluata preostalog krutog ostatka je zadovoljavao uvjete za odlaganje na odlagalište inertnog otpada. Njegovom primjenom za obradu otpadnih voda od pocinčavanja pri optimalnim uvjetima (pH = 8; tkon. = 20 min.) je uklonjeno između 99,17% i 100% teških metala čime su postignute vrijednosti koncentracija elemenata pogodne za ispust u okoliš. Otpadni mulj je regeneriran izdvajanjem cinka postupkom alkalne ekstrakcije a preostali kruti ostatak ponovo uspješno primjenjen za pročiščavanje kiselih otpadnih voda sa sličnom učinkovitosti uklanjanja kao i u prethodnom eksperimentu., The objective of our work was to isolate zinc from electric arc furnace dust using the procedure of alkaline extraction with strong sodium hydroxide base and high neutralization/coagulation effect of the remaining alkaline solid residue for treating acidic industrial wastewater. The possibility of sludge regeneration was also tested using the procedure of alkaline zinc extraction and the application of the remaining solid residue for treating acidic wastewater. To this end, seven samples of composite electric arc furnace dust from the Sisak steel mill with zinc content ranging from 5.71% to 28.18% were used. By means of alkaline extraction, between 62.4 and 84.6% zinc was isolated. The composition of eluate from the remaining solid residue met the criteria for disposal at inert waste disposal sites. Its use in treating wastewater from the galvanizing process in optimal conditions (pH = 8; tcon = 20 min.) removed between 99.17% and 100% of heavy metals, thus achieving the concentration values of elements suitable for discharge into the environment. The sludge was regenerated by zinc isolation using alkaline extraction while the remaining solid residue was successfully reused for treating acidic wastewater with a similar removal efficiency as in the previous experiment., Das Ziel dieser Arbeit ist Extraktion von Zink aus dem Lichtbogenofenstaub durch alkalische Extraktion mit einer starken Base NaOH und die Verwendung der starken neutralisierenden Wirkung und Koagulationswirkung des alkalischen festen Rückstands in der Behandlung von sauren Industrieabwässern. Außerdem wurden die Möglichkeit der Regeneration des Abfallschlammes im Verfahren der alkalischen Extraktion von Zink und die Möglichkeit der Verwendung des festen Rückstands in der Behandlung von sauren Abwässern geprüft. Zu diesem Zwecke wurden sieben Verbundwerkstoffproben vom Lichtbogenofenstaub mit dem Zinkanteil zwischen 5,71% und 28,18% aus dem Stahlwerk Sisak verwendet. Durch alkalische Extraktion wurde zwischen 62,4 und 84,6% Zink extrahiert, und die Zusammensetzung des Eluats befriedigte die Bedingungen für die Entsorgung auf einer Inertabfalldeponie. Durch die Anwendung der alkalischen Extraktion in der Behandlung vom Prozessabwasser aus der Verzinkerei unter optimalen Bedingungen (pH = 8; Kontaktzeit = 20 min) wurden zwischen 99,17% und 100% Schwermetalle beseitigt, womit die Konzentrationswerte von Elementen erzielt wurden, die Freisetzung in die Umwelt erlauben. Der Abfallschlamm wurde durch die alkalische Extraktion von Zink regeneriert, und der feste Rückstand wurde wieder in der Behandlung von sauren Abwässern mit einer ähnlichen Wirksamkeit wie in der ersten Untersuchung verwendet.

Svrha ovog rada bila je razviti sustav pročišćavanja podzemne vode koja se koristi za ljudsku potrošnju s visokim koncentracijama arsena i mangana te povišenim vrijednostima amonija i organskog opterećenja. U tu svrhu je korištena podzemna voda iz četiri bunara s područja Vukovarsko-srijemske županije (Andrijaševci, Antin, Komletinci i Vrbanja). Najviše vrijednosti arsena su izmjerene u Vrbanji (179 µg dm-3) a mangana u Antinu (154,5 µg dm-3). Zbog kompleksnog sastava podzemne vode sustav pročišćavanja je uključivao kombinirani pristup uključujući prethodno ozoniranje, glavnu elektrokemijsku obradu primjenom željezovih i aluminijevih elektroda bez/sa istovremenim ozoniranjem te završnu oksidaciju reaktivnim oksidativnim produktima nastalim istovremenom primjenom UV zračenja, ozona i ultrazvuka. Nakon kombiniranog postupka pročišćavanja svi mjereni pokazatelji u vodi iz sva četiri bunara su bili niži od MDK. Postignuto je potpuno uklanjanje arsena, boje, mutnoće, suspendirane tvari, organskih pokazatelja, nitrata, nitrita i fluorida te teških metala Hg, Co, Ni, Pb i Cd. Uklanjanje mangana se kretalo od 99,55 % do 99,99 % a amonija u rasponu od 99,5% do 99,7 %. Navedenim postupcima obrade dobivena je pitka voda sigurna za ljudsku potrošnju s kemijskog i toksikološkog stajališta., The purpose of the paper is the development of a treatment system for groundwater used for human consumption with high arsenic and manganese concentrations and increased values of ammonium and organic load. To this end, groundwater from four wells in the Vukovar – Srijem County (Andrijaševci, Antin, Komletinci and Vrbanja) was used. The highest arsenic value was measured in Vrbanja (179 µg dm-3) and the highest manganese value in Antin (154.5 µg dm-3). Due to a complex groundwater composition, the treatment system included a combined approach with prior ozonation, main electrochemical treatment using iron and aluminium electrodes with/out simultaneous ozonation and final oxidation using reactive oxidative products generated by simultaneous application of UV radiation, ozone and ultrasound. Following the combined treatment procedure, all measured indicators in water from all four wells were lower than the MAC. The complete removal of arsenic, colour, turbidity, suspended solids, organic indicators, nitrates, nitrites and fluorides as well as heavy metals (Hg, Co, Ni, Pb and Cd) was achieved. The removal of manganese ranged from 99.55 % to 99.99 % while the ammonium removal ranged from 99.5% to 99.7 %. These treatment procedures resulted in drinking water that is safe for human consumption from the chemical and toxicological viewpoints., Das Ziel dieser Arbeit war es, ein Konzept zu entwickeln zur Reinigung des Grundwassers, das für den menschlichen Gebrauch bestimmt ist, weist aber höhere Arsen- und Mangankonzentrationen, erhöhte Ammoniumwerte und organische Belastung auf. Vier Tiefbrunnen in der Gespanschaft Vukovar-Srijem – Andrijaševci, Antin, Komletinci und Vrbanja – sind in die Arbeit einbezogen worden. Die höchsten Arsenwerte wurden in Vrbanja (179 µg dm-3) und die höchsten Manganwerte in Antin (154,5 µg dm-3) gemessen. Wegen der komplexen Zusammensetzung des Grundwassers besteht das Reinigungssystem aus einer Kombination von Vorozonung, Hauptbehandlung, die aus dem elektrochemischen Verfahren unter Verwendung von Eisen- und Aluminiumelektroden mit oder ohne gleichzeitige Ozonung besteht, und Endozonung mit reaktiven Oxidationsprodukten, die bei gleichzeitiger Anwendung von UV-Bestrahlung, Ozon und Ultraschall entstanden. Nach diesem Kombinationsverfahren wurden die Werte aller Parameter im Wasser aus allen vier Brunnen niedriger als die höchstzulässigen Werte. Vollständige Entfernung von Arsen, Farbe, Trübung, Schwebstoffen, organischen Indikatoren, Nitraten, Nitriten, Fluoriden und Schwermetallen Hg, Co, Ni, Pb und Cd wurde erzielt. 99,55 % bis 99,99 % Mangan sowie 99,5% bis 99,7 % Ammonium wurde auch entfernt. Durch den Einsatz der angeführten Verfahren wird das Wasser vom chemischen und toxikologischen Standpunkt als Trinkwasser für den menschlichen Gebrauch geeignet sein.

Since there are several predicting factors associated with the comet assay parameters, we have decided to assess the impact of seasonal variations on the comet assay results. A total of 162 volunteers were retrospectively studied, based on the date when blood donations were made. The groups (winter, spring, summer and autumn) were matched in terms of age, gender, smoking status, body mass index and medical diagnostic exposure in order to minimise the impact of other possible predictors. Means and medians of the comet assay parameters were higher when blood was sampled in the warmer period of the year, the values of parameters being the highest during summer. Correlation of meteorological data (air temperature, sun radiation and sun insolation) was observed when data were presented as the median per person. Using multivariate analysis, sampling season and exposure to medical radiation were proved to be the most influential predictors for the comet assay parameters. Taken together, seasonal variation is another variable that needs to be accounted for when conducting a cohort study. Further studies are needed in order to improve the statistical power of the results related to the impact of sun radiation, air temperature and sun insolation on the comet assay parameters.

Since the production of printed circuit boards (PCBs) generates wastewater contaminated with heavy metals and organic matter, PCB factories represent potential pollution sites. The wastewater toxicologically tested in this study contained several metals and the most abundant were copper and iron. At two exposure times tested (4 and 24 h) PCB wastewater (PCBW) proved to be cytotoxic (decreased cell viability) and genotoxic (increased comet assay tail intensity and tail moment) to human blood peripheral lymphocytes in vitro, and the oxidative stress parameter (malondialdehyde concentration) was also found to be higher. After application of combined treatment by waste base, ozone and waste sludge methods, concentrations of metals in purified PCBW were below the upper permitted levels and all tested toxicological parameters did not differ compared to the negative control. Taken together, similar methods could be implemented in PCB factories before discharging potentially toxic wastewater into the environment because purified PCBW does not represent a threat from the aspect of cytotoxicity and genotoxicity.

Objective/Purpose: The objective of this study was efficacy and safety assessment of Bioapifit® wound care ointment consisted of honey, Cera flava, glycerin, the oil macerates of astringent and soothing herbs combined with essential oils for the treatment of diabetic neuropathic foot ulcers of grade II. Materials and methods: 50 patients with Wagner grade II diabetic foot ulcers were randomized into experimental and control group (25 patients each). The experimental group was treated 28 days with Bioapifit® wound care ointment applied on the wound after cleaning with povidone iodine once a day and covered with sterile gauze and bandage during the whole course of the study. The control group wounds were cleaned with povidone iodine once a day and covered with sterile gauze and bandage during the whole course of the study without further treatment. The ulcers surface area was measured at baseline and after 14 and 28 days of the treatment. Results: In the end of the treatment the mean values and standard deviation of the surface area in the experimental group dropped from 8.27±6.1 cm 2 to 0.74±0.21 cm 2 for males and from 9.01±5.9 cm 2 to 0.81±0.11 cm 2 for females. Slight, insignificant decrease was also observed in the control population (up to 25%). No side-effects were observed during the course of the study. Conclusion/Discussion: Four weeks treatment with Bioapifit® wound care ointment resulted in complete wound closure in 84% of the patients and 91% reduction in the wound surface area in the rest of them.

Environmental pollution from metals needs to be constantly monitored due to their predominantly negative impacts on liv-ing organisms. As apian products stored in hives are considered useful bioindicators, the objective of this study was to: (a) investigate and compare the essential and toxic metal concentrations in freshly constructed combs (light combs, LC) and old combs (dark combs, DC) in use for two to three beekeeping seasons, and (b) compare the mineral content of beeswax combs from apiaries exposed to different levels of environmental pollution using the energy dispersive x-ray fluorescence method. Concentrations of ten elements (Cr, Pb, Cu, Ni, Fe, Zn, Mn, Sr, Rb, Ca) were determined in 18 honeybee wax comb samples from three apiaries in continental Croatia. The results showed that the influence of comb age and/or geographical origin (representing varying levels of environmental pollution exposure) on the elemental composition of beeswax was evident for the toxic elements Cr, Pb, Cu and Ni, and for the essential elements Fe, Zn, Mn and Sr, but not Rb. In addition to monitoring the environmental element content, wax combs can be used to determine contamination levels. Additionally, in-time analysis results can enable beekeepers to adjust management practices, such as moving apiaries to better positions. They can also be useful in the creation of policies on acceptable limits for toxic metal levels in particular geographical areas.

Objective / Purpose : The objective of the study was assessment of the clinical efficacy and safety of Bioapigyn O vaginal ointment and pessaries compared to Acidosalus O pessaries and vaginal probiotic in alleviating vulvo-vaginal disorders. Materials and methods : 124 females were randomly selected into four groups (each of 31 participants) and treated once a day for ten days with: A) Bioapigyn O vaginal pessaries (one pessary per day); B) 2.5 mL of Bioapygin O vaginal ointment; C) Acidosalus O vaginal pessaries (one pessary per day); D) 2.5 mL of Acidosalus O vaginal probiotic. All the patients were subjected to gynecological examination, measurement of vaginal pH, Pap test, native and KOH test, self-assessment and clinical assessment of the symptoms at baseline and following the therapy. Results : Following the treatment with Bioapigin O vaginal ointment, Bioapigyn O pessaries, Acidosalus O pessaries, Acidosalus O vaginal probiotic the total score of vulvo-vaginal disorders decreased for 85.2%, 88.9%, 82.7% and 78%, respectively and vaginal pH decreased between 9.1% and 14.3%. Native test showed normalization of the vaginal flora following the treatment with all four products with no significant difference among the products. Conclusion/Discussion : Both Bioapigyn O and Acidosalus O products were highly efficient in alleviation of vulvo-vaginal disorders. The products created unfavorable conditions for pathogenic growth through the lowering of vaginal pH value, promoting the growth of lactobacilli, creating the environment with low water activity and creating a protective layer on the damaged mucosa that creates a physical barrier to the entrance of the pathogens into the cells and enables the recovery of the vaginal mucosa.

The purpose of this work was the development and application of a new herbal ointment and pessaries for the topical treatment of menorrhagia using macerates and essential oils of medicinal plants as active ingredients. Fifty subjects with proven menorrhagia ranging from 32 to 54 years were divided into two groups (each had 25 participants) of similar age, health status and lifestyle. The first group used 2 g of ointment every eight hours while the second group used pessaries instead. The results were obtained at baseline and following the third menstrual cycle. In both groups a significant decrease was observed for all the symptoms (p

Owing to its proven toxicity and mutagenicity, arsenic is regarded a principal pollutant in water used for drinking. The objective of this study was the toxicological and chemical evaluation of groundwater samples obtained from arsenic enriched drinking water wells before and after electrochemical and ozone-UV-H2O2- based advanced oxidation processes (EAOP). For this purpose, acute toxicity test with Daphnia magna and chronic toxicity test with Lemna minor L. were employed as well as in vitro bioassays using human peripheral blood lymphocytes (HPBLs). Several oxidative stress parameters were estimated in L.minor. Physicochemical analysis showed that EAOP treatment was highly efficient in arsenic but also in ammonia and organic compound removal from contaminated groundwater. Untreated groundwater caused only slight toxicity to HPBLs and D. magna in acute experiments. However, 7-day exposure of L. minor to raw groundwater elicited genotoxicity, a significant growth inhibition and oxidative stress injury. The observed genotoxicity and toxicity of raw groundwater samples was almost completely eliminated by EAOP treatment. Generally, the results obtained with L. minor were in agreement with those obtained in the chemical analysis suggesting the sensitivity of the model organism in monitoring of arsenic- contaminated groundwater. In parallel to chemical analysis, the implementation of chronic toxicity bioassays in a battery is recommended in the assessment of the toxic and genotoxic potential of such complex mixtures.

The purpose of this work was to assess the risk to the environment arising from the electroplating sludge from both chemical and toxicological point of view. Both approaches were used for the assessment of the treatment efficiency which consisted of CaO based solidification followed by thermal treatment at 400 C. The elemental composition was determined in the bulk samples and the leachates of untreated sludge. The toxicity of the leachate was determined using two human colorectal adenocarcinoma cell lines (Caco- 2 and SW 480) and Hordeum vulgare L. based plant bioassay. The same toxicity tests were employed to the leachate of the treated sludge. Untreated sludge showed extremely high cytotoxic effect to both human and plant bio-system in dose-dependent manner. The percentages higher than 0.5% and 0.05% of the leachate caused significant cytotoxic effect on Caco-2 and SW 480 cells, respectively. The percentages of the leachate higher than 0.05% also showed significant toxic effect to H. vulgare L. bio-system with complete arrest of seed germination following the treatment with 100% to 5% of the leachate. The leachate of the treated sludge showed no toxicity to any of the test systems confirming the efficiency and justification of the employed procedures for the detoxification of electroplating sludge.

The purpose of this study was development of the optimal conditions for the inertization of the polluted marine sediments using groundwater treatment sludge highly enriched in iron and aluminum. For that purpose fine-grained sediment (>85% clay and silt fraction) highly enriched in copper and zinc was amended with the waste sludge (from 10% to 50%). The sample with the optimum percentage of the waste sludge was further subjected the thermal treatment at 200–800 C. The efficiency of the treatment was determined by the leaching tests and toxicity testing using Hordeum vulgare L. as biosystem. The percentage of the seed germination, the root elongation, and the germination index before and following the treatment were determined. Untreated sediment leachate caused significant arrest in the percentage of the seed germination (6.7 § 6.7%), the root elongation (1.9 § 2.2%), and the germination index (0.2 § 0.3%) with EC50 of 24.9%, suggesting a significant toxic potential of the sediments. After amendment with 30% of the waste sludge the concentrations of the considered micropollutants decreased below regulated values while all three toxicological parameters showed no significant difference compared to the negative control. The toxicity of the sediment was completely removed following the thermal treatment at 400 C.

U radu je praćena detoksifikacija otpadne vode od prerade grožđa kroz različite faze kemijske i elektrokemijske obrade. U cilju uklanjanja organskih/anorganskih onečišćivala iz otpadne vode korištena je oksidacija ozonom i taloženje pomoću CaO kao faza predobrade te tri elektrokemijske metode (elektrooksidacija, elektroredukcija i elektrokoagulacija) korištenjem elektroda od nehrđajućeg čelika, željeza i aluminija uz istovremeno ozoniranje u svrhu glavne obrade. Toksični učinak otpadne vode prije i nakon svake od faza pročišćavanja praćen je preko vrijednosti parametara klijavosti nakon izlaganja biljke Hordeum vulgare L. uzorcima nepročišćene/pročišćene otpadne vode. Otpadna voda je okarakterizirana niskom pH vrijednošću (4,02), intenzivnim mirisom i obojenjem (28400 PtCo), visokim vrijednostima organskih pokazatelja (18430 mg dm-3 KPK, 1340 mg dm-3 ukupnih fenola, 1720 mg dm-3 BPK5) te povišenim vrijednostima hranjivih soli i teških metala. Sinergijski i aditivni učinak između organskih pokazatelja, prvenstveno fenola i teških metala te niska pH vrijednost su vjerojatno odgovorni za izuzetno visok fitotoksični učinak s EC50 vrijednošću od svega 0,08 % te potpunim zastojem klijavosti nakon izlaganja sjemena nerazrijeđenoj otpadnoj vodi. Predobrada vapnom pri kojoj je uklonjeno između 46% i 99,8% teških metala, 90,4 % boje, 98,3 % mutnoće, 98,6 % UST, 95,4 % fosfata, 91,5 % sulfata te između 39 % i 47 % organskih pokazatelja je rezultirala 50 %-tnim smanjenjem toksičnog učinka. Završnom obradom dobiven je bistar efluent bez mirisa i s jedva primijetim obojenjem sa stupnjem uklanjanja karakterističnih pokazatelja između 73,8 % i 100 %, čime je u potpunosti uklonjen i njegov toksični učinak (Klijavost = 99,2±0,2 %; Indeks klijavosti = 99,2±0,2 %). Iz navedenog je moguće zaključiti da je odabrani set metoda pogodan za detoksifikaciju biološki slabo razgradljivih efluenata vrlo složenog i varijabilnog sastava kao što su vinarijske otpadne vode. Utvrđivanje parametara klijavosti na biljci Hordeum vulgare L. se pokazalo kao vrlo osjetljiv, jednostavan i jeftin test sustav za praćenje toksičnog učinka industrijskih efluenata te praćenje stupnja njihove detoksifikacije u toku različitih faza i metoda obrade., The paper monitors detoxification of wastewater from the processing of grapes through various phases of chemical and electrochemical treatment. For the purpose of removing organic / inorganic pollutants from wastewater, oxidation with ozone and sedimentation with CaO were used as preliminary treatment phases as well as three electrochemical methods (electro-oxidation, electro-reduction and electro-coagulation) utilizing electrodes made of stainless steel, iron an aluminium, with a simultaneous ozonation as the primary treatment. The toxic effect of wastewater before and after each treatment phase was monitored through the values of the germination parameter after exposure of the plant Hordeum vulgare L. to the samples of untreated/treated wastewater. The wastewater was characterized by low pH value (4.02), intense odour and colouring (28400 PtCo), high values of organic pollutants (18430 mg dm-3 COD, 1340 mg dm-3 total phenols, 1720 mg dm-3 BOD5) and elevated values of nutrients and heavy metals. The synergic and additive impact among organic indicators, primarily phenols and heavy metals and a low pH value, were probably responsible for an extremely high phytotoxic impact with the EC50 value of only 0.08 % and a full cessation of the germination after the seed exposure to undiluted wastewater. A preliminary treatment with lime, which removed 46% - 99.8% of heavy metals, 90.4 % of colour, 98,3 % of turbidity, 98.6 % total suspended solids, 95,4 % of phosphates, 91.5 % of sulphates and 39 % - 47 % of organic indicators, resulted in 50 % toxic impact reduction. The final treatment resulted in clear effluent without odour and a barely noticeable colouring, with a removal degree of characteristic indicators from 73.8 % to 100 %, which also fully removed its toxic impact (germination = 99.2±0.2 %; germination index = 99.2±0.2 %). Based on the above stated, it can be concluded that the selected set of methods is suitable for detoxification of biologically poorly degradable effluents of a very complex and variable composition, such as wastewater from the wine-making process. The determination of the germination parameters on the plant Hordeum vulgare L. proved to be a very sensitive, simple and inexpensive test system for monitoring the toxic impact of industrial effluents and the degree of their detoxification in different treatment phases and with different methods.

U radu je ispitana mogućnost primjene elektrokemijskih metoda (elektroredukcije, elektrokoagulacije, indirektne anodne oksidacije) korištenjem željezovog i aluminijevog seta elektroda sa ili bez dodatka elektrolita za obradu otpadne vode koja nastaje u procesu površinske zaštite metala. Otpadna voda je karakterizirana visokim vrijednostima cinka (2029 mg dm-3) i željeza (78,4 mg dm-3) te povišenim vrijednostima Cr(VI) (5,4 mg dm-3) i kemijske potrošnje kisika (820 mg dm-3) koje premašuju granične vrijednosti za ispust u okoliš za 1014, 39, 56, odnosno 6,6 puta. U svrhu optimizacije procesa u radu je ispitan utjecaj vrste elektroda (željezo, aluminij), kontaktnog vremena (5-30 minuta), mase elektrolita (0,5-1,5 g NaCl) te jakosti struje (20-50 A) na stupanj uklanjanja navedena četiri pokazatelja. Između dvije testirane elektrode, željezova se pokazala značajno efikasnijom u uklanjanju svih mjerenih pokazatelja, a naročito Cr(VI) i KPK. Statistički značajno bolji rezultati u uklanjanju KPK za obje elektrode su postignuti dodatkom elektrolita te porastom jakosti struje s 20 na 40 A. Najveći udio anorganskog onečišćenja se ukloni u prvih 5 minuta obrade. Najbolji rezultati su postignuti kombinacijom dviju elektroda uz dodatak klorida kao elektrolita. Nakon 15 minuta elektroredukcije/elektrokoagulacije/indirektne anodne oksidacije pomoću željezovih elektroda, 15 minuta elektrokoagulacije pomoću aluminijevih elektroda te 20 minuta koagulacije/flokulacije i oksidacije zrakom uklonjeno je 99,79% Cr(VI), 99,97% Fe, 98,23% Ni, 99,23% Cu, 99,999% Zn, 98,00% Pb i 86,46% KPK a svi mjereni pokazatelji su zadovoljavali uvjete za ispust u okoliš, dok su se izlazne koncentracije teških metala kretale od 0,009 do 0,023 mg dm-3., The paper investigated a possibility of implementing electrochemical methods (electroreduction, electrocoagulation, indirect anodic oxidation) by using iron and aluminium electrode sets, with or without the addition of electrolytes for treatment of wastewater generated in the process of surface protection of metals. The wastewater is characterized by high values of zinc (2029 mg dm-3) and iron (78.4 mg dm-3) as well as increased values of Cr(VI) (5.4 mg dm-3) and chemical oxygen demand (820 mg dm-3) that exceed limit values for discharge into the environment by 1014, 39, 56 and 6.6 times, respectively. In order to optimize the process, the paper investigated the impact of electrode type (iron, aluminium), contact time (5-30 minutes), electrolyte mass (0.5-1.5 g NaCl) and amperage (20-50 A) on the removal level of the stated four indicators. Of the two tested electrode types, iron electrodes proved to be significantly more efficient in the removal of all measured indicators, in particular Cr(VI) and COD. A statistically significant improvement of the results in COD removal for both electrode types was achieved by the addition of electrolytes and increased amperage from 20 to 40 A. The majority of inorganic pollution is removed in the first 5 minutes of treatment. The best results are achieved by a combination of the two electrode types, with the addition of chloride as an electrolyte. After 15 minutes of electroreduction / electrocoagulation / indirect anodic oxidation by iron electrodes, 15 minutes of electrocoagulation by aluminium electrodes and 20 minutes of coagulation / flocculation and oxidation by air, 99.79% Cr(VI), 99.97% Fe, 98.23% Ni, 99.23% Cu, 99.999% Zn, 98.00% Pb and 86.46% COD were removed. All measured indicators complied with the conditions for discharge into the environment whereas all output concentrations of heavy metals ranged from 0.009 to 0.023 mg dm-3.

U radu je ukratko opisan proces proizvodnje etanola iz melase obzirom da isti direktno utječe na količinu i sastav nastalih otpadnih voda. Dani su podatci o sastavu otpadnih voda iz dostupne svjetske literature te toksični učinci ovih voda na različitim test organizmima. Dan je literaturni pregled najčešće korištenih postupaka pročišćavanja te njihove prednosti i nedostatci. Otpadne vode iz destilerija melase su tamne boje, niske pH vrijednosti, visoke vodljivosti, visoko su opterećene organskom tvari niske biorazgradivosti, ekstremno su toksične te se kao takve ne smiju bez prethodne obrade ispustiti u okoliš ili sustav javne odvodnje. Stoga, u svrhu smanjenja rizika za sastavnice prirode i okoliša, destilerijske otpadne vode zahtijevaju visok stupanj obrade kombinacijom različitih postupaka kako bi ih se učinilo neškodljivim za prirodu i okoliš te zadovoljili propisani zakonski kriteriji za ispust u okoliš., The paper briefly describes the process of ethanol production from molasses which directly affects the quantity and composition of generated wastewater. The data on wastewater composition are quoted from available international literature, and include data on the toxic impacts of this wastewater on different test organisms, as well as a literature overview of the most frequently used treatment procedures and their advantages and disadvantages. Wastewater from molasses-based distilleries is characterized by dark colour, low pH value, high conductivity, and has a high load of organic matter with low biodegradability. It is extremely toxic and cannot be discharged into the environment or public wastewater systems without preliminary treatment. Therefore, in order to reduce the risks for nature and environment components, distillery wastewater requires a high level of treatment as a combination of different procedures to render it harmless for the nature and environment and comply with the prescribed legal criteria for discharges into the environment.

Purpose of this research was to study the rate at which the semi-enclosed bay such as the Kaštela Bay reacts to the coastal processes of industrialization and urbanization, the extent of the influence of human activities on the bay, and the sediment distribution affected by anthropogenic influence. Temporal and spatial sedimentation rate variations were observed between three studied periods: 1954–2005, 1963– 2005/2006, and 1986–2005/2006. Sedimentation rates were in the following ranges: 0.29–0.49 cm/yr for the 1954–2005 period, 0.58–0.95 cm/yr for the 1963–2005/2006 period, and 0.50–1.32 cm/yr for the 1986–2005/2006 period. The average total sedimentation rates for three periods were 0.41cm/yr, 0.81 cm/yr, and 0.61 cm/yr, respectively. Sedimentation rate for the individual 1963–1986 period marked with two Cs- 137 marker peaks was in the 0.65–1.30 cm/yr range, while the mean value was 1.06 cm/yr. Long-term sedimentation rate increase in the whole Kaštela Bay was observed and clearly connected to the industrialization and urbanization processes in the coastal area. These processes reflect very quickly, in terms of years, in the sedimentation rates. Intensive anthropogenic activities in the coastal area are reflected in the whole bay depending on the amount of the discharged sediment material, topography of the sea bottom, and water currents. Some localized areas of sediment accumulation may form.

U radu je prikazan postupak obrade kiselog efluenta nastalog u toku eksploatacije i prerade bakrene rude kompleksa Borskih rudnika (Bor- Krivelj-Cerovo) pomoću crvenog mulja - otpadnog produkta iz procesa proizvodnje glinice u bivšoj tvornici glinice iz Obrovca te primjena nastalog otpadnog mulja za pročišćavanje otpadnih voda iz prališta brodova. Izvršena je karakterizacija otpadnih voda i crvenog mulja te su utvrđeni optimalni uvjeti uklanjanja ključnih pokazatelja iz otpadnih voda. Rudnička otpadna voda je karakterizirana niskom pH vrijednošću (3,21), visokom koncentracijom sulfata (10830 mg dm-3), visokim vrijednostima željeza (921 mg dm-3), mangana (107 mg dm-3), bakra (92 mg dm-3) i cinka (59 mg dm-3), dok su u otpadnoj vodi iz prališta brodova ključna onečišćivala bakar (34 mg dm-3), cink (59 mg dm-3) i boja (11470 PtCo). Obzirom na visok neutralizacijski i sorpcijski kapacitet crvenog mulja, njegovo miješanje s rudničkom otpadnom vodom u optimalnim omjerima dovodi do neutralizacije oba otpadna produkta te uklanjanja teških metala iz otpadne vode ispod graničnih vrijednosti. Pri optimalnim uvjetima uklanjanja (pH = 8; kontaktno vrijeme = 15 minuta) uklonjeno je više od 99,9% Cr, Mn, Fe, Cu i Zn te 65,5% sulfata. Preostali otpadni mulj je moguće ponovo upotrijebiti za pročišćavanje otpadnih voda iz prališta brodova visoko opterećenih bojama protiv obraštaja, a s jednom dozom mulja je moguće izvršiti pet ciklusa pročišćavanja s učinkovitošću uklanjanja ključnih pokazatelja preko 99%., The paper presents a procedure for treating acidic effluent generated during the exploitation and proce¬ssing of copper ore at the Bor mining complex (Bor-Krivelj-Cerovo) by application of red mud, a waste by-product of the alumina production process at the now-defunct alumina plant in Obrovac, and the application of the generated waste mud to treating wastewater from ship cleaning facilities. The characterisation of wastewater and red mud was carried out, resulting in the determination of optimal conditions for the removal of key indicators from wastewater. The acidic mine wastewater is characterised by a low pH value (3.21), high sulfate concentration (10,830 mg dm-3), high values of iron (921 mg dm-3), manganese (107 mg dm-3), copper (92 mg dm-3) and zinc (59 mg dm-3), whereas the key polluters in the wastewater from ship cleaning facilities include copper (34 mg dm-3), zinc (59 mg dm-3) and paint (11470 PtCo). Considering a high neutralisation and adsorption capacity of red mud, its mixing with mine drainage wastewater in op¬timal ratios leads to the neutralisation of both waste by-products and the removal of heavy metals from wastewater to below their limit values. Under the optimal removal conditions (pH = 8; contact time = 15 minutes), more than 99.9% of Cr, Mn, Fe, Cu and Zn as well as 65.5% of sulfates were removed. The remaining waste mud can be reused in the treatment of wastewater from ship cleaning facilities which has a high load of anti-fouling paint. A single mud dosage is sufficient for five treatment cycles and has a key indicator removal efficiency rate of over 99%.

The purpose of this work was to develop a pilot plant purification system and apply it to groundwater used for human consumption, containing high concentrations of arsenic and increased levels of phosphates, ammonia, mercury and color. The groundwater used was obtained from the production well in the Vinkovci County (Eastern Croatia). Due to a complex composition of the treated water, the purification system involved a combined electrochemical treatment, using iron and aluminum electrode plates with simultaneous ozonation, followed by a post-treatment with UV, ozone and hydrogen peroxide. The removal of the contaminant with the waste sludge collected during the electrochemical treatment was also tested. The combined electrochemical and advanced oxidation treatment resulted in the complete removal of arsenic, phosphates, color, turbidity, suspended solids and ammonia, while the removal of other contaminants of interest was up to 96.7%. Comparable removal efficiencies were obtained by using waste sludge as a coagulant.

Summary Leachates from active and closed municipal solid waste landfills can be a major source of contamination to groundwater and surface waters. In the present study the toxic and genotoxic potential of leachate from an old sanitary landfill prior to and following chemical and electrochemical treatments were assessed using Lemna, Allium, and comet tests. Photosynthetic pigments, malondialdehyde (indicator of lipid peroxidation) and antioxidant enzyme activities were evaluated as additional indicators of toxicity in duckweed. Following duckweed exposure to 25 % dilution of landfill leachate, growth rate and photosynthetic pigments content significantly decreased while lipid peroxidation increased despite stimulation of antioxidative defence mechanisms. Diluted leachate induced DNA strand breaks in duckweed cells as evidenced by the comet assay. Regarding the Allium test, untreated leachate caused inhibition of Allium cepa cell division and induction of mitotic and chromosomal aberrations. Although both water treatments completely reduced genotoxicity of leachate, the electrochemical method was found to be more efficient in removing toxic substances present in landfill leachate and thus more suitable for treating such leachates prior to their discharge into the environment. As landfill leachates pose a risk to human health and environment in general due to their (geno)toxicity, the present study demonstrates that the ecotoxicity/genotoxicity assays should be used in leachate risk assessment together with physicochemical analysis.

article i nfo A history of metalinputand changes inthe environmental conditionsofthe karst ecosystem of KrkaRiver during the last several decades was investigated by statistical evaluation of the combination of several proxies including sediment content of minor (Pb, Zn, Cu, As, Cr, Ni, Co, V, Ga, Y, Rb, Sr) and major (Ca, K, Fe, Mn, Ti, Al) elements, concentrations of sedimentary organic carbon (Corg) and nitrogen (N), their stable isotope compositions (δ 13 Corg and δ 15 N),aswell asstableisotope composition of sedimentary carbonate (δ 13 Ccarband δ 18 Ocarb).The re- sults show that measured trace and major elements are predominately of terrigenous origin, reflecting the geo- logical background of the area, whereas the sedimentary organic matter is predominantly authigenic. Although Zn amounts in sediments are results of anthropogenic pressures, its distribution in investigated sediment col- umns is influenced by natural processes, i.e. occasional re-sedimentation and self-purification of the water col- umn caused by the particulate Zn deposition in lakes formed by the tufa barrages. Levels of Pb in sediment columns are low except in the K2 which is close to the crossroads, especially in the period of lead fuel use. Trace element concentrations in sediment columns are compared to consensus-based sediment quality guide- lines (SQG) for freshwater ecosystems. Some of the As, Zn and particularly Ni sediment concentrations were found to be above threshold effect concentration (TEC) range. The stableisotopesof Corgand Corg/N ratiossuggestthatthesedimentary organicmatterispredominately of algal and bacterial origin, while the carbonate is a mixture of terrigenic detritus and in-situ precipitates. The average grain size distribution and carbonate content of sediment indicate decreasing input of terrestrial non- carbonate fraction, as a consequence of afforestation and land use changes in studied area.

This article presents a pilot-plant study of the electroplating wastewater treatment by the processes of electroreduction with iron electrode plates, and electrocoagulation/ozonation with aluminum electrode set, followed by the process of ozonation. The initial effluent was found to be highly enriched in heavy metals and to possess the elevated levels of organic contaminants. The values of Cr(VI), Fe, Ni, Cu, Zn, Pb, TOC, and COD exceeded the upper permissible limits of 63, 220.2, 1.1, 7, 131.3, 1.7, 12.3, and 11.4 times, respectively. The heavy metal removal was forced either by the coagulation/flocculation using Fe(II), Fe(III), and Al(III) ions released into the treated solution by the electrochemical corrosion of the sacrificial iron and aluminum electrodes, or the precipitation of the metal hydroxides as well as co-precipitation with iron and aluminum hydroxides. The principle organic matter destruction mechanisms were ozone oxidation and the indirect oxidation with chlorine/hypochlorite formed by the anodic oxidation of chloride already present in the wastewater. Following the combined treatment, the removal efficiencies of Cr(VI), Fe, Ni, Cu, Zn, Pb, TOC, and COD were 99.94%, 100.00%, 95.86%, 98.66%, 99.97%, 96.81%, 93.24%, and 93.43%, respectively, thus complying with the regulated values.

Mass fractions of Al, K, Ca, Fe, Ti, Mn, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Pb, and As were determined in the Cretaceous limestones, foraminiferal limestones, calcarenites, marls, stream sediments, and soils of the Kastela Bay coastal area. Relationships between 18 studied elements and between the researched sediments and sedimentary rocks were established. The highest mass fractions of Ca and Sr were found in the limestones and calcarenites, while the highest contents of other elements were determined in marls, stream sediments, and soils. Possible influence of the heavy mineral assemblage originating from basic and ultrabasic rocks of the Dinaric area was reflected in elevated Ni, Cr, and Zn contents in limestones and elevated Ni and Zn contents in marls. Naturally higher mass fractions of Ti, Mn, V, Cr, Ni, Cu, Zn, Pb, and As were found in the terra rossa soils. Three groups of elements were distinguished: (1) carbonates bound elements; (2) elements reflecting possible anthropogenic influence or the specific mineralogical assemblages; and (3) alumosilicates bound elements. It was suggested that Sr was only partly bound to CaCO3 and that Cu, Zn, and Pb were not primarily bound to any of the considered group of minerals. Three populations were differentiated according to their elemental composition and type of the sample: (1) samples with naturally higher mass fractions of Ca and Sr and lower mass fractions of other elements; (2) samples with naturally lower Ca and Sr mass fractions and higher mass fractions of other elements; and (3) samples with elevated mass fractions of Cu, Zn, and/or Pb, reflecting possible anthropogenic influence.

U radu su ukratko prikazani trendovi u svjetskoj i domaćoj proizvodnji vina. Dani su podatci o sastavu otpadnih voda iz dostupne svjetske literature te toksični učinci ovih voda na različitim test sustavima. Dan je literaturni pregled najčešće korištenih metoda pročišćavanja te njihove prednosti i nedostaci. Iz iznesenih podataka moguće je zaključiti da otpadne vode iz procesa proizvodnje vina zbog svoje kompleksnosti sastava te dokazanog visokog toksičnog učinka predstavljaju značajan rizik za sastavnice okoliša i prirode. Visoke vrijednosti organskog onečišćenja, sezonalnost, te prisutnost toksičnih tvari zahtijevaju kombinaciju različitih metoda obrade kako bi se ove vode učinile neškodljivim za okoliš te zadovoljili propisani zakonski kriteriji za ispust u okoliš. Najviši stupanj detosikacije se postiže kombinacijom bioloških metoda i naprednih oksidacijskih procesa (kao predobrade ili završne obrade)., The paper briefly presents the trends in global and domestic wine production. It contains data on wastewater composition from available world literature and toxic impacts of this water in different test systems. An overview of the most frequently implemented treatment methods in the literature is provided as well, including their advantages and disadvantages. Based on the presented data, it can be concluded that wastewater from the wine production process, due to the complexity of its composition and proven high toxic impact, poses a significant risk for environmental and nature components. High levels of organic pollutants, seasonality and the presence of toxic substances require a combination of different treatment methods for rendering this wastewater harmless for the environment and compliance with the prescribed legal criteria for discharges into the environment. The highest detoxification level is achieved by implementing a combination of biological methods and advanced oxidation processes (including preliminary or final treatment).

U radu je prikazan novi kombinirani pristup u obradi otpadne vode koja nastaje u procesu prerade krumpira u čips kombinacijom elektrokemijskih metoda i ozoniranja. Otpadna voda je karakterizirana visokim vrijednostima ukupne suspendirane tvari (1517 mg dm-3), kemijske potrošnje kisika (2240 mg dm-3) te biokemijske potrošnje kisika (1780 mg dm-3) koje premašuju granične vrijednosti za ispust u okoliš za 43, 18 odnosno 71 puta. U svrhu optimizacije procesa u radu je ispitan utjecaj vrste elektroda (nehrđajući čelik, željezo, aluminij), kontaktnog vremena (5-30 minuta) te jakosti struje (30-100 A) na stupanj uklanjanja navedena tri parametra. Iako se aluminijev set elektroda pokazao najefikasnijim za uklanjanje navedenih pokazatelja, značajno bolji rezultati su dobiveni kombinacijom sve tri vrste elektroda uz istovremeno ozoniranje. Nakon 10 minuta elektrokoagulacije/elektroksidacije pomoću elektroda od nehrđajućeg čelika, 5 minuta elektrokoagulacije/ozoniranja pomoću željezovih elektroda, 15 elektrokoagulacije/ozoniranja pomoću aluminijevih elektroda te 15 minuta ozoniranja uklonjeno je 100% boje, mutnoće i UST, 94,5% KPK te 98,9% BPK5 a svi mjereni pokazatelji su zadovoljavali uvjete za ispust u okoliš., The paper presents a new approach which combines electrochemical methods and ozonation to wastewater treatment from potato processing in potato chips production. This wastewater is characterized by high values of total suspended solids (1517 mg dm-3), chemical oxygen demand (2240 mg dm-3) and biochemical oxygen demand (1780 mg dm-3) that exceed the limit values for discharges into the environment by 43.18 and 71 times, respectively. For the purpose of optimisation of this process, the paper investigated the impact of different electrode types (stainless steel, iron, aluminium), contact time (5-30 minutes) and amperage (30-100 A) on the degree of removal of these three parameters. Although the aluminium electrode set proved the most effective for the removal of these indicators, significantly better results were obtained by a combination of all three electrode types with simultaneous ozonation. After 10 minutes of electrocoagulation / electrooxidation with stainless steel electrodes, 5 minutes of electrocoagulation / ozonation with iron electrodes, 15 minutes of electrocoagulation / ozonation with aluminium electrodes and 15 minutes of ozonation, 100% colour, turbidity and TSS, 94.5% COD and 98. 9% BOD5 were removed, and all measured indicators met the requirements for discharges into the environment.

Landfill leachate presents hardly treatable, highly complex and very toxic environmental effluent originated in the municipal solid waste degradation process. Although, numerous treatment methods were developed so far, none of them alone could achieve permissible limits of the primary pollutants to discharge into natural recipients. The current study aimed to develop and apply the process to treat landfill leachate by simultaneous application of electrochemical methods, ultrasound, electromagnetic field and ozonation to achieve the legal criteria for its discharge into natural recipient and minimize its adverse environmental impacts. For this purpose, old landfill leachate was taken from the Piskornica (Koprivnica, Croatia) sanitary landfill. Prior to the treatment, the leachate was supplemented with NaCl (2 g/L) and subjected to simultaneous treatment with stainless steel electrode plates, ultrasound and recirculation through electromagnetic field. After 45 minutes, stainless steel electrode plates were replaced by iron electrodes and treated for another 10 minutes followed by 15 minutes of the treatment with aluminum electrode plates. Ultrasound and recirculation through electromagnetic field were also applied during Fe and Al electrode treatment. Finally, the electrodes were removed and the suspension was mixed with ozone for another 30 minutes and allowed to settle for an hour. Following the combined treatment, the removal efficiency for the turbidity, color, suspended solids, ammonium, phosphates and heavy metals was 99% or higher, while the removal of COD was 97%. All the measured parameters in the treated leachate were lower compared to upper permissible limit for discharge into natural recipient.

The subject of this study was chemical and radiological characterization of the fly and bottom ash, by-product of the combustion of coal used as an energy source in the former sulfate pulp factory in Plaški. The research involves determination of the concentration of macro, micro and trace elements and activities of the radionuclides in: (i) ash from different positions of the landfill; (ii) soil samples in the zone of the influence of the landfill; (iii) control soil samples and (iv) sediment sample from the river Dretulja. Besides, in situ measurement of an effective dose rate above ash/soil was also determined. In relation with the control soil the average increase of the concentrations of the elements Ca, Cd, Hg, Ni, Se, Sr, Th and U in the samples taken from the fly and bottom ash landfill as well as soil samples within the radius of 300 m from the landfill was 38.3, 6.7, 9.9, 8.5, 9.4, 7.2, 3.6 and 5.7 times, respectively. In these samples, the concentrations of the above mentioned elements were in the following ranges: calcium from 7.94 to 19.7 %; cadmium from 0.33 to 1.66 mg/kg; mercury from 0.18 to 0.49 mg/kg; nickel from 260 to 1500 mg/kg; selenium from 2.7 to 21 mg/kg; strontium from 176 to 542 mg/kg; thorium from 8 to 55 mg/kg and uranium from 5.6 to 19.7 mg/kg. Compared to the world's average soil concentration, uranium and thorium values increased 3.7 and 1.7 times, respectively. The mean value of the total effective dose rate measured in the air at the height of 1 m for all samples of ash and soil under the influence of the landfill was 1.60 mSv/yr. Compared to the Croatian average (0.7015 mSv/yr), the determined mean value for the Plaški landfill is two times higher. However, compared to the local background (0.14 mSv/yr), the mean value of the total effective dose rate measured above the Plaški landfill is 11.4 times higher. In the samples of ash and contaminated soil regardless of the sampling location the activity concentrations of the radionuclides in Bq/kg vary in the following ranges: (226)Ra from 82.10 to 314.90 (mean value 145.99), (232)Th from 32.50 to 223.60 (mean value 76.76) and (238)U from 69.10 to 243.20 (mean value 134.38). Compared to the mean values found in the background soil (226)Ra and (238)U mean activity concentrations increased from 1.6 to 6.4 times and (232)Th from 1.4 to 4.3 times. In order to reduce total effective dose rate to the local "background" values and to prevent redistribution of the radionuclides and heavy metals from the deposited material into the environment fly and bottom ash landfill must be sealed with 10 cm thick layer of the material with low permeability.

The aim of this research was development of appropriate procedure for the treatment of landfill leachate taken from the Visevac, Mraclinska Dubrava and Piskornica sanitary landfills. Due to the complex nature of the effluents a combined treatment approach was applied. The pretreatment step included simultaneous treatment with calcium oxide and electrocoagulation/electrooxidation by stainless steel electrode set. The main treatment included electrocoagulation/electrooxidation using the set of stainless steel, iron and aluminum electrodes. The pretreatment allowed the destruction and/or coagulation of the high molecular weight organic substances as well as optimization of pH values for the formation of reactive oxidative species, and the transformation of NH(4)-N into volatile NH(3)-N. In the presence of added calcium oxide and electrochemically generated coagulant the removal of the fluorides, phosphates and heavy metals occur through the formation of poorly soluble fluorapatite, hydroxyl apatite, and various hydroxides. During the main treatment electrochemically generated reactive oxidative species carried out rapid decomposition of the organic matter and ammonia, resulting in the removal of COD from 74.9% to 94.2%, color from 98.8% to 99.7%, turbidity from 98.4% to 99.3%, suspended solids from 97.1% to 99.3%, and ammonia from 99.6% to 99.7%. Slightly better results for the removal efficiency of color, turbidity and suspended solids were obtained in the case of Piskornica landfill compared with the other two landfills, while the COD removal efficiency decreases in the following order: Piskornica >Mraclinska Dubrava >Visevac. This could be related to the age of the landfill, which increases in the same order. Consequently, with the increasing age of the landfill the degree of degradability of the organic matter reduces significantly. Applied treatment approach resulted in clear, colorless and odorless effluent with the values of all measured parameters significantly lower compared to the upper permissible limit for discharge into the environment.

Objective The objective of this study was determination of causative factors of the genital infections and their correlation with various predictor variables. Secondary objectives included: (1) determination of the presence and the type of low molecular weight metabolites in the samples of vaginal secretion formed in vivo, (2) determination of the concentration of 2- phenylethanol formed in vitro for each Candida species, (3) determination of the relationship between fungal/bacterial/viral infections with the metabolites formed in vivo using multivariate analysis. Methods One hundred and ninety-seven women in the age range from 18 to 65 years were included in the study. After the completion of questionnaire, all the patients were subjected to Pap test, cervical swabs for the presence of aerobic bacteria, yeasts, Ureaplasma urealyticum, Chlamydia trachomatis, Mycoplasma, and hrHPV DNA. The presence and the concentration of low- molecular weight metabolites in vitro and in vivo were determined by gas chromatography-mass spectrometry (GC–MS) method. Multivariate analysis methods were used for statistical evaluation. Results The most important risk factors of fungal/bacterial/viral infections were determined. The presence of 2-phenylethanol in vivo was confirmed in 14 of 74 tested samples and connected with the Candida species. The presence of symptoms, hrHPV DNA and Ureaplasma urealyticum are the predictor variables with the highest influence on the formation of the metabolite in vivo. The results in vitro confirmed that various Candida species produced 2-phenylethanol with the concentrations ranging from 0.6 to 4.64 μg/mL. Conclusion The medical exposure to irradiation, marital status, and number of partners as well as stress factors (miscarriages, chronic, viral, or tumor illnesses) had the highest influence on the development of the bacterial/fungal/viral infections. The formation of 2-phenylethanol, both in vivo and in vitro, was confirmed and connected with Candida species. Besides, according to statistical tests, it seems that presence of symptoms, hrHPV DNA, and Ureaplasma urealyticum had also significant role on the formation of 2- phenylethanol in vivo.

Chemical analysis and an in vitro approach were performed to assess elemental composition and genotoxic effects of the samples of landfill leachate taken from Lokva Vidotto sanitary landfill the official landfill for Rovinj town, Croatia. Two samples of landfill leachate were collected and analyzed in order to evaluate macro, micro and trace elements by atomic absorption spectroscopy, energy dispersive X-ray spectrometry and colorimetry. Genotoxicity of sanitary landfill leachate was evaluated in human lymphocytes by the use of the micronucleus test and comet assay. Samples were characterized with relatively low concentrations of heavy metals while organic component level exceeded upper permissible limit up to 39 times. Observed genotoxic effects should be connected with high concentrations of ammonia nitrogen, which exceeded permissible limit up to 180 times. Leachate samples of both sanitary landfills increased the frequency of micronuclei, nucleoplasmic bridges and nuclear buds. Increase of DNA damage in human lymphocytes was also detected by virtue of measuring comet assay parameters. All parameters showed statistically significant difference compared to negative control. Increased micronucleus and comet assay parameters indicate that both samples of sanitary landfill leachate are genotoxic and could pose environmental and human health risk if discharged to an aquatic environment.

Boat Pressure Washing Wastewater Treatment with Calcium Oxide and/or Ferric ChlorideThe aim of this study was to investigate the efficiency of (1) chemical precipitation by calcium oxide, (2) coagulation/flocculation by ferric chloride (FC), and (3) the combination these two methods in reducing the toxicity of wastewater generated by boat pressure washing. All three methods gave satisfactory results in the removal of colour, turbidity, Cr, Fe, Cu, Zn, and Pb. The concentrations of heavy metals were lowered below national limits with 1 g of CaO, 2.54 mg of Fe3+ in the form of FeCl3x6H2O, and the combination of 0.25 g of CaO and 5.08 mg of Fe3+ per 50 mL of wastewater. Both CaO (1.50 g per 50 mL of wastewater) and FC proved efficient, but their combination yielded a significantly better performance: 99.41 %, 100.00 %, 97.87 %, 99.09 %, 99.90 %, 99.46 % and 98.33 % for colour, turbidity, Cr, Fe, Cu, Zn, and Pb respectively. For colour, Cr, Cu, Zn, and Pb removal efficiencies increased in the following order: FC

Purpose of this research was to study the rate at which the semi-enclosed bay such as the Kaštela Bay reacts to the coastal processes of industrialization and urbanization, the extent of the influence of human activities on the bay, and the sediment distribution affected by anthropogenic influence. Temporal and spatial sedimentation rate variations were observed between three studied periods: 1954-2005, 1963-2005/2006, and 1986-2005/2006. Sedimentation rates were in the following ranges: 0.29-0.49 cm/yr for the 1954-2005 period, 0.58-0.95 cm/yr for the 1963-2005/2006 period, and 0.50-1.32 cm/yr for the 1986-2005/2006 period. The average total sedimentation rates for three periods were 0.41 cm/yr, 0.81 cm/yr, and 0.61 cm/yr, respectively. Sedimentation rate for the individual 1963-1986 period marked with two

Waters can be polluted by heavy metals which are accumulated and concentrated by fish ; therefore they show the degree of environmental pollution. The aim of this paper was to determine concentrations of heavy metals in water, mud and fish organs, to determine whether these concentrations are allowed and in accordance with normative provisions and, considering the pollution by heavy metals, if the fish meat is hygienically safe food of animal origin. Concentrations of heavy metals (lead, chromium, manganese, iron, copper, and zinc) were determined in water, mud and different organs (liver, kidney, intestine, milt and skin + muscle) of pike (Esox lucius) and European catfish (Silurus glanis) by Energy Dispersive X – Ray Fluorescence Method (EDXRF). Statistically significant difference was determined between the concentrations of heavy metals in mud and water (p< 0.05), as well as in fish organs (p< 0.05). The obtained results show that the highest concentrations of heavy metals were determined in liver, and the lowest ones in skin and muscle, i.e. in edible fish parts. In accordance with normative provisions of the European Union and the Republic of Croatia, the determined values are lower than the maximally allowed concentrations of heavy metals in fish muscle. When the pollution by heavy metals is taken into account, it indicates that the researched fish meat is hygienically safe food of animal origin.

Chemical Profile of Plomin Bay SedimentsGranulometric, chemical, and leaching properties of sediments dredged in the Plomin Bay (Northern Adriatic Sea, Croatia) were investigated in order to asses the risk of remobilisation of heavy metals into the water column. In total 65 samples from 65 sampling sites were taken from different sediment depths within the bay. Analysis of variance confirmed the homogeneity of granulometric and elemental composition of the investigated sediment throughout its volume. Granulometric analysis showed that all samples corresponded to a pelitic fraction (-1 of V, 0.04 mg kg-1 of Cr, 0.07 mg kg-1 of Ni, 0.33 mg kg-1 of Cu, 0.67 mg kg-1 of Zn and 0.06 mg kg-1 of Pb could be remobilised from sediment material into the water column. However, these values increased three to ten times in case of leaching with organic acids.

This paper presents a new treatment procedure applied on phosphogypsum transport water. Untreated transport water is highly acidic (pH 1.79), having fluoride content of 1540 mg/L and elevated values of phosphates (215 mg/L) and heavy metals (Fe = 25.8 mg/L ; Zn = 5.7 mg/L ; Mn = 2.7 mg/L, V = 1.7 mg/L). Neutralization/purification of the transport water was carried out with wood fly ash, otherwise a rich source of calcium, composed of calcite, dipotassium calcium carbonate and hydroxylapatite. Maximum removal efficiency of fluoride was observed at pH 7 (99.99%) and phosphate at pH 9 (96.29%). The removal of fluorides was a consequence of the formation of fluorite and fluorapatite mineral phases derived from the reaction of calcium (released from the fly ash minerals) and fluorides (from the transport water). The removal of phosphates resulted from the formation of fluorapathite and hydroxilapatite. At the optimum conditions removal efficiencies for the elements Pb, V, Cr(VI), Mn, Fe, Ni, Cu, and Zn were 95%, 98.14%, 91.11%, 100%, 99.71%, 96.33%, 97.24%, and 99.65%, respectively. Optimal heavy metal removal occurred in major cases at pH 7.

In vitro genotoxic effects of leachates of electric arc furnace dust (EAFD) on human peripheral lymphocytes, assessed prior and following the treatment with a strong alkaline solution were investigated using the alkaline comet assay. Prior and following the treatment, lymphocytes were incubated with leachate of EAFD for 6 and 24 hours at 37 degrees C. Negative controls were also included. Mean values of the tail lengths established in the samples treated with the leachate stemming from the original dust for 6 and 24 hours, were 15.70 microm and 16.78 microm, respectively, as compared to 12.33 microm found in the control sample. Slight, but significant increase in the tail length was also found with the dust treated with a strong alkaline solution (13.37 microm and 13.60 microm). In case of high heavy metal concentrations (the extract of the original furnace dust), the incubation period was revealed to be of significance as well. The obtained results lead to the conclusion that alkaline comet assay could be used as a rapid, sensitive and low-cost tool when assessing genotoxicity of various waste materials, such as leachates of the electric arc furnace dust.

Toxicological safety of new procedure for the neutralisation/purification of wastewater originated from zinc plating facility was investigated. Wastewater was treated with alkaline solid residue-by-product of zinc recovery from electric arc furnace dust. For determination of cytotoxic potential of untreated and purified wastewater MTT test on HEp2 (human laryngeal carcinoma) and HeLa (human cervical carcinoma) cells lines and alkaline comet assay on human leukocytes were used. Then 100% of the sample as well as different dilutions were tested. Compared to negative control 100, 75 and 50% of the sample of untreated wastewater significantly decreased survival of both HEp2 and HeLa cell lines. In the presence of undiluted sample survival percentage of HeLa and HEp2 cells were only 2.3 and 0.3% respectively. Only undiluted purified wastewater showed slight but insignificant decrease of the survival of both cell lines. Even 0.5% of the sample of original electroplating wastewater exhibited significantly higher value of all comet assay parameters compared to negative control. There was no significant difference between negative control and purified wastewater for any of comet assay parameters. Significantly lower level of primary DNA damage recorded after treatment with purified water, even comparable with negative control, confirmed effectiveness of the purification process.

Applying a combination of different methods – X-ray diffraction, scanning electron microscopy, gamma-spectroscopy and X-ray spectroscopy, a suite of uranium minerals, meta-torbernite, meta-uranospinite and meta-zeunerite was identified in metasediments of the Radlovac series at the Mt. Papuk area, Croatia. The accessory minerals galenaa, zircon, rutile, chalcopyrite and cuprite, as well as an unidentified Ni-bearing phase are also present. The mineral assemblage indicates a sequence of epigenetic and supergene processes affecting the Radlovac series.

To investigate whether occupational exposure to tobacco dust is genotoxic, a group of employees in a tobacco factory was tested for structural chromosome aberrations (CA), cytokinesis-block micronucleus assay (CBMN) and sister chromatid exchanges (SCE) that are well established as indicators of early biological effects. The study group consisted of 40 tobacco workers and an equal number of matched controls. The results obtained in the exposed group showed a significant increase in chromosome aberrations (R = 0.26), micronucleus frequency (R = 0.56) and in sister chromatid exchanges (R = 0.75), which was additionally influenced by smoking. A significant increase in high frequency cells (HFC) in the exposed group was also observed. Like the SCE frequency, the HFC frequency increased significantly in smokers of the control and exposed smokers. The study indicates that occupational exposure to tobacco dust induces genome damage. A higher risk was observed in women. The micronucleus frequency and sister chromatid exchange tests seem to be more reliable indicators of genome damage than chromosome aberrations in monitoring chronically exposed subjects.