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El cadmio (Cd) está considerado como un elemento persistente y ubicuo. A pesar de que la mayor parte de la población general está expuesta a dosis relativamente bajas, existen controversias acerca de sus posibles efectos adversos sobre la salud a largo plazo. Este estudio se concibió como un primer paso para evaluar la idoneidad del tejido adiposo como matriz biológica para estimar la posible exposición crónica a Cd. Específicamente, el objetivo de este trabajo fue cuantificar los niveles de Cd en muestras de tejido adiposo e identificar sus principales determinantes sociodemográficos, dietéticos y de estilo de vida. El estudio se realizó sobre una submuestra de la cohorte GraMo constituida por 226 adultos reclutados de dos hospitales públicos de Granada (España). Los niveles de Cd en tejido adiposo fueron analizados mediante ICP-MS. Las variables independientes se recogieron a través de cuestionarios. Los factores asociados a las concentraciones de Cd se evaluaron mediante regresión lineal multivariante. Se encontraron niveles detectables de Cd en el tejido adiposo de todos los participantes del estudio, con una concentración media (± desviación estándar) de 12, 66±18, 91 ng/Kg. Los niveles de Cd aumentaban con la edad ( =0.014 ; p

The oxygen and carbon isotope compositions of carbonate samples from the carbonatite-like dyke of the Madenska River complex at the Kriva Lakavica section, samples of calcite skarns from the Damjan Fe-ore deposit and the Sasa Pb-Zn ore deposit, and samples of marbles from the Pohorje Mountains were analyzed to provide critical evidence in favor of the magmatic or sedimentary origin of this carbonatite-like dyke. We suggest that the carbonatite-like dyke is not a "normal" carbonatite, but instead represents melted carbonates, which can be associated with an unexposed, deep-seated, causative magmatic body. This dyke has a fluidal texture and carries xenoliths of ultramafic rocks that can be up to 35 cm in size. Its isotopic composition plots between primary unaltered carbonatites and marine carbonates, and ranges between 13.79? and 18.89? for Δ18OVSMOW and between -1.22? and 1.31? for Δ13CVPDB. These values are significantly lower than those observed in carbonatites analyzed during this study and range between 6.53? and 8.10? for δ18OVSMOW and between -5.82? and -4.32? for Δ13CVPDB, which is the primary isotope signature of most magmatic carbonatites. Similarly high δ18O and Δ13C values were found in skarns of the Damjan Fe deposit close to the Madanska River complex and in the Sasa Pb-Zn deposit, as well as in high-grade regional metamorphic calcitic marbles of the Pohorje massive. The emplacement levels of the carbonatite-like dyke, due to several tectonic processes, are uncertain. The type of country rocks (sedimentary carbonates, ultramafic, mafic, and granitic rocks), hydrothermal alternation, and metasomatic and regional metamorphic processes seem to be the most important parameters that affect the O and C isotopic patterns found in the Kriva Lakavica carbonatite-like dyke and in the investigated samples.

Makirina Bay (N. Dalmatia, Republic of Croatia) represents one of the major and most important sites where organic-rich sediments accumulate along the eastern Adriatic coast. According to their organoleptic properties, these sediments (peloids) are suitable for application as a raw material for different therapeutic, cosmetic, and wellness-related purposes. In addition, Makirina Bay peloids are already frequently used by local people and tourists as pomades ; peloids are collected in situ from the bay, applied directly on the skin, and sun dried. Several characteristics of Makirina bay peloids were determined, including their granulometry, cation exchange capacity (CEC), mineral and elemental composition, potentially toxic elements (PTE) mobility/bioavailability and thermal properties (specific heat, thermal conductivity and thermal difussivity) in order to evaluate the suitability of their application for medical/therapeutic purposes in balneotherapy and pelotherapy. Our results showed that Makirina bay peloids are represented mostly by sandy silt and have a relatively high CEC value (63.82 meq/100g). The mineral composition of peloids is dominated by dolomite and quartz, followed by illite/muscovite, aragonite, halite, calcite, and pyrite. Oriented preparations of the clay fraction revealed illite/muscovite, chlorite, and kaolinite as the dominant clay minerals. PTE concentrations in surficial (0-5 cm) peloids are [in mg/kg]: As (14.47), Cd (0.27), Cu (27.64), Mn (232.4), Mo (13.82), Ni (26.51), Pb (23.74) and Zn (47.67). The results of the sequential extraction procedure indicated that majority of PTE (except Cd, Mn and Mo) in Makirina bay peloids are not readily mobile or bioavailable since only a small percentage of PTE is extracted in the first two steps (e.g. water-soluble and exchangeable fraction). Thermal properties of Makirina bay peloids are as follows: specific heat 2050 J/kgK, thermal conductivity 0.99 W/mK and thermal diffusivity 2.84*10-7 m2/s.

The determination of inorganic constituents in biological samples of high fat content is usually accomplished with atomic spectrometry methods. Their use is often preceded by challenging analytical preparation steps like clean-up, dry or wet digestion and extraction. Micellar systems and emulsions are increasingly utilized in separation and preconcentration procedures because they permit the design of simple, rapid and non-toxic extraction schemes. The method applied in this work includes direct spectrophotometric determination of lead in adipose tissue by reaction with dithizone in cationic surfactant medium (CTAB). The sensitivity and accuracy of method for trace lead determinations was compared with ETAAS measurements of microwave digested tissues and samples of the most similar reference materials. Both methods revealed that lead content in examined adipose tissue was lower than estimated level of dietary exposures for adults (1.16 µg kg-1, ESFA, 2012).

This mineralogical, geochemical and isotopic characteristics of recent lacustrine sediments, of Anodonta cygnea shells and of fish species Rutilus rutilus dojranensis from the Lake Dojran (FY Republic of Macedonia, southern part of the Serbo-Macedonian Massif (SMM)), which provide indirect evidence regarding biomineralization and calcification processes as well as various geological problems. Environmental pollution can seriously impair physiological functions such as the secretion of carbonate material into the shells. For comparison, sediments and fish species Vimba melanops from the Lake Kalimanci, located in northern part of the SMM, were also included into the study. X-ray powder diffraction (XRD), inductively coupled plasma mass spectrometry (ICP-MS) and carbon (C) and oxygen (O) stable isotope analyses were performed, and thereupon enrichment factor (EF) values were calculated. The XRD results revealed close association of sediment mineralogy with the prevailing metamorphic, volcanic and igneous rocks of the region surrounding both lakes (Dojran and Kalimanci). According to the EF value results, surficial Lake Dojran sediments are slightly enriched with Co, Cr, Cu, Pb, and Zn, moderately enriched with Au, Ni and Sb, moderately to severely enriched with Au, severely enriched with Sb and extremely enriched with As. This elemental enrichment originates from various geogenic (geological background and polymetallic mineralization) and anthropogenic (tourism, traffic, coatings, untreated wastewater discharge and agrochemicals) sources. Calculated EF revealed that surficial sediments from Lake Kalimanci are extremely enriched with Pb, Zn, and Cd, meanwhile As and Cu shows very severe enrichment. Comparing to Lake Dojran, calculated EF is much higher in Lake Kalimanci than in Dojran. Stable isotope signature results showed that Lake Dojran sediments were strongly influenced by evaporation effect. Their δ18O values range from -5.60 to +1.49 ‰ and the δ13CVPDB composition range from -6.45 to -1.65 ‰. Shells of A. cygnea are mainly composed of mineral aragonite and their δ18O values varies between 0.43 ‰ and +1.94 ‰, and δ13CVPDB between -2.48 to -1.72 ‰. δ18O signature in shells might be explained by precipitation of the carbonate from isotopically heavier oxygen lake water. The unusually high skeletal oxygen suggests calcification at elevated temperature and evaporation. Analyses also identify particularly high levels for Cr, Hg, Ni and Pb in fishes (V. melanops) and frog (Rana temporaria) samples from Lake Kalimanci with mean values [μgkg-1]: 1090 – 6.5, 339 – 117, 567 – 5100 and 1127 – 435, respectively. Meanwhile, the contents of Cr, Hg, Ni and Pb in fishes samples (R. rutilus dojranensis) from Lake Dojran are a bit lower [μgkg-1]: 2320, 1690, 700 and 50.

Recentne morske sedimente iz zaliva Makirina lahko glede na njihove organoleptične lastnosti obravnavamo kot zdravilno blato ali peloid, ki ga nekateri domačini in turisti že uporabljajo v obliki blatnih oblog. Uporaba peloidov v balneoterapiji je namenjena predvsem zdravljenju mišičnih, kostnih in kožnih obolenj ter sproščanju in velnesu. Številne nedavne raziskave peloidov so pokazale, da so eni izmed glavnih dejavnikov, ki pogojujejo (ne)uporabo peloida v balneoterapevtske namene, zrnavost, mineraloška sestava, kationska izmenjevalna kapaciteta (KIK), elementna in mikrobiološka sestava izvornega »geološkega materiala«. Iz rezultatov predhodnih raziskav je razvidno, da peloid iz zaliva Makirina gradi zelo slabo sortiran peščen mulj z visoko kationsko izmenjevalno kapaciteto (63, 82 meq/100g). V mineralni sestavi peloida prevladujeta dolomit in kremen, sledijo ilit/muskovit, aragonit, kalcit, halit in pirit. Povprečne koncentracije potencialno toksičnih elementov (PTE) v peloidu iz zaliva Makirina, določenih v tokratni raziskavi znašajo: As (17, 6 mg/kg), Cr (92, 09 mg/kg), Cu (44, 5 mg/kg), Mo (31, 8 mg/kg), Pb (28, 9 mg/kg) in Zn (69, 2 mg/kg) in so primerljive z rezultati preteklih študij. Koncentracije PTE v bentoški algi Codium bursi (C. bursa) so sledeče: As (8, 8 mg/kg), Cr (15, 7 mg/kg), Cu (5, 6 mg/kg), Mo (0, 7 mg/kg), Pb (3, 6 mg/kg) in Zn (16, 3 mg/kg). Izračunani faktorji prenosa (TF) za PTE iz površinskega peloida (0–5 cm) v bentoško algo C. burso so manjši od 1, kar pomeni, da se PTE iz peloida ne prenašajo oziroma se v C. bursi ne akumulirajo. Rezultati prisotnosti koliformnih bakterij in E. coli se ujemajo s preteklimi rezultati, ki so pokazali, da jih v peloidu ni, kar nakazuje, da peloid ni fekalno kontaminiran. Peloid iz zaliva Makirina ima (z izjemo povišanih koncentracij Cr in Mo) primerljive lastnosti s peloidi, ki se trenutno že uspešno uporabljajo v različnih spa-centrih po svetu, vendar je treba pred potencialno uporabo opraviti dodatne raziskave, kot je na primer določitev mobilnosti Cr in Mo.

The research focuses on determination of Geochemical characteristics and distribution of Rareearth elements (REEs) in Makirina Bay sediments. The overall REEs concentrations in Makirina Bay sediments samplesdetected during study ranged from 123.94 ppm to 188.74 ppm. REEs content showed a gradual increase towardsthe depth of sediments. The average UCC-normalized REEs pattern pointed out negative δCe values and positive δEuvalues, indicating reductive conditions prevailing in Makirina Bay sediments. Calculated enrichment factor values arein the range of natural variability with no addition of different anthropogenic components. According to sequentialextraction procedure results, the studied fractions can be followed from highest to lowest percentage of REEs as: oxidizable> exchangeable > reducible+residual > reducible > water soluble fraction. The calculated transfer factor valuesgenerally confirmed the sequential extraction procedure results. The concentrations of all studied REEs are higherin above-ground than in below-ground biomass of seagrass Cymodocea nodosa.

Tailings dam failures arc relatively rare but can cause extremely high and long-term impacts on the environment. The Sasa tailings dam collapsed in August 2003 and caused an intensive flow of tailings material through the Kamenica River all the way to Lake Kalimanci, where most of the tailings material discharged. This study deals with the characterization of surficial lake sediments from Lake Kalimanci in eastern Macedonia. Mineralogical, geochemical, and statistical analyses of surficial sediments in two sampling years, before and after the Sasa tailings dam failure, were carried out. To determine the pollution status of surficial lake sediments, two environmental indexes were calculated for 2001 and 2007. Spatial distribution of the analyzed heavy metals and metalloids shows that the highest concentrations were measured on the northern part of the lake, where the Kamenica River enters.

Wide zones of intensive hydrothermal alterations were determined at the Borović area. Silicification, limonitization, kaolinization etc., are the progressive alterations with distinctive occurrences at the surface. Stockwork veins and veinlets are dominant too. Detailed studies have shown that this system at the Borović has been mineralized, where at few randomly taken samples from the silicificied zones has been determined presence of gold within the range of 0.10 up to 0.62 g/t Au, followed by increased concentrations of copper, silver, molybdenum etc. Also, in this mineralized system have been determined presence of geothermal mineralized waters with temperatures up to 50ºC and artesian flow of about Q=10 l/s within the Povisica river flow. Isotopic studies of hydrogen and oxygen or ratios H/D and δ18O in samples taken from thermomineral waters from wells in the Borović locality have shown values within the range -10.62÷ -8.61 δ18O and -72.70÷ - 56.90 δD, which points out that the origin of these mineralized waters is mainly of meteoric character.. Namely, there were slight discrepancies from the MWL (Meteoric Water Line), which reflects the direct fractionation of O and H isotopes in meteoric water at the contact with adjacent rocks and deep hydrothermal fluxes

This research is aimed at investigating the mineralogical characteristics of the tailings material and heavy metal contents of the tailings material deposited close to the Sasa Pb-Zn Mine in the Osogovo Mountains (eastern Macedonia) and on its possible impact on Lake Kalimanci. The mineral composition of Sasa Mine tailings material is dominated by quartz, pyrite, galena, sphalerite, magnetite and others. Geochemical analysis was performed in a certified commercial laboratory for the following elements: Mo, Cu, Pb, Zn, Ni, As, Cd, Sb, Bi, Ag, Al, Fe, Mn, S. Analysis revealed very high concentrations of toxic metals in the tailing material – with average values �mg kg-1�: Mo 2.9, Cu 279, Pb 3975, Zn 5320, Ni 30, As 69, Cd 84, Sb 4.2, Bi 9.4 and Ag 4.1. The multi-element contamination of Sasa Mine tailings material was assigned a pollution index greater of 15, indicating that the tailings material from Sasa Mine contains very high amounts of toxic metals and represents a high environmental risk for surrounding ecosystems. For this reason the influence of discharged tailings dam material into Lake Kalimanci which lies approximately 12 km lower than Sasa Mine, was also established. Calculated pollution index values for Lake Kalimanci sediments vary from 21 to 65 and for Sasa mine surficial tailings dam material from 15 to 60.

A major disaster happened in the eastern Macedonia (Europe), when part of the Sasa Mine tailings dam collapsed and caused an intensive fow of tailings material which ended up in Lake Kalimanci. The aim of this study was to assess the heavy metal contamination (Ag, As, Cd, Cu, Mo, Pb, Sb and Zn) of the surfcial sediments from Lake Kalimanci. The pollution status of the sediments was evaluated by application of two environmental indices: the enrichment factor and a geoaccumulation index. The enrichment factor values (Cd 735; Pb 386; Zn 151; Ag 146; As 48; Cu 21; Sb 10 and Mo 2) revealed extremely elevated heavy metal concentrations in the investigated samples. The geoaccumulation index indicated that surf-cial sediments of Lake Kalimanci can be treated as moderately to strongly polluted with Pb and Cd, moderately polluted with Zn and Ag, unpolluted to moderately polluted with Cu and As and unpolluted with Mo and Sb.