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Background: Pretreatment differentiation between glioblastoma and metastasis is a frequently encountered dilemma in neurosurgical practice. Distinction is required for precise planning of resection or radiotherapy, and also for defining further diagnostic procedures. Morphology and spectroscopy imaging features are not specific and frequently overlap. This limitation of magnetic resonance imaging and magnetic resonance spectroscopy was the reason to initiate this study. The aim of the present study was to determine whether the dataset of diffusion tensor imaging metrics contains information which may be used for the distinction between primary and secondary intra-axial neoplasms. Methods: Two diffusion tensor imaging parameters were measured in 81 patients with an expansive, ring-enhancing, intra-axial lesion on standard magnetic resonance imaging (1.5 T system). All tumors were histologically verified glioblastoma or secondary deposit. For qualitative analysis, two regions of interest were defined: intratumoral and immediate peritumoral region (locations 1 and 2, respectively). Fractional anisotropy and mean difusivity values of both groups were compared. Additional test was performed to determine if there was a significant difference in mean values between two locations. Results: A statistically significant difference was found in fractional anisotropy values among two locations, with decreasing values in the direction of neoplastic infiltration, although such difference was not observed in fractional anisotropy values in the group with secondary tumors. Mean difusivity values did not appear helpful in differentiation between these two entities. In both groups there was no significant difference in mean difusivity values, neither in intratumoral nor in peritumoral location. Conclusion: The results of our study justify associating the diffusion tensor imaging technique to conventional morphologic magnetic resonance imaging as an additional diagnostic tool for the distinction between primary and secondary intra-axial lesions. Quantitative analysis of diffusion tensor imaging metric, in particular measurement of fractional anisotropy in peritumoral edema facilitates accurate diagnosis.

Background/Aim. Although considered rare, gliomas cause morbidity and mortality disproportionate to their incidence. The aim of the study was to determine whether pre and post-therapeutic metric values, derived from the FDG PET/CT maximal standardized uptake value (SU-Vmax) and calculated ratios between tumor and normal brain tissue, may provide a predictive/prognostic biomarker information in estimating overall survival of glioblastoma patients. Methods. In 26 out of 31 patients with glioblastoma treated with standard Stupp protocol after maximal safe reductive surgery, we performed a baseline 18F-FDG PET/CT examination before commencing combined and concomitant chemotherapy/radiotherapy (pre-therapy FDG PET/CT) and a second examination three months after the therapy completion (post-therapy FDG PET/CT). Two-graded SUVmax values and a calculated ratio of uptake in tumor-to-normal-tissue (T/N ratio) value, divided into two grades by the calculated cut-off value, were measured in all patients at both pre- and post-therapy FDG PET/CT studies. Data sets were statistically analyzed by the Kaplan-Meier survival test and Log-rank was calculated, with the level of confidence determined at p < 0.05. Results. Pre-therapy FDG PET/CT two-grade T/N ratio value and both pre-and post-therapy FDG PET/CT derived two-grade SUVmax values had a strong predictive impact on overall survival of glioblastoma patients. Conclusion. Based on two-grade SUVmax and T/N ratio values assessment, FDG PET/CT could provide valuable predictive survival information in glioblastoma patients and serve as a selection tool for identifying patients at higher risk from worse outcomes and shorter survival time.

Introduction. Joubert syndrome (JS) and related disorders (JSRD) are a group of rare multiple congenital anomalies syndromes, defined by complex midbrain-hindbrain malformation that creates the “molar tooth sign” (MTS) on brain imaging and may be associated with multisystem organ pathology, mainly of the retina, kidney, liver and skeleton. Prenatal diagnosis of JSRD has proved difficult because of the rarity of the condition and low sensitivity of ultrasound in evaluation of the fetal posterior fossa (PF) in most affected fetuses. Case report. We presented an unusual case of JSRD, pure Joubert syndrome with unilateral frontal polymicrogyria and supratentorial white matter microcysts, diagnosed by magnetic resonance imaging (MRI), in fetus aged 30 gestational weeks. The distinctive MRI features of this rare ciliopathy were confirmed by 6-months postnatal MRI study. The postnatal outcome was poor; clinical follow- up in the first 6 months of life confirmed hypotonia, developmental delay, oculomotor apraxia and seizures. Conclusion. To the best of our knowledge, fetal MRI features of the coexistence of pure JS and supratentorial abnormalities leading to postnatal cerebellar dysfunction and epilepsy, have never been reported before. Presented case may contribute to the broadening of the spectrum of sparse prenatal features of JRSD, and support the stand that presence of neuronal migration abnormalities can affect the clinical outcome and prognosis of fetuses with JSRD.

In the modern ages of rapid technological and computational advances, development of numerous novel diagnostic imaging techniques have enabled not only visual detection of disease processes, but also provided the tools to achieve quantified functional, structural, dynamic, metabolic, and molecular information. A pathway toward the quantitative imaging by use of quantitative imaging biomarkers analysis has been widely opened, enabling further development of radiomics, radiogenomics, and radioproteinomics analysis in addition, and initiating the dawn of theranostics, eventually bringing the wishful personalised medicine concept closer to reality.

Introduction: Although they represent an important mediator between patients and National Pharmacovigilance Centre, pharmacists still don't participate enough in system of reporting adverse drug reactions (ADR). By reporting ADR both quality of therapy and quality of patient's life are improving, and pharmaceutical industry is also encouraged to invent and produce new formulations which will be better beared and whose use will significantly improve risk-benefi t ratio. Aim: The aim of this work is that by collecting information about ADRs, based on direct contact of a pharmacist and patients, explain and improve the role of a pharmacist in pharmacovigilance system. Subjects and Methods: Information about adverse reactions were being collected in three private pharmacies in Inđija and in one private pharmacy in Sombor. In period from 20.12.2017.-10.01.2018. pharmacists collected data about adverse reactions of medicines. In period from 11.01.-01.02.2018. patients were additionally informed about unexpected and adverse drug reactions. The standard form for reporting an adverse reaction, which was taken from the site of Medicines and Medical Devices Agency of Serbia (ALIMS), was fi lled for each reported case and sent to National Pharmacovigilance Center (NPC). Suspect drugs were classified in categories according to Anatomical-Therapeutic-Chemical classification (ATC). Results: In first period, there were 19 reported reactions. After additional information given to patients, there were 33 reported adverse reactions. The most numerous adverse drug reactions were reported for the group of cardiovascular drugs (32.7%), the group of anti-infective drugs with systemic effects (15.4%) and for group of drugs which affect nervous system (13.5%). After analyzing reported reactions, according to NPC all of reactions were expected (52), but 3 of them fulfilled criteria of seriousness. Conclusions: Thanks to additional information and direct communication between a pharmacist and patients, reporting unexpected and adverse drug reactions is significantly improving.

Copyright of Acta Chirurgica Iugoslavica is the property of Association of Yugoslav Surgeons and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Copyright of Acta Chirurgica Iugoslavica is the property of Association of Yugoslav Surgeons and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Copyright of Acta Chirurgica Iugoslavica is the property of Association of Yugoslav Surgeons and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Copyright of Acta Chirurgica Iugoslavica is the property of Association of Yugoslav Surgeons and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Globalization, competition, development of the Internet, strengthening of the role of consumers in the global market, technology development and consumer homogenization contributed to a situation in which national markets have become tight. This is why many companies expand their business activities by finding new markets, which are becoming an important factor in their future growth and development. The rapid globalization processes, economic and political integration, the development of modern technologies and new ways of communication have opened the possibility of the development of small and medium-sized enterprises (SMEs) which constitute an integral sector of all economies and present a major contribution to economic development, in terms of both flexible entrepreneurial ideas and employment. Small and medium-sized enterprises promote private ownership and entrepreneurial skills, and in developed countries they represent the 'engine of economic development', whereas their propelling impact in countries in transition is still insufficient. The comparative advantage of these companies is that they can relatively quickly adapt to changes and meet the requirements of the market. This paper emphasizes the fact that the experiences of developed as well as developing countries indicate that proportional development of companies of all sizes and their integration into the main stream of international economy through the process of internationalization, should all lead to a stable and steady development of economy as the ultimate goal.

Spa tourism in Serbia has a considerable tourist potential. Today there is a strong competition on the tourist market, particularly among destinations in spa tourism. Competitiveness of any tourist destination, in particular a spa tourism desti¬nation, greatly depends on key attributes of tourism supply. This paper includes the result of a study which was carried out in order to improve tourists' perception of the importance of the attributes of tourism supply in Vrnjacka Banja. By reviewing the literature, attributes were extracted and grouped into factors in order to decide which groups had the greatest importance in the minds of spa tourists. There were six factors in total. After that and based on t-test, a statistically significant difference between the tourists who plan to visit Vrnjacka Banja again and to recommend this tourist destina¬tion and those who do not was determined according to their attitudes towards these factors. Finally, using ANOVA test, the study proves a statistically significant differ¬ence related to the attributes depending on how long the tourists stayed in Vrnjacka Banja. By recognizing the key attributes of a spa tourist destination in the spa tourists' perception, organizations and individuals who are responsible for the development of tourism will be able to form a supply which suits tourists' needs best, while achieving a high-level competitiveness on the tourist market at the same time.

Introduction. Extraction of impacted mandibular third molars is often accompanied by intraoperative and postoperative complications such as damage of the inferior alveolar nerve, prolonged difficulty in mouth opening, alveolitis, pain and swelling in the region of surgery. The aim of this study was to compare two surgical techniques (standard and piezo) in the extraction of mandibular third molars and to assess their postoperative complications. Material and Methods. Study included 16 patients (8 male and 8 female) age 17 to 32 years treated in the period from 2012 to 2014. All patients had both mandibular molars impacted. One third molar was extracted using classical technique while the other one using a piezo device. Preoperative preparation was the same for all patients and included radiological analysis and verification of teeth by ortopan tomography (OPG) and CT. Patients were assessed one, seven and 14 days after the procedure. Results. After the extraction, all patients were followed for postoperative symptoms: pain, swelling and paresthesia of the inferior alveolar nerve. The results confirmed advantages of piezosurgery in the removal of impacted mandibular third molars. Average duration of the intervention was 18 minutes with standard technique while the duration with piezo technique was 23 minutes. According to the visual-analog scale (VAS) the average pain in the standard group was 9 whereas in the piezo group it was 6. Postoperative swelling was 10 mm (pronounced) the first day after the procedure in the standard group while in the piezo group it was 6 mm (moderate). Conclusion. The use of piezo technology for the extraction of impacted wisdom teeth is reliable method which reduces the risk of the most common postoperative complications following mandibular wisdom teeth removal.

Beckground/Aim. Cerebrovascular diseases are the third leading cause of mortality in the world, following malignant and cardiovascular diseases. Therefore, their timely and precise diagnostics is of great importance. The aim of this study was to compare duplex scan Color Doppler ultrasonography (CDU) with multislice computed tomography angiography (MSCTA) in detection of morphological and functional disorders at extracranial level of carotid arteries. Methods. The study included 75 patients with 150 carotid arteries examined in the period from January 2008 to April 2009. The patients were firstly examined by CDU, then MSCTA, followed by the surgery of extracranial segment of carotid arteries. In 10 patients, the obtained material was referred for histopathological (HP) examination. We used both CDU and MSCT in the analysis of: plaque surface, plaque structure, degree of stenosis, and the presence of intraplaque hemorrhage. Results. The results obtained by CDU and MSCTA were first compared between themselves, and then to intraoperative findings. Retrospective analysis showed that MSCTA is more sensitive than CDU in assessment of plaque surface (for smooth plaques CDU 89% : MSCTA 97%; for plaques with irregular surface CDU 75% : MSCTA 87%; for ulcerations CDU 54% : MSCTA 87%). Regarding determination of plaque structure (mixed plaque CDU 66% : MSCTA 70%; correlation with HP findings CDU 94% : MSCTA 96%) and localization (CDU 63% : MSCTA 65%), and in terms of sensitivity and specificity, both methods showed almost the same results. Also, there is no statistical difference between these two methods for the degree of stenosis (CDU 96% : MSCTA 98%). Conclusion. Atherosclerotic disease of extracranial part of carotid arteries primarily affects population of middle-aged and elderly, showing more associated risk factors. Sensitivity and specificity of CDU and MSCTA regarding plaque composition, the degree of stenosis and plaque localization are almost the same. These results and the fact that there are no adverse effects (high radiation dose) compared to MSCTA indicate that CDU should be the initial method in diagnostic algorythm for carotid arteries.

Introduction. New methods for studying brain functions have provided the new insights into human brain. It is really possible to study a cortical adaptation in adults who have sustained injury. We reported cortical changes in a left frontal low-grade glioma patient during disease progression and after reoperation by functional magnetic resonance imaging (fMRI). Case report. The use of fMRI exams for localisation of eloquent motor and language areas were performed three times in a period of 15 months: seven years after initial tumor resection, eleven months later and three months after the reoperation. The first fMRI demonstrated cortical activation for motor tasks in the expected location of primary motor area while later examinations showed activations of both primary motor areas for right hand movement. The first exam language evaluation showed the left hemisphere dominance for both language tasks, while the second fMRI demonstrated the right hemisphere dominance for complex word generation task, but the left hemisphere remained dominant in simple language task. After the reoperation, language mapping revealed the left hemisphere dominance for both language tasks. Conclusion. fMRI evaluation of cortical changes in low-grade glioma patients may additionally optimize and individualize neurosurgical treatment.

Background/Aim. Bone scintigraphy is well-known method for the detection of neoplastic lesions with a high sensitivity and, at the same time, a lower specificity. On the other hand magnetic resonance imaging (MRI) is previously established noninvasive imaging method regarding its diagnostic specificity. The aim of this study was to determine the possibilities and to correlate two different diagnostic methods - bone scintigraphy and MRI in the detection of bone metastasis in the spine and pelvic bones. Methods. A total of 123 patients who underwent both bone scintigraphy and spine and pelvic MRI on 1.5 T MR imager were enrolled in this study. Scans were subsequently analyzed in total and divided in regions of interest (cervical, upper, middle and lower thoracic, upper and lower lumbar and pelvic region, which includes sacral spinal segment); afterwards the total number of 585 matching regions were compared and statistically analyzed. Results. The statistical analysis demonstrated significant correlation between the findings of both methods in total. Divided by regions of interest, significant degrees of correlation were demonstrated in all of them, except in the cervical spine region where the r-value was in the range of low correlation. Conclusion. Having a high mutual correlation, bone scintigraphy and MRI are to be considered as the complementary diagnostic methods in the detection of bone metastases. Still, increased diagnostic potential of MRI may highlights negative bone scintigraphy findings in the patients with solitary metastatic lesions or diffuse vertebral infiltration. Advances in the bone scintigraphy (single photon emission tomography - SPECT, SPECTcomputed tomography - SPECT-CT) and MRI (whole body MRI, diffusion MRI), make it possible the diagnostic potential of both methods will result in a further improvement in bone metastasis detection.

Background/Aim. A vast majority of current radiogical techniques, such as computerized tomography (CT) and magnetic resonance imaging (MRI) have great potential of visualization and delineation of cerebrospinal fluid spaces morphology within cerebral aqueduct. The aim of this study was to determine the possibilities of two differently acquired FISP (Fast Imaging with Steady State Precession) 2D MR sequences in the estimation of the pulsatile cerebrospinal fluid (CSF) flow intensity through the normal cerebral aqueduct. Methods. Sixty eight volunteers underwent brain MRI on 1.5T MR imager with additionally performed ECG retrospectively gated FISP 2D sequences (first one, as the part of the standard software package, with following technical parameters: TR 40, TE 12, FA 17, Matrix: 192 × 256, Acq 1, and the second one, experimentally developed by our investigation team: TR 30, TE 12, FA 70, Matrix: 192 × 256, Acq 1) respectively at two fixed slice positions - midsagittal and perpendicular to cerebral aqueduct, displayed and evaluated by multiplegated images in a closed-loop cinematographic (CINE) format. Results. Normal brain morphology with preserved patency of the cerebral aqueduct in all of 68 healthy volunteers was demonstrated on MRI examination. Cerebrospinal fluid flow within the cerebral aqueduct was distinguishable on both CINE MRI studies in midsagittal plane, but the estimation of intraaqueductal CSF flow in perpendicular plane was possible on CINE MRI studies acquired with experimentally improved FISP 2D (TR 30, FA 70) sequence only. Conclusion. Due to the changes of technical parameters CINE MRI study acquired with FISP 2D (TR 30, FA 70) in perpendicular plane demonstrated significantly higher capability in the estimation of the CSF pulsation intensity within the cerebral aqueduct. .

Large bone defects in the jaws can occur as a result of previous trauma, tumor or bone destruction caused by infection. Significant loss of bone volume also may be caused by premature loss of teeth, application of inadequate extraction technique, periodontitis or trauma caused by incorrect prosthetic reconstruction. Very few of these defects are treated using materials for bone augmentation or regeneration in order to preserve the total volume of bone. Depending on the size of a defect, spontaneous bone regeneration of untreated defects is limited by proliferation of surrounding soft tissue. Bone replacement by connective tissue leads to loss of stability, reduces function and disturbs anatomical form of the jaws. The aim of the study was to present a case from clinical praxis which demonstrates bone regeneration provided by bone substitute or its combination with bone grafts.

Introduction. An arteriovenous fistula (AVF) is an abnormal connection between an artery and a vein which may result from traumatic injury or may occur as congenital abnormality. Stent graft repair through arteriovenous fistula could lead to complications. Case report. Endovascular stent graft repair in a 23-year-old patient with posttraumatic superficial femoral arteriovenous fistula was performed to cover a fistula. During the procedure the device migrated through the fistula into the femoral vein. Due to eventual risk of migration to the heart, a prompt decision was made to fix the stent graft with three puncture needles in the common femoral vein region under fluoroscopy guidance. The vascular surgeon was called to perform open surgery. Conclusions. The presented way of treating this rare complication in an extreme and uncommon situation is very efficient, safe and inexpensive.

Introduction. Foetal tumours are relatively rare; prenatal diagnosis enables additional diagnostics, and thus the decision on the continuation of pregnancy and planning of delivery. The paper presents prenatal ultrasound diagnostics of foetal head tumour with additionally analyzed magnetic resonance imaging (MRI). Case Outline. On ultrasound imaging, in a 27-year old nullipara, a tumour of the foetal head was suspected at the 22nd gestational week. By consultative ultrasound, a 45x41x50 mm echogenic soft tissue tumour with hypoechogenic areas was confirmed, which originated from the left side of the skull spreading towards the neck on the left behind the ear. On colour Doppler no vascularisation was seen within the tumour but several vessels were seen along the border-line and on the surface. The scan showed no associated abnormalities. Karyotype was 46, XY. MRI scan using triplanar SSFSE and HASTE sequences was done at 26 weeks and confirmed a 84Č45Č71 mm tumour originating from the scalp, spreading along the endocranium over the entire surface of the fronto-temporal sqama and left parietal bone. The tumour did not disturb the integrity of the internal tabula, and did not spread intracranially. Based on these findings, the diagnosis of haemangioma was made. At 38 weeks gestation, a 3810 g male infant was delivered by Caesarean section. A bluish, well-defined, non-pulsatile tumour arising from the left frontoparietal region was seen, thus confirming the diagnosis of haemangioma. Conclusion. MRI improved delineation of the tumour facilitating better planning of postnatal management and mode of delivery, with the information on the postnatal course and prognosis. In the prenatal period, MRI following an ultrasound diagnosed foetal tumour, is an additional part of diagnostic examinations, and is not contraindicated during pregnancy.

This study incorporated hydrogeochemical facies, the entropy-weighted water quality index (EWQI), multivariate statistics, and probabilistic human exposure assessment to investigate hydrogeochemistry, analyze groundwater quality, and estimate potential risks to human health in a lithium-rich ore area (Jadar River basin, Serbia). The findings designated the Ca·Mg-HCO 3 hydrogeochemical type as the predominant type of groundwater, in which rock weathering and evaporation control the major ion chemistry. Due to the weathering of a lithium-rich mineral (Jadarite), the lithium content in the groundwater was very high, up to 567 mg/L, with a median value of 4.3 mg/L. According to the calculated EWQI, 86.4% of the samples belong to poor and extremely poor quality water for drinking. Geospatial mapping of the studied area uncovered several hotspots of severely contaminated groundwater. The risk assessment results show that groundwater contaminants pose significant non-carcinogenic and carcinogenic human health risks to residents, with most samples exceeding the allowable limits for the hazard index (HI) and the incremental lifetime cancer risk (ILCR). The ingestion exposure pathway has been identified as a critical contaminant route. Monte Carlo risk simulation made apparent that the likelihood of developing cancerous diseases is very high for both age groups. Sensitivity analysis highlighted ingestion rate and human body weight as the two most influential exposure factors on the variability of health risk assessment outcomes., (© 2024. The Author(s), under exclusive licence to Springer Nature B.V.)

Historical changes of sediment characteristics and levels of inorganic and organic contaminants were studied in dated sediment cores from the Visovac Lake, situated in the Krka National Park, Croatia, to identify the main sources of anthropogenic pressures on this highly protected system. Depth distributions of lithogenic elements showed a steady decrease of terrigenous inputs due to the reduction in agricultural activities in the area, which was particularly pronounced during the 1991-1995 war in Croatia. Vertical and longitudinal distributions of Cd and Zn indicated that they are predominately of anthropogenic origin. The historical profiles of these toxic metals coincide well with the recorded production of metal industry in the upper reach of the Krka River with a sharp decrease reflecting the interruption by the war and slow recovery afterwards. By contrast, the recovery of the tourist industry in Krka NP after the war was accompanied by increasing contamination by elements characteristic of boat and car traffic (Sn, Cu, Pb) as well as oil pollution. The contamination with polycyclic aromatic hydrocarbons and polychlorinated biphenyls was only moderate. Although levels of metallic and organic contamination can be considered relatively low, the observed shift from industrial to tourism-related sources indicated that touristic activities should also be regarded as a possible threat for this vulnerable karst aquatic ecosystem., (© 2024. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Due to rapid urbanization and industrial growth, groundwater globally is continuously deteriorating, posing significant health risks to humans. This study employed a comprehensive methodology to analyze groundwater in the Western Banat Plain (Serbia). Using Piper and Gibbs plots, hydrogeochemistry was assessed, while the entropy-weighted water quality index (EWQI) was used to evaluate groundwater quality. Pollution sources were identified using positive matrix factorization (PMF) accompanied by Pearson correlation and hierarchical cluster analysis, while Monte Carlo simulation assessed health risks associated with groundwater consumption. Results showed that groundwater, mainly Ca-Mg-HCO 3 type, is mostly suitable for drinking. Geogenic pollution, agricultural activities, and sewage were major pollution sources. Consumption of contaminated groundwater poses serious non-carcinogenic and carcinogenic health risks. Additionally, arsenic from geogenic source was found to be the main health risks contributor, considering its worryingly elevated concentration, ranging up to 364 μg/L. These findings will be valuable for decision-makers and researchers in managing groundwater vulnerability. PRACTITIONER POINTS: Groundwater is severely contaminated with As in the northern part of the study area. The predominant hydrochemical type of groundwater in the area is Ca-Mg-HCO 3 . The PMF method apportioned three groundwater pollution sources. Monte Carlo identified rock dissolution as the primary health risk contributor. Health risks and mortality in the study area are positively correlated., (© 2024 Water Environment Federation.)

In this study, we investigated the levels of macro, minor, and trace elements in roasted ground and instant coffees (n = 56). We assessed dietary mineral intake and health risks associated with potentially toxic elements (PTEs) using deterministic and probabilistic approaches. The limits of detection (LOD) ranged from 0.13 µg/kg for Be to 3.7 mg/kg for K, with corresponding limits of quantification (LOQ) at 0.43 µg/kg and 12.2 mg/kg. The recovery values (R%) ranged from 89 to 107%. The most abundant element was K, followed by Mg, Ca, and Na. Other elements followed this order: Fe > Mn > B > Cu > Sr > Zn > Al > Ba > Ni > Cr > Co > Se > Sn > Pb > Li > Ag > V > As > Cd > Hg > Be. Instant coffees generally exhibited higher K, Mg, and Na levels than ground-roasted coffees. Notably, Hg, Li, and Se were not detected in 34, 2, and 1 samples, respectively. Coffee samples were generally a good source of dietary elements such as Cu, Mn, Cr, and Se. The PTEs found in coffee products posed negligible risks to human health. The total target hazard quotient (TTHQ) remained below 1, and the incremental lifetime cancer risk (ILCR) did not exceed the threshold of 1 × 10 -6 . Nevertheless, coffee consumption contributed to Pb and As levels below 15% of the benchmark dose lower confidence limit (BMDL) values, and Sn, Hg, and Cd levels below 0.90% of the provisional tolerable weekly intake (PTWI)., (© 2024. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Leafy plants are commonly consumed as vegetables in India due to their high nutrient and vitamin content. This study, conducted in Ambagarh Chowki (India), investigated the accumulation potential of 52 elements (including Al, As, Ba, Be, Bi, Ca, Cd, Ce, Co, Cr, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Ho, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni, P, Pb, Pr, Rb, Sb, Sc, Se, Sm, Sn, Sr, Tb, Te, Th, Ti, Tl, Tm, U, V, W, Y, Yb, and Zn) in seven leafy vegetable species, namely Amaranthus tricolor L., Corchorus olitorius L., Cordia myxa L., Hibiscus sabdariffa L., Ipomoea batatas (L.) Lam., Moringa oleifera Lam., and Spinacia oleracea L. Technique: Inductively coupled plasma mass spectrometry (ICP-MS) was employed for analysis. The maximum concentrations of elements such as Al, Ba, Be, Bi, Cd, Co, Cr, Fe, Ga, Ge, Li, Mn, Ni, Pb, Sb, Th, Tl, U, V, W, and REEs were observed in S. oleracea leaves, indicating their highest accumulation potential. In contrast, the maximum concentrations of As were found in H. sabdariffa leaves; Ca and Si in M. oleifera leaves; Mg, Sr, and Mo in A. tricolor leaves; and P, K, Cu, and Zn in C. myxa leaves, respectively. Twenty-one elements (Cr, Cd, Pb, Ni, Co, V, Cu, Zn, Fe, Mn, Th, Sb, Ba, Be, Li, Sr, Tl, U, Se, Sn, and REEs) exceeded permissible limits set by the WHO. The elevated hazard index values indicated significant non-carcinogenic effects. The sources of these elements could be attributed to a combination of geological factors and agricultural practices. This study highlights the need for further investigation into the potential health implications of consuming these vegetables in the aforementioned region., (© 2024. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

A common evolutionary mechanism in biology to drive function is protein oligomerization. In prokaryotes, the symmetrical assembly of repeating protein units to form homomers is widespread, yet consideration in vitro of whether such assemblies have functional or mechanistic consequences is often overlooked. Dye-decolorizing peroxidases (DyPs) are one such example, where their dimeric α + β barrel units can form various oligomeric states, but the oligomer influence, if any, on mechanism and function has received little attention. In this work, we have explored the oligomeric state of three DyPs found in Streptomyces lividans, each with very different mechanistic behaviors in their reactions with hydrogen peroxide and organic substrates. Using analytical ultracentrifugation, we reveal that except for one of the A-type DyPs where only a single sedimenting species is detected, oligomer states ranging from homodimers to dodecamers are prevalent in solution. Using cryo-EM on preparations of the B-type DyP, we determined a 3.02 Å resolution structure of a hexamer assembly that corresponds to the dominant oligomeric state in solution as determined by analytical ultracentrifugation. Furthermore, cryo-EM data detected sub-populations of higher-order oligomers, with one of these formed by an arrangement of two B-type DyP hexamers to give a dodecamer assembly. Our solution and structural insights of these oligomer states provide a new framework to consider previous mechanistic studies of these DyP members and are discussed in terms of long-range electron transfer for substrate oxidation and in the "storage" of oxidizable equivalents on the heme until a two-electron donor is available., (© 2024 The Author(s). Protein Science published by Wiley Periodicals LLC on behalf of The Protein Society.)

Population growth, urbanization, industry, floods, and agriculture globally degrade groundwater in river plains, necessitating action for its quality assessment and management. Hence, a comprehensive methodology, including hydrogeochemical facies (Piper, Gibbs), irrigation indices (SAR, Wilcox), entropy-weighted water quality index (EWQI), positive matrix factorization (PMF), and Monte Carlo simulation of source-specific health risks was used in this study to analyze groundwater in the Morava river plain (Serbia). The results revealed a prevalent Ca-Mg-HCO3 groundwater type, influenced by water-rock interactions. Although groundwater was found suitable for irrigation, only 66.7 % of the samples were considered drinkable. Agricultural activities, natural processes, and municipal wastewater were identified as primary pollution sources. The incremental lifetime cancer risk (ILCR) and hazard index (HI) threshold exceedance for adults and children ranged from 8.5 % to 39 % of the samples, with arsenic identified as the most risk-contributing contaminant. These findings provide valuable insights for researchers studying groundwater vulnerability in river plains., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

This study investigated the occurrence and distribution of rare earth elements (REEs), including 14 lanthanoids, scandium (Sc), and yttrium (Y), in groundwater around a large coal-fired thermal power plant (TPP). The ICP-MS technique was used to analyze 16 REEs in groundwater samples collected from monitoring wells. REE concentrations ranged from 59.9 to 758 ng/L, with an average of 290 ng/L. The most abundant was Sc, followed by La, accounting for 54.2% and 21.4% of the total REE concentration, respectively. Geospatial analysis revealed the REE enrichment at several hotspots near the TPP. The highest REE concentrations were observed near the TPP and ash landfill, decreasing with the distance from the plant and the landfill. REE fractionation ratios and anomalies suggested the Light REE dominance, comprising over 78% of the total REEs. Correlation and principal component analyses indicated similar behavior and sources for most REEs. Health risk assessment found hazard indices (HI) of 1.36 × 10 -3 and 1.98 × 10 -3 for adults and children, respectively, which are far below the permissible limit (HI = 1). Likewise, incremental lifetime cancer risks (ILCR) were all below 1 × 10 -6 . Nevertheless, ongoing ash disposal and potential accumulation in the environment could elevate the REE exposure over time.

This paper investigates occurrence of metal(loid)s, and size-dependent changes in their concentration in recent marine sediments from coastal and open-sea environments in the eastern Adriatic. Size fractionation of sediments was performed after removal of organic matter (OM), and the individual fractions, comprising particles below 8 μm, 4 μm, 2 μm, 1 μm and 0.45 μm, were analysed using HR ICP-MS. The concentrations of most elements increased with decreasing particle size, as a result of accumulation of clay minerals and Fe and Mn (oxyhydr)oxides. A decrease in concentrations was observed for Ba, Sr, Ti and U, due to lowering of the carbonate content and presence in the coarse-grained and heavy mineral fraction. The highest element concentrations were determined in the fraction comprising particles below 1 μm. Occasionally, depending on the sedimentological environment and/or the element in question, the peak concentrations occurred in the <2 μm or <0.45 μm fraction. The lowest size-dependent enrichment was observed for elements associated with aluminosilicates (Al, Be, Cs, Co, Fe, K, Li, Rb). A different size-dependent behaviour of the elements was observed between deep-sea areas and shallow environments under greater coastal influence, mainly due to differences in sediment sorting, and between the northern and central vs. southern Adriatic due to the different catchment geologies. The Fe and Mn (oxyhydr)oxides, abundant in the deep-sea sediments, played an important role in the geochemical cycle of As, Cd, Co, Mo, Sb and V., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

A capacity to determine the provenance of high-value food products is of high scientific and economic interest. With the aim to develop a tool for geographical traceability of Croatian extra virgin olive oils (EVOO), multielement composition and 13 C/ 12 C isotope ratio in EVOO as well as the geochemistry of the associated soils were analysed in samples collected from three regions along the Croatian Adriatic coast. Soil geochemistry was shown to influence the transfer and elemental composition of EVOO. The most discriminating variables to distinguish EVOO from different regions were S, Mo, Rb, Mg, Pb, Mn, Sn, K, V and δ 13 C. The predictive models achieved high sensitivity and specificity, especially when carbon isotope composition was added. The results suggest that interregional geographical traceability of Croatian EVOO is possible based on matching their multielement composition with that of the soils in the provenance area., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

In heme enzymes, such as members of the dye-decolorising peroxidase (DyP) family, the formation of the highly oxidising catalytic Fe(iv)-oxo intermediates following reaction with hydrogen peroxide can lead to free radical migration (hole hopping) from the heme to form cationic tyrosine and/or tryptophan radicals. These species are highly oxidising (∼1 V vs. NHE) and under certain circumstances can catalyse the oxidation of organic substrates. Factors that govern which specific tyrosine or tryptophan the free radical migrates to in heme enzymes are not well understood, although in the case of tyrosyl radical formation the nearby proximity of a proton acceptor is a recognised facilitating factor. By using an A-type member of the DyP family (DtpAa) as an exemplar, we combine protein engineering, X-ray crystallography, hole-hopping calculations, EPR spectroscopy and kinetic modelling to provide compelling new insights into the control of radical migration pathways following reaction of the heme with hydrogen peroxide. We demonstrate that the presence of a tryptophan/tyrosine dyad motif displaying a T-shaped orientation of aromatic rings on the proximal side of the heme dominates the radical migration landscape in wild-type DtpAa and continues to do so following the rational engineering into DtpAa of a previously identified radical migration pathway in an A-type homolog on the distal side of the heme. Only on disrupting the proximal dyad, through removal of an oxygen atom, does the radical migration pathway then switch to the engineered distal pathway to form the desired tyrosyl radical. Implications for protein design and biocatalysis are discussed., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

This study investigates the effects of ultrasound, in combination with chemical pretreatments, on the quality attributes (total phenolic and carotenoid content, antioxidant activity (2,2-Diphenyl-1-picrylhydrazyl assay (DPPH)), ferric-reducing ability (FRAP), CIE L* a* b* color, non-enzymatic browning, rehydration ratio, textural and morphological properties) of red pepper subjected to drying (hot air drying or freeze drying). The fractional factorial design was used to assess the impact of factors. The global Derringer desirability function was used to determine the optimal conditions for the best quality attributes of dried pepper. The drying method influenced total phenolic content, a* (redness), and initial rehydration ratio; pretreatment time significantly affected FRAP antiradical activity, a*, chroma and non-browning index, while pH-value had a significant effect on the texture of dried pepper. Non-enzymatic browning was reduced to 72.6%, while the DPPH antioxidant capacity of freeze-dried peppers was enhanced from 4.2% to 71.9%. Ultrasonic pretreatment led to changes in the pepper morphology, while potassium metabisulfite (KMS) was a more effective additive than citric acid., Competing Interests: The authors have declared no conflicts of interest for this article.

Pesticides are extensively used in the cultivation and postharvest protection of citrus fruits, therefore continuous monitoring and health risk assessments of their residues are required. This study aimed to investigate the occurrence of pesticide residues on citrus fruits and to evaluate the acute and chronic risk for adults and children. The risk ranking of twenty-three detected pesticides was carried out according to a matrix ranking scheme. Multiple residues were detected in 83% of 76 analyzed samples. In addition, 28% contained pesticides at or above maximum residue levels (MRLs). The most frequently detected pesticides were imazalil, azoxystrobin, and dimethomorph. According to the risk ranking method, imazalil was classified in the high-risk group, followed by prochloraz, chlorpyrifos, azinphos-methyl, tebufenpyrad, and fenpiroximate, which were considered to pose a medium risk. The majority of detected pesticides (74%) posed a low risk. The health risk assessment indicated that imazalil and thiabendazole contribute to acute (HQa) and chronic (HQc) dietary risk, respectively. The HQc was negligible for the general population, while the HQa of imazalil and thiabendazole exceeded the acceptable level in the worst-case scenario. Cumulative chronic/acute risk (HIc/HIa) assessment showed that chronic risk was acceptable in all samples for children and adults, while the acute risk was unacceptable in 5.3% of citrus fruits for adults and 26% of citrus fruits for children. Sensitivity analyses indicated that the ingestion rate and individual body weight were the most influential risk factors.

The remnants of historical industrial contamination can be detected in many aquatic ecosystems worldwide even at present time. Mrežnica is a river in Croatia that has been, for more than a hundred years, continually exposed to effluents of various industries, which have, in modern time, mostly ceased to operate. Our aim was to establish the level of current contamination and pollution of the Mrežnica river-water and sediments. The study of river contamination at three sites (reference site; site nearby former cotton industry facility in Duga Resa - DRF; industrial zone of Karlovac town - KIZ) in three sampling campaigns (May 2020, April and September 2021) encompassed analyses of physico-chemical water parameters, screening of 369 pesticides, measurement of metal (loid) concentrations in the sediments, and in the dissolved and particulate phases of the river-water. The sediment pollution was assessed through the analyses of total bacteria abundance (by targeting 16S rRNA genes), and their associated metal resistance genes (cnrA, pbrT and czcD) and class 1 integrons (intl1). At the DRF site, industrial organic contaminants that can be traced to textile production were detected (dye and nylon components), as well as increased levels of some metals bound to suspended particulate matter and sediments. At the most downstream KIZ site, occasional high level of industrial herbicide neburon was measured in the river-water, and metal contamination of suspended particulate matter and sediments was evident. Although, based on the comparison with legislation and literature data, the level of contamination was rather mild, the effects on microbial communities were unquestionable, confirmed by increased abundance of the czcD gene at DRF site and the intI1 gene at both industrially impacted sites. Obtained results indicated long-term sediment retention of some industrial contaminants at the places of historical freshwater contamination, and, thus, the necessity for their monitoring even after the termination of contamination sources., Competing Interests: Declaration of competing interest There are no conflicts to declare., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Controlling the reactivity of high-valent Fe(IV)-O catalytic intermediates, Compounds I and II, generated in heme enzymes upon reaction with dioxygen or hydrogen peroxide, is important for function. It has been hypothesized that the presence (wet) or absence (dry) of distal heme pocket water molecules can influence whether Compound I undergoes sequential one-electron additions or a concerted two-electron reduction. To test this hypothesis, we investigate the role of water in the heme distal pocket of a dye-decolorizing peroxidase utilizing a combination of serial femtosecond crystallography and rapid kinetic studies. In a dry distal heme site, Compound I reduction proceeds through a mechanism in which Compound II concentration is low. This reaction shows a strong deuterium isotope effect, indicating that reduction is coupled to proton uptake. The resulting protonated Compound II (Fe(IV)-OH) rapidly reduces to the ferric state, giving the appearance of a two-electron transfer process. In a wet site, reduction of Compound I is faster, has no deuterium effect, and yields highly populated Compound II, which is subsequently reduced to the ferric form. This work provides a definitive experimental test of the hypothesis advanced in the literature that relates sequential or concerted electron transfer to Compound I in wet or dry distal heme sites., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

The history of metal pollution in the semi-enclosed and human-influenced marine system of the Boka Kotorska Bay (Southern Adriatic) was studied considering geological composition of the surrounding catchment, the sedimentation rate and the mineralogical and early diagenetic processes in the recent sediments. The determination of background concentrations of metals, undertaken for the first time in this environment, proved to be particularly important for Ni and Cr, which are naturally enriched in the sediments of the southern Adriatic. The results showed widespread moderate contamination with Pb and Sn since the 1970s, while the upper layers of sediments near shipyards, marinas and urban areas were more contaminated with Sn, Cu, Pb, Zn, Cd, As, Sb and Mo. The transport of material through the narrow straits separating different parts of Boka Kotorska Bay resulted in a different geochemical composition of the smaller bays and a limited distribution of contaminated sediments from local sources., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

The spatial and temporal variability of dissolved trace elements (Al, As, Ba, Cd, Co, Cr, Cu, Fe, Li, Mn, Mo, Ni, Pb, Sb, Sr, Ti, U, V and Zn) in the upper and middle reaches of the Sava River during two campaigns (2007/2008 and 2017/2018) was examined. The study also included important tributaries and wastewater effluents. No crucial change in metal concentrations in the Sava River water between the two sampling periods was detected. Elements Co, Cr, Cu, Fe, Sb and Zn had higher concentrations at several sites in the first period, whereas Ba, Cd and Pb in the second period. The influence of wastewater discharges proved to be negligible. The highest levels of potentially toxic metals (Cd, Cr, Cu, Sb, V and Zn) were found downstream of the industrial town of Sisak. Concentration-discharge relationship of dissolved elements showed a chemostatic behaviour for As, Cr, Cu, Sr and V and chemodynamic behaviour for all other elements. The UNMIX model, used to identify and quantify metal sources, indicated that soil weathering was the main source of most elements (Al, As, Ba, Co, Cu, Fe, Li, Ni, Sb, Sr and V), with an anthropogenic contribution for Cd, Mo, Pb, Ti and Zn, while Mn and U were associated with colloid formation. The Sava River was defined as moderately polluted regarding metals, whose water quality meets environmental quality standards (EQS). These results may help to better understand the behaviour of dissolved metals in rivers under anthropogenic pressure and to control pollution in the Sava River Basin., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.