Photocatalytic reduction of carbon dioxide over Cu/TiO<Subscript>2</Subscript> photocatalysts

The photocatalytic reduction of CO₂ with H₂O was investigated using Cu/TiO₂ photocatalysts in aqueous solution. For this purpose, Cu/TiO₂ photocatalysts (with 0.2, 0.9, 2, 4, and 6 wt.% of Cu) have been synthesized via sol-gel method. The photocatalysts were extensively characterized by means of inductively coupled plasma optical emission spectrometry (ICP-OES), N₂ physisorption (BET), XRD, UV-vis DRS, FT-IR, Raman spectroscopy, TEM-EDX, and photoelectrochemical measurements. The as-prepared photocatalysts contain anatase as a major crystalline phase with a crystallite size around 13 nm. By increasing the amount of Cu, specific surface area and band gap energy decreased in addition to the formation of large agglomeration of CuO. Results revealed that the photocatalytic reduction of CO₂ decreased in the presence of Cu/TiO₂ in comparison to pure TiO₂, which might be associated to the formation of CuO phase acting as a recombination center of generated electron-hole pair. Decreasing of photoactivity can also be connected with a very low position of conduction band of photocatalysts with high Cu content, which makes H₂ production necessary for CO₂ reduction more difficult.     

Stakeholders' expectations from the agri-environmental programme in Slovenia and Croatia

The agri-environmental programme (AEP) is the European Union policy instrument used for the delivery of environmental services expected by the society, but societal expectations for these environmental services are insufficiently assessed. In order to realistically meet the expectations of AEP, this research utilises analytical hierarchy process based web survey to assess the importance that various societal stakeholders in the European countries of Slovenia and Croatia give to specific environmental services and to also identify the agricultural practices that have the greatest potential to realise the expectations that society values the most. All stakeholders (overall group) from Slovenia and Croatia ranked water quality and availability as the first most important environmental service, and reduction of pesticides as the most important agricultural practice to deliver societal expectations. The results indicate that there is similar demand for environmental services in these two countries that differ in their agricultural settings.     

First inter-laboratory comparison exercise for the determination of anticancer drugs in aqueous samples

The results of an inter-laboratory comparison exercise to determine cytostatic anticancer drug residues in surface water, hospital wastewater and wastewater treatment plant effluent are reported. To obtain a critical number of participants, an invitation was sent out to potential laboratories identified to have the necessary knowledge and instrumentation. Nine laboratories worldwide confirmed their participation in the exercise. The compounds selected (based on the extent of use and laboratories capabilities) included cyclophosphamide, ifosfamide, 5-fluorouracil, gemcitabine, etoposide, methotrexate and cisplatinum. Samples of spiked waste (hospital and wastewater treatment plant effluent) and surface water, and additional non-spiked hospital wastewater, were prepared by the organising laboratory (Jo?ef Stefan Institute) and sent out to each participant partner for analysis. All analytical methods included solid phase extraction (SPE) and the use of surrogate/internal standards for quantification. Chemical analysis was performed using either liquid or gas chromatography mass (MS) or tandem mass (MS/MS) spectrometry. Cisplatinum was determined using inductively coupled plasma mass spectrometry (ICP-MS). A required minimum contribution of five laboratories meant that only cyclophosphamide, ifosfamide, methotrexate and etoposide could be included in the statistical evaluation. z-score and Q test revealed 3 and 4 outliers using classical and robust approach, respectively. The smallest absolute differences between the spiked values and the measured values were observed in the surface water matrix. The highest within-laboratory repeatability was observed for methotrexate in all three matrices (CV?≤?12 %). Overall, inter-laboratory reproducibility was poor for all compounds and matrices (CV 27–143 %) with the only exception being methotrexate measured in the spiked hospital wastewater (CV?=?8 %). Random and total errors were identified by means of Youden plots.     

Edaphic factors affecting the vertical distribution of radionuclides in the different soil types of Belgrade, Serbia

The specific activities of natural radionuclides ((40)K, (226)Ra and (232)Th) and Chernobyl-derived (137)Cs were measured in soil profiles representing typical soil types of Belgrade (Serbia): chernozems, fluvisols, humic gleysols, eutric cambisols, vertisols and gleyic fluvisols. The influence of soil properties and content of stable elements on radionuclide distribution down the soil profiles (at 5 cm intervals up to 50 cm depth) was analysed. Correlation analysis identified associations of (40)K, (226)Ra and (137)Cs with fine-grained soil fractions. Significant positive correlations were found between (137)Cs specific activity and both organic matter content and cation exchange capacity. Saturated hydraulic conductivity and specific electrical conductivity were also positively correlated with the specific activity of (137)Cs. The strong positive correlations between (226)Ra and (232)Th specific activities and Fe and Mn indicate an association with oxides of these elements in soil. The correlations observed between (40)K and Cr, Ni, Pb and Zn and also between (137)Cs and Cd, Cr, Pb and Zn could be attributed to their common affinity for clay minerals. These results provide insight into the main factors that affect radionuclide migration in the soil, which contributes to knowledge about radionuclide behaviour in the environment and factors governing their mobility within terrestrial ecosystems.     

New beach in a shallow estuarine lagoon: a model-based <Emphasis Type="Italic">E. coli</Emphasis> pollution risk assessment

A 3D hydrodynamic model has been applied to the Curonian Lagoon to study the pollution impact of E. coli on a new beach that might be opened in the lagoon. Through a field survey the E. coli inputs were measured and then used in the numerical model, and through laboratory experiments the decay rate of E. coli was established. The model has been calibrated and validated for the year 2015, and several scenarios have been studied, such as sewage system breakdown, severe weather conditions or high river loads. The model has then been run for a period of 12 years to obtain a robust statistics for the pollution on the planned beach. Results show that the decay rate of E. coli is between 0.55 days and 2.3 days and the modeled decay times are compatible with these numbers. The only scenario that would create a risk for the bathing waters of the beach is a breakdown of the sewage system on the Curonian Spit. In this case the hours (and days) over legally allowable bathing threshold were computed in order to estimate the number of days the beach could be closed. These results have been confirmed by the 12 year simulations. With an influence map analysis the two most critical sewage systems could be identified.     

Implementation of Neural Networks for Classification of Moss and Lichen Samples on the Basis of Gamma-Ray Spectrometric Analysis

Mosses and lichens have an important role in biomonitoring. The objective of this study is to develop a neural network model to classify these plants according to geographical origin. A three-layer feed-forward neural network was used. The activities of radionuclides ((226)Ra, (238)U, (235)U, (40)K, (232)Th, (134)Cs, (137)Cs and (7)Be) detected in plant samples by gamma-ray spectrometry were used as inputs for neural network. Five different training algorithms with different number of samples in training sets were tested and compared, in order to find the one with the minimum root mean square error. The best predictive power for the classification of plants from 12 regions was achieved using a network with 5 hidden layer nodes and 3,000 training epochs, using the online back-propagation randomized training algorithm. Implementation of this model to experimental data resulted in satisfactory classification of moss and lichen samples in terms of their geographical origin. The average classification rate obtained in this study was (90.7 +/- 4.8)%.     

Spatio-temporal analysis of land use/land cover change and its effects on soil erosion (Case study in the Oplenac wine-producing area,Serbia)

In this paper, various spatial modelling techniques were applied to analyse changes in soil cover and their impact on soil erosion in the Oplenac wine-producing area in Serbia in the past (1985 and 2013) and in the future (with predictions for 2041). The Integrated Valuation of Ecosystem Services and Trade-offs Sediment Delivery Ratio (InVEST SDR) model and the Modules for Land Use Change Evaluation (MOLUSCE) model, integrated with methods of remote sensing, were successfully applied and were shown to be valid tools for predicting the impact of Land Use Land Cover (LULC) changes when estimating soil loss. The results revealed that the greatest impact of land use changes between 1985 and 2013 was on a reduction in areas under vineyards and an extension of meadow and pasturelands as an individual and social response to economic conditions during the research period. The forecast for 2041 reflected the trends observed in the previous period, with the greatest changes witnessing an increase in urban areas and a decrease in areas of arable land. It was also found that the effect of LULC changes on spatio-temporal patterns in the Oplenac wine-producing area did not have a major impact on soil loss, meaning this area, with its good agro-climatic characteristics, is suitable for the intensification of agricultural production.     

Photocatalytic decomposition of methanol over La/TiO<Subscript>2</Subscript> materials

Lanthanum-modified TiO₂ photocatalysts (0.2–1.5 wt% La) were investigated in the methanol decomposition in an aqueous solution. The photocatalysts were prepared by the common sol-gel method followed by calcination. The structural (X-ray diffraction, Raman, X-ray photoelectron spectroscopy), textural (N₂ physisorption), and optical properties (diffuse reflectance spectroscopy, photoelectrochemical measurements) of all synthetized nanomaterials were correlated with photocatalytic activity. Both pure TiO₂ and La-doped TiO₂ photocatalysts proved higher yields of hydrogen in comparison to photolysis. The photocatalyst with optimal amount of lanthanum (0.2 wt% La) showed almost two times higher amount of hydrogen produced at the same time as in the presence of pure TiO₂. The photocatalytic activity increased with both increasing photocurrent response and decreasing amount of lattice and surface O species. It has been shown that both direct and indirect mechanisms of methanol photocatalytic oxidation participate in the production of hydrogen. Both direct and indirect mechanisms take part in the formation of hydrogen.     

A field screening test for the assessment of concentrations and mobility of potentially toxic elements in soils: a case study on urban soils from Rome and Novi Sad

The increasing demand for environmental pollution control results in the development and use of new procedures for the determination of dangerous chemicals. Simple screening methods, which can be used directly in the field for a preliminary assessment of soil contamination, seem to be extremely advantageous. In our laboratory, we developed and optimized a rapid test for a preliminary evaluation of both the concentration and the mobility of some potentially toxic metals in soils. This screening test consists of a single extraction of the soil sample with a buffer solution, followed by the titration of the extracted solution with dithizone to determine the contents of bi-valent heavy metals (such as Pb, Cu, Zn, and Cd). This screening method was then directly applied in the field during the sampling campaign in the framework of an Italian–Serbian collaborative project, finalized in the study of metal availability in soils. The results obtained in the field with the rapid test were compared with those obtained in the laboratory following the conventional procedure commonly used to evaluate metal bioavailability (diethylenetriaminepentaacetic extraction). Moreover, selected samples were analyzed sequentially in the laboratory using the standardized BCR three-step sequential extraction procedure. The screening test gave results conceptually in good agreement with those obtained via the BCR procedure. These preliminary data show that the proposed screening test is a reliable method for the preliminary rapid evaluation of metal total concentrations and of potential metal mobility in soils, supporting sampling activities directly in the field.