Development of a fast instrumental method for the analysis of pharmaceuticals in environmental and wastewaters based on ultra high performance liquid chromatography (UHPLC)-tandem mass spectrometry (MS/MS)

This work describes the development, optimization and validation of an analytical method for the simultaneous detection and identification of 74 pharmaceutically active compounds (PhACs), from various therapeutic groups, in both environmental (ground and surface water) and wastewaters (WW). The method is based on the simultaneous extraction of all target compounds by solid phase extraction (SPE), using a hydrophilic-lipophilic balanced polymer followed by ultra high performance liquid chromatography (UHPLC) tandem mass spectrometry (MS/MS). Two selected reaction monitoring (SRM) transitions have been monitored per compound in order to fulfil the EC guidelines, as well as to ensure an accurate identification of target compounds in the samples. Quantification is performed by internal standard approach, applying 24 specific isotopically labeled compounds. The main advantages of the developed method, besides the selectivity and reliability of the results, is its high throughput. All compounds are extracted in a single step and the instrumental analysis lasts 5 min (NI mode) + 8 min (PI mode), allowing fast throughput of samples. The limits of detection range from 0.01 to 50 ng L⁻¹, depending on the matrix, for most of the compounds. Finally, the method developed has been applied to the analysis of pharmaceuticals in the Ebro river basin (NE Spain).     

Terrestrial Biodiversity Analyses in Dalmatia (Croatia): A Complementary Approach Using Diversity and Rarity

Here we present the methodology used for terrestrial biodiversity analysis and site selection in Phase B of the UNDP/GEF COAST project. The analysis was focused on the problem of biodiversity evaluation in four Croatian counties stretching from sea level to the highest mountain in Croatia. Data on habitats, vascular flora, and fauna (mammals, birds, reptiles, amphibians, butterflies, ground beetles, and underground invertebrates) were collected and analyzed for each of the four counties. Emphasis was given to the richness of endangered species and the rarity of endemic species. Based on the spatial analyses of habitat, fauna, and flora data, four to six areas were selected from each county and ranked according to their biodiversity importance. Overlap between areas important for richness and those important for rarity was highest for data on flora (65.5%) and lowest for data on fauna (16.7%). When different data sets were compared, the lowest overlap was between flora and fauna (17.1%) and largest between fauna and habitats (23.9%). Simultaneous overlap among all three data sets was found in just 6.5% of the overall selected areas. These results suggest that less specific data, with respect to taxa threat status, could better serve as surrogate data in estimating overall biodiversity. In summary, this analysis has demonstrated that Dalmatia is a region with a high overall biodiversity that is important in a broader European context.     

Principal component analysis of indicator PCB profiles in breast milk from Poland

Principal component analysis (PCA) was applied to a data set containing the levels of indicator polychlorinated biphenyls (PCBs) in human milk of mothers living in the Wielkopolska region, Poland, in order to investigate the information captured in the PCB patterns and to elucidate the relationship between PCB concentrations in milk and donor characteristics. According to the obtained PCA results milk fat content was the most influential factor affecting the PCB levels in milk of the Wielkopolska cohort. The lifestyle data collected from the questionnaire completed by the donors appeared to have no influence on PCB concentrations in breast milk. The score plots revealed the PCB contents of milk were quite low and uniform with a few outliers, without discrimination observed either between the primipareous and secundipareous females or between donors from the urban and rural areas. Comparison of the PCB levels and profiles of human milk from the Wielkopolska region and from various European and Asian locations made by PCA reflected a generally low background exposure and indicated the possible reasons for the outlying of some samples. In order to enhance the chances of observing the relationship between donor habits and PCB levels in breast milk it was suggested that the questionnaire be redesigned to gather information about vegetable product consumption and indoor air exposure.     

Spatial distribution of trace metals in the Krka River, Croatia: an example of the self-purification

The spatial distribution of dissolved and total trace metals (Zn, Cd, Pb and Cu) in the Krka River (partly located in the Krka National Park) has been studied using a "clean" sampling, handling and analysis technique. Differential pulse anodic stripping voltammetry (DPASV) with a hanging mercury drop electrode (HMDE) has been used for trace metal analysis. The Krka River has been divided into the upper and lower flow region with respect to the metals concentration and main physico-chemical parameters. A significant increase in trace metal concentration as the result of the untreated waste water discharge downstream of Knin Town has been registered in the upper flow region. Due to a specific characteristic of the Krka, the so-called self-purification process, a decrease in the elevated trace metals concentration from the water column takes place at numerous small lakes formed by tufa barriers (at the end of the upper flow region). The clean groundwater input at the beginning of the lower flow region additionally contributes to the observed decrease in trace metals concentration in the Krka, maintaining them at a very low level in the remaining region of fresh-water flow. The determined median total concentrations were zinc 120-7400 ng l(-1), cadmium 3-8 ng l(-1), lead 11-250 ng l(-1) and copper 110-440 ng l(-1). Karst rivers, such as the Krka River, with extremely low natural concentrations of trace metals are highly sensitive to the anthropogenic influence. Therefore, such aquatic systems require implementation of strict protection regimes in the entire catchments area.     

Epiphytic lichens as biomonitors of atmospheric pollution in Slovenian forests

Two country-wide surveys using epiphytic lichens as biomonitors of atmospheric pollution carried out during 2000 and 2001 in Slovenia were compared with surveys in 1991 and 1992. In the first survey, epiphytic lichen cover was studied in more than 500 plots of the 4 x 4 km national grid carried out within the framework of forest decline inventories. In the second survey, the epiphytic lichen Hypogymnia physodes (L.) Nyl., was collected on a 16 x 16 km bioindication grid and analysed for S, N, As, Br, Ce, Cd, Cr, K, La, Mo, Rb, Sb, Th, U and Zn contents. Only 'forested area' sampling points were included in the present study. Lichen cover was low, with about 70% of plots with less than 10% foliose lichen cover. No relationship was found between Hypogymnia trace element, N and S concentrations and foliose epiphytic lichen cover.     

Optimizing the SO2 total emission control strategy: case study—Bor (Serbia)

Mumbai, a megacity of India, and its adjacent marine environment, though heavily stressed from various anthropogenic interferences, harbor ~146 km² of mangrove cover. Manori creek, in the close vicinity of Mumbai, sustains relatively better mangrove formations. A creek habitat had been evaluated for its biological and environmental characteristics, and is compared with similar but relatively lesser stressed Mandovi estuary (~475 km south of Mumbai). Several evidences of deteriorating environment of Manori creek have been described with respect to Water quality index and various biotic community structures. Water quality index of <55 indicated unacceptable aquatic conditions of Manori creek. Dominance of Avicennia marina and poor abundance and diversity of mangrove and associated biological features indicate highly stressed environment. Dominance of stress-tolerant phytoplankton spp. such as Skeletonema costatum and benthic fauna such as Polychaeta further supported the view. The data presented in the present document would help in developing rational approach towards conservation, protection, and sustainable development of mangrove-dominated creek and estuarine wetlands.     

Evaluating Spatio-temporal Complexities of Forest Management: An Integrated Agent-based Modeling and GIS Approach

The objective of this study is to integrate agent-based modeling and geographic information systems (GIS) for examining how interactions within forest management lead to patterns of land-cover change. Specifically, this study evaluates how management agents behave in the presence of variable timber prices, harvesting costs, and accessibility to timber and how their actions influence the spatial characteristics of the forest landscape over time. The GIS calculates the average harvested patch size, number of patches, and total harvested area as measures of emergent patterns resulting from agent actions. The results from the agent-based GIS model reveal that good economic conditions lead to few but large harvested patches, while deteriorating conditions will see more patches of smaller size if forest companies have access to high-quality timber. This study emphasizes the need for a complex systems approach to forest management as the model illustrates how system elements interact in a manner to produce emergent spatial patterns over time.     

Uranium oxide and other airborne particles deposited on cypress leaves close to a nuclear facility

Enhanced activity of actinides and some decay products has been reported for the leaves of cypress trees (Chamaecyparis nootkatensis) at the edge of the Malvési uranium-processing facility, southwestern France. The enhanced activity is due to the release of actinides via the smokestacks and from artificial ponds inside the facility. This study was conducted to characterize airborne particulate matter deposited on the leaf surfaces and to investigate whether or not radioactive particles may be identified. Air-dried leaf samples were examined by scanning electron microscopy, in combination with energy-dispersive X-ray spectrometry. The samples were scanned systematically in both secondary and backscattered electron modes. Particles ranging in size from <200 nm to ~40 μm were found on most portions of the adaxial leaf surface, but they are especially abundant at the boundary between facial and lateral leaves. The majority of the analyzed particles could be attributed to five principal classes: carbonates, silicates, sulfates, oxides/hydroxides, and halides. In addition, other types of particles were found, including Fe alloys; scheelite-group phases; phosphates; sulfides; and fly ash spheres. Similar particles were also observed on the surface of a wheat sample used for comparison. Of special interest are U-rich particles, which were observed on the cypress leaves only and which were identified as U oxides, except for one particle, which was a U-oxide-fluoride. These U-rich particles were released into the atmosphere by the nuclear facility prior to their deposition on the leaf surfaces. As most of the U-rich particles are <2.5 μm across, they are respirable. Once inhaled, particles containing alpha-emitting isotopes represent a potentially long-term source of ionizing radiation inside the lungs and thus, pose a threat to the health of people living nearby.     

Biomonitoring of heavy metals in fish from the Danube River

The Croatian part of the Danube River extends over 188 km and comprises 58 % of the country’s overall area used for commercial freshwater fishing. To date, the heavy metal contamination of fish in the Croatian part of the Danube has not been studied. The main purpose of this study was to determine heavy metal levels in muscle tissue of sampled fish species and to analyze the measured values according to feeding habits of particular groups. Lead ranged from 0.015 μg^?1 dry weight in planktivorous to 0.039 μg^?1 dry weight in herbivorous fish, cadmium from 0.013 μg^?1 dry weight in herbivorous to 0.018 μg^?1 dry weight in piscivorous fish, mercury from 0.191 μg^?1 dry weight in omnivorous to 0.441 μg^?1 dry weight in planktivorous fish and arsenic from 0.018 μg^?1 dry weight in planktivorous to 0.039 μg^?1 dry weight in omnivorous fish. Among the analyzed metals in muscle tissue of sampled fish, only mercury exceeded the maximal level (0.5 mg kg^?1) permitted according to the national and EU regulations determining maximum levels for certain contaminants in foodstuffs, indicating a hazard for consumers of fish from the Danube River.