Priority and emerging organic microcontaminants in three Mediterranean river basins: Occurrence, spatial distribution, and identification of river basin specific pollutants.

There is a worldwide growing use of chemicals by our developed, industrialized, and technological society. More than 100,000 chemical substances are thus commonly used both by industry and households. Depending on the amount produced, physical-chemical properties, and mode of use, many of them may reach the environment and, notably, the aquatic receiving systems. This may result in undesirable and harmful side-effects on both the human and the ecosystem's health. Mediterranean rivers are largely different from Northern and Central European rivers in terms of hydrological regime, climate conditions (e.g. air temperature, solar irradiation, precipitation), and socio-economics (e.g. land use, tourism, crop types, etc.), with all these factors leading to differences in the relative importance of the environmental stressors, in the classes and levels of the pollutants found and their environmental fate. Furthermore, water scarcity might be critical in affecting water pollution because of the lowered dilution capacity of chemicals. This work provides raw chemical data from different families of microcontaminants identified in three selected Mediterranean rivers (the Sava, Evrotas, and Adige) collected during two sampling campaigns conducted in 2014 and 2015 in three different matrices, namely, water, sediments, and biota (fish). More than 200 organic micropollutants were analyzed, including relevant groups like pharmaceuticals, personal care products, perfluorinated compounds, pesticides, pyrethroid insecticides, flame retardants, and persistent organic pollutants. Data obtained were summarized with some basic statistics for all compound families and matrices analyzed. Observed occurrence and spatial patterns were interpreted both in terms of compound physical-chemical properties and local environmental pressures. Finally, their spatial distribution was examined and their ecotoxicological risk in the water phase was assessed. This allowed locating, at each basin, the most polluted sites ("hot spots") and identifying the respective river basin specific pollutants (RBSPs), prioritizing them in terms of the potential ecotoxicological risk posed to the aquatic ecosystems.

Levels of regulated POPs in fish samples from the Sava River Basin. Comparison to legislated quality standard values.

Fish samples of different species (i.e. rainbow trout (Onchorhynchus mykiss), barbel (Barbus barbus) and European chub (Squalius cephalus)) were collected from the Sava River Basin for a preliminary investigation of the levels of PCDD/Fs, PCBs, PBDEs and PFAS as a whole. Concentrations of PCDD/Fs, in terms of pg WHO-TEQ/g ww, were below the maximum limit established at the Commission Regulation (EU) No 1259/2011. On the contrary, when DL-PCBs were also included, levels increase up to 11.7 pg WHO-TEQPCDD/Fs+DL-PCBs/g ww in a particular case, with two samples out of a total of ten exceeding the maximum set at this EU Regulation and the EQS established at the European Directive regarding priority substances in the field of water policy (0.0065 ng WHO-TEQPCDD/Fs+DL-PCBs/g ww). A similar trend was also observed for NDL-PCBs, whit the same two samples, from the lower stretch of the river basin, exceeding the maximum limit allowed at the EU Regulation (125 ng/g ww). For PBDEs, levels found in all the samples exceeded the EQS (0.0085 ng/g ww) up to more than a thousand times and 40% of the samples presented PFOS values above the EQS. Data from this study were compared to values reported at the literature for fish from other geographical areas.

Ecological and human exposure assessment to PBDEs in Adige River.

The interest for environmental issues and the concern resulting from the potential exposure to contaminants were the starting point to develop methodologies in order to evaluate the consequences that those might have over both the environment and human health. Considering the feature of POPs, including PBDEs, such as bioaccumulation, biomagnification, long-range transport and adverse effects even long time after exposure, risk assessment of POPs requires specific approaches and tools. In this particular context, the MERLIN-Expo tool was used to assess the aquatic environmental exposure of Adige River to PBDEs and the accumulation of PBDEs in humans through the consumption of possible contaminated local aquatic food. The aquatic food web models provided as output of the deterministic simulation the time trend of concentrations for twenty years of BDE-47 and total PBDEs, expressed using the physico-chemical properties of BDE-47, in aquatic organisms of the food web of Adige River. For BDE-47, the highest accumulated concentrations were detected for two benthic species: Thymallus thymallus and Squalius cephalus whereas the lowest concentrations were obtained for the pelagic specie Salmo trutta marmoratus. The trend obtained for the total PBDEs, calculated using the physico-chemical properties of BDE-47, follows the one of BDE-47. For human exposure, different BDE-47 and total PBDEs concentration trends between children, adolescent, adults and elderly were observed, probably correlated with the human intake of fish products in the daily diet and the ability to metabolize these contaminants. In detail, for the adolescents, adults and elderly a continuous accumulation of the target contaminants during the simulation's years was observed, whereas for children a plateau at the end of the simulation period was perceived.

Occurrence of halogenated and organophosphate flame retardants in sediment and fish samples from three European river basins.

Classic (polybromodiphenyl ethers, PBDEs) and emerging halogenated flame retardants (HFRs) such as decabromodiphenyl ethane (DBDPE) and halogenated norbornenes, as well as organophosphate flame retardants (OPFRs) were analysed in 52 sediments and 27 fish samples from three European river basins, namely the Evrotas (Greece), the Adige (Italy) and the Sava (Slovenia, Croatia, Bosnia and Herzegovina and Serbia). This is the first time that FR levels have been reported in these three European river basins. The highest contamination was found in the Adige and Sava rivers, whereas lower values were obtained for the Evrotas. The levels in sediment samples ranged between 0.25 and 34.0ng/g dw, and between 0.31 and 549ng/g dw, for HFRs and OPFRs respectively. As regards levels in fish, concentrations ranged between 9.32 and 461ng/g lw and between 14.4 and 650ng/g lw, for HFRs and OPFRs, respectively. Thus, whereas OPFR values were higher in sediments, similar concentrations (in the Evrotas) and even lower concentrations than HFRs (Sava) were found for OPFRs in the fish samples, indicating the lower bioaccumulation potential of OPFRs. Biota to sediment accumulation factors (BSAFs) were calculated and higher values were obtained for HFRs compared to those assessed for OPFRs.

Analysis of organophosphorus flame retardants in environmental and biotic matrices using on-line turbulent flow chromatography-liquid chromatography-tandem mass spectrometry.

A fast on-line analytical method based on turbulent flow chromatography (TFC) in combination with tandem mass spectrometry (MS-MS) has been applied for the analysis of fourteen organophosphorus flame retardants (OPFRs) in sediment and fish samples. Applying this technique, time-consuming sample preparation steps were eliminated. The extraction was performed by ultrasound liquid extraction for biota and by pressurized liquid extraction for sediments. After extraction, environmental and biotic extracts were directly injected to the chromatographic system and analytes were concentrated into the cleanup loading column. Thereafter, analytes were transferred into the analytical column for subsequent detection by MS-MS. Analytical parameters showed acceptable recoveries (between 47 and 112% for sediment, and between 47 and 98% for fish) with very low relative standard deviations (always below 8.8% for sediment, and below 16% for fish). Moreover, mLODs and mLOQs are similar or even lower than those reported in other works using off-line methodologies. mLODs ranged between 0.02 and 1.25ng/g dry weight (dw) and between 0.19 and 19.3ng/g lipid weight (lw) for sediments and fish samples, respectively. The applicability of the developed methodology was demonstrated by the analysis of real samples, corresponding to river sediments as well as river and marine fish samples. OPFRs were detected in all samples, with values up to 549ng/g dw, 15.8ng/g lw and 646ng/g lw for sediment, marine fish and river fish, respectively.

Human exposure to endocrine disrupting compounds: Their role in reproductive systems, metabolic syndrome and breast cancer. A review.

Endocrine disrupting chemicals (EDCs) are released into the environment from different sources. They are mainly used in packaging industries, pesticides and food constituents. Clinical evidence, experimental models, and epidemiological studies suggest that EDCs have major risks for humans by targeting different organs and systems in the body (e.g. reproductive system, breast tissue, adipose tissue, pancreas, etc.). Due to the ubiquity of human exposure to these compounds the aim of this review is to describe the most recent data on the effects induced by phthalates, bisphenol A and parabens in a critical window of exposure: in utero, during pregnancy, infants, and children. The interactions and mechanisms of toxicity of EDCs in relation to human general health problems, especially those broadening the term of endocrine disruption to 'metabolic disruption', should be deeply investigated. These include endocrine disturbances, with particular reference to reproductive problems and breast, testicular and ovarian cancers, and metabolic diseases such as obesity or diabetes.