Assessing human-induced pressures on coastal areas with publicly available data

The assessment of human-induced pressures on the coastal area is essential to target management plans effectively, and moreover is required by the EU Water Framework Directive. A simple and cost-effective assessment of human-induced pressures on the coastal zone is applied using two methodologies: a qualitative visual assessment which uses satellite images; and a quantitative assessment based on governmental census data. These methods are applied to defined areas (23 areas) of four Italian regions: Liguria, Tuscany, Latium and Sardinia. The results show a high agreement (83%) between these two methods, in which only four of the 23 areas are classified differently. These differences may mainly be ascribed to the qualitative or quantitative properties of the methods, and to the different geographical units adopted. These characteristics however provide complementary information, which suggests that the application of both proposed methods confirms reliability and allows fine-tuning of the assessment. The pressure assessment proposed is simple, time and cost-effective, and repeatable over time and space. It therefore can be applied in different contexts to respond to legislative requirements or to target management plans and remedial actions effectively.     

Lichens as an integrating tool for monitoring PAH atmospheric deposition: A comparison with soil, air and pine needles

The aim of this study was to validate lichens as biomonitors of PAH atmospheric deposition; for that, an inter-comparison between the PAH profile and concentrations intercepted in lichens with those of air, soil and pine needles was performed. The study was conducted in a petro-industrial area and the results showed that PAH profiles in lichens were similar to those of the air and pine needles, but completely different from those of soils. Lichens accumulated higher PAH concentrations when compared to the other environmental compartments and its concentrations were significantly and linearly correlated with concentrations of PAHs in soil; we showed that a translation of the lichen PAHs concentrations into regulatory standards is possible, fulfilling one of the most important requirements of using lichens as biomonitors. With lichens we were then able to characterize the air PAHs profile of urban, petro-industrial and background areas.     

210Pb-dating of a lake sediment core from Lough Carra (Co. Mayo, western Ireland): use of paleolimnological data for chronology validation below the 210Pb dating horizon

The chronologies and sediment accumulation rates for a lake sediment sequence from Lough Carra (Co. Mayo, western Ireland) were established by applying the constant initial concentration (CIC) and constant rate of supply (CRS) hypotheses to the measured ²¹⁰Pb_excess profile. The resulting chronologies were validated using the artificial fallout radionuclides ¹³⁷Cs and ²⁴¹Am, which provide independent chronostratigraphic markers for the second half of the 20th century. The validity of extrapolating the derived CIC and CRS dates below the ²¹⁰Pb dating horizon using average sedimentation rates was investigated using supplementary paleolimnological information and historical data. Our data confirm that such an extrapolation is well justified at sites characterised by relatively stable sedimentation conditions.     

Performance of data acceptance criteria over 50 months from an automatic real-time environmental radiation surveillance network

The automatic real-time environmental radiation surveillance network of Catalonia (Spain) comprises two subnetworks; one with 9 aerosol monitors and the other with 8 Geiger monitors together with 2 water monitors located in the Ebre river. Since September 2006, several improvements were implemented in order to get better quality and quantity of data, allowing a more accurate data analysis. However, several causes (natural causes, equipment failure, artificial external causes and incidents in nuclear power plants) may produce radiological measured values mismatched with the own station background, whether spurious without significance or true radiological values. Thus, data analysis for a 50-month period was made and allowed to establish an easily implementable statistical criterion to find those values that require special attention. This criterion proved a very useful tool for creating a properly debugged database and to give a quick response to equipment failures or possible radiological incidents. This paper presents the results obtained from the criterion application, including the figures for the expected, raw and debugged data, percentages of missing data grouped by causes and radiological measurements from the networks. Finally, based on the discussed information, recommendations for the improvement of the network are identified to obtain better radiological information and analysis capabilities.     

Identification of new ozonation disinfection byproducts of 17β-estradiol and estrone in water

Estrogens are a class of micro-pollutants found in water at low concentrations (in the ng L⁻¹ range), but often sufficient to exert estrogenic effects due to their high estrogenic potency. Disinfection of waters containing estrogens through oxidative processes has been shown to lead to the formation of disinfection byproducts, which may also be estrogenic. The present work investigates the formation of disinfection byproducts of 17β-estradiol (E2) and estrone (E1) in the treatment of water with ozone. Experiments have been carried out at two different concentrations of the estrogens in ground water (100 ng L⁻¹ and 100 μg L⁻¹) and at varying ozone dosages (0-30 mg L⁻¹). Detection of the estrogens and their disinfection byproducts in the water samples has been performed by means of ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) with a triple quadrupole (QqQ) and a quadrupole-time of flight (QqTOF) instrument. Both E2 and E1 have been found to form two main byproducts, with molecular mass (MM) 288 and 278 in the case of E2, and 286 and 276 in the case of E1, following presumably the same reaction pathways. The E2 byproduct with MM 288 has been identified as 10epsilon-17beta-dihydroxy-1,4-estradieno-3-one (DEO), in agreement with previously published results. The molecular structures and the formation pathways of the other three newly identified byproducts have been suggested. These byproducts have been found to be formed at both high and low concentrations of the estrogens and to be persistent even after application of high ozone dosages.     

Phototransformation of ibuprofen and ketoprofen in aqueous solutions

The UV (254 nm) and UV/VUV (254/185 nm) photolysis of two anti-inflammatory drugs, ibuprofen and ketoprofen, have been studied in aqueous solutions as a possible process for the removal of non-biodegradable compounds.We have examined the effects of dissolved oxygen and initial target concentration. Upon irradiation at 254 nm, the decomposition rate of ketoprofen is almost forty times higher as it of ibuprofen whilst VUV irradiation only increased the ibuprofen decomposition rate. The presence of dissolved oxygen accelerated the photodegradation of ibuprofen, whereas no effect was observed on the degradation of ketoprofen. The maximum quantum yield for the phototransformation was 0.2. The rate of mineralization in both cases was ∼60%, even after 1 h of treatment and this suggests the formation of stable by-products which were identified using GC-MS and HPLC-MS, respectively.     

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).     

Responses of evergreen and deciduous Quercus species to enhanced ozone levels

Plants of one evergreen oak (Quercus ilex) and three deciduous oaks (Q. faginea, with small leaves; Q. pyrenaica and Q. robur, with large leaves) were exposed both to filtered air and to enhanced ozone levels in Open-Top Chambers. Q. faginea and Q. pyrenaica were studied for the first time. Based on visible injury, gas exchange, chlorophyll content and biomass responses, Q. pyrenaica was the most sensitive species, and Q. ilex was the most tolerant, followed by Q. faginea. Functional leaf traits of the species were related to differences in sensitivity, while accumulated ozone flux via stomata (POD_1.6) partly contributed to the observed differences. For risk assessment of Mediterranean vegetation, the diversity of responses detected in this study should be taken into account, applying appropriate critical levels.     

Diastereoisomer- and enantiomer-specific determination of hexabromocyclododecane in fish oil for food and feed

Fish oils are one of the main sources of ω-3 fatty acids. However, they can present elevated levels of some lipophilic pollutants, such as hexabromocyclododecanes (HBCDs). Since data about HBCDs in fish oil samples are very limited, in this study, 25 samples of fish oil for feed and food have been analyzed. Total HBCDs, as well as, α-, β- and γ-diastereoisomers have been determined. Total HBCDs ranged from 0.09 to 26.8 ng g⁻¹, with higher concentrations in fish oil for feed (average value of 9.69 ng g⁻¹) than those for food (1.14 ng g⁻¹). Concentrations of α-HBCD (average value of 4.12 ng g⁻¹ in feed samples and 0.48 ng g⁻¹ in food samples) and γ-HBCD (5.05 and 0.43 ng g⁻¹ respectively) were higher than that of β-HBCD (0.52 and 0.19 ng g⁻¹ respectively) in most of the samples. However, none of them was predominant in the samples. Concentrations of HBCDs were compared to concentrations of other pollutants and correlation between dioxin and dioxin-like PCBs levels and HBCDs levels were observed. Intake of HBCDs was calculated for fish oil with human consumption purposes and it ranged from 0.08 to 5.38 ng HBCDs d⁻¹, which could contribute significantly to HBCDs total intake. Enantiomeric fractions were also determined. No clear enrichment was observed for γ-HBCD, while (−)-α-HBCD enrichment was detected in some samples.     

Occurrence of multiclass UV filters in treated sewage sludge from wastewater treatment plants

Many substances related to human activities end up in wastewater and accumulate in sewage sludge. So far, there is only one extensive survey on the occurrence of UV filter residues in sewage sludge. However, more data are required to draw a reliable picture of the fate and effects of these compounds in the environment. This study attempts to fill this gap through the determination of selected UV filters and derivatives namely 4-methylbenzylidenecamphor, benzophenone-3, octocrylene, ethylhexylmethoxycinnamate, ethylhexyldimethyl PABA, 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone, and 4,4′-dihydroxybenzophenone in treated sewage sludge.The target compounds were extracted using pressurized liquid extraction and after this, determined by ultra high resolution liquid chromatography-tandem mass spectrometry. The determination was fast and sensitive, affording limits of detection lower than 19 ng g⁻¹ dry weight (dw) except for 2,4-dihydroxybenzophenone (60 ng g⁻¹ dw). Good recovery rates, especially given the high complexity of sludge matrix (between 70% and 102% except for 2,4-dihydroxybenzophenone (30%)) were achieved.The application of developed method allowed reporting for the first time the occurrence of two major degradation products of benzophenone-3 that have estrogenic activity in sewage sludge: 4,4′-dihydroxybenzophenone (in 5/15 WWTPs) and 4-hydroxybenzophenone (in 1/15 WWTPs). Results revealed the presence of UV filters in 15 wastewater treatment plants in Catalonia (Spain) at concentrations ranging from 0.04 to 9.17 μg g⁻¹ dw.