Seasonal variation of pharmaceutically active compounds in surface (Tagus River) and tap water (Central Spain)

Numerous studies have shown the presence of pharmaceutically active compounds (PhACs) in different environmental compartments, for example, in surface water or wastewater ranging from nanograms per litre to micrograms per litre. Likewise, some recent studies have pointed to seasonal variability, thus indicating that PhAcs concentrations in the aquatic environment may depend on the time of year. This work intended to find out (1) whether Tagus fluvial and drinking water were polluted with different groups of PhACs and (2) if their concentrations differed between winter and summer seasons. From the 58 substances analysed, 41 were found belonging to the main therapeutic groups. Statistical differences were seen for antibacterials, antidepressants, anxiolytics, antiepileptics, and cardiovascular drugs, with higher concentrations being detected in winter than in summer. These results might indicate that the PhACs analysed in this study undergo lower environmental degradation in winter than in summer. In order to confirm these initial results, a continuous monitoring should be performed especially on those PhACs that either because of an elevated consumption or an intrinsic chemical persistence are poorly degraded during winter months due to low temperatures and solar irradiation. It is especially important to identify which of these specific PhACs are in order to recommend their substitution by equally effective and safe substances but also environmentally friendly.     

Pilot monitoring study of ibuprofen in surface waters of north of Portugal

Ibuprofen is amongst the most worldwide consumed pharmaceuticals. The present work presents the first data in the occurrence of ibuprofen in Portuguese surface waters, focusing in the north area of the country, which is one of the most densely populated areas of Portugal. Analysis of ibuprofen is based on pre-concentration of the analyte with solid phase extraction and subsequent determination with liquid chromatography coupled to fluorescence detection. A total of 42 water samples, including surface waters, landfill leachates, Wastewater Treatment Plant (WWTP), and hospital effluents, were analyzed in order to evaluate the occurrence of ibuprofen in the north of Portugal. In general, the highest concentrations were found in the river mouths and in the estuarine zone. The maximum concentrations found were 48,720 ng?L^?1 in the landfill leachate, 3,868 ng?L^?1 in hospital effluent, 616 ng?L^?1 in WWTP effluent, and 723 ng?L^?1 in surface waters (Lima river). Environmental risk assessment was evaluated and at the measured concentrations only landfill leachates reveal potential ecotoxicological risk for aquatic organisms. Owing to a high consumption rate of ibuprofen among Portuguese population, as prescribed and non-prescribed medicine, the importance of hospitals, WWTPs, and landfills as sources of entrance of pharmaceuticals in the environment was pointed out. Landfill leachates showed the highest contribution for ibuprofen mass loading into surface waters. On the basis of our findings, more studies are needed as an attempt to assess more vulnerable areas.     

Bioaccumulation and effects of perfluorinated compounds (PFCs) in zebra mussels (Dreissena polymorpha)

Perfluorinated chemicals (PFCs) have been used for many years in numerous industrial products and are known to accumulate in organisms. A recent survey showed that tissue levels of PFCs in aquatic organisms varied among compounds and species being undetected in freshwater zebra mussels Dreissena polymorpha. Here we studied the bioaccumulation kinetics and effects of two major PFCs, perfluorooctane sulfonic acid compound (PFOS) and perfluorooctanoic acid (PFOA), in multixenobiotic transporter activity (MXR) and filtration and oxygen consumption rates in zebra mussel exposed to a range of concentrations of a PCF mixture (1–1,000 μg/L) during 10 days. Results indicate a low potential of the studied PFCs to bioaccumulate in zebra mussel tissues. PFCs altered mussel MXR transporter activity being inhibited at day 1 but not at day 10. Bioaccumulation kinetics of PFCs were inversely related with MXR transporter activity above 9 ng/g wet weight and unrelated at tissue concentration lower than 2 ng/g wet weight suggesting that at high tissue concentrations, these type of compounds may be effluxed out by MXR transporters and as a result have a low potential to be bioaccumulated in zebra mussels. Oxygen consumption rates but not filtering rates were increased in all exposure levels and periods indicating that at environmental relevant concentrations of 1 μg/L, the studied PFCs enhanced oxidative metabolism of mussels. Overall, the results obtained in this study confirm previous findings in the field indicating that an important fraction of PFC accumulated in mussel tissues is eliminated actively by MXR transporters or other processes that are metabolically costly.     

Adverse birth outcomes in the vicinity of industrial installations in Spain 2004–2008

Industrial activity is one of the main sources of ambient pollution in developed countries. However, research analyzing its effect on birth outcomes is inconclusive. We analyzed the association between proximity of mother’s municipality of residence to industries from 24 different activity groups and risk of very (VPTB) and moderate (MPTB) preterm birth, very (VLBW) and moderate (MLBW) low birth weight, and small for gestational age (SGA) in Spain, 2004–2008. An ecological study was defined, and a “near vs. far” analysis (3.5 km threshold) was carried out using Hierarchical Bayesian models implemented via Integrated Nested Laplace Approximation. VPTB risk was higher for mothers living near pharmaceutical companies. Proximity to galvanization and hazardous waste management industries increased the risk of MPTB. Risk of VLBW was higher for mothers residing near pharmaceutical and non-hazardous or animal waste management industries. For MLBW many associations were found, being notable the proximity to mining, biocides and animal waste management plants. The strongest association for SGA was found with proximity to management animal waste plants. These results highlight the importance of further research on the relationship between proximity to industrial sites and the occurrence of adverse birth outcomes especially for the case of pharmaceutical and animal waste management activities.     

Accumulation of arsenic, lead, copper, and zinc, and synthesis of phytochelatins by indigenous plants of a mining impacted area

Several native plants, able to grow in an unconfined mining impacted area that is now in close vicinity with urban areas, were evaluated for their ability to accumulate heavy metals. The main soil contaminants were As, Pb, Cu, and Zn. Sampling of the rhizospheric metal polluted soil showed that Euphorbia prostrata Aiton, Parthenium incanum Kunth, and Zinnia acerosa (DC.) A. Gray were able to grow in the presence of high amounts of mixtures of these elements. The plants accumulated the metals in the above ground parts and increased the synthesis of thiol molecules. E. prostrata showed the highest capacity for accumulation of the mixture of elements (588 μg g DW^?1). Analysis of the thiol-molecules profile showed that these plants synthesized high amounts of long-chain phytochelatins, accompanied by low amounts of monothiol molecules, which may be related to their higher resistance to As and heavy metals. The three plants showed translocation factors from roots to leaves >1 for As, Pb, Cu, and Zn. Thus, by periodically removing aerial parts, these plants could be useful for the phytoremediation of semi-arid and arid mining impacted areas, in which metal hyper-accumulator plants are not able to grow.     

Comparative analysis of selected biomarkers and pesticide sensitivity in juveniles of Solea solea and Solea senegalensis

The common sole, Solea solea (Linneus, 1758), and the Senegalese sole, Solea senegalensis (Kaup, 1858), are two important commercial species that coexist in the NW Mediterranean. In order to assess the species' ability to respond to chemical insults, a comparison of activities on enzymes involved in xenobiotic metabolism was carried out. Juveniles of both species were sampled in winter 2011 from the Ebro Delta region, and activities of selected enzymes such as acetylcholinesterase (AChE), carboxylesterase (CbE), ethoxyresorufin O-deethylase (EROD) and glutathione S-transferase (GST) were determined in several tissues. Lipid peroxidation (LP) levels in plasma were measured as a sign of oxidative stress. In vitro exposures to selected pesticides were contrasted, analysing AChE and CbE activities in several tissue homogenates. Overall, enzymatic activities were higher in S. solea except for gill GST and CbE and kidney GST, while plasmatic LP levels were similar. In vitro contrasts revealed lower IC50 values for CbE activities in S. solea, suggesting a greater buffer capacity of this enzyme to potentially reduce pesticide toxicity over AChE.     

Trace metal and metalloid levels in surface water of Marcal River before and after the Ajka red mud spill, Hungary

The aim of this study was to compare and assess the dissolved concentrations of trace elements (As, Zn, Hg, Cd, Cr, Ni, Pb and Cu) in surface water of Marcal River before and after the red mud spill that occurred in Ajka, western Hungary, in October 2010. The caustic sludge flooded the surrounding settlements and polluted the nearby Torna Creek, which flows through the Marcal and Raba rivers into the Danube. A total of 92 surface water samples were collected from the Marcal River in the period of 2007–2012 and analysed for dissolved trace metal(loid)s by atomic absorption spectroscopy method. After the spill, the water management authority initially focused on acid dosing of surface waters to lower pH and was effective in lowering both pH and metal(loid) concentrations. Among the dissolved trace metal(loid)s, arsenic and nickel levels were moderately higher in the Marcal River 2 years since the spill compared to that observed in the pre-disaster period. The concentrations of dissolved trace metal(loid)s did not exceed the European water quality standards and the US Environmental Protection Agency aquatic life criteria values (excluding one sample for cadmium).     

Partitioning, sources and variability of regional and local oxidant (OX = O3 + NO2) in a coastal rural area in the southwest of Iberian Peninsula

The purpose of this work is to investigate the behaviour and variability of oxidant levels (OX?=?NO₂?+?O₃), for the first time, in a rural coastal area in the southwest of the Iberian Peninsula, affected by several air masses types. Detailed database (built-up over the years 2008 to 2011, and containing around 500,000 data) from the Atmospheric Sounding Station “El Arenosillo” was used. The observed daily cycles of NO _x and OX were influenced by air masses coming from industrial and urban area. It can be seen that the concentration of OX is made up of a NO _x -independent ‘regional’ contribution (i.e. the O₃ background), and a linearly NO _x -dependent ‘local’ contribution from primary emissions, such as traffic. The local emission is very low in this area. Also, the regional contribution is similar to unpolluted sites and presents seasonal variation, being higher in May. However, our measurements showed that the proportion of OX in the form of NO₂ increases with the increase in NO _x concentration during the day. The higher proportion of NO₂ observed at night must be due to the conversion of NO to NO₂ by the NO?+?O₃ reaction. With regards to the source of the local NO _x -dependent contribution, it may be attributed to industrial emission, or the termolecular reaction 2NO?+?O₂?=?2NO₂, at high-NO _x levels and stagnant air during several days. Finally, we estimated the photolysis rate of NO₂, J _NO2, an important key atmospheric reaction coupled with ozone. We also present surface plots of annual variation of the daily mean NO _x and OX levels, which indicate that oxidants come from transport processes instead of local emissions associated as local photochemistry.     

A study on As, Cu, Pb and Zn (bio)availability in an abandoned mine area (São Domingos, Portugal) using chemical and ecotoxicological tools

The aim of this study was to relate the results obtained by chemical methods, used to assess environmental (bio)availability, with the ecotoxic response and bioaccumulation of trace elements (TE) by the earthworm Eisenia fetida exposed to field-contaminated, metal-polluted soils from a sulphide mine. The extracting solution 0.5 M NH₄CH₃COO, 0.5 M CH₃COOH and 0.02 M EDTA (pH 4.7), was able to predict environmental bioavailability of TE to E. fetida. However, the toxicological bioavailability could not be predicted from the results of the chemical extractions or from the bioaccumulation results: E. fetida reproduction was higher in soils where environmental bioavailability of TE and bioaccumulation values were also higher. In this study, the toxic response of the organism seemed to be more influenced by the overall nutritional status of the soil (e.g. pH, organic matter, plant nutrient availability and cation exchange capacity) than by its TE contamination. In the case of anthropogenic multi-contaminated sites, the different soil characteristics exert an important and confounding influence in the toxic response and the relationship between different bioavailable fractions cannot be easily established, emphasising the need to combine results from chemical methods with those from bioassays when evaluating the bioavailability of TE in these soils.     

Four years of continuous monitoring of the Meirama end-pit lake and its impact in the definition of future uses

Following the technical closure of the brown lignite Meirama mine (NW Spain) in April 2008, the reclamation of the mined area is being accomplished with the controlled flooding of its large pit. During the first 7 months of flooding, the sequential arrest of the ground water dewatering system led to the growth of an acidic water body of about 2 hm³. Since October 2008, the surface waters from some local streams have been diverted towards the pit so that these have become the major water input in the flooding process. Surface water has promoted a major change in the chemical composition of the lake water so that, at present, its surface has a circum neutral pH, net alkalinity, and low conductivity. At present, the lake has slightly more than one half of its final volume, and it is expected the overflow in 3 to 3.5 years. The lake is meromictic, with a sharp chemocline separating the acidic monimolimnion (pH?≈?3.2, acidity?≈?150 mg CaCO₃/L, κ ₂₅?≈?2.4 mS/cm) from the main water body (pH?≈?6.5, alkalinity?≈?15 mg CaCO₃/L, κ ₂₅?≈?0.3 mS/cm). Oxygen is being depleted at the bottom of the lake so that the monimolimnion became anoxic in January 2011. Above the chemocline, the composition of the lake is similar, but not identical, to that of the flooding stream waters. Close to the surface, some constituents (pH, metals) show strong seasonal variations in coincidence with the phytoplankton growing periods. Those parameters whose limits are legally prescribed comply with the corresponding water quality standards, and they are also consistent with the forecasting results obtained in early modeling. At present, a project considering the construction of an uptake tunnel to exploit the lake is being developed for the emergency water supply of the metropolitan area of A Coruña.