Irene de Bustamante

Emerging organic contaminants in surface water and groundwater: a first overview of the situation in Italy.

This paper provides the first review of the occurrence of 161 emerging organic compounds (EOCs) in Italian surface water and groundwater. The reported EOCs belong to the groups of industrials, pharmaceuticals, estrogens and illicit drugs. Occurrence of 137 pesticides was also reported. The reviewed research works have been published between 1997 and 2013. The majority of the studies have been carried out in Northern Italy (n. 30) and to a lower extent in Central Italy (n. 13). Only a limited number of research studies report EOC concentrations in water resources of Southern Italy. The EOCs that have been more frequently studied are in the following descending order, pesticides (16), pharmaceuticals (15), industrials (13), estrogens (7) and illicit drugs (2). Research activities investigating the EOC occurrence in surface water are more numerous than those in groundwater. This is consistent with the higher complexity involved in groundwater sampling and EOC detection. Among the reported EOCs, industrials and pesticides are those occurring in both surface water and groundwater with the highest concentrations (up to 15 × 10(6) and 4.78 × 0(5)ng L(-1), respectively). Concentrations of pharmaceuticals in surface water reach a maximum of 3.59 × 10(3)ng L(-1), whereas only the antimicrobial agent josamycin has been encountered in groundwater with a concentration higher than 100 ng L(-1). Both estrogens and illicit drugs appeared in surface water with concentrations lower than 50 ng L(-1). Groundwater concentrations for estrogens were measured to be below the detection limits, whereas illicit drugs have so far not been studied in groundwater. The present review reveals the serious contamination status of Italian surface water and groundwater especially by pesticides, industrials and to a lower extent by pharmaceuticals and the necessity to foster the research on EOC occurrence in Italian water resources, in particular in Southern Italy where a limited number of investigations currently exist.

Sorption/desorption of non-hydrophobic and ionisable pharmaceutical and personal care products from reclaimed water onto/from a natural sediment

In the present work, the sorption of pharmaceutical and personal care products (PPCPs) (acetaminophen, atenolol, carbamazepine, caffeine, naproxen and sulphamethoxazole) onto the natural organic matter (NOM) and the inorganic surfaces of a natural sandy loam sediment was quantified separately. The quantification was based on the PPCP charge, their degree of ionisation, their octanol-water partitioning coefficient (KOW) and the sediment organic carbon fraction (ƒOC). PPCP desorption from the sediment was examined under conditions of infiltrating water containing a high concentration of inorganic ions (mimicking infiltrating reclaimed water), and a low concentration (and smaller diversity) of inorganic ions (mimicking rainwater infiltration). Batch tests were performed using a sediment/water ratio of 1:4 and a PPCP initial concentration ranging from 1 to 100 μg L(-1). The results showed the type and degree of PPCP ionisation to strongly influence the sorption of these compounds onto the sediment. The sorption of cationic species onto the sediment was higher than that of anionic species and mostly reversible; the sorption of neutral species was negligible. The anionic species sorbed less onto the sediment, but also desorbed less easily. More than 70% of the total sorption was due to interaction with mineral surfaces. This holds especially true for cationic species (atenolol and caffeine) which sorption was enhanced by the negative surface charge of the sediment. The presence of inorganic ions had no impact on the desorption of the PPCPs from the sediment. According to the calculated percentages of removal, the mobility followed the order: carbamazepine>acetaminophen>naproxen>atenolol>sulfamethoxazole>caffeine.

Pilot survey of chemical contaminants from industrial and human activities in river waters of Spain

Over the past decades there has been significant progress in the treatment of sewage and industrial wastewaters in order to minimise discharges of urban effluents with lots of contaminants. Nowadays, the status of contamination of bodies of water continues to be a key task for further environmental management actions. This paper reports the presence of 88 contaminants belonging to several chemical groups (pharmaceuticals, personal care products, disinfectants and pesticides), in river waters of the region of Madrid, one of the more densely populated areas of Spain. Three different monitoring campaigns were performed over a period of seven months. For quality assessment of river water analyses, an analytical protocol was developed employing a solid-phase extraction (SPE) method, followed by two methods based on liquid chromatography-mass spectrometry (two LC-MS systems with ion trap and time-of-flight analysers) in order to carried out the unequivocal detection and quantification of the target contaminants. The method detection limits achieved were in range 0.1–60 ng L−1. Recovery values were higher to 70% for the most of the compounds and only two analytes (amoxicillin and tamoxifen) were not recovered with the SPE method applied. The results obtained during the monitoring campaign were classified in turn into two categories: contaminants in general called ‘emergents’, and priority substances or candidate pollutants from domestic and industrial activities. This classification allows us to evaluate the impact of both contributions, typically domestic and industrial, on the river waters. At the same time it enables us to get a first idea about the effectiveness of the urban wastewater treatment plants (WWTPs) that release the effluents to those rivers in eliminating or removing contaminants. The concentration ranges detected were between 110 and 9942 ng L−1 for emerging contaminants and 1 and 652 ng L−1 for priority or candidate pollutants.

Response of microcrustacean communities from the surface—groundwater interface to water contamination in urban river system of the Jarama basin (central Spain)

In order to evaluate the water quality at the surface/groundwater interface (hyporheic zone), the pattern of microcrustacean assemblages in response to environmental stress caused by urban industrial contamination was studied in the Jarama River basin (central Spain) during high water discharges (March and April 2011). The clustering of biological variables and the concentration of urban contaminants in hyporheic waters showed that pristine hyporheic waters have moderate species diversity (two to seven species) and dominance of k strategist stygobites, whereas excessively contaminated sites are devoid by crustaceans. An intermediate level of disturbance in hyporheic waters is associated with a peak of species taxonomic diversity (four to nine species) and proliferation of r strategist more tolerant species. Typical species found in hyporheic zone, e.g., Paracyclops imminutus (Copepoda, Cyclopoida), Cryptocandona vavrai (Ostracoda) and Herpetocypris chevreuxi (Ostracoda), were good indicators of high concentrations of Cr, Mn, Ni, Cd, Pb and VOCs; whereas the stygobites do not show any significant correlation. The effectiveness of hyporheic crustaceans as efficient bioindicators for assessing the current ecological status of river ecosystems is emphasised.

Environmental risk of combined emerging pollutants in terrestrial environments: chlorophyll a fluorescence analysis

The risk assessment in terrestrial environments has been scarcely studied for mixtures of organic contaminants. To estimate toxicity due to these compounds, an ecotoxicological test may be done with the appropriate organism and biomarker. Photosynthesis is principally performed at photosystem II, and its efficiency is affected by any environmental stress. Consequently, the measure of this efficiency may be a good indicator of toxicity if different parameters are employed, e.g., the quantum efficiency of photosystem II and the photochemical quenching coefficient. We did a series of assays to determine the toxicity of two organic contaminants, ibuprofen and perfluorooctanoic acid, using a higher plant (Sorghum bicolor). The results showed more toxicity for the perfluorinated compound and greater sensibility for the quantum efficiency of photosystem II. Regarding the binary combination, three methods were applied to calculate EC50: combination index, concentration addition, and independent action. Synergistic behavior is the principal toxicological profile for this mix. Therefore, the combination index, which considers interactions among chemicals, gave the best estimation to determine risk indices. We conclude that the inhibition of photosynthesis efficiency can be a useful tool to determine the toxicity of the mixtures of organic pollutants and to estimate ecological risks in terrestrial environments.

Clinoptilolite and palygorskite as sorbents of neutral emerging organic contaminants in treated wastewater: Sorption-desorption studies

Water reuse for aquifer recharge could be an important route for the introduction of emerging organic contaminants (EOCs) into the environment. The installation of a Horizontal Permeable Reactive Barrier (H-PRB) could constitute a tertiary treatment process to remove EOCs from treated domestic wastewater prior to recharge activities. The sorption-desorption behaviour of six neutral EOCs present in treated domestic wastewater (acetaminophen, caffeine, carbamazepine, cotinine, 4-acetamidoantipyrine (4-AAA) and 4-formylaminoantipyrine (4-FAA)) has been evaluated. Clinoptilolite and palygorskite have been studied as sorbents to be installed in the H-PRB. Batch tests were carried out using an EOC initial concentration ranging from 5 to 100xa0μgxa0L-1. Apart from acetaminophen and caffeine, both materials showed a limited sorption capacity of neutral EOCs (Kdxa0=xa00.63-5.42xa0Lxa0kg-1). In general, the experimental results show that EOCs exhibit a higher sorption affinity for clinoptilolite than for palygorskite. With the exception of carbamazepine, the sorption of the compounds occurs mainly by interactions with mineral surfaces as indicated by the comparison of the partition coefficients into organic matter and into mineral surfaces. According to the molecular geometry of the compounds and the sorption sequences observed, it appears that the dimensions of the organic molecules play a key role in the sorption process. All the studied EOCs exhibit irreversible sorption and sorption-desorption hysteresis.

Investigating natural attenuation of pharmaceuticals through unsaturated column tests

The growing consumption of pharmaceuticals together with their incomplete removal in wastewater treatment plants (WWTPs) implies the occurrence of these compounds in natural water resources. To investigate the natural attenuation of selected pharmaceuticals (caffeine, acetaminophen, sulfamethoxazole, naproxen and carbamazepine) during vadose zone infiltration, unsaturated column (L 26.67xa0cm, Ø 7.62xa0cm) experiments, filled with a sandy-loamy soil, were performed using two input concentrations (100 and 1000xa0μgxa0L-1). The software Hydrus 1D was used to simulate experimental data. Caffeine and acetaminophen were never detected at the column outlet indicating a low environmental concern. On the other hand, attenuation of the detected pharmaceuticals could be reproduced by a combination of retardation and removal approaches. Carbamazepine is among the selected contaminants the most persistent. A dependence of removal rates on input concentrations was detected for sulfamethoxazole (μw from 2.78xa0d-1 to 1.16xa0d-1) and naproxen (μw from 1.16xa0d-1 to 0.63xa0d-1) attributed mainly to decreased metabolism of microorganisms when a higher input concentration is applied. Two transformation products (TPs) (N4-Acetylsulfamethoxazole and epoxycarbamazepine) derived from sulfamethoxazole and carbamazepine transformation, respectively, were detected during the experiment with the highest input concentration.

Soil amendment using poplar woodchips to enhance the treatment of wastewater-originated nutrients

Vegetation filters, a nature based wastewater regeneration technology, have been reported as a feasible solution for small municipalities and scattered populations with limited access to sewage networks. However even when such a treatment is properly planned, the leaching of contaminants through the unsaturated zone may occur. The amendment of soil with a readily-labile source of carbon is supposed to ameliorate the removal of contaminants by stimulating microbial activity and enhancing sorption processes. In this study, lab-scale leaching column experiments were carried out to explore if the addition of woodchips to the soil could be a feasible strategy to be integrated in a vegetation filter. Two different types of arrangement of soil and woodchips layers were tested. The soil was collected from an operating vegetation filter treating wastewater of an office building characterised by a high nutrient load. Daily pulse of synthetic wastewater were applied into the columns and effluent samples were collected and analyzed for major ions, total nitrogen (NT), total phosphorous (PT) and chemical oxygen demand (COD). By the end of the experiment, NT, NO3-N and PT soil contents were also measured. Results indicate that amendments with woodchips enhance the elimination of wastewater-originated contaminants. NT removal in the columns with woodchips reaches a value of 99.4%. The main processes responsible for this elimination are NH4-N sorption and nitrification/denitrification. This latter fostered by the reduced redox conditions due to the enhanced microbial activity. High removal of PT (99%) is achieved independently of the woodchips presence due to retention and/or precipitation phenomena. The COD removal efficiency is not affected by the presence of the woodchips. The leaching of organic carbon occurs only during the experimental start-up period.

Advances in Geoconservation in Cuba: Assessment of the Guaniguanico Range and Guanahacabibes Plain (Pinar del Río)

The application of geoconservation concepts in Cuba is very recent, despite the wide body of knowledge accumulated through the study of Cuban geology. Recently, the establishment and consolidation of a National System of Protected Areas that stresses interaction with scientific institutions has greatly helped initiate geoconservation in Cuba. In this study, we review the geoconservation criteria used in the management of protected areas, their precedents and administrative framework. We used the methodology proposed by Bruschi (2007) for the characterisation, assessment and management of geodiversity resources, and modified its criteria for use in selecting geosites. We have applied the methodology to assess the Guaniguanico Range and the Guanahacabibes Plain where 162 geosites were defined. Of the 162 geosites assessed, 107 were at Viñales National Park, so it could be a potential area to become the first Caribbean Geopark.