Victoria Osorio

Solar photocatalytic treatment of trimethoprim in four environmental matrices at a pilot scale: Transformation products and ecotoxicity evaluation

The pilot-scale solar degradation of trimethoprim (TMP) in different water matrices (demineralized water: DW, simulated natural freshwater: SW; simulated wastewater: SWW; and real effluent: RE) was investigated in this study. DOC removal was lower in the case of SW compared to DW, which can be attributed to the presence of inorganic anions which may act as scavengers of the HO·. Furthermore, the presence of organic carbon and higher salt content in SWW and RE led to lower mineralization per dose of hydrogen peroxide compared to DW and SW. Toxicity assays in SWW and RE were also performed indicating that toxicity is attributed to the compounds present in RE and their by-products formed during solar Fenton treatment and not to the intermediates formed by the oxidation of TMP. A large number of compounds generated by the photocatalytic transformation of TMP were identified by UPLC-QToF/MS. The degradation pathway revealed differences among the four matrices; however hydroxylation, demethylation and cleavage reactions were observed in all matrices. To the best of our knowledge this is the first time that TMP degradation products have been identified by adopting a solar Fenton process at a pilot-scale set-up, using four different aqueous matrices.

Photofate of Oseltamivir (Tamiflu) and Oseltamivir Carboxylate under Natural and Simulated Solar Irradiation: Kinetics, Identification of the Transformation Products, and Environmental Occurrence

In this work the photodegradation pathways and rates of oseltamivir ester (OE) and oseltamivir carboxylate (OC) were studied under artificial and natural solar irradiation with the goal of assessing the potential of photolysis as a removal mechanism in aquatic environments. The structures of the photoproducts of OE, elucidated by ultra performance liquid chromatography-quadrupole-time-of-flight-mass spectrometry (UPLC-QToF-MS), were proposed to originate from hydration of the cyclohexene ring (TP330), ester hydrolysis (TP284), a combination thereof (TP302), intramolecular cyclization involving the ester (TP312), and cleavage of the ethylpropoxy side chain (TP226). The only photoproduct detected in case of OC was postulated to correspond to the hydration of the α,β-unsaturated acid (TP302). Under simulated solar irradiation the degradation rate of OC was approximately 10 times slower than that of OE, with half-lives ranging from 48 h in ultrapure water to 12 h in surface water from Sant Joan Despi, Llobregat river. The photodegradation under natural solar irradiation during the season of pandemic Influenza peak incidence was about 150 days for OC and 15 days for OE. In general, the photoproducts proved to be more resistant toward further photodegradation than the parent antivirals. In a monitoring survey of surface waters from the Ebro river (NE Spain), OC and OE were detected along with the photoproducts TP330 and 312.

Effects of pesticides and pharmaceuticals on biofilms in a highly impacted river

We investigated the effects of pharmaceuticals and pesticides detected in a Mediterranean river, on fluvial biofilms by translocation experiments performed under controlled conditions. Water was sampled from three sites along a pollution gradient. Biofilms grown in mesocosms containing relatively clean water were translocated to heavily polluted water. Several biofilm descriptors were measured before and after translocations. Fifty-seven pharmaceuticals and sixteen pesticides compounds were detected in river waters. The translocation from less to more polluted site was the most effective. Autotrophic biomass and peptidase increased while phosphatase and photosynthetic efficiency decreased. Multivariate analysis revealed that analgesics and anti-inflammatories significantly affected biofilm responses. Ibuprofen and paracetamol were associated with negative effects on photosynthesis, and with the decrease of the green algae/cyanobacteria ratio, while diclofenac was associated with phosphatase activity. The effects of these emerging compounds on biofilms structure and function may cause important alterations in river ecosystem functioning.

Concentration and risk of pharmaceuticals in freshwater systems are related to the population density and the livestock units in Iberian Rivers

Considerable amounts of pharmaceuticals are used in human and veterinary medicine, which are not efficiently removed during wastewater and slurries treatment and subsequently entering continuously into freshwater systems. The intrinsic biological activity of these non-regulated pollutants turns their presence in the aquatic environment into an ecological matter of concern. We present the first quantitative study relating the presence of pharmaceuticals and their predicted ecotoxicological effects with human population and livestock units. Four representative Iberian River basins (Spain) were studied: Llobregat, Ebro, Júcar and Guadalquivir. The levels of pharmaceuticals were determined in surface water and sediment samples collected from 77 locations along their stream networks. Predicted total toxic units to algae, Daphnia and fish were estimated for pharmaceuticals detected in surface waters. The use of chemometrics enabled the study of pharmaceuticals for: their spatial distribution along the rivers in two consecutive years; their potential ecotoxicological risk to aquatic organisms; and the relationships among their occurrence and predicted ecotoxicity with human population and animal farming pressure. The Llobregat and the Ebro River basins were characterized as the most polluted and at highest ecotoxicological risk, followed by Júcar and Guadalquivir. No significant acute risks of pharmaceuticals to aquatic organisms were observed. However potential chronic ecotoxicological effects on algae could be expected at two hot spots of pharmaceuticals pollution identified in the Llobregat and Ebro basins. Analgesics/antiinflammatories, antibiotics and diuretics were the most relevant therapeutic groups across the four river basins. Among them, hydrochlorothiazide and gemfibrozil, as well as azithromycin and ibuprofen were widely spread and concentrated pharmaceuticals in surface waters and sediments, respectively. Regarding their predicted ecotoxicity, sertraline, gemfibrozil and loratidine were identified as the more concerning compounds. Significantly positive relationships were found among levels of pharmaceuticals and toxic units and population density and livestock units in both surface water and sediment matrices.

Formation of diclofenac and sulfamethoxazole reversible transformation products in aquifer material under denitrifying conditions: batch experiments.

Soil-aquifer processes have proven to work as a natural treatment for the attenuation of numerous contaminants during artificial recharge of groundwater. Nowadays, significant scientific effort is being devoted to understanding the fate of pharmaceuticals in subsurface environments, and to verify if such semipersistent organic micropollutants could also be efficiently removed from water. In this context we carried out a series of batch experiments involving aquifer material, selected drugs (initial concentration of 1 μg/L and 1 mg/L), and denitrifying conditions. Diclofenac and sulfamethoxazole exhibited an unreported and peculiar behavior. Their concentrations consistently dropped in the middle of the tests but recovered toward the end, which suggest a complex effect of denitrifying conditions on aromatic amines. The transformation products Nitro-Diclofenac and 4-Nitro-Sulfamethoxazole were detected in the biotic experiments, while nitrite was present in the water. Their concentrations developed almost opposite to those of their respective parent compounds. We conjecture that this temporal and reversible effect of denitrifying conditions on the studied aromatic amines could have significant environmental implications, and could explain at least partially the wide range of removals in subsurface environments reported in literature for DCF and SMX, as well as some apparent discrepancies on SMX behavior.

Hydrological variation modulates pharmaceutical levels and biofilm responses in a Mediterranean river

The Llobregat is a Mediterranean river that is severely impacted by anthropogenic pressures. It is characterized by high flow variability which modulates its chemical and biological status. The present work evaluates the effects of flow changes on the concentration of pharmaceutically active compounds (PhACs) and their relationship to cellular parameters of river biofilms. To this end, at two selected sampling sites at the lower course of the Llobregat river, surface water samples were collected twice a week over two hydrologically different periods exhibiting low and high river flows. Higher levels of PhACs were detected at the downstream sampling site. Irrespective of the flow regime, analgesics, anti-inflammatories and lipid regulators were the most abundant substances at both sampling sites with total concentrations of up to 1,000 ng/L and 550 ng/L at the upstream and downstream sites, respectively. Antibiotics (fluoroquinolones) and psychiatric treatment drugs were also detected at high levels in the second campaign achieving concentrations of up to 500 ng/L. The principal component analysis (PCA) performed with the PhACs concentrations of the two campaigns revealed differences in the various therapeutic groups depending on sampling site and period. After a flash flood event during the second sampling period, dilution of PhACs occurred, but their average concentrations measured before the flood were restored within two weeks. For the majority of compounds, PhAC concentrations displayed an inverse relationship with river discharge The effects of water containing different concentrations of PhACs on biofilm communities were evaluated and related to flow regime variations. Translocation of biofilm communities from a less to a more polluted site of the river demonstrated an increase in bacteria mortality in the translocated biofilms. After the flood, extracellular peptidase activity and chlorophyll-a concentration were significantly reduced, and biofilm growth rate was significantly lower.

Investigating the formation and toxicity of nitrogen transformation products of diclofenac and sulfamethoxazole in wastewater treatment plants.

Diclofenac (DCF) and sulfamethoxazole (SMX) are highly consumed pharmaceuticals and concentrated in effluents from conventional wastewater treatment plants (WWTPs) since they are not completely eliminated. Under microbial mediated nitrification/denitrification processes occurring in nitrifying activated sludge DCF biotransformed into its nitroso and nitro derivatives (NO-DCF and NO2-DCF, respectively). SMX was biotransformed under denitrification conditions in water/sediment batch reactors into its nitro and desamino derivatives (NO2-SMX and Des-SMX, respectively). Four transformation products (TPs) from DCF and SMX were analized in wastewaters (WW) and receiving surface waters (SW). Nitrifying/denitrifying-derivatives of DCF and SMX were detected for the first time in WW and SW at one order of magnitude lower than their parent compounds. Relationships observed among levels of NO-DCF, NO2-DCF and nitrogen-species tentatively suggested that nitrification/denitrification processes are involved in nitration and nitrosation of DCF during biological WW treatment. Acute toxicity of analytes to Daphnia magna and Vibrio fischeri was assessed individually and in mixtures with other relevant micropollutants. Individual effects showed these compounds as not harmful and not toxic. However, synergism effects observed in mixtures evidenced that contribution of these compounds to overall toxicity of complex environmental samples, should not be dismissed.

Modelling the emerging pollutant diclofenac with the GREAT-ER model: application to the Llobregat River Basin.

The present research aims at giving an insight into the increasingly important issue of water pollution due to emerging contaminants. In particular, the source and fate of the non-steroidal anti-inflammatory drug diclofenac have been analyzed at catchment scale for the Llobregat River in Catalonia (Spain). In fact, water from the Llobregat River is used to supply a significant part of the Metropolitan Area of Barcelona. At the same time, 59 wastewater treatment plants discharge into this basin. GREAT-ER model has been implemented in this basin in order to reproduce a static balance for this pollutant for two field campaigns data set. The results highlighted the ability of GREAT-ER to simulate the diclofenac concentrations in the Llobregat Catchment; however, this study also pointed out the urgent need for longer time series of observed data and a better knowledge of wastewater plants outputs and their parameterization in order to obtain more reliable results.

Transcriptomic, biochemical and individual markers in transplanted Daphnia magna to characterize impacts in the field

Daphnia magna individuals were transplanted across 12 sites from three Spanish river basins (Llobregat, Ebro, Jucar) showing different sources of pollution. Gene transcription, feeding and biochemical responses in the field were assessed and compared with those obtained in re-constituted water treatments spiked with organic eluates obtained from water samples collected at the same locations and sampling periods. Up to 166 trace contaminants were detected in water and classified by their mode of action into 45 groups that included metals, pharmaceuticals, pesticides, illicit drugs, and other industrial compounds. Physicochemical water parameters differentiated the three river basins with Llobregat having the highest levels of conductivity, metals and pharmaceuticals, followed by Ebro, whereas the Jucar river had the greatest levels of illicit drugs. D. magna grazing rates and cholinesterase activity responded similarly than the diversity of riparian benthic communities. Transcription patterns of 13 different genes encoding for general stress, metabolism and energy processes, molting and xenobiotic transporters corroborate phenotypic responses differentiated sites within and across river basins. Principal Component Analysis and Partial Least Square Projections to Latent Structures regression analyses indicated that measured in situ responses of most genes and biomarkers and that of benthic macroinvertebrate diversity indexes were affected by distinct environmental factors. Conductivity, suspended solids and fungicides were negatively related with the diversity of macroinvertebrates cholinesterase, and feeding responses. Gene transcripts of heat shock protein and metallothionein were positively related with 11 classes of organic contaminants and 6 metals. Gene transcripts related with signaling paths of molting and reproduction, sugar, protein and xenobiotic metabolism responded similarly in field and lab exposures and were related with high residue concentrations of analgesics, diuretics, psychiatric drugs, β blockers, illicit drugs, trizoles, bisphenol A, caffeine and pesticides. These results indicate that application of omic technologies in the field is a promising subject in water management.

The Effect of PhACs on Biological Communities in Rivers: Field Studies

Abstract This chapter aims to review the current literature on field studies assessing the effects of pharmaceutically active compounds (PhACs) on fluvial biological communities. The importance of the use of these communities in the ecological risk assessment of PhACs in river ecosystems is tackled. The chapter reviews the literature about the potential effects of PhACs on the communities commonly belonging to the bottom and the top of river food chain (i.e., microbial and fish communities). In this framework, the Llobregat river is presented as a greatly PhAC-polluted case, where numerous field studies have been performed. Particularly, evidences of PhACs effects on biofilm, macroinvertebrate, and fish communities of the Llobregat, reported by diverse investigations, are reviewed in this chapter. The conclusions suggest that the continuous population growth and the subsequent increase of sewage waste discharge on the aquatic systems may be reflected in even more pronounced effects of PhACs on biological communities.