Rosa María Baena-Nogueras

Degradation kinetics of pharmaceuticals and personal care products in surface waters: photolysis vs biodegradation

Poor removal of many pharmaceuticals and personal care products (PPCPs) in sewage treatment leads to their discharge into the receiving waters, where they may cause negative effects. Their elimination from the water column depends of several processes, including photochemical and biological degradation. We have focused this research on comparing the degradation kinetics of a wide number (n=33) of frequently detected PPCPs considering different types of water, pH and solar irradiation. For those compounds that were susceptible of photodegradation, their rates (k) varied from 0.02 to 30.48h-1 at pH7, with the lowest values for antihypertensive and psychiatric drugs (t1/2>1000h). Modification of the pH turned into faster disappearance of most of the PPCPs (e.g., k=0.072 and 0.066h-1 for atenolol and carbamazepine at pH4, respectively). On the other hand, biodegradation was enhanced by marine bacteria in many cases, for example for mefenamic acid, caffeine and triclosan (k=0.019, 0.01 and 0.04h-1, respectively), and was faster for anionic surfactants. Comparing photodegradation and biodegradation processes, hydrochlorothiazide and diclofenac, both not biodegradable, were eliminated exclusively by irradiation (t1/2=0.15-0.43h and t1/2=0.14-0.17h, respectively). Salicylic acid and phenylbutazone were efficiently photo (t1/2<3h) and biodegraded (t1/2=116-158h), whereas some compounds such as ibuprofen, carbamazepine and atenolol had low degradation rates by any of the processes tested (t1/2=23-2310h), making then susceptible to persist in the aquatic media.

Determination and occurrence of secondary alkane sulfonates (SAS) in aquatic environments.

A new methodology has been developed for the determination of secondary alkane sulfonates (SAS), an anionic surfactant, in environmental matrices. Sediment and sludge samples were extracted using pressurized liquid extraction and sonication, whereas wastewater and surface water samples were processed using solid-phase extraction. Extraction recoveries were acceptable for both aqueous (78-120%) and solid samples (83-100%). Determination of SAS was carried out by high or ultra performance liquid chromatography - mass spectrometry using ion trap and time-of-flight detectors. The methodology was applied to samples from Guadalete River (SW Spain), where SAS concentrations below 1 μg L(-1) were measured in surface water, and from 72 to 9737 μg kg(-1) in sediments. Differential partitioning was observed for SAS homologues as those having a longer hydrocarbon chain which preferentially sorbed onto particulate matter. A preliminary environmental risk assessment also showed that SAS measured levels were not harmful to the aquatic community in the sampling area.

Occurrence, distribution and environmental risk of pharmaceutically active compounds (PhACs) in coastal and ocean waters from the Gulf of Cadiz (SW Spain)

In this study, we have evaluated the occurrence and distribution of 78 pharmaceuticals in different aquatic marine environments from the Gulf of Cadiz (SW Spain) for the first time. The obtained results revealed that pharmaceuticals were present in seawater at total concentrations ranging 61-2133 and 16-189ngL-1 in coastal and oceanic transects, respectively. Potential marine pollution hotspots were observed in enclosed or semi-enclosed water bodies (Cadiz Bay), showing concentrations that were one or two orders of magnitude higher than in the open ocean. The presence of these chemicals in local sewage treatment plants (STPs), one of the main contamination sources, was also assessed, revealing total concentrations of up to 23μgL-1 in effluents. PhACs with the highest detection frequencies and concentrations in the sampling region were analgesics and anti-inflammatories followed by antibiotics in the case of samples from Cadiz Bay or caffeine in oceanic seawater samples. Risk quotients, expressed as ratios between the measured environmental concentration (MEC) and the predicted no-effect concentrations (PNEC) were higher than 1 for two compounds (gemfibrozil and ofloxacin) in effluent of Jerez de la Frontera sewage treatment plant (STP). No high environmental risk was detected in both coastal and oceanic sampling areas, although the information available about the effects of these chemicals on marine biota is still very limited and negative effects on non-target species cannot be discarded.

Are WWTPs effluents responsible for acute toxicity? Seasonal variations of sediment quality at the Bay of Cádiz (SW, Spain)

Abstract Adverse effects of wastewater treatment plants (WWTPs) on sediment quality at the Bay of Cádiz (SW, Spain) were evaluated by a battery of acute bioassays and chemical contamination. Five sites directly affected by WWTPs effluents and one control site were chosen. Results evidenced clear deterioration of ecological sediment quality parameters and possible effects on aquatic communities towards WWTPs areas. Acute toxicity and chemical contamination varied significantly across the studied sites and differed between winter and summer seasons. The Bay of Cádiz is contaminated by PAHs, metals, detergents (SAS) and pharmaceutical products. Principal Component Analyses indicated metals, SAS and pharmaceutical products as the major environmental stresses. Sea-urchin embryo-larval and microalgae growth rate were the most sensitive bioassays to evaluate resuspension of contaminants (elutriate) from bulk sediment. Amphipods mortality and Microtox® solid phase test bioassays were recommended to evaluate bulk sediment quality. Therefore, the use of multiple-bioassays, sensitive to sediment pollution, may provide complementary information to diagnose environmental factors that can impair aquatic communities. The battery of bioassays is recommended to assess and monitor marine sediments directly affected by a mixture of contaminants released from WWTPs.

Photolysis of Antibiotics under Simulated Sunlight Irradiation: Identification of Photoproducts by High-Resolution Mass Spectrometry

There is growing concern regarding the widespread use of antibiotics and their presence in the aqueous environment. Their removal in the water column is mediated by different types of degradation processes for which the mechanisms are still unclear. This research is focused on characterizing the photodegradation kinetics and pathways of two largely employed antibiotics families: sulfonamides (9 SDs) and fluoroquinolones (6 FQs). Degradation percentages and rates were measured in pure water exposed to simulated natural sunlight at a constant irradiance value (500 W m-2) during all the experiments, and the main photoproducts formed were characterized through accurate mass measurement using ultraperformance liquid chromatography-quadrupole-time-of-flight-mass spectrometry (UPLC-QToF-MS). Over 200 different phototransformation products were identified for SDs and FQs, 66% of them, to the best of our knowledge, have not been described before. Their sequential formation and disappearance over the course of the experiments reveals the existence of several pathways for the degradation of target antibiotics. Occurrence of new photoproducts derived from desulfonation and/or denitrification, as well as hydroxylation of photo-oxidized heterocyclic rings, have been identified during photodegradation of SDs, whereas a new pathway yielding oxidation of the benzene ring after the cleavage of the piperazine ring (e.g., CIP product with m/z 280) is described for FQs.

Determination of Pharmaceuticals in Coastal Systems Using Solid Phase Extraction (SPE) Followed by Ultra Performance Liquid Chromatography – tandem Mass Spectrometry (UPLC-MS/MS)

This paper describes the optimization and validation of an analytical method for the determination of 83 13 pharmaceutically active compounds (PhACs) in aqueous samples using solid-phase extraction (SPE) followed by 14 ultra performance liquid chromatography-triple quadrupole mass spectrometry (UPLC-QqQ-MS/MS). First, several 15 experiments were conducted to optimize different SPE extraction parameters such as pH, elution solvents, and 16 Na2EDTA addition. Extraction recovery percentages were between 17 and 146%, being higher than 70% for 47 target 17 analytes. The method limits of detection (LOD) and quantification (LOQ) were below 1 ng L for most compounds 18 (> 90%), and the precision of the method, calculated as the relative standard deviation (RSD) of replicate extractions 19 and analyses, was less than 20%. The optimized method was successfully applied to the analysis of real water 20 samples in estuarine and coastal systems from SW Spain (Cadiz Bay and Huelva Estuary). 49 out of 83 target 21 compounds were found in 75% of samples. Ibuprofen, atenolol, gemfibrozil and caffeine were the most commonly 22 substances detected, reaching concentrations up to 195 ng L. These are among the first data available on the 23 occurrence of a wide range of pharmaceuticals in European coastal waters. 24

Removal of pharmaceuticals in urban wastewater: High rate algae pond (HRAP) based technologies as an alternative to activated sludge based processes

Microalgae biotechnology is a promising tool for many applications, including the elimination of nutrients and other contaminants from wastewater. In this work, we measured the removal efficiency of two wastewater treatment processes: an activated-sludge based conventional process and another based on microalgae biotechnology using high-rate algae ponds (HRAPs). The latter was tested using two different configurations. In the first one, HRAPs were placed after an UASB reactor and used as a tertiary treatment to remove nutrients. In the second, the UASB reactor was disconnected so the HRAPs were directly fed with pretreated wastewater. Additional treatment was performed using dissolved air flotation (DAF). The performances of both configurations (UASB-HRAP and HRAP-DAF) were compared to that of the conventional line including primary and secondary biological treatments and operating in parallel within the same wastewater treatment plant (WWTP). Sixty-four out of 81 target PhACs were detected in the influent of the WWTP, at an average concentration of 223 μg L-1, whereas 55 and 54 were measured in the conventional (14 μg L-1) and non-conventional (17 μg L-1) effluents. Average removal efficiencies were similar (94 vs. 92%) for both treatment lines when comparing total PhACs concentrations. The compositional patterns of the resulting effluents, however, were not, suggesting the occurrence of differential removal mechanisms depending on the chemicals and wastewater treatments considered. Highly consumed compounds such as ibuprofen and acetaminophen were predominant in the non-conventional effluent (>1 μg L-1), denoting lower removal than in the conventional line. On the other hand, elimination of diclofenac and some specific antibiotics and diuretics (e.g., hydrochlorothiazide) was between 15 and 50% higher using HRAPs. Overall, the efficiency of the microalgae technology removing PhACs was found to be comparable to that used in conventional WWTPs. This, combined with a higher efficiency removing nutrients, shows the potential of HRAP technology for wastewater treatment as an alternative (or addition as tertiary treatment) to more conventional approaches based on activated sludge.

Sources and trends of artificial sweeteners in coastal waters in the bay of Cadiz (NE Atlantic)

This is the first comprehensive study on the input, occurrence, and distribution of artificial sweeteners (ASs) in coastal wastewater treatment plants (WWTPs) and their receiving coastal waters. Acesulfame (ACE), aspartame (ASP), cyclamate (CYC), saccharine (SAC), and sucralose (SUC) were monitored for 6 months in Cadiz Bay (SW Spain). ASP was always detected at <0.1 μg L-1 and removal efficiencies were >90% for SAC and CYC. Higher ACE removal efficiencies were observed during warmer months. Persistence of ACE and SUC was observed in both WWTPs and their receiving coastal surface waters, where values up to 0.6 and 3 μg L-1 were measured, respectively. The highest concentrations were measured in a sewage-impacted estuary located in the north of the bay, where conservative behavior was confirmed. The source specificity and recalcitrance of ACE and SUC make them suitable for being used as sewage-pollution markers in coastal environments.