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.

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.

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.

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.

Effects of novobiocin and methotrexate on the benthic amphipod Ampelisca brevicornis exposed to spiked sediments.

The marine amphipod Ampelisca brevicornis was used as model organism of benthic macrofauna to assess the possible adverse effects of pharmaceuticals bound to sediments. Organisms were exposed to sediment spiked with novobiocin (NOV) and methotrexate (MTX) for 10 days in order to estimate the acute toxicity (lethal effects) produced by the two compounds. The surviving organisms were pooled and analyzed to determine their sublethal responses associated with different phases of metabolism (enzyme activities in phases I and II), oxidative stress (antioxidant enzyme activities and lipid peroxidation), and genotoxicity (DNA damage in the form of strand breaks). No lethal or sublethal effects were observed in the amphipods exposed to NOV. For organisms exposed to sediments spiked with MTX the results were found to calculate the concentration that was lethal to 50% of the organisms exposed in the toxicity tests (LC50 of 30.36 ng/g). MTX also induced the metabolism of enzyme detoxification activities in phases I and II. Oxidative stress and DNA damage in particular were also observed, indicating responses associated with MTX's mechanism of action. Both mortality and the set of applied biomarkers allowed for the assessment of bioavailability, oxidative stress, and genotoxicity of NOV and MTX. The information obtained in this investigation can assist in ecological risk assessment of marine sediments contaminated by pharmaceuticals.

Reactivity and fate of secondary alkane sulfonates (SAS) in marine sediments.

This research is focused on secondary alkane sulfonates (SAS), anionic surfactants widely used in household applications that access aquatic environments mainly via sewage discharges. We studied their sorption capacity and anaerobic degradation in marine sediments, providing the first data available on this topic. SAS partition coefficients increased towards those homologues having longer alkyl chains (from up to 141 L kg(-1) for C14 to up to 1753 L kg(-1) for C17), which were those less susceptible to undergo biodegradation. Overall, SAS removal percentages reached up to 98% after 166 days of incubation using anoxic sediments. The degradation pathway consisted on the formation of sulfocarboxylic acids after an initial fumarate attack of the alkyl chain and successive ß-oxidations. This is the first study showing that SAS can be degraded in absence of oxygen, so this new information should be taken into account for future environmental risk assessments on these chemicals.

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.