Biodegradability of the anticancer drug etoposide and identification of the transformation products

Etoposide susceptibility to microbiological breakdown was studied in a batch biotransformation system, in the presence or absence of artificial wastewater containing nutrients, salts and activated sludge at two concentration levels. The primary focus of the present study was to study etoposide transformation products by ultra-high performance liquid chromatography coupled to high-resolution hybrid quadrupole-Orbitrap tandem mass spectrometry (MS/MS). Data-dependent experiments combining full-scan MS data with product ion spectra were acquired to identify the molecular ions of etoposide transformation products, to propose the molecular formulae and to elucidate their chemical structures. Due to the complexity of the matrix, visual inspection of the chromatograms showed no clear differences between the controls and the treated samples. Therefore, the software package MZmine was used to facilitate the identification of the transformation products and speed up the data analysis. In total, we propose five transformation products; among them, four are described as etoposide transformation products for the first time. Even though the chemical structures of these new compounds cannot be confirmed due to the lack of standards, their molecular formulae can be used to target them in monitoring studies.     

Sediments as a sink for UV filters and benzotriazoles: the case study of Upper Iguaçu watershed,Curitiba (Brazil)

Ingredients in home and personal care products, including UV filters and benzotriazoles, are high production volume chemicals extensively used in our daily life, despite several studies revealed their potential eco-toxicity and endocrine-disrupting capacity. Due to some features, such as high lipophilicity, low degradability, and persistence of many of these compounds, sediments can be considered a sink for them in the aquatic environment. In the present study, nine organic UV filters and three benzotriazoles were investigated for the first time in sediments from four urban rivers in Brazil. The contaminants were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The results revealed that octocrylene (OC), etylhexyl-methoxycinnamate (EHMC), benzophenone-3 (oxybenzone, BP3), and benzotriazole (BZT) were the predominant compounds adsorbed on the sediments, with concentrations ranging from 5.6 to 322.2 ng g⁻¹ dry weight. The results reported in this work constitute the first data on the accumulation of polar benzotriazoles and lipophilic organic UV filters in sediments from Brazil.

     

Occurrence and distribution of six selected endocrine disrupting compounds in surface- and groundwaters of the Romagna area (North Italy)

Environmental Science and Pollution Research - Endocrine disrupting compounds (EDCs) are a wide group of contaminants of emerging concern known to be harmful for organisms. The aim of the study was...     

First inter-laboratory comparison exercise for the determination of anticancer drugs in aqueous samples

The results of an inter-laboratory comparison exercise to determine cytostatic anticancer drug residues in surface water, hospital wastewater and wastewater treatment plant effluent are reported. To obtain a critical number of participants, an invitation was sent out to potential laboratories identified to have the necessary knowledge and instrumentation. Nine laboratories worldwide confirmed their participation in the exercise. The compounds selected (based on the extent of use and laboratories capabilities) included cyclophosphamide, ifosfamide, 5-fluorouracil, gemcitabine, etoposide, methotrexate and cisplatinum. Samples of spiked waste (hospital and wastewater treatment plant effluent) and surface water, and additional non-spiked hospital wastewater, were prepared by the organising laboratory (Jo?ef Stefan Institute) and sent out to each participant partner for analysis. All analytical methods included solid phase extraction (SPE) and the use of surrogate/internal standards for quantification. Chemical analysis was performed using either liquid or gas chromatography mass (MS) or tandem mass (MS/MS) spectrometry. Cisplatinum was determined using inductively coupled plasma mass spectrometry (ICP-MS). A required minimum contribution of five laboratories meant that only cyclophosphamide, ifosfamide, methotrexate and etoposide could be included in the statistical evaluation. z-score and Q test revealed 3 and 4 outliers using classical and robust approach, respectively. The smallest absolute differences between the spiked values and the measured values were observed in the surface water matrix. The highest within-laboratory repeatability was observed for methotrexate in all three matrices (CV?≤?12 %). Overall, inter-laboratory reproducibility was poor for all compounds and matrices (CV 27–143 %) with the only exception being methotrexate measured in the spiked hospital wastewater (CV?=?8 %). Random and total errors were identified by means of Youden plots.     

Photodegradation of azithromycin in various aqueous systems under simulated and natural solar radiation: kinetics and identification of photoproducts

This article describes the photolysis of azithromycin, a macrolide antibiotic with reported occurrence in environmental waters, under simulated solar radiation. The photodegradation followed first-order reaction kinetics in five matrices examined. In HPLC water, the degradation rate was the slowest (half-life: 20 h), whereas in artificial freshwater supplemented with nitrate (5 mg L⁻¹) or humic acids (0.5 mg L⁻¹) the degradation of azithromycin was enhanced by factors of 5 and 16, respectively, which indicated the role of indirect photolysis involving the formation of highly reactive species. Following chromatographic separation on a UPLC system, the characterization of the transformation products was accomplished using high-resolution QqToF-MS analysis. The presence of seven photoproducts was observed and their formation was postulated to originate from (bis)-N-demethylation in the desosamine sugar, O-demethylation in the cladinose sugar, combinations thereof, as well as from hydrolytic cleavages of the desosamine and/or cladinose residue. Two of these photoproducts could also be detected in natural photodegradation process in river water which was spiked with azithromycin.     

Sorption of alkylphenols on Ebro River sediments: comparing isotherms with field observations in river water and sediments

This study reports sorption isotherms of the endocrine disruptors nonylphenol (NP) and octylphenol (OP) in three sediment samples from the Ebro River basin (NE Spain), with organic carbon fractions (f_OC) ranging from 0.0035 to 0.082 g_OC g⁻¹. All isotherms were fitted to the Freundlich model with slightly nonlinear exponents ranging from 0.80 to 0.94. The solubility of the compounds as well as the organic carbon (OC) content had the strongest influences on the sorption behavior of these compounds. Comparison of the laboratory-spiked samples with the native contamination of NP of 45 water and concurrent sediment samples resulted in reasonable matches between both data sets, even though the lowest concentrations in the field were not completely reached in laboratory tests. This good agreement indicates that sorption laboratory data can be extrapolated to environmental levels and therefore the distribution of nonylphenol between sediments and water can be predicted with a precision of one order of magnitude. Furthermore, laboratory experiments with simultaneous loading of NP and OP revealed negligible competition for sorption sites at low concentrations.     

Removal of a broad range of surfactants from municipal wastewater--comparison between membrane bioreactor and conventional activated sludge treatment

Elimination of alkylphenol ethoxylates (APEO) and their degradation products (alkylphenols and alkylphenoxy carboxylates), as well as linear alkylbenzene sulfonates (LAS) and coconut diethanol amides (CDEA), was studied in a pilot plant membrane bioreactor (MBR) working in parallel to a full-scale wastewater treatment plant (WWTP) using conventional activated sludge (CAS). In the CAS system 87% of parent long ethoxy chain NPEOs were eliminated, but their decomposition yielded persistent acidic and neutral metabolites which were poorly removed. The elimination of short ethoxy chain NPEOs (NP(1)EO and NP(2)EO) averaged 50%, whereas nonylphenoxy carboxylates (NPECs) showed an increase in concentrations with respect to the ones measured in influent samples. Nonylphenol (NP) was the only nonylphenolic compound efficiently removed (96%) in the CAS treatment. On the other hand, MBR showed good performance in removing nonylphenolic compounds with an overall elimination of 94% for the total pool of NPEO derived compounds (in comparison of 54%-overall elimination in the CAS). The elimination of individual compounds in the MBR was as follows: 97% for parent, long ethoxy chain NPEOs, 90% for short ethoxy chain NPEOs, 73% for NPECs, and 96% for NP. Consequently, the residual concentrations were in the low mug/l level or below it. LAS and CDEA showed similar elimination in the both wastewater treatment systems that were investigated, and no significant differences were observed between the two treatment processes. Nevertheless, for all studied compounds the MBR effluent concentrations were consistently lower and independent of the influent concentrations. Additionally, MBR effluent quality in terms of chemical oxygen demand (COD), NH(4)(+) concentration and total suspended solids (TSS) was always superior to the ones of the CAS and also independent of the influent quality, which demonstrates high potential of MBRs in the treatment of municipal wastewaters.     

Assessing and forecasting the impacts of global change on Mediterranean rivers. The SCARCE Consolider project on Iberian basins

Introduction

The Consolider-Ingenio 2010 project SCARCE, with the full title ??Assessing and predicting effects on water quantity and quality in Iberian Rivers caused by global change?? aims to examine and predict the relevance of global change on water availability, water quality, and ecosystem services in Mediterranean river basins of the Iberian Peninsula, as well as their socio-economic impacts. Starting in December 2009, it brought together a multidisciplinary team of 11 partner Spanish institutions, as well as the active involvement of water authorities, river basin managers, and other relevant agents as stakeholders.

Methods

The study areas are the Llobregat, Ebro, Jucar, and Guadalquivir river basins. These basins have been included in previous studies and projects, the majority of whom considered some of the aspects included in SCARCE but individually. Historical data will be used as a starting point of the project but also to obtain longer time series. The main added value of SCARCE project is the inclusion of scientific disciplines ranging from hydrology, geomorphology, ecology, chemistry, and ecotoxicology, to engineering, modeling, and economy, in an unprecedented effort in the Mediterranean area. The project performs data mining, field, and lab research as well as modeling and upscaling of the findings to apply them to the entire river basin.

Results

Scales ranging from the laboratory to river basins are addressed with the potential to help improve river basin management. The project emphasizes, thus, linking basic research and management practices in a single framework. In fact, one of the main objectives of SCARCE is to act as a bridge between the scientific and the management and to transform research results on management keys and tools for improving the River Basin Management Plans. Here, we outline the general structure of the project and the activities conducted within the ten Work Packages of SCARCE.     

Occurrence and distribution of pharmaceuticals in surface water, suspended solids and sediments of the Ebro river basin, Spain

The occurrence of 43 pharmaceuticals belonging to predominant therapeutic classes and their distribution in surface water, suspended solids and sediments has been investigated in the Ebro river basin in the Northeast of Spain. WWTP effluents were found to be a main source of contamination and the spatial distribution was affected by the river flow at the sampling point and corresponding dilution factor, resulting in higher concentrations and higher loads in small tributary rivers than in the Ebro river. The study showed that some compounds are preferentially found bound to suspended solids and not detected in river water. Generally, compounds with basic characteristics (pKa > 7) showed higher tendency to bind to suspended solids. The sediment samples generally presented lower concentrations than suspended solids.