Use of Fluorescence Spectroscopy and Chemometrics to Visualise Fluoroquinolones Photodegradation Major Trends: A Confirmation Study with Mass Spectrometry.

In this work, we employed EEM-PARAFAC (fluorescence excitation-emission matrices-parallel factor analysis) as a low-cost tool to study the oxidation pathways of (fluoro)quinolones. Amounts of 12.5 µM of enrofloxacin (ENR), ciprofloxacin (CIP), ofloxacin (OFL), oxolinic acid (OA), and flumequine (FLU), as individual solutions, were irradiated under UVA light. A 5-component PARAFAC model was obtained, four of them related to the parent pollutants, named as ENR-like (including CIP), OFL-like, OA-like, and FLU-like, and an additional one related to photoproducts, called ENRox-like (with an emission red-shift with respect to the ENR-like component). Mass spectrometry was employed to correlate the five PARAFAC components with their plausible molecular structures. Results indicated that photoproducts presenting: (i) hydroxylation or alkyl cleavages exhibited fingerprints analogous to those of the parent pollutants; (ii) defluorination and hydroxylation emitted within the ENRox-like region; (iii) the aforementioned changes plus piperazine ring cleavage emitted within the OA-like region. Afterwards, the five antibiotics were mixed in a single solution (each at a concentration of 0.25 µM) in seawater, PARAFAC being also able to deconvolute the fingerprint of humic-like substances. This approach could be a potential game changer in the analysis of (fluorescent) contaminants of emerging concern removals in complex matrices, giving rapid visual insights into the degradation pathways.

Wastewater treatment by microalgae.

The growth of the world's population increases the demand for fresh water, food, energy, and technology, which in turn leads to increasing amount of wastewater, produced both by domestic and industrial sources. These different wastewaters contain a wide variety of organic and inorganic compounds which can cause tremendous environmental problems if released untreated. Traditional treatment systems are usually expensive, energy demanding and are often still incapable of solving all challenges presented by the produced wastewaters. Microalgae are promising candidates for wastewater reclamation as they are capable of reducing the amount of nitrogen and phosphate as well as other toxic compounds including heavy metals or pharmaceuticals. Compared to the traditional systems, photosynthetic microalgae require less energy input since they use sunlight as their energy source, and at the same time lower the carbon footprint of the overall reclamation process. This mini-review focuses on recent advances in wastewater reclamation using microalgae. The most common microalgal strains used for this purpose are described as well as the challenges of using wastewater from different origins. We also describe the impact of climate with a particular focus on a Nordic climate.

New insights into submarine tailing disposal for a reduced environmental footprint: Lessons learnt from Norwegian fjords.

Submarine tailing disposal (STD) in fjords from land-based mines is common practice in Norway and takes place in other regions worldwide. We synthesize the results of a multidisciplinary programme on environmental impacts of STDs in Norwegian fjords, providing new knowledge that can be applied to assess and mitigate impact of tailing disposal globally, both for submarine and deep-sea activities. Detailed geological seafloor mapping provided data on natural sedimentation to monitor depositional processes on the seafloor. Modelling and analytical techniques were used to assess the behaviour of tailing particles and process-chemicals in the environment, providing novel tools for monitoring. Toxicity tests showed biological impacts on test species due to particulate and chemical exposure. Hypersedimentation mesocosm and field experiments showed a varying response on the benthos, allowing to determine the transition zone in the STD impact area. Recolonisation studies indicate that full community recovery and normalisation of metal leakage rates may take several decades due to bioturbation and slow burial of sulfidic tailings. The results are synthesised to provide guidelines for the development of best available techniques for STDs.

Sustainable microalgae-based technology for biotransformation of benzalkonium chloride in oil and gas produced water: A laboratory-scale study.

Many countries have implemented stringent regulatory standards for discharging produced water (PW) from the oil and gas extraction process. Among the different chemical pollutants occurring in PW, surfactants are widely applied in the oil and gas industry to provide a barrier from metal corrosion. However, the release of these substances from the shale formation can pose serious hazardous impacts on the aquatic environment. In this study, a low-cost and eco-friendly microalgae laboratory-scale technology has been tested for biotransformation of benzalkonium chloride (BACC12 and BACC14) in seawater and PW during 14-days of treatment (spiked at 5 mg/L). From the eight microalgae strains selected, Tetraselmis suecica showed the highest removal rates of about 100% and 54% in seawater and PW, respectively. Suspect screening analysis using liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS) allowed the identification of 12 isomeric intermediates generated coming from biotransformation mechanisms. Among them, the intermediate [OH-BACC12] was found as the most intense compound generated from BACC12, while the intermediate [2OH-BACC14] was found as the most intense compound generated from BACC14. The suggested chemical structures demonstrated a high reduction on their amphiphilic properties, and thus, their tendency to be adsorbed into sediments after water discharge. In this study, Tetraselmis suecica was classified as the most successful specie to reduce the surfactant activity of benzalkonium chloride in treated effluents.

Elimination study of the chemotherapy drug tamoxifen by different advanced oxidation processes: Transformation products and toxicity assessment.

Tamoxifen is a chemotherapy drug considered as recalcitrant contaminant (with low biodegradability in conventional activated sludge wastewater treatment), bioaccumulative, ubiquitous, and potentially hazardous for the environment. This work studies the removal of Tamoxifen from water by advanced oxidation processes, paying special attention to the formation of transformation products (TPs) and to the evolution of toxicity (using the Microtox® bioassay) during the oxidation processes. Five types of treatments were evaluated combining different technologies based on ozone, hydrogen peroxide and UV radiation: i) O3, ii) O3/UV, iii) O3/H2O2 (peroxone), iv) UV and v) UV/H2O2. Complete removal of tamoxifen was achieved after 30 min for all the treatments carried out with O3 while a residual concentration (about 10% of initial one) was observed in the treatments based on UV and UV/H2O2 after 4 h of reaction. Eight TPs were tentatively identified and one (non-ionizable molecule) was suspected to be present by using ultra high performance liquid chromatography coupled to high resolution mass spectrometry. An increase of toxicity was observed during all the oxidation processes. In the case of ozone-based treatments that increase was attributed to the presence of some of the TPs identified, whereas in the case of UV-based treatments there was no clear correlation between toxicity and the identified TPs.

Enhanced sulfamethoxazole degradation through ammonia oxidizing bacteria co-metabolism and fate of transformation products.

The occurrence of the widely-used antibiotic sulfamethoxazole (SFX) in wastewaters and surface waters has been reported in a large number of studies. However, the results obtained up-to-date have pointed out disparities in its removal. This manuscript explores the enhanced biodegradation potential of an enriched culture of Ammonia Oxidizing Bacteria (AOB) towards SFX. Several sets of batch tests were conducted to establish a link between SFX degradation and specific ammonia oxidation rate. The occurrence, degradation and generation of SFX and some of its transformation products (4-Nitro SFX, Desamino-SFX and N(4)-Acetyl-SFX) was also monitored. A clear link between the degradation of SFX and the nitrification rate was found, resulting in an increased SFX removal at higher specific ammonia oxidation rates. Moreover, experiments conducted under the presence of allylthiourea (ATU) did not present any removal of SFX, suggesting a connection between the AMO enzyme and SFX degradation. Long term experiments (up to 10 weeks) were also conducted adding two different concentrations (10 and 100 µg/L) of SFX in the influent of a partial nitrification sequencing batch reactor, resulting in up to 98% removal. Finally, the formation of transformation products during SFX degradation represented up to 32%, being 4-Nitro-SFX the most abundant.

Identification of markers of cancer in urban sewage through the use of a suspect screening approach.

The administration of anticancer drugs during chemotherapy treatments has increased considerably in recent years, and based on the growing incidence of cancer worldwide there is a foreseen increase in their use over the coming years. Many anticancer drugs are not removed by conventional wastewater treatment plants (WWTPs) and can therefore reach the aquatic environment and potentially threaten aquatic life. The objective of this work was to apply a suspect screening methodology to detect chemotherapy and radiotherapy drugs and their related compounds such metabolites and/or biomarkers in wastewater. The use of logical pre-determined criteria to refine the suspect list down to a relatively small number of relevant compounds greatly improved the efficiency of the analysis. Mass accuracy, isotopic patterns and predicted retention time were used to tentatively identify the suspects. Successful identification of cancer-related suspects included two antineoplastic hormones, two X-ray contrast agents and a pyrrolizidine alkaloid related to an herbal medicine. This is the first time that a suspect screening paradigm has been successfully applied to the identification of pharmaceuticals and biomarkers related to chemotherapy in wastewater.

Suspect screening of emerging pollutants and their major transformation products in wastewaters treated with fungi by liquid chromatography coupled to a high resolution mass spectrometry.

A new approach for the screening of 33 pharmaceuticals and 113 of their known transformation products in wastewaters was developed. The methodology is based on the analysis of samples by liquid chromatography coupled to high resolution mass spectrometry (HRMS) followed by data processing using specific software and manual confirmation. A home-made library was built with the transformation products reported in literature for the target pharmaceuticals after treatment with various fungi. The method was applied to the search of these contaminants in 67 samples generated along treatment of wastewaters with white-rot fungus Trametes versicolor. The screening methodology allowed the detection of different transformation products (TPs) generated from degradation of parent compounds after fungal treatment. This approach can be a useful tool for the rapid screening and tentative detection of emerging contaminants during water treatment in both full and batch-scale studies when pure standards are not available.

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 (Jozef 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.

Non conventional biological treatment based on Trametes versicolor for the elimination of recalcitrant anticancer drugs in hospital wastewater.

This work presents a study about the elimination of anticancer drugs, a group of pollutants considered recalcitrant during conventional activated sludge wastewater treatment, using a biological treatment based on the fungus Trametes versicolor. A 10-L fluidized bed bioreactor inoculated with this fungus was set up in order to evaluate the removal of 10 selected anticancer drugs in real hospital wastewater. Almost all the tested anticancer drugs were completely removed from the wastewater at the end of the batch experiment (8 days) with the exception of Ifosfamide and Tamoxifen. These two recalcitrant compounds, together with Cyclophosphamide, were selected for further studies to test their degradability by T. versicolor under optimal growth conditions. Cyclophosphamide and Ifosfamide were inalterable during batch experiments both at high and low concentration, whereas Tamoxifen exhibited a decrease in its concentration along the treatment. Two positional isomers of a hydroxylated form of Tamoxifen were identified during this experiment using a high resolution mass spectrometry based on ultra-high performance chromatography coupled to an Orbitrap detector (LTQ-Velos Orbitrap). Finally the identified transformation products of Tamoxifen were monitored in the bioreactor run with real hospital wastewater.

Determination of 81 pharmaceutical drugs by high performance liquid chromatography coupled to mass spectrometry with hybrid triple quadrupole-linear ion trap in different types of water in Serbia.

The aim of the work was to study the occurrence of pharmaceuticals in waste, surface, underground, and drinking water samples collected in Serbia. A multi-residue method for the analysis of 81 pharmaceutical drugs from different therapeutic classes in the various types of water was applied. Twenty-five composite water samples were prepared using solid-phase extraction and the presence of 81 pharmaceutical compounds in the extracts was analyzed by ultra-high performance liquid chromatography coupled to mass spectrometry with hybrid triple quadrupole-linear ion trap (UPLC-QqLIT-MS/MS). Forty seven compounds of 81 drugs were found in four different types of analyzed water. The highest concentrations of ibuprofen of 20.1 µg L(-1), 10,11-epoxycarbamazepine of 16.2 µg L(-1), 2-hydroxycarbamazepine of 15.9 µg L(-1) and acetaminophen of 15.7 µg L(-1) were found in municipal waste water sample. Results revealed the presence of salicylic acid in 41.67% of water samples, carbamazepine in 36.11%, propranolol and irbesartan in 30.56%. The obtained results were discussed in relation to the relevant data available in literature. This is the first attempt to assess the occurrence of these 81 pharmaceutical residues in water samples in Serbia.

Degradation of pharmaceuticals in non-sterile urban wastewater by Trametes versicolor in a fluidized bed bioreactor.

The constant detection of pharmaceuticals (PhACs) in the environment demonstrates the inefficiency of conventional wastewater treatment plants to completely remove them from wastewaters. So far, many studies have shown the feasibility of using white rot fungi to remove these contaminants. However, none of them have studied the degradation of several PhACs in real urban wastewater under non-sterile conditions, where mixtures of contaminants presents at low concentrations (ng L(-1) to µg L(-1)) as well as other active microorganisms are present. In this work, a batch fluidized bed bioreactor was used to study, for the first time, the degradation of PhACs present in urban wastewaters at their pre-existent concentrations under non-sterile conditions. Glucose and ammonium tartrate were continuously supplied as carbon and nitrogen source, respectively, and pH was maintained at 4.5. Complete removal of 7 out of the 10 initially detected PhACs was achieved in non-sterile treatment, while only 2 were partially removed and 1 of the PhACs analyzed increased its concentration. In addition, Microtox test showed an important reduction of toxicity in the wastewater after the treatment.

Comprehensive study of ibuprofen and its metabolites in activated sludge batch experiments and aquatic environment.

Even though Ibuprofen is one of the most studied pharmaceutical in the aquatic environment, there is still a lack of information about its fate and the generation of different transformation products along wastewater treatment plants (WWTPs). Ibuprofen biotransformation products can be generated by human metabolism or by microorganisms present in WWTPs and in natural waters, soils, and sediments, which increase the probability to find them in environment. In this work, the presence of ibuprofen and its main metabolites: ibuprofen carboxylic acid (CBX IBU), 2-hydroxylated ibuprofen (2-OH IBU) and 1-hydroxylated ibuprofen (1-OH IBU), was monitored quantitatively along the biodegradation processes occurring in different batch activated sludge (BAS) experiments under different working conditions. Total ibuprofen removal, achieved in almost all the experiments, was related in part to the formation of the metabolites mentioned. Another ibuprofen metabolite, 1,2-dihydroxy ibuprofen, was detected in BAS experiments for the first time. The metabolites 2-OH IBU and 1-OH IBU remained in solution at the end of ibuprofen biodegradation experiments whereas CBX IBU disappeared faster than hydroxylated metabolites. In addition, also the biodegradation of 1-OH IBU, 2-OH IBU and CBX IBU was evaluated in batch experiments: CBX IBU removal occurred at the highest rate followed by IBU, 2-OH IBU, and 1-OH IBU, which exhibited the lowest removal rate. Finally, Ibuprofen and ibuprofen metabolites were monitored in sewage and natural water samples, where they were found at higher levels than expected: the maximum concentration in influent wastewater samples were 13.74, 5.8, 38.4, 94.0µg/L for IBU, 1-OH IBU, CBX IBU and 2-OH IBU respectively; whereas maximum levels in effluent wastewater samples were 1.9, 1.4, 10.7, 5.9 µg/L for IBU, 1-OH IBU, CBX IBU and 2-OH IBU respectively. High levels of the compounds were also found in river samples, in particular for CBX IBU, which was detected up to 3.9 µg/L.