Emerging pollutants

[CEST2019_00977] Autonontarget: An R Package to Perform Automatic Non-Target Screening
by Aalizadeh R.,Thomaidis N.

Recent advances on Liquid Chromatography-High Resolution Mass Spectrometry (LC-HRMS) has revolutionized identification of new compounds, having various polarity, over various scientific fields especially in the environmental science. The continuous growing of LC-HRMS applications yet increased the “peak inventories”. This is achieved within three main workflows of “Target”, “Suspect” and “Non-target” screening. Although targeted analysis is the best way to confirm the identification of a compound, it is sometime not practical due to limited access to reference standards. The vast majority of the peaks detected in the samples generally remain unidentified and supportive information such as retention time prediction, MS/MS (experimental and estimated one) along with ionization behavior would help increase the identification confidence. As “peak inventories” expands and number of regulatory databases grows, retrieving possible candidates and screening them often become a time-consuming task and requires large amount of efforts. Thus, an automatic approach could be of great need to screen known-unknown compounds in the samples. The aim of this study is to propose a workflow (Automatic Non-target Screening (AutoNonTarget)) to screen a peaks-list, created by LC-HRMS instrument, from the environmental samples such as influent/effluent wastewater (IWW and EWW) or sewage sludge samples.

Session: 34, Room: D, at Fri, 09/06/2019 - 16:45 to 17:00
Oral presentation in Emerging pollutants
[CEST2019_00973] Determination of more than 2,400 emerging contaminants in apex predators and their prey from European Specimen Banks and Natural History Museums by novel and complementary High Resolution Mass Spectrometry Techniques
by Gkotsis G., Alygizakis N., Cincinelli A., Dekker R., Duke G., Glowacka N., Knopf B., Koschorreck J., Martellini T., Movalli P., Nika M.C., Nikolopoulou V., Ruedel H., Shore R., Thomaidis N., Treu G., Slobodnik J.

Overwhelming evidence over many decades has shown that many organic compounds have been released in the environment due to anthropogenic activities. The term “chemicals of emerging concern (CEC)” has been established for chemicals, which are not subjected to marketing restrictions and regulatory monitoring programmes but are candidates for future regulation, due to their frequent detection in environmental samples and their potential hazardous properties (Thomaidis et al, 2012; Gavrilescu et al, 2015; Dulio et al, 2018). Despite the fact that their chemical and physical properties allow them to enter marine, freshwater and/or terrestrial ecosystems, data for the potential bioaccumulation and biomagnification of CECs though the food are missing, which increases the concern about their effects on the ecosystems, biota and human health. CECs, in many studies, are determined by targeted methods, based on the analysis of reference standards (e.g., plant protection products, OCPs, PAHs, PFAS, pharmaceuticals and veterinary medicines). However, despite the high selectivity and sensitivity of targeted methods, using mainly selected reaction monitoring (SRM) mode of detection, they are limited to the determination of a restricted number of compounds.

Session: 34, Room: D, at Fri, 09/06/2019 - 16:15 to 16:30
Oral presentation in Emerging pollutants
[CEST2019_00975] Wide-scope target analysis of >2,100 emerging contaminants in landfill leachates by LC-QTOFMS and investigation of their potential ecological threat
by Nika M.C., Ntaiou K., Elytis K., Stasinakis A.S., Thomaidi V.S., Gatidoy G., Thomaidis N.

Organic micropollutants are compounds which are normally detected at concentrations up to microgram per liter in the aquatic environment and they are considered to be potential threats to the ecosystem. Some of them have been studied in detail since 1980s and are already included in existing national or international legislative documents, while others are characterized as emerging contaminants (ECs) and no regulations currently require their environmental monitoring. During the last decade, several studies have been focused on the investigation of possible sources of emerging contaminants’ distribution into the environment. According to the literature, sewage treatment plants are considered as major point sources of these compounds into the environment, as they receive domestic and industrial wastewater, as well as urban and -in some cases- agricultural runoff (Ratola et al., 2012; Luo et al., 2014; Arvaniti and Stasinakis, 2015). On the other side, the contribution of landfills, via the produced leachates, in transferring emerging pollutants to the environment, is not well reported so far (Oturan et al., 2015). Besides European policy for recycling and waste-to-energy, landfilling still remains one of the alternative options for municipal solid waste management in EU-28, where 58 × 106 tonnes of municipal solid waste were disposed to landfills in 2017 (Eurostat, 2018).

Session: 34, Room: D, at Fri, 09/06/2019 - 16:30 to 16:45
Oral presentation in Emerging pollutants
[CEST2019_00939] Wastewater treatment and emerging contaminants removal in electro membrane bioreactor using self-forming dynamic membranes
by Castrogiovanni F., Borea L., Millanar-Marfa J.M.J., Napodano P., Balakrishnan M., Ballesteros F.C.J., Hasan S.W., Belgiorno V., Naddeo V.

In recent years, the technical-scientific community has been paying increasing attention to the presence of emerging contaminants that are intercepted in surface water and wastewater since these compounds could have harmful effects on human health and on environment too.
Conventional wastewater treatment installations represent a source of pollution from emerging contaminants because they are not designed to remove these compounds from the wastewater in their treatment cycle.
Several studies have shown the possibility of removing successfully these compounds from wastewater through the use of membrane bioreactors (MBR) combined with electrochemical processes, using conventional membranes.
The present study first examined the possibility of combining electrochemical processes with MBR (eMBR), through the use of self-forming dynamic membranes (SFDM) for the removal of emerging contaminants from municipal wastewater.
Thanks to this extremely innovative hybrid system, it has been possible to reduce the problems linked to the use of traditional membranes, in particular the high costs both of initial investment and of cleaning following fouling.

Session: 34, Room: D, at Fri, 09/06/2019 - 17:00 to 17:15
Oral presentation in Emerging pollutants
[CEST2019_00971] Development of a novel GC-APCI-QTOFMS methodology for the determination of more than 300 organic compounds in Asopos river water samples
by Panagopoulou E.I, Nika M.C., Damalas D., Koulis G., Thomaidis N.S

The site of interest of this study is Asopos river which is located in Sterea Ellada, north of Athens, and passes through areas where 20% of total Greece industrial production takes place. The extensive installation of industries in the area near the river, and the uncontrolled disposal of industrial and agricultural wastes into the river, make the water quality of Asopos questionable. The environmental problem of Asopos river basin is known since 1969, due to the detection of high Cr (VI) concentrations in ground and river water samples with potential carcinogenic effects to human health. However, the probable occurrence of industrial and agricultural organic chemicals with unknown toxic effects has not been studied so far. To the best of our knowledge, this is the first environmental monitoring study in Greece including not only the determination of legislated compounds, but also the wide-scope screening of organic chemicals for which no occurrence data exist.

Session: 34, Room: D, at Fri, 09/06/2019 - 15:45 to 16:00
Oral presentation in Emerging pollutants
[CEST2019_00972] Screening thousands of emerging contaminants in Asopos river basin by UPLC-QToF-MS
by Nikolopoulou V.I., Nika M.C., Aalizadeh R., Alygizakis N., Thomaidis N.S.

Monitoring activities over several decades have revealed the ubiquitous presence of organic contaminants in environmental compartments. Asopos river basin, located in Sterea Ellada, has been the focus of many environmental studies over the last decades, mainly due to its geomorphology and the extensive industrial activities that take place in this territory. The detection of high Cr(VI) concentrations, causing potential carcinogenic effects, have attracted the attention of media and raised the consciousness of the citizens. Although there are many studies in recent literature focusing on the occurrence of heavy metals in Asopos river basin, there is a lack of information concerning the presence of emerging contaminants. The aim of this study is the determination of thousands of emerging contaminants in the environmental samples (river water and sediments) form Asopos river basin, following wide-scope target screening methodologies. Solid-Phase Extraction (SPE) by mixed-mode sorbent was used during the sample preparation of river water samples to ensure the extraction of various classes of compounds with a wide range of physicochemical properties. The extracts were analyzed by complimentary chromatographic techniques, including Reversed Phase (RP) and Hydrophilic Interaction Liquid Chromatography (HILIC) coupled to Quadrupole-Time-of-Flight Mass Spectrometry (QToF-MS).

Session: 34, Room: D, at Fri, 09/06/2019 - 16:00 to 16:15
Oral presentation in Emerging pollutants
[CEST2019_00922] Development and application of methods for the determination of pesticide residues in natural waters and sediments, coupled to GC-MS
by Kapsi M., Sakkas V., Albanis T.

The main objectives of this study were to develop rapid and accurate screening multiresidue pesticide methods on the basis of Solid-Phase Extraction (SPE) technique for the determination of 10 pesticides in water samples and on the basis of QuEChERS technique regarding sediments samples. The target compounds were determined by Gas Chromatography-Mass Spectrometry (GC-MS). The method was validated in terms of accuracy, precision, linearity, detection and quantification limits. The recovery percentages obtained for the pesticides in water samples at three different concentration levels, ranged between 73.2 to 101.2%, with relative standard deviations below 9.3%. The corresponding results from the sediment ranged between 69.5 to 122.7% with relative standard deviations below 11.2%. The limits of detection for the pesticides in water and sediment were below 12 ng L-1 and 9 mg kg-1, respectively. The optimized methods were applied in Epirus region (North-Western Greece) to determine the concentration level of the target compounds in sea water and sediment samples. The analytical methodologies exhibited excellent analytical characteristics and proved to be reliable for the estimation of the pollutant load in sea water and sediment samples from marine aquaculture.

Session: 28, Room: D, at Fri, 09/06/2019 - 13:33 to 13:36
Flash presentation in Emerging pollutants
[CEST2019_00803] Dioxin-Like Polychlorinated Biphenyls at Dilijan Landfills (Republic of Armenia)
by Aleksandryan A., Khachatryan A., Bunyatyan Y.

Polychlorinated biphenyls (PCBs) are substances of wide distribution, high toxicity, persistence, and ability to long-distance migration. They are characterized by unique properties: temperature stability; high boiling point; non-combustibility; resistance to chemical and physical influences; high dielectric constants.
The presence and concentration of dioxin-like and non- dioxin-like PCBs in old and new landfills of Dilijan district (Republic of Armenia) were investigated. Municipal waste dumps of Dilijan are active sources of PCBs accumulation and spread. In soil samples from both the old and new landfills excess concentrations of PCBs were found in 100% of cases compared to normative level, and the summary concentrations of the latter multiply exceeded the normative level.
PCBs-related environmental pollution is of great concern because the emergence and spread of PCBs in nature is not always subject to control and regulation, as the sources of PCBs formation are diverse.

Session: 34, Room: D, at Fri, 09/06/2019 - 15:15 to 15:30
Oral presentation in Emerging pollutants
[CEST2019_00807] Screening of 102 organic pollutants in groundwater along the Beijing-Hangzhou Grand Canal in China by GC×GC-TOFMS
by Liang M., Liu L., Rao Z., Gong J., Zhu T.

Screening of 102 organic pollutants in groundwater along the Beijing-Hangzhou Grand Canal in China by GC×GC-TOFMS. A total of 45 samples were collected. The targets of the investigation involve multiple types of organic pollutants such as Polycyclic aromatic hydrocarbons (PAHs) and their derivatives, phthalates (PAEs), phenols, anilines, polychlorinated naphthalenes (PCNs), polychlorinated biphenyls (PCBs) et al. The results showed that naphthalene, fluoranthene and phthalates are commonly detected compounds. There are 8 categories of organic pollutants detected. The highest concentration of 4-nitrobiphenyl is as high as 430 μg/L, and other targets were detected at the higher concentration in the sample. It means groundwater in the sites have been polluted by micro organic pollutant.

Session: 34, Room: D, at Fri, 09/06/2019 - 15:30 to 15:45
Oral presentation in Emerging pollutants
[CEST2019_00682] A nine-year study on the temporal changes of licit and illicit drug use patterns as revealed from the chemical analysis of influent wastewater from the wastewater treatment plant of Athens
by Galani K., Alygizakis N.A., Borova V., Thomaidis N.S.

Daily flow-proportional composite influent wastewater was collected from the Wastewater Treatment Plant (WWTP) in Athens during a nine-year sampling campaign (2010-2019). Analytes in influent wastewater are markers of the consumption and the exposure of the chemicals in the population. Wastewater samples were cleaned up and enriched 200 times using a generic solid phase extraction protocol based on a mixture of four sorbent materials capable of retaining a wide-range of analytes. Extracts were analyzed by a wide-scope targeted LC-QTOFMS and by highly-sensitive LC-MS/MS methods for the determination of pharmaceuticals such as antidepressants, anxiolytics, antipsychotics, antibiotics, antiepileptics, analgesics, nonsteroidal anti-inflammatory drugs (NSAIDs), diuretics, antihypertensives, antiulcer, and steroids as well as the main illicit drugs and their metabolites among others. Furthermore, the daily consumption of the substances was back-calculated with the aim of revealing trends in the use patterns of the compounds and associate the changes with socioeconomic phenomena, law enforcements and financial indicators.

Session: 28, Room: D, at Fri, 09/06/2019 - 13:30 to 13:33
Flash presentation in Emerging pollutants
[CEST2019_00683] NORMAN Non-target screening (NTS) prioritisation scheme for ranking thousands of contaminants of emerging concern in effluent wastewater collected from Europe.
by Alygizakis N.A., Dulio V., Von der Ohe P. , Slobodnik J., Thomaidis N.

Prioritisation of contaminants of emerging concern (CECs) remains a challenging task of primary importance for environmental managers and the scientific community as regards the definition of priority actions for pollution prevention & control and for the allocation of resources to address current knowledge gaps. The NORMAN prioritisation scheme combines the traditional risk-based ranking process with the preliminary application of a decision tree, which allows the allocation of substances into six action categories, based on the knowledge gaps and actions needed to fill them, e.g. development of more powerful analytical methods, launch of monitoring campaigns and performing additional ecotoxicity tests. The ranking within each category is then evaluated by occurrence, hazard and risk criteria. The tremendous improvements in high-resolution mass spectrometry and the development of advanced chemometric tools resulted in the update of the NORMAN prioritisation scheme, so that it incorporates the automatic retrieval of the occurrence of CECs through retrospective suspect screening. The objective of the study was to present a) the updated NORMAN prioritization scheme and the modifications introduced and b) the application of the scheme for the prioritization of more than 40,000 CECs in 46 effluent wastewater samples collected from Europe.

Session: 34, Room: D, at Fri, 09/06/2019 - 15:00 to 15:15
Oral presentation in Emerging pollutants
[CEST2019_00631] Biodegradation of pharmaceuticals by bacteria isolated from estuarine environment - cleanup technologies through nature-based processes
by Fernandes J.P., Duarte P., Almeida C.M.R., Carvalho M.F. ,Mucha A.P.

New sustainable technologies are needed to tackle pharmaceuticals contamination in different environmental compartments. Bioremediation technology, using native microorganisms with capacity for partial or complete elimination of contaminants, can be considered. This work investigated the capability of different bacterial strains to biodegrade paroxetine and bezafibrate, either as a bacterial consortium or as a single strain. These strains were isolated from bacterial cultures previously enriched under static conditions with paroxetine or bezafibrate, using as inoculum an estuarine sediment. All strains were identified through 16S rRNA gene sequencing. Degradation potential was accessed by analyzing pharmaceutical compounds in the culture medium and fluoride ion release (only for paroxetine). The genus Pseudomonas, widely reported in biodegradation studies, was predominant among the isolated bacterial strains. Most bacterial strains showed potential to degrade paroxetine (55%-100%) as a single strain in co-metabolism with sodium acetate. Furthermore, bacterial consortia also presented high removal efficiencies (>85%) for paroxetine throughout 4 weeks. For bezafibrate, tests showed a high potential of the bacterial consortia to degrade this compound (>90%).

Session: 28, Room: D, at Fri, 09/06/2019 - 12:30 to 12:45
Oral presentation in Emerging pollutants
[CEST2019_00542] Magnetic solid-phase extraction of pesticides in environmental water samples using Fe3O4@SiO2@C18 nanoparticles coupled to GC-MS determination
by Kapsi M., Sakkas V., Albanis T.

A rapid magnetic solid-phase extraction (MSPE) method coupled to Gas Chromatography-Mass Spectrometry (GC-MS) was developed for the simultaneous extraction of ten pesticides belonging to various categories (insecticides, herbicides and fungicides) in environmental water samples. The magnetic Fe3O4@SiO2@C18 nanoparticles were synthesized by coprecipitation of Fe2+ and Fe3+ ions, at alkaline conditions, under hydrothermal treatmentand andused as adsorbents of MSPE.
The proposed method is optimized by means of experimental design and response surface methodology. Several parameters influencing MSPE efficiency were investigated. The most important were the amount of the sorbent and the extraction time. Under optimal conditions, the MSPE-GC-MS method presented fast simple separation and analysis, and excellent linearity in the range of 6.4–5000.0 ng/L, with coefficients of determination (R2) higher than 0.9901 for all compounds. Moreover, the performance of the MSPE method was compared to a conventional SPE and the MSPE method was comperable.
Finally, the optimized method was applied in a case-control study carried out in Rivers Aliakmonas, Loudias and Axios (Macedonia Region-North Greece). The most frequently detected compounds were atrazine, methyl-parathion, chlorpyriphos and irgarol.
The magnetic Fe3O4@SiO2@C18 composites based MSPE method proved promising for convenient and efficient determination of pesticides in environmental water samples.

Session: 28, Room: D, at Fri, 09/06/2019 - 12:45 to 13:00
Oral presentation in Emerging pollutants
[CEST2019_00550] Liquid chromatography coupled to high-resolution-Orbitrap mass spectrometry for the determination of nitrofuran metabolites in fish samples
by Trantopoulos E., Kosma C., Karkabounas A., Boti V., Albanis T.

Nitrofurans (NFs) are synthetic antibiotic drugs employed for the treatment of bacterial diseases in livestock production or as food additives in industrial farming of food-producing animals. The most widely used NFs in veterinary medicine are nitrofurantoin (NFT), furazolidone (FZD), nitrofurazone (NFZ) and furaltadone (FTD). After intake, NFs are extensively metabolized into their corresponding metabolites (NFMs), identified as 1-amino-hydantoin (AHD), 3-amino-2-oxazolidone (AOZ), semicarbazide (SEM) and 3-amino-5-methyl-morpholino-2-oxazolidinone (AMOZ), for nitrofurantoin, furazolidone, nitrofurazone and furaltadone, respectively. NFs and their metabolites are suspected to possess carcinogenic and mutagenic potency, therefore their application in food and animal production was banned in the EU in 1995 and in the USA in 2002. Since parent NFs are extensively metabolized to tissue-bond metabolites, recent analytical methods have been focused on the determination of the NFMs instead of the parent compounds. In the present study a modified extraction technique including at first a hydrolysis-derivatization step [O’Keeffe et al., 2004] was validated and applied for the simultaneous determination of four of NFMs residues (AHD, AOZ, SEM, AMOZ) in fish samples from aquacultures located in North Western Greece.

Session: 28, Room: D, at Fri, 09/06/2019 - 13:36 to 13:39
Flash presentation in Emerging pollutants
[CEST2019_00551] Pharmaceutical residues in hospital and urban wastewaters: Occurrence, removal and potential risk assessment
by Martinaiou P., Trantopoulos E., Kosma C., Albanis T.

The presence of ten pharmaceutical compounds (bupropion, venlafaxine, mirtazapine, sertraline, citalopram, caffeine, triclosan, carbamazepine, diazepam, clozapine) which belong to different treatment categories was studied in one hospital and three urban WWTPs in north and northwestern Greece. The pharmaceuticals have been selected due to their high usage rate but also because of their proven presence in both wastewater treatment plants and the aquatic environment. Analytical methodology was based on gas chromatography coupled to mass spectrometry (GC-MS) detection after the application of a solid phase extraction (SPE) step. In addition, elimination of these compounds in the WWTPs was assessed as well as their ecotoxicological impact on the aquatic environment was estimated by means of risk quotient (RQ). The results showed that the most often detectable compounds were caffeine, triclosan and venlafaxine. High concentration levels of caffeine, up to 22142.1 ng/L were found, while removal rates were up to 99 %. In addition, high levels of acute and chronic toxicity were observed for triclosan (RQ>1).

Session: 34, Room: D, at Fri, 09/06/2019 - 17:15 to 17:18
Flash presentation in Emerging pollutants
[CEST2019_00522] Determination of pharmaceutical residues in natural waters using high performance liquid chromatography coupled to quadrupole-Orbitrap mass spectrometry
by Kifokeri D., Nannou C., Boti V., Albanis T.

The presence of residual pharmaceuticals in the aquatic environment is an important environmental issue. Since the drugs are designed to cause biological responses, they could pose a risk to organisms in their natural environment. In this study, the presence of selected pharmaceutical compounds (paracetamol, phenazone, ketoprofen, budensonide and atenolol) in surface waters was studied. Six sampling points along the aquatic system of the River Louros, close to the city of Ioannina (Epirus, NW Greece), were selected for the assessment of their pollutant load. Analytical method was based on solid-phase extraction of water samples, using Oasis HLB cartridges, followed by high performance liquid chromatography coupled to Orbitrap high resolution mass spectrometry (UHPLC-LTQ/Orbitrap-MS). The methodology exhibited good analytical characteristics (R>65%, R2 >0.9990, LOQs between 1.5 and 11.0 ng/L). Results revealed the presence of only paracetamol (although in levels below LOQ) in two sampling stations. The proposed analytical methodology proved to be fast, easy and reliable for the systematic monitoring of pharmaceuticals residues in natural waters.

Session: 28, Room: D, at Fri, 09/06/2019 - 13:24 to 13:27
Flash presentation in Emerging pollutants
[CEST2019_00537] Optimization of fabric phase sorptive extraction for the determination of selected pharmaceuticals in environmental waters
by Jimenez Holgado C., Vourdas N., Stathopoulos V., Sakkas V.

There is a growing public and scientific concern about the possibility of ecosystem and human health effects from pharmaceuticals in environment. Results have shown that several types of environmental waters (drinking water, groundwater, surface water, treated water) were contaminated by the presence of pharmaceutical compounds including psychiatric drugs. For this reason, it is imperative to develop analytical methods of extraction and pre-concentration to allow for subsequent instrumental analysis of these drugs. In this work, fabric phase sorptive extraction (FPSE) is investigated for the extraction of citalopram, clozapine and sertraline (used in the treatment of mental diseases) in water samples with the aid of chemometric tools and high performance liquid chromatography-photodiode array detection (HPLC-UV/DAD). Parameters affecting the efficiency of FPSE were evaluated in depth. The method shows good linearity, with RSD of less than 15%. Relative recoveries higher than 59% were obtained for the studied compounds

Session: 34, Room: D, at Fri, 09/06/2019 - 17:18 to 17:21
Flash presentation in Emerging pollutants
[CEST2019_00375] Identification of biotransformation products of veterinary drugs present in piggery wastewater during treatment with photobioreactors based on microalgae-bacteria and purple phototrophic bacteria consortia
by López-Serna R., García D., Bolado S., Jiménez J.J., Lai F.Y., Golovko O., Ahrens L., Wiberg K., Gago-Ferrero P., Muñoz R.

This work identified transformation products (TPs) from 16 antibiotics, 1 anti-parasitic, 1 analgesic and 1 hormone, present in spiked real piggery wastewater (PWW) before and after two different treatments in two open photobioreactors operated continuously with a consortium of microalgae-bacteria and purple photosynthetic bacteria. For this purpose, suspect and non-target strategies based on liquid chromatography quadrupole-time-of-flight mass spectrometry (LC-QTOF-MS) were used. The application of quantitative structure-retention relationship (QSRR) prediction models, in addition to a comprehensive evaluation of the obtained MS/MS spectra, provided valuable information to support the identifications. The confirmation of the TPs was carried out with the corresponding reference standards, when these were commercially available. Alternatively, probable structures of the TPs based on diagnostic evidence were proposed. To the best of our knowledge, some of the identified TPs have never been reported before. A transformation pathway for their biotransformation has been proposed. The presence of the identified TPs was assessed in real PWW samples through retrospective analysis. Ultimately, the potential ecotoxicological risk posed by these nineteen veterinary drugs and their TPs was evaluated by means of risk quotients.

Session: 22, Room: D, at Fri, 09/06/2019 - 09:30 to 09:45
Oral presentation in Emerging pollutants
[CEST2019_00376] Evaluation of innovative water treatments at molecular level based on high resolution mass spectrometry and advanced statistical analysis tools
by Gago-Ferrero P., Alygizakis N.A., Velo-Gala I., Sbardella L., Gernjak W., Petrovic M.

This work aims at integrating the last advances in high resolution mass spectrometry (HRMS) and statistical analysis of data to develop and optimize a smart methodology (workflow) for the assessment of the performance of innovative water treatments using different technological approaches based on advanced oxidation processes with UV-254nm: (i) UV/K2S2O8, where oxidation takes place mainly following the initial formation of sulfate radicals, (ii) UV/KHSO5, where oxidation begins with the formation of both sulfate and hydroxyl radicals and (iii) UV/H2O2, when only the formation of hydroxyl radicals takes place initially.
Experiments were carried out using secondary effluent from a local wastewater treatment plant. The developed workflow allows the evaluation of the treatments in terms of overall oxidation through the careful study of Van Krevelen diagrams, where all the masses of the HRMS chromatograms are considered. The potential formation of transformation products with sulfur due to the sulfate radicals was also evaluated using statistical tools based on the isotopic pattern and accurate mass. Finally, the behavior of a large number of micropollutants with a wide range of physicochemical properties was studied using suspect screening strategies.

Session: 28, Room: D, at Fri, 09/06/2019 - 12:00 to 12:15
Oral presentation in Emerging pollutants
[CEST2019_00379] Analysis of degradation of the micro pollutant amoxicillin by photolysis and evaluation of the degradation products.
by Hoehne L., Vettorello G., Ethur E.M., Kuhn D., De Freitas E.M., Steffens C.

Emerging micro pollutants are substances that have recently been identified in environmental matrices, of which information on environmental permanence and toxicity is still scarce. Due to their chemical structure, antibiotics are more stable and require more complex processes for degradation. The present study aimed to elaborate a proposal for the degradation of the β-lactam antibiotic amoxicillin by photolysis, evaluating the formation of by-products. As a methodology, 100 μg /L amoxicillin solutions were submitted to different ultraviolet light bulbs irradiations, at different power and distances, by means of a 100 mL batch quartz reactor. To evaluation degradation of amoxicillin and of the products generated, the high-performance liquid chromatography-mass spectrometry was used.  As a result, the best degradation condition (greater than 90% reduction of the original molecule) was with a 95W light bulb, at a distance of 5 cm from the sample at 10 min irradiation time. Two by-products originated under different pH conditions of the irradiated solution were identified. Based on the obtained results, it is concluded that this prototype and the applied method can be used in the future to reduce this pollutant.

Session: 28, Room: D, at Fri, 09/06/2019 - 13:18 to 13:21
Flash presentation in Emerging pollutants
[CEST2019_00416] Combined use of anaerobic and aerobic moving bed biofilm reactors for micropollutants’ removal from wastewater
by Kora E., Theodorelou D., Herpich A., Gatidou G., Fountoulakis M.S., Stasinakis A.

A novel laboratory-scale continuous flow wastewater treatment system, consisting of an anaerobic moving bed biofilm reactor (AnMBBR) and an aerobic MBBR, was used for investigating the removal of hydroxybenzothiazole (OH-BTH) and selected benzotriazoles from municipal wastewater. The system was operated under three different Experimental Phases where different organic loadings were applied: 0.82 kg COD m-3 d-1 (Phase A), 0.2 kg COD m-3 d-1 (Phase B) and 2.1 kg COD m-3 d-1 (Phase C). The system achieved sufficient COD removal, nitrification and biogas production. All target micropollutants were partially removed during the experiments. Total removal efficiencies ranged from 32% for 5-methyl-1H-benzotriazole (5TTR) to 97% for OH-BTH. The contribution of the strictly anaerobic bioreactor was important for 5TTR, 5-chlorobenzotriazole (CBTR) and xylytriazole (XTR), while the use of aerobic bioreactors resulted to important increase of target compounds removal and it was exclusively responsible for the removal of OH-BTH and benzotriazole (BTR).

Session: 28, Room: D, at Fri, 09/06/2019 - 12:15 to 12:30
Oral presentation in Emerging pollutants
[CEST2019_00418] Investigation of food additives readily biodegradability in respirometric tests
by Vazaiou N., Gatidou G., Arvaniti O.S., Stasinakis A.S.

The biodegradability of fourteen (14) food additives, belonging to different groups such as artificial sweeteners, preservatives and coloring agents, was evaluated using the OECD 301F protocol (manometric respirometry test). According to the results, eight out of fourteen compounds, namely Aspartame, Cyclamate Na, Saccharin, Erythritol, Potassium Sorbate, Benzoic Acid, Sodium Ascorbate and Xylitol are characterized as readily biodegradable with biodegradation rates of 83.6 ± 11.4%, 91.5 ± 5.8%, 76.4 ± 10.3%, 70.6 ± 9.0%, 99.3 ± 7.9%, 97.5 ± 4.0%, 83.8 ± 6.1% and 68.9 ± 2.6%, respectively, during the 28-d experiment. On the other hand, Alitame, Curcumin, Ponceau 4R, Allura Red, Sunset Yellow and Azorubine did not meet the strict definition of ready biodegradability. Further biodegradations tests are required for these compounds in order to investigate their biodegradation potential under different experimental conditions.

Session: 28, Room: D, at Fri, 09/06/2019 - 13:21 to 13:24
Flash presentation in Emerging pollutants
[CEST2019_00214] Characterization of Natural Organic Matter and Disinfection By-products Formed After Chemical Disinfection of Water
by Postigo C., Andersson A., Harir M., Bastviken D., Gonsior M., Schmitt-Kopplin P., Gago-Ferrero P., Ahrens L., Ahrens L., Wiberg K.

The present work aims at investigating the effects of chlorine and chloramine-based disinfection processes on organic matter and the formation of disinfection byproducts (DBPs) in drinking water treatment plants (WTPs). For this, water from four water treatment plants with different characteristics in terms of the type of disinfectant used (chlorine or chloramine) and source water type (groundwater, surface water, or artificially recharged groundwater) was analysed before and after the chemical disinfection process. Specific and generic extraction approaches, and target, suspect and non-target screening approaches using advanced mass spectrometry were used and are currently being explored to characterize the different water matrices.

Session: 28, Room: D, at Fri, 09/06/2019 - 13:27 to 13:30
Flash presentation in Emerging pollutants
[CEST2019_00218] Removal of PFAS from wastewater by bio-waste adsorbent: material characterization and adsorption kinetic study.
by Bavasso I., Bracciale M.P., Sbardella F., Scarsella M., Di Palma L.

Per- and polyfluoroalkyl substances (PFAS) are considered emerging contaminants and have been increased their attention due to their distribution in water body. These compounds are acid and characterized by a thermal stability to make them resistant to degradation processes. Activities such as tannery, paper and cardboard production, waterproof cloths, produce wastewater rich in PFAS and heavy metals. The adsorption process is one of the technologies used for the treatment of wastewater and food residues are getting increased attention as bio-adsorbent because they can be found easily as wastes or by-products and at almost no cost. In this work the removal of PFAS was performed by using food waste such as Yerba Mate (YM) as bio-adsorbent. To achieve the mineralization of Heptadecafluorooctanesulfonic acid adopted as model compounds TiO2 photocatalysis tests were performed. The concentration of pollutants was determined by HPLC, UV-VIS and TOC analysis. SEM-EDS, XRD, FT-IR and BET were done to achieve a characterization of the adsorbent material.

Session: 28, Room: D, at Fri, 09/06/2019 - 13:00 to 13:15
Oral presentation in Emerging pollutants
[CEST2019_00130] Mass balance of selected pharmaceuticals in an Austrian river catchment area: estimation of the different source contributions
by Ghirardini A., Verlicchi P., Zoboli O., Zessner M.

The study refers to the assessment of the annual mass loadings of two pharmaceuticals (PhCs), sulfamethoxazole (SMX) and carbamazepine (CBZ), released in the river of an Austrian catchment area by wastewater treatment plant (WWTP) effluent, combined sewage overflows (CSOs), surface runoff, tile drainage and deep water (referring to the sludge- or manure-amended soil).
WWTP effluent and excess sludge loadings, based on PhC national human consumption, literature excretion rates, were modeled by Activity SimpleTreat. CSO loading was modelled by MoRE. PhC load in manure was estimated on the basis of the animal annual production and literature data of concentration. Surface runoff, tile drainage and deep water loadings were modelled integrating a literature “leachate” approach with the expected PhC phenomena of accumulation, degradation and erosion occurring in the soil.
The study develops a mass balance of the different pharmaceutical loading contributions to the receiving water body by means of STAN model and highlights the uncertainties associated to the selected values in the estimation. It emerges that manure amount applied on the soil is fundamental in defining the priority contributions among the different sources (WWTP effluent, CSOs, surface runoff, tile drainage and deep water).

Session: 22, Room: D, at Fri, 09/06/2019 - 09:45 to 10:00
Oral presentation in Emerging pollutants
[CEST2019_00143] Adsorption technology in waste water treatment processes utilizing activated carbons as adsorbent materials prepared from waste vehicular tires: Recent research and trends in the removal of various toxic and persistent organic and inorganic pollutants
by Vagi M.C., Petsas A.S.

Various toxic contaminants when are present in the environment pose a threat to the inhabitants of natural ecosystems owing to their non-biodegradable nature that increases their high toxicity towards non-target organisms. The large mass of solid wastes that are generated from waste rubber tires unquestionably consists a serious threat of environmental pollution around the world. Consequently, scientific interest has focused on several recycling strategies and practices converting them into more valuable products such as adsorbents widely utilized for the removal of several different inorganic and organic compounds from environmental samples. Hence, the main objective of the present study is to review all the data in the available published bibliography concerning the recent research and future trends on using granulated adsorbent materials and activated carbons obtained and prepared from waste tires and afterwards applied for the removal of persistent and residual quantities of pollutants.

Session: 22, Room: D, at Fri, 09/06/2019 - 10:00 to 10:15
Oral presentation in Emerging pollutants
[CEST2019_00157] The pyrolysis of perfluorocarboxylic acids - effect of chain length
by Dixon L., Weber N., Stockenhuber S., Molloy S., Lucas J., Grimison C., Stockenhuber M., Mackie J., Kennedy E.

Per- and polyfluoroalkyl substance (PFAS) are increasingly becoming the contamination issue of our time, due to their environmental persistence, bioaccumulation and mounting evidence of their toxicity. Herein we examined the pyrolytic decomposition of a series of perfluorocarboxylic acids via the production of CO and CO2, utilizing FTIR and GC/MS analysis.
We observed the presence of a parallel surface-mediated reaction in conjunction with the gas-phase pyrolysis.

Session: 22, Room: D, at Fri, 09/06/2019 - 10:15 to 10:30
Oral presentation in Emerging pollutants
[CEST2019_00097] Extended suspect screening to identify organic micropollutants and their transformation products as potential markers of wastewater contamination in riverine and coastal ecosystems
by Čelić M., Jaén-Gil A., Briceño-Guevara S., Rodriguez-Mozaz S., Gros M., Petrović M.

In this study, a comprehensive suspect screening of organic micropollutants (MPs), and some of their transformation products (TPs) and metabolites, was performed in waste, river and coastal waters from the Ebro Delta region (Catalonia, Spain). For this purpose, an automated suspect screening workflow was developed using two analytical steps: (i) identification of suspected compounds using on-line databases; and (ii) semi-quantification of identified compounds by using isotopic labelled standards. Using this strategy, several pollutants were identified comprising pharmaceuticals, pesticides, abused substances, personal care products, industrial chemicals and surfactants of major relevance in Catalonia. Additionally, their occurrence was evaluated along the wastewater-recipient water chain until they reach estuaries and the Mediterranean Sea. The most ecologically relevant compounds detected, that could be considered as suitable markers of wastewater contamination in freshwater and coastal ecosystems, were highlighted. Results reveal that some suspected TPs and metabolites were more ubiquitous than their parent compound and found at similar concentration levels. These results evidence that suspect screening methodologies can be a useful tool for the identification of relevant markers of wastewater contamination.

Session: 28, Room: D, at Fri, 09/06/2019 - 13:15 to 13:18
Flash presentation in Emerging pollutants