The distribution coefficient (Kd) and the organic carbon distribution coefficient (KOC) were dete... more The distribution coefficient (Kd) and the organic carbon distribution coefficient (KOC) were determined for four Perfluorinated Compounds (PFCs) to three different types of sludge taken from a conventional Sewage Treatment Plant (STP). Batch experiments were performed in six different environmental relevant concentrations (200ngL(-1)to 5μgL(-1)) containing 1gL(-1) sludge. Kd values ranged from 330 to 6015, 329 to 17432 and 162 to 11770Lkg(-1) for primary, secondary and digested sludge, respectively. The effects of solution's pH, ionic strength and cation types on PFCs sorption were also evaluated. Sorption capacities of PFCs significantly decreased with increased pH values from 6 to 8. Furthermore, the divalent cation (Ca(2+)) enhanced PFCs sorption to a higher degree in comparison with the monovalent cation (Na(+)) at the same ionic strength. The obtained Kd values were applied to estimate the sorbed fractions of each PFC in different stages of a typical STP and to calculate th...
... Speciation Analysis and Environment Determination of migration of n-butyltins and n-octyltins... more ... Speciation Analysis and Environment Determination of migration of n-butyltins and n-octyltins to food simulants by gas chromatographymass spectrometry Sophia D. Papaspyrou1, Nikolaos S. Thomaidis1*, Eugenia N. Lampi2 and Alexandros Lioupis2 ...
Both photodegradation and hydrolysis of non-steroidal anti-inflammatory drugs (NSAIDs) and endocr... more Both photodegradation and hydrolysis of non-steroidal anti-inflammatory drugs (NSAIDs) and endocrine disrupting chemicals (EDCs) were investigated in order to evaluate their photochemical fate in aquatic environment and to assess the effect of season and specific characteristics of water (pH, humic acids and nitrate concentration) on the removal of target EDCs and NSAIDs through photodegradation. An additional objective was the identification of the photodegradation by-products of specific NSAIDs and their dependence on irradiation time. Selected compounds' transformation was investigated under natural sunlight radiation while control experiments were conducted in the dark. As expected, most of compounds' degradation rate decreased with decreasing light intensity between two different experimental periods. Most of the tested compounds exhibited different rates of degradation during direct and indirect photolysis. The degradation rate of the selected compounds increased in th...
ABSTRACT The scope of this study was to investigate the uptake of chromium and nickel by onions (... more ABSTRACT The scope of this study was to investigate the uptake of chromium and nickel by onions (Allium cepa) and potatoes (Solanum tuberosum) and their impact on plant enzymes catalase (CAT, E.C. 1.11.1.6) and peroxidase (POX, E.C. 1.11.1.7). A greenhouse experiment was conducted, simulating the irrigating conditions existing in the two biggest tuber-producing regions of Greece (Asopos and Messapia). Plants were cultivated for 4 months in six irrigation lines, each one supplied by an aqueous solution, containing levels of Cr(VI) and Ni(II) ranging from 0 μg/L (control) to 1,000 μg/L. Significant statistical correlations were observed between (i) the levels of heavy metals in plants, (ii) the levels of heavy metals in plants and in irrigation water, and (iii) the levels of heavy metals and the enzymatic activities in plants. The existing EU legislation has no legal limits for Ni and Cr in food, and the nutritional implications of this study are discussed.
This study presents the atmospheric pressure photoionization (APPI) of high-chlorinated (five or ... more This study presents the atmospheric pressure photoionization (APPI) of high-chlorinated (five or more chlorine atoms) polychlorinated biphenyls (PCBs) using toluene as dopant, after liquid chromatographic separation. Mass spectra of PCB 101, 118, 138, 153, 180, 199, 206 and 209 were recorded by using liquid chromatography-APPI-tandem mass spectrometry (LC-APPI-MS/MS) in negative ion full scan mode. Intense peaks appeared at m/z that correspond to [M - Cl + O](-) ions, where M is the analyte molecule. Furthermore, a detailed strategy, which includes designs of experiments, for the development and optimization of LC-APPI-MS/MS methods is described. Following this strategy, a sensitive and accurate method with low instrumental limits of detection, ranging from 0.29 pg for PCB 209 to 8.3 pg for PCB 101 on column, was developed. For the separation of the analytes, a Waters XSELECT HSS T3 (100 mm × 2.1 mm, 2.5 µm) column was used with methanol/water as elution system. This method was applied for the determination of the above PCBs in water samples (surface water, tap water and treated wastewater). For the extraction of PCBs from water samples, a simple liquid-liquid extraction with dichloromethane was used. Method limits of quantification, ranged from 4.8 ng l(-1), for PCB 199, to 9.4 ng l(-1), for PCB 180, and the recoveries ranged from 73%, for PCB 101, to 96%, for PCB 199. The estimated analytical figures were appropriate for trace analysis of high-chlorinated PCBs in real samples.
The present work describes the development and validation of a highly sensitive analytical method... more The present work describes the development and validation of a highly sensitive analytical method for the simultaneous determination of 68 compounds, including illicit drugs (opiates, opioids, cocaine compounds, amphetamines, and hallucinogens), psychiatric drugs (benzodiazepines, barbiturates, anesthetics, antiepileptics, antipsychotics, antidepressants, and sympathomimetics), and selected human metabolites in influent and effluent wastewater (IWW and EWW) by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The method involves a pre-concentration and cleanup step, carried out by solid-phase extraction (SPE) using the adsorbent Strata-XC, followed by the instrumental analysis performed by LC-MS/MS, using a Kinetex pentafluorophenyl (PFP) reversed-phase fused-core column and electrospray ionization (ESI) in both positive and negative modes. A systematic optimization of mobile phases was performed to cope with the wide range of physicochemical properties of the analytes. The PFP column was also compared with two reversed-phase columns: fused-core C18 and XB-C18 (with a cross-butyl C18 ligand). SPE optimization and critical aspects associated with the trace level determination of the target compounds (e.g., matrix effects) have been also considered and discussed. Fragmentation patterns for all the classes were proposed. The validated method provides absolute recoveries between 75 and 120% for most compounds in IWW and EWW. Low method limits of detection were achieved (between 0.04 and 10.0 ng/L for 87% of the compounds), allowing a reliable and accurate quantification of the analytes at trace level. The method was successfully applied to the analysis of these compounds in five wastewater treatment plants in Santorini, a touristic island of the Aegean Sea, Greece. Thirty-two out of 68 compounds were detected in all IWW samples in the range between 0.6 ng/L (for nordiazepam) and 6,822 ng/L (for carbamazepine) and 22 out of 68 in all EWW samples, with values between 0.4 ng/L (for 9-OH risperidone) and 2,200 ng/L (for carbamazepine). The novel methodology described herein maximizes the information on the environmental analysis of these substances and also provides a first profile of 68 drugs in a Greek touristic area.
Environmental Science and Pollution Research, 2014
The main objective of the current study was to estimate the potential environmental risks associa... more The main objective of the current study was to estimate the potential environmental risks associated with human consumption of antimicrobials in Greece. Consumption data was collected for the 24 most often used antimicrobials for the years 2008-2010, and their predicted environmental concentrations (PECs) in raw and treated wastewater were calculated using mass balances and literature data on human excretion and elimination efficiency during wastewater treatment. The ecotoxicological risk was estimated by calculating the ratio of PEC to predicted no-effect concentration (PNEC) for three categories of aquatic organisms (algae, daphnids, and fish). PNEC values were calculated based on experimental ecotoxicity data and data originated from the Ecological Structure Activity Relationship (ECOSAR). PEC values in raw sewage ranged between 0.02 μg L(-1) (erythromycin) and 27 μg L(-1) (amoxicillin), while in treated wastewater, the highest concentration was predicted for cefuroxime axetil (6.6 μg L(-1)). Based on acute toxicity data for algae, risk quotient (RQ) values higher than 1 were obtained for 7 out of the 24 target antimicrobials in raw and treated wastewater, while no significant risk was estimated for daphnids and fish. Regarding the possible risk due to the chronic toxicity of antimicrobials, RQ values higher than 80 were obtained for amoxicillin and clarithromycin in algae. The use of baseline toxicity data from ECOSAR showed that the environmental risk from exposure to mixtures of antimicrobials was low for all three aquatic species. However, further studies on toxicity of mixtures should be performed as calculation of toxicity ratio (TR) values showed that 90 % of the target antimicrobials seem to exhibit a specific mode of toxic action when present in mixtures rather than baseline toxicity. As a result, an underestimation of toxicity based on the ECOSAR model is possible for the mixture of target antimicrobials. For Greek rivers where low (dilution factor, D<10) and medium (D=10-100) dilution of wastewater occurs, moderate to high risk is expected due to the existence of individual antimicrobials such as amoxicillin, clarithromycin, ciprofloxacin, azithromycin, erythromycin, and levofloxacin in discharged treated wastewater.
The ecological threat associated with emerging pollutants detected in wastewater was estimated in... more The ecological threat associated with emerging pollutants detected in wastewater was estimated in country level. Treated wastewater was analyzed for pharmaceuticals and illicit drugs; whereas the concentrations of all emerging contaminants determined in Greek Sewage Treatment Plants were recorded through literature review. Toxicity data was collected after literature review or using ECOSAR and risk quotients (RQs) were calculated for treated wastewater and 25 Greek rivers, for 3 different aquatic organisms (fish, daphnia magna, algae). According to the results, monitoring data was available for 207 micropollutants belonging to 8 different classes. RQ>1 was calculated for 30 compounds in secondary treated wastewater. Triclosan presented RQ>1 (in algae) for all studied rivers; decamethylcyclopentasilane (in daphnia magna), caffeine (in algae) and nonylphenol (in fish) presented RQ>1 in rivers with dilution factors (DF) equal or lower to 1910, 913 and 824, respectively. The class of emerging contaminants that present the greatest threat due to single or mixture toxicity was endocrine disrupters. The mixture of microcontaminants seems to pose significant ecological risk, even in rivers with DF equal to 2388. Future national monitoring programs should include specific microcontaminants that seem to possess environment risk to surface water.
The distribution coefficient (Kd) and the organic carbon distribution coefficient (KOC) were dete... more The distribution coefficient (Kd) and the organic carbon distribution coefficient (KOC) were determined for four Perfluorinated Compounds (PFCs) to three different types of sludge taken from a conventional Sewage Treatment Plant (STP). Batch experiments were performed in six different environmental relevant concentrations (200ngL(-1)to 5μgL(-1)) containing 1gL(-1) sludge. Kd values ranged from 330 to 6015, 329 to 17432 and 162 to 11770Lkg(-1) for primary, secondary and digested sludge, respectively. The effects of solution's pH, ionic strength and cation types on PFCs sorption were also evaluated. Sorption capacities of PFCs significantly decreased with increased pH values from 6 to 8. Furthermore, the divalent cation (Ca(2+)) enhanced PFCs sorption to a higher degree in comparison with the monovalent cation (Na(+)) at the same ionic strength. The obtained Kd values were applied to estimate the sorbed fractions of each PFC in different stages of a typical STP and to calculate th...
... Speciation Analysis and Environment Determination of migration of n-butyltins and n-octyltins... more ... Speciation Analysis and Environment Determination of migration of n-butyltins and n-octyltins to food simulants by gas chromatographymass spectrometry Sophia D. Papaspyrou1, Nikolaos S. Thomaidis1*, Eugenia N. Lampi2 and Alexandros Lioupis2 ...
Both photodegradation and hydrolysis of non-steroidal anti-inflammatory drugs (NSAIDs) and endocr... more Both photodegradation and hydrolysis of non-steroidal anti-inflammatory drugs (NSAIDs) and endocrine disrupting chemicals (EDCs) were investigated in order to evaluate their photochemical fate in aquatic environment and to assess the effect of season and specific characteristics of water (pH, humic acids and nitrate concentration) on the removal of target EDCs and NSAIDs through photodegradation. An additional objective was the identification of the photodegradation by-products of specific NSAIDs and their dependence on irradiation time. Selected compounds' transformation was investigated under natural sunlight radiation while control experiments were conducted in the dark. As expected, most of compounds' degradation rate decreased with decreasing light intensity between two different experimental periods. Most of the tested compounds exhibited different rates of degradation during direct and indirect photolysis. The degradation rate of the selected compounds increased in th...
ABSTRACT The scope of this study was to investigate the uptake of chromium and nickel by onions (... more ABSTRACT The scope of this study was to investigate the uptake of chromium and nickel by onions (Allium cepa) and potatoes (Solanum tuberosum) and their impact on plant enzymes catalase (CAT, E.C. 1.11.1.6) and peroxidase (POX, E.C. 1.11.1.7). A greenhouse experiment was conducted, simulating the irrigating conditions existing in the two biggest tuber-producing regions of Greece (Asopos and Messapia). Plants were cultivated for 4 months in six irrigation lines, each one supplied by an aqueous solution, containing levels of Cr(VI) and Ni(II) ranging from 0 μg/L (control) to 1,000 μg/L. Significant statistical correlations were observed between (i) the levels of heavy metals in plants, (ii) the levels of heavy metals in plants and in irrigation water, and (iii) the levels of heavy metals and the enzymatic activities in plants. The existing EU legislation has no legal limits for Ni and Cr in food, and the nutritional implications of this study are discussed.
This study presents the atmospheric pressure photoionization (APPI) of high-chlorinated (five or ... more This study presents the atmospheric pressure photoionization (APPI) of high-chlorinated (five or more chlorine atoms) polychlorinated biphenyls (PCBs) using toluene as dopant, after liquid chromatographic separation. Mass spectra of PCB 101, 118, 138, 153, 180, 199, 206 and 209 were recorded by using liquid chromatography-APPI-tandem mass spectrometry (LC-APPI-MS/MS) in negative ion full scan mode. Intense peaks appeared at m/z that correspond to [M - Cl + O](-) ions, where M is the analyte molecule. Furthermore, a detailed strategy, which includes designs of experiments, for the development and optimization of LC-APPI-MS/MS methods is described. Following this strategy, a sensitive and accurate method with low instrumental limits of detection, ranging from 0.29 pg for PCB 209 to 8.3 pg for PCB 101 on column, was developed. For the separation of the analytes, a Waters XSELECT HSS T3 (100 mm × 2.1 mm, 2.5 µm) column was used with methanol/water as elution system. This method was applied for the determination of the above PCBs in water samples (surface water, tap water and treated wastewater). For the extraction of PCBs from water samples, a simple liquid-liquid extraction with dichloromethane was used. Method limits of quantification, ranged from 4.8 ng l(-1), for PCB 199, to 9.4 ng l(-1), for PCB 180, and the recoveries ranged from 73%, for PCB 101, to 96%, for PCB 199. The estimated analytical figures were appropriate for trace analysis of high-chlorinated PCBs in real samples.
The present work describes the development and validation of a highly sensitive analytical method... more The present work describes the development and validation of a highly sensitive analytical method for the simultaneous determination of 68 compounds, including illicit drugs (opiates, opioids, cocaine compounds, amphetamines, and hallucinogens), psychiatric drugs (benzodiazepines, barbiturates, anesthetics, antiepileptics, antipsychotics, antidepressants, and sympathomimetics), and selected human metabolites in influent and effluent wastewater (IWW and EWW) by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The method involves a pre-concentration and cleanup step, carried out by solid-phase extraction (SPE) using the adsorbent Strata-XC, followed by the instrumental analysis performed by LC-MS/MS, using a Kinetex pentafluorophenyl (PFP) reversed-phase fused-core column and electrospray ionization (ESI) in both positive and negative modes. A systematic optimization of mobile phases was performed to cope with the wide range of physicochemical properties of the analytes. The PFP column was also compared with two reversed-phase columns: fused-core C18 and XB-C18 (with a cross-butyl C18 ligand). SPE optimization and critical aspects associated with the trace level determination of the target compounds (e.g., matrix effects) have been also considered and discussed. Fragmentation patterns for all the classes were proposed. The validated method provides absolute recoveries between 75 and 120% for most compounds in IWW and EWW. Low method limits of detection were achieved (between 0.04 and 10.0 ng/L for 87% of the compounds), allowing a reliable and accurate quantification of the analytes at trace level. The method was successfully applied to the analysis of these compounds in five wastewater treatment plants in Santorini, a touristic island of the Aegean Sea, Greece. Thirty-two out of 68 compounds were detected in all IWW samples in the range between 0.6 ng/L (for nordiazepam) and 6,822 ng/L (for carbamazepine) and 22 out of 68 in all EWW samples, with values between 0.4 ng/L (for 9-OH risperidone) and 2,200 ng/L (for carbamazepine). The novel methodology described herein maximizes the information on the environmental analysis of these substances and also provides a first profile of 68 drugs in a Greek touristic area.
Environmental Science and Pollution Research, 2014
The main objective of the current study was to estimate the potential environmental risks associa... more The main objective of the current study was to estimate the potential environmental risks associated with human consumption of antimicrobials in Greece. Consumption data was collected for the 24 most often used antimicrobials for the years 2008-2010, and their predicted environmental concentrations (PECs) in raw and treated wastewater were calculated using mass balances and literature data on human excretion and elimination efficiency during wastewater treatment. The ecotoxicological risk was estimated by calculating the ratio of PEC to predicted no-effect concentration (PNEC) for three categories of aquatic organisms (algae, daphnids, and fish). PNEC values were calculated based on experimental ecotoxicity data and data originated from the Ecological Structure Activity Relationship (ECOSAR). PEC values in raw sewage ranged between 0.02 μg L(-1) (erythromycin) and 27 μg L(-1) (amoxicillin), while in treated wastewater, the highest concentration was predicted for cefuroxime axetil (6.6 μg L(-1)). Based on acute toxicity data for algae, risk quotient (RQ) values higher than 1 were obtained for 7 out of the 24 target antimicrobials in raw and treated wastewater, while no significant risk was estimated for daphnids and fish. Regarding the possible risk due to the chronic toxicity of antimicrobials, RQ values higher than 80 were obtained for amoxicillin and clarithromycin in algae. The use of baseline toxicity data from ECOSAR showed that the environmental risk from exposure to mixtures of antimicrobials was low for all three aquatic species. However, further studies on toxicity of mixtures should be performed as calculation of toxicity ratio (TR) values showed that 90 % of the target antimicrobials seem to exhibit a specific mode of toxic action when present in mixtures rather than baseline toxicity. As a result, an underestimation of toxicity based on the ECOSAR model is possible for the mixture of target antimicrobials. For Greek rivers where low (dilution factor, D<10) and medium (D=10-100) dilution of wastewater occurs, moderate to high risk is expected due to the existence of individual antimicrobials such as amoxicillin, clarithromycin, ciprofloxacin, azithromycin, erythromycin, and levofloxacin in discharged treated wastewater.
The ecological threat associated with emerging pollutants detected in wastewater was estimated in... more The ecological threat associated with emerging pollutants detected in wastewater was estimated in country level. Treated wastewater was analyzed for pharmaceuticals and illicit drugs; whereas the concentrations of all emerging contaminants determined in Greek Sewage Treatment Plants were recorded through literature review. Toxicity data was collected after literature review or using ECOSAR and risk quotients (RQs) were calculated for treated wastewater and 25 Greek rivers, for 3 different aquatic organisms (fish, daphnia magna, algae). According to the results, monitoring data was available for 207 micropollutants belonging to 8 different classes. RQ>1 was calculated for 30 compounds in secondary treated wastewater. Triclosan presented RQ>1 (in algae) for all studied rivers; decamethylcyclopentasilane (in daphnia magna), caffeine (in algae) and nonylphenol (in fish) presented RQ>1 in rivers with dilution factors (DF) equal or lower to 1910, 913 and 824, respectively. The class of emerging contaminants that present the greatest threat due to single or mixture toxicity was endocrine disrupters. The mixture of microcontaminants seems to pose significant ecological risk, even in rivers with DF equal to 2388. Future national monitoring programs should include specific microcontaminants that seem to possess environment risk to surface water.
The NORMAN Network (www.norman-network.com) is a unique network of reference laboratories, resear... more The NORMAN Network (www.norman-network.com) is a unique network of reference laboratories, research centres and related organisations for monitoring of emerging environmental substances, through European and across the world. Key activities of the network include prioritization of emerging substances and non-target screening. A recent collaborative trial revealed that suspect screening (using specific lists of chemicals to find “known unknowns”) was a very common and efficient way to expedite non-target screening (Schymanski et al. 2015, DOI: 10.1007/s00216-015-8681-7). As a result, the NORMAN Suspect Exchange was founded (http://www.norman-network.com/?q=node/236) and members were encouraged to submit their suspect lists. To date 20 lists of highly varying substance numbers (between 52 and 30,418), quality and information content have been uploaded, including valuable information previously unavailable to the public. All preparation and curation was done within the network using open access cheminformatics toolkits. Additionally, members expressed a desire for one merged list (“SusDat”). However, as a small network with very limited resources (member contributions only), the burden of curating and merging these lists into a high quality, curated dataset went beyond the capacity and expertise of the network. In 2017 the NORMAN Suspect Exchange and US EPA CompTox Chemistry Dashboard (https://comptox.epa.gov/) pooled resources in curating and uploading these lists to the Dashboard (https://comptox.epa.gov/dashboard/chemical_lists). This talk will cover the curation and annotation of the lists with unique identifiers (known as DTXSIDs), plus the advantages and drawbacks of these for NORMAN (e.g. creating a registration/resource inter-dependence). It will cover the use of “MS-ready structure forms” with chemical substances provided in the form observed by the mass spectrometer (e.g. desalted, as separate components of mixtures) and how these efforts will support other NORMAN activities. Finally, limitations of existing cheminformatics approaches and future ideas for extending this work will be covered. Note: This abstract does not reflect US EPA policy.
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