Nikolaos S. Thomaidis

Spatial differences and temporal changes in illicit drug use in Europe quantified by wastewater analysis

Aims To perform wastewater analyses to assess spatial differences and temporal changes of illicit drug use in a large European population. Design Analyses of raw wastewater over a 1-week period in 2012 and 2013. Setting and Participants Catchment areas of wastewater treatment plants (WWTPs) across Europe, as follows: 2012: 25 WWTPs in 11 countries (23 cities, total population 11.50 million); 2013: 47 WWTPs in 21 countries (42 cities, total population 24.74 million). Measurements Excretion products of five illicit drugs (cocaine, amphetamine, ecstasy, methamphetamine, cannabis) were quantified in wastewater samples using methods based on liquid chromatography coupled to mass spectrometry. Findings Spatial differences were assessed and confirmed to vary greatly across European metropolitan areas. In general, results were in agreement with traditional surveillance data, where available. While temporal changes were substantial in individual cities and years (P ranging from insignificant to <10−3), overall means were relatively stable. The overall mean of methamphetamine was an exception (apparent decline in 2012), as it was influenced mainly by four cities. Conclusions Wastewater analysis performed across Europe provides complementary evidence on illicit drug consumption and generally concurs with traditional surveillance data. Wastewater analysis can measure total illicit drug use more quickly and regularly than is the current norm for national surveys, and creates estimates where such data does not exist.

Characterization of lead, cadmium, arsenic and nickel in PM2.5 particles in the Athens atmosphere, Greece

Concentrations of Pb, Cd, As and Ni in PM(2.5) particles were measured in samples collected, using low volume PM(2.5) samplers (Harvard Impactor system, HI) at two sites in Athens basin; Patission Street in Athens city center and Rentis, a semi-urban and industrial area, during March 1995-March 1996. Sample analysis for Pb, Cd, Ni and As was accomplished by electrothermal atomic absorption spectrometry after total digestion. Annual geometric mean values in 183 PM(2.5) particles samples were found to be: Pb: 143 nanogram(-3); Cd: 0.34 nanogram(-3); Ni: 4.55 nanogram(-3); As: 0.79 nanogram(-3). The geographical and temporal distribution patterns were investigated. Pb exhibited higher values during the winter period. For the other elements no significant seasonal variation was observed. Wind direction, air temperature and relative humidity affected element concentrations. Principal component analysis was applied on the data to enable source apportionment of toxic elements in PM(2.5) particles. It was found that Pb, As and Ni have common sources, which could be vehicles emissions/oil combustion and resuspended road dust. Cd and a portion of As originate from industrial activities.

Widespread occurrence of bisphenol A diglycidyl ethers, p-hydroxybenzoic acid esters (parabens), benzophenone type-UV filters, triclosan, and triclocarban in human urine from Athens, Greece.

Biomonitoring of human exposure to bisphenol A diglycidyl ethers (BADGEs; resin coating for food cans), p-hydroxybenzoic acid esters (parabens; preservatives), benzophenone-type UV filters (BP-UV filters; sunscreen agents), triclosan (TCS; antimicrobials), and triclocarban (TCC; antimicrobials) has been investigated in western European countries and North America. Nevertheless, little is known about the exposure of Greek populations to these environmental chemicals. In this study, 100 urine samples collected from Athens, Greece, were analyzed by liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) for the determination of total concentrations of five derivatives of BADGEs, six parabens and their metabolite (ethyl-protocatechuate), five derivatives of BP-UV filters, TCS, and TCC. Urinary concentrations of BADGEs, parabens, ethyl-protocatechuate, BP-UV filters, TCS and TCC (on a volume basis) ranged 0.3-20.9 (geometric mean: 0.9), 1.6-1010 (24.2), <2-71.0 (2.1), 0.5-1120 (4.4), <0.5-2580 (8.0) and <0.5-1.9 (0.6) ng/mL, respectively. All 19 target chemicals were found in urine, and the highest detection rates were observed for methyl paraben (100%), bisphenol A bis (2,3-dihydroxypropyl) ether (90%), ethyl paraben (87%), 2,4-dihydroxybenzophenone (78%), propyl paraben (72%), and TCS (71%). Estimated daily intakes (EDIurine), calculated on the basis of the measured urinary concentrations, ranged from 0.023 μg/kg bw/day for Σ5BADGEs to 31.4 μg/kg bw/day for Σ6Parabens.

Fate of selected pharmaceuticals and synthetic endocrine disrupting compounds during wastewater treatment and sludge anaerobic digestion

The concentrations of nine emerging contaminants, including pharmaceutically active compounds (PhACs) (ibuprofen, IBF; naproxen, NPX; diclofenac, DCF; ketoprofen, KFN) and endocrine disrupting chemicals (triclosan, TCS; bisphenol, BPA; nonylphenol, NP; nonylphenol monoethoxylate, NP1EO; nonylphenol diethoxylate, NP2EO), were determined in wastewater and sludge samples of two wastewater treatment plants (WWTPs) in Greece. Average concentrations in raw and treated wastewater ranged from 0.39 (KFN) to 12.52 μg L(-1) (NP) and from <LOD (IBF) to 0.80 μg L(-1) (DCF), respectively. A significant part of nonylphenols (NPs) and TCS in influent wastewater was bound to the particulate phase, while PhACs and BPA were mainly detected in the aqueous phase. Removal of target compounds during wastewater treatment ranged between 39% (DCF) and 100% (IBF). Except of DCF and BPA, similar removal efficiencies were observed in both WWTPs and no effect of WWTPs size and operational conditions was noticed. Use of mass balances showed that accumulation on sludge was a significant removal mechanism for NPs and TCS, while biodegradation/biotransformation was the major mechanism for the other compounds. Sampling of raw and digested sludge demonstrated that IBF and NPX are significantly removed (>80%) during anaerobic digestion, whereas removal of EDCs was lower, ranging up to 55% for NP1EO.

Effect of chromium(VI) on bacterial kinetics of heterotrophic biomass of activated sludge.

The effect of hexavalent chromium, Cr(VI), on the maximum specific growth rate, mu(m) and biomass yield, Y(H), of heterotrophic biomass was studied in batch tests conducted under high (= 10) and low (= 1.5) substrate-to-biomass ratios (S0/X0). The effects of sludge age and biomass acclimatization to Cr(VI) on the bacterial kinetics were also studied. The mu(m) values were determined by measuring oxygen uptake rate (OUR) and volatile suspended solids (VSS) increase. Cr(VI) concentrations equal or greater than 10 mg l(-1) inhibited the growth of unacclimatized activated sludge and caused a significant decrease in mu(m) and Y(H) values. The acclimatization of biomass and the selection of a high operating sludge age reduced the inhibitory effect of Cr(VI). At a sludge age of 20 days, Cr(VI) concentrations of <10 mg l(-1) stimulated bacterial growth as evidenced by an increase in both the mu(m) and Y(H) values. Determining mu(m) values by OUR and VSS methods, revealed that the presence of Cr(VI) in unacclimatized biomass caused an inhibitory effect mostly on substrate oxidation, while in acclimatized biomass, anabolic pathways were inhibited more.

Contribution of primary and secondary treatment on the removal of benzothiazoles, benzotriazoles, endocrine disruptors, pharmaceuticals and perfluorinated compounds in a sewage treatment plant

The occurrence and fate of 36 emerging contaminants, belonging to five different classes, (benzotriazoles, BTRs; benzothiazoles, BTHs; perfluorinated compounds, PFCs; non-steroidal anti-inflammatory drugs, NSAIDs and endocrine disruptors, EDCs) were investigated in raw, treated wastewater (both particulate and dissolved phases), and in sludge from a sewage treatment plant (STP) in Athens, Greece. The average concentrations of BTRs, BTHs, NSAIDs and EDCs in raw wastewater ranged between 11 ng L(-1) and 7.27 μg L(-1), while PFCs did not exceed 100 ng L(-1). In dewatered sludge, the average concentrations ranged between 0.8 ng g(-1) dw (perfluorohexanoic acid, PFHxA) and 3895 ng g(-1) dw (nonylphenol, NP). The distribution of emerging contaminants between particulate and dissolved phase was different among the compounds. BTRs and BTHs showed lower solid-liquid distribution coefficients (Kd) than all other compounds. For 9 over the 27 compounds detected in influents, the removal efficiency was higher than 70%, while the others either were removed to a lesser extent or detected at higher concentrations in effluents. Based on this, advanced treatment processes should be applied in the future for achieving adequate emerging contaminants removal in STPs. Regarding removal mechanisms, almost 60% of BTRs and 30 to 75% of BTHs were removed in bioreactors, while the contribution of primary and secondary clarifiers was of minor importance. Sorption to primary sludge was a significant mechanism affecting EDCs fate in STP.

Progress in the biological and chemical treatment technologies for emerging contaminant removal from wastewater: A critical review

This review focuses on the removal of emerging contaminants (ECs) by biological, chemical and hybrid technologies in effluents from wastewater treatment plants (WWTPs). Results showed that endocrine disruption chemicals (EDCs) were better removed by membrane bioreactor (MBR), activated sludge and aeration processes among different biological processes. Surfactants, EDCs and personal care products (PCPs) can be well removed by activated sludge process. Pesticides and pharmaceuticals showed good removal efficiencies by biological activated carbon. Microalgae treatment processes can remove almost all types of ECs to some extent. Other biological processes were found less effective in ECs removal from wastewater. Chemical oxidation processes such as ozonation/H2O2, UV photolysis/H2O2 and photo-Fenton processes can successfully remove up to 100% of pesticides, beta blockers and pharmaceuticals, while EDCs can be better removed by ozonation and UV photocatalysis. Fenton process was found less effective in the removal of any types of ECs. A hybrid system based on ozonation followed by biological activated carbon was found highly efficient in the removal of pesticides, beta blockers and pharmaceuticals. A hybrid ozonation-ultrasound system can remove up to 100% of many pharmaceuticals. Future research directions to enhance the removal of ECs have been elaborated.

Recent trends in biomonitoring of bisphenol A, 4-t-octylphenol, and 4-nonylphenol.

Bisphenol A (BPA), 4-t-octylphenol (4-t-OP), and 4-nonylphenol (4-NP) are man-made alkylphenolic environmental contaminants possessing controversial endocrine disruption properties. Nowadays, an increased interest is raised for their accurate determination in biological media in order to estimate the exposure to these compounds and the associated health risk. The aim of this review is to present the available analytical methodologies for biomonitoring these three EDCs in human population. In non-occupational human exposure, they are detected in human matrices in trace level concentrations, commonly lower than 1ng/mL. The use of mass spectrometry based methods is particularly emphasized due to their well known superiority over sensitivity, selectivity and precision, even in difficult matrices, such as blood plasma and serum. Recent and most applicable sample preparation techniques are thoroughly presented. The benefits of solid phase extraction (SPE) and expected developments are demonstrated. Recent results from exposure assessment and epidemiologic studies for BPA, 4-t-OP and 4-NP are summarized and future trends are discussed.

Effects of chromium (VI) addition on the activated sludge process.

The effect of hexavalent chromium, Cr(VI), addition on various operating parameters of activated sludge process was evaluated. To accomplish this, two parallel lab-scale continuous-flow activated sludge plants were operated. One was used as a control plant, while the other received Cr(VI) concentrations equal to 0.5, 1, 3 and 5 mgl(-1). Cr(VI) concentrations of 0.5 mgl(-1) caused significant inhibition of the nitrification process (up to 74% decrease in ammonia removal efficiency). On the contrary, the effect of Cr(VI) on organic substrate removal was minor for concentrations up to 5 mgl(-1), indicating that heterotrophic microorganisms are less sensitive to Cr(VI) than nitrifiers. Activated sludge floc size and structure characterization showed that Cr(VI) concentrations higher than 1 mgl(-1) reduced the filaments abundance, causing the appearance of pin-point flocs and free-dispersed bacteria. Additionally, the variability of protozoa and rotifers was reduced. As a result of disperse growth, effluent quality deteriorated, since significant amounts of suspended solids escaped with the effluent. Termination of Cr(VI) addition led to a partial recovery of the nitrification process (up to 57% recovery). Similar recovery signs were not observed for activated sludge floc size and structure. Finally, shock loading to the control plant with 5 mgl(-1) Cr(VI) for 2 days resulted in a significant inhibition of the nitrification process and a reduction in filamentous microorganisms abundance.

Migration of bisphenol A from polycarbonate baby bottles under real use conditions

Migration of the potential endocrine disrupter, bisphenol A (BPA), from 31 polycarbonate (PC) baby bottles into aqueous food simulants was studied under real repetitive use, using a sensitive and fully validated liquid chromatographic method with fluorescence detection. Confirmation of the presence of BPA was performed by liquid chromatography–mass spectrometry (LC–MS). The effects of cleaning in a dishwasher or with a brush, sterilization with boiling water and the temperature of migration were examined. It was shown that temperature was the crucial factor for the migration of BPA from the plastic bottles to water. All samples released BPA in the concentration range 2.4–14.3 µg kg−1 when filled with boiled water and left at ambient temperature for 45 min. The decrease of BPA release in the sterilization water and in the food simulant over 12 cycles of use indicated that the hypothesis of polymer degradation in water is dubious. Estimated infantile dietary exposure, regarding the use of PC baby bottles, ranged between 0.2 and 2.2 µg kg−1 bw day−1, which is below the Tolerable Daily Intake of 50 µg kg−1 bw recently established by EFSA.