Tomáš Mackuľak

National study of illicit drug use in Slovakia based on wastewater analysis

The aim of this study was to analyze illicit drugs and their metabolites in wastewater from eight selected wastewater treatment plants (WWTPs) in Slovakia. The effect of two of the biggest music festivals in Slovakia on illicit drugs in wastewater was also investigated. Urinary bio-markers of amphetamine, methamphetamine, cocaine, cannabis and ecstasy use were analyzed by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). We then compared our results with data obtained in other parts of Europe and the world. This study demonstrates that Slovakia has one of highest methamphetamine consumption rates in Europe. Within Slovakia, the highest level of methamphetamine consumption was found in Petržalka, where the mean specific load of this drug in sewage was 169 mg/day/1000 inhabitants; the next highest loads were detected in Piešťany (128 mg/day/1000 inhabitants) and Bratislava (124 mg/day/1000 inhabitants). Amphetamine, ecstasy and cannabis consumption in our study were comparable to that found in other European cities, whereas cocaine consumption was lower. We also analyzed the pattern of drug consumption over the course of a week. The load of the cocaine metabolite benzoylecgonine in wastewater increased during the weekend. The use of this drug was most common in the capital of Slovakia. Increased consumption was also found during a folk festival in Piešťany. The ecstasy load in wastewater from larger cities also significantly increased over the weekend. An increase of drug consumption was also detected during a music festival in Trenčín, especially for ecstasy. The specific load of ecstasy during this festival increased from 3mg/day/1000 inhabitants to 29 mg/day/1000 inhabitants. The possible influence of music styles on the consumption of certain drugs was also observed. During a folk festival, methamphetamine and cocaine were more commonly used.

Pilot study of seasonal occurrence and distribution of antibiotics and drug resistant bacteria in wastewater treatment plants in Slovakia.

This work presents environmental and quality-control data from the analyses of 33 antibiotics in influent and effluent water from two waste water treatment plants (WWTPs) in the capital and the biggest city of Slovakia. Seeing that consumption of antibiotics depends on epidemiological season, samples were collected during February and August. Among assessed antibiotics ciprofloxacin and clarithromycin were detected in highest concentrations in influent water. Seasonal changes were observed only in plant A when antibiotic concentrations decreased. On the other hand an increase in some cases was observed in plant B. Insufficient degradation of some macrolides, sulfonamides and trimethoprim was detected according to their higher concentrations in effluent water. Contact of antibiotics in subinhibitory concentrations and sludge bacteria in WWTPs represent the base for the development of significant levels of microbial resistance. Simultaneously, antibiotic resistance of fecal coliforms and fecal streptococci from sewage sludge was evaluated. Majority of coliform bacteria were found to be resistant to ampicillin and gentamicin. A significant seasonal difference was determined only in case of high-level resistance. In summer samples, an increase in the strains resistant to concentrations higher than the resistance breakpoints established by EUCAST and NCCLS was observed. No antibiotic resistance in streptococci was observed. However, as a part of sewage sludge is mixed with compost and utilized in agriculture, better processing of sludge should be considered.

Increase of biogas production from pretreated hay and leaves using wood-rotting fungi

Wood-decaying mushrooms can be applied for the pretreatment of lignocellulosic substrates such as leaves, hay and straw. The use of wood-decaying fungus Auricularia auricula-judae for the decomposition of sweet chestnut (Castanea sativa) leaves and hay is discussed in the proposed paper. Such pretreated substrate was employed in the anaerobic processes for biogas production. Comparison of pretreated and non-pretreated substrate revealed that an increase of 15 % in the biogas production can be achieved using the pretreated substrate. Composition of organic compounds in the sludge during the anaerobic process was identified by HPLC. The obtained results show that the utilization of pretreated leaves and hay leads to a gradual increase of the concentration of formic, acetic, and volatile fatty acids as well as to the formation of some aldehydes, ketones, and alcohols.

Fenton-like reaction: A possible way to efficiently remove illicit drugs and pharmaceuticals from wastewater

We analyzed 13 psychoactive pharmaceuticals, illicit drugs and their metabolites in wastewater treatment plant influent and effluent and the possibility of their degradation by biological and chemical processes. Tramadol (413-853 ng/L) and methamphetamine (460-682 ng/L) were the most concentrated compounds in the wastewater in winter and summer, respectively. A significant decrease in the concentration of tramadol in wastewater was measured during the summer. The lowest efficiency was observed for tramadol, venlafaxine, citalopram and oxazepam (∼ 10%) and the highest efficiency was observed for amphetamine and THC-COOH (∼ 80%). The efficiency of compound degradation via the Fenton reaction, a modified Fenton reaction and different degradation (by algae, wood-rotting fungi and enzymes at influent versus effluent) was determined. The Fenton reaction and its modification were efficient at eliminating these substances in comparison with the tested biological processes.

Utilization of Fenton-like reaction for antibiotics and resistant bacteria elimination in different parts of WWTP.

Utilization of relatively low-cost modification of Fenton reaction for the elimination of selected antibiotics and resistant coliforms in different part of wastewater treatment plant (WWTP) was studied. The concentration of antibiotics and occurrence of resistant gems in different stages of WWTP in the capital city of Slovakia - Bratislava was analyzed by LC-MS/MS technique. Consequently, Fenton-like reaction was applied for the elimination of chemical and biological contaminants. Comparative study with classical Fenton reaction was also done. Very high concentrations of clarithromycin, ciprofloxacin and azithromycin in influent water were found. Coliform bacteria were predominantly resistant to ampicillin, ciprofloxacin and gentamicin. After the mechanical stage, the concentration of antibiotics in water was significantly decreased because of the sorption during this step. Biological step degraded 12 types of antibiotics. Analyses of effluent water showed very bad elimination of azithromycin (919ng/L) and clarithromycin (684ng/L). Contrary, ciprofloxacin was removed with very high efficiency (95%). The number of resistant bacteria was also significantly decreased in effluent water. In the case of Escherichia coli only ampicillin and gentamicin resistance bacteria were detected. Our results show that antibiotics as well as resistant bacteria were eliminated by the modification of classical Fenton reaction with high efficiency. The modification of the Fenton reaction can decrease the process wages, environmental impact. Moreover, the degradation process was easily controlled, monitored and tuned.

Fate of psychoactive compounds in wastewater treatment plant and the possibility of their degradation using aquatic plants.

In this study we analyzed and characterized 29 psychoactive remedies, illicit drugs and their metabolites in single stages of wastewater treatment plants in the capital city of Slovakia. Psychoactive compounds were present within all stages, and tramadol was detected at a very high concentration (706 ng/L). Significant decreases of codeine, THC-COOH, cocaine and buprenorphine concentration were observed in the biological stage. Consequently, we were interested in the possibility of alternative tertiary post-treatment of effluent water with the following aquatic plants: Cabomba caroliniana, Limnophila sessiliflora, Egeria najas and Iris pseudacorus. The most effective plant for tertiary cleansing was I. pseudacorus which demonstrated the best pharmaceutical removal capacity. After 48 h codeine and citalopram was removed with 87% efficiency. After 96 h were all analyzed compounds were eliminated with efficiencies above 58%.

Zerovalent iron and iron(VI): Effective means for the removal of psychoactive pharmaceuticals and illicit drugs from wastewaters

Herein we report the analysis of 27 selected psychoactive compounds found in the wastewater of the largest suburb in the eastern part of Central Europe Bratislava—Petržalka, Slovakia. Thirteen of them (MDMA, methamphetamine, amphetamine, THC-COOH, benzoylecgonine, codeine, tramadol, venlafaxine, oxazepam, citalopram, methadone, EDDP, cocaine) were found in concentrations above 30 ng/L. These compoundswere selected for further monitoring. The possibility of complete degradation of these 13 substances by zerovalent iron and iron(VI) was studied in thewastewater from the Petržalka treatment plant. During the week the concentration of themajority of the studied compounds inwastewaterwas stable. Concentrations of MDMA, cocaine, tramadol, and oxazepam reached significantly higher levels during the weekend.Only about 10% removal efficiency for tramadol, venlafaxine, oxazepam, MDMA, citalopram, methadone, and EDDP was observed at the treatment plant. In contrast, methamphetamine, amphetamine, and codeine were removed with 68%, 83%, and 53% efficiency, respectively. The degradation of synthetic drugs (methamphetamine, cocaine, MDMA) in wastewater is limited, while cannabis (of natural biological origin) is degradedwith efficiency greater than 90%. After utilization of the Fenton reaction, its modification, and use of ferrate(VI), a high efficiency of eliminating all of these substances to values below the limit of detection was achieved.

Biodegradation of Benzo[a]Pyrene through the use of algae

AbstractIn this work for disposal of the biologically hard decomposed pollutant Benzo[a]Pyrene (BaP) photooxidation Chlorella kessleri was used. The simulation model system under the different experimental conditions (varying biomass and light intensity) was evaluated. For quantitative analysis of the decrease in BaP, GC/MS technique was used. The highest degradation efficiency was achieved in the case of biomass from the culture of live algae (29%) and light intensity at level of 13.5 W m−2. When the dry biomass was used, degradation under the same conditions was lower because of lack of enzymatic activity in the system.

Estimation of amount of selected pharmaceuticals sorbed onto digested sludge from wastewater treatment plant Bratislava-Petržalka

&NA; Antibiotics and antidepressants are among the most successful drugs used for human therapy. Their concentration in influent on WWTP is relative high and there can be removed by biodegradation or sorption. The aim of this study was to define the amounts of sorbed pharmaceuticals on digested sludge from WWTP Bratislava – Petržalka. The amounts of sorbed pharmaceuticals were calculated from knowing partition coefficients for selected pharmaceuticals and from analytically measured pharmaceuticals concentrations in sludge liquor. From this calculation were estimated the one‐year sorbed amount of pharmaceutical onto sludge from wastewater treatment plant Petržalka (26,066 g/y for ciprofloxacin, 756 g/y for azithromycin, 647 g/y for clarithromycin, 445 g/y for venlafaxine and 148 g/y for citalopram). Graphical abstract: Figure. No caption available. HighlightsInfluent on WWTP and sludge liquor contains broad range of pharmaceuticals.Citalopram and ciprofloxacin are removed on WWTP by sorption.Azithromycin, clarithromycin and venlafaxine are partially removed by sorption.

Evaluation of different smoking habits during music festivals through wastewater analysis.

Wastewater analysis is a powerful method that can provide useful information about the abuse of legal and illicit drugs. The aim of our study was to determine nicotine consumption during four different music festivals and to find a connection between smoking and preferences for specific music styles using wastewater analysis. The amount of the nicotine metabolite cotinine was monitored in wastewater at the influent of three waste water treatment plants WWTPs in the Czech Republic and Slovakia, where the festivals took place. Urinary bio-markers of nicotine utilization were analyzed by LC-HRMS. More than 80,000 festival participants were monitored during our study from June to September 2014. A significant increase of nicotine consumption was observed in wastewaters during music festivals. The nicotine ingestion level was back-calculated and expressed as mass of pure drug consumed per day and per 1000 inhabitants for selected cities of both countries. The highest differences between typical levels of cotinine in wastewaters and the levels during music festivals were detected in Piešťany: 4 g/L/1000 inhabitants during non-festival days compared to 8 g/L/1000 inhabitants during the Topfest pop-rock festival and 6g/L/1000 inhabitants during the Grape dance festival. No significant increase of the amounts of cotinine in wastewater was recorded for the Country and Folk festivals.