Drugs In Surface Waters Research Articles

Activation of peroxymonosulfate by boron nitride loaded with Co mixed oxides and boron vacancy for ultrafast removal of drugs in surface water

The mediation of vacancy in catalysts is crucial for the enhancement of oxidant activation. Here the boron nitride loaded with Co mixed oxides (Co2O3-CoO) and boron vacancy (Bv) catalyst (Co/BN-X) was prepared to degrade sulfamethoxazole (SMX) by activating peroxymonosulfate (PMS). Under dark condition, Co/BN-3+PMS system can completely remove SMX in surface water within 15 min, and its removal efficiency constant (0.5154 min−1) was 4.0 and 6.7 times greater than those of Co/BN-2+PMS (0.1284 min−1) and Co/BN-1+PMS (0.0771 min−1), respectively. The system showed excellent performance in different influencing factors and cyclic experiments, and exhibited good practical application potential in secondary effluent. Electron paramagnetic resonance, radical quenching and electrochemical tests certified that singlet oxygen (1O2) was the major active species, followed by •O2–, and SO4•–, further elaborating the activation pathway of PMS in Co/BN-3+PMS system. The density functional theory (DFT) calculations confirmed that CoO and PMS-O2 sites were the main reaction sites, and the existence of Bv reduced the adsorption energy of Co/BN-3 for PMS. This work reveals the synergistic effect between Co oxide sites and Bv on the catalyst surface and offers a potential modification method to accelerate Fenton-like reaction.

Flow analysis-solid phase extraction system and UHPLC-MS/MS analytical methodology for the determination of antiviral drugs in surface water

An automated flow analysis-solid phase extraction (FA-SPE) system and methodology of ultra-high-performance liquid chromatography with tandem mass spectrometry (UHPLC-MS/MS) analysis were developed for the determination of selected antiviral drugs (acyclovir, amantadine, rimantadine, and oseltamivir) in water samples. The proposed FA-SPE approach enables the integration of various extraction stages and elimination of the sample evaporation step and offers individual customisation of SPE parameters, inter alia sample, and eluate flow rate and volume. Using the developed FA-SPE procedure, e.g. a 100-fold preconcentration of the target analytes in 1 h was achieved. A method for chromatographic analysis was also developed to determine the selected antiviral drugs in combination with the use of the FA-SPE system. The developed FA-SPE UHPLC-MS/MS method was validated including the determination of linearity of analytical graphs, limits of detection (5.5–99.9 pg mL−1) and quantification (18.3–329.8 pg mL−1), intra-day (1.8–8.3%) and inter-day (3.0–9.2%) precision, recovery (95.6–105.3%), and matrix effects (− 12.9 to 13.2%). The proposed method was successfully applied to analyse tap, drinking, and river water samples, revealing the presence of amantadine at a concentration of 40.1 pg mL−1 in one sample. The environmental impact of the developed FA-SPE sample preparation procedure was also assessed using the AGREEprep metric tool and compared with five other literature methods, achieving the most sustainable outcome.Graphical abstract

Illicit Drugs in Surface Waters: How to Get Fish off the Addictive Hook.

The United Nations World Drug Report published in 2022 alarmed that the global market of illicit drugs is steadily expanding in space and scale. Substances of abuse are usually perceived in the light of threats to human health and public security, while the environmental aspects of their use and subsequent emissions usually remain less explored. However, as with other human activities, drug production, trade, and consumption of drugs may leave their environmental mark. Therefore, this paper aims to review the occurrence of illicit drugs in surface waters and their bioaccumulation and toxicity in fish. Illicit drugs of different groups, i.e., psychostimulants (methamphetamines/amphetamines, cocaine, and its metabolite benzoylecgonine) and depressants (opioids: morphine, heroin, methadone, fentanyl), can reach the aquatic environment through wastewater discharge as they are often not entirely removed during wastewater treatment processes, resulting in their subsequent circulation in nanomolar concentrations, potentially affecting aquatic biota, including fish. Exposure to such xenobiotics can induce oxidative stress and dysfunction to mitochondrial and lysosomal function, distort locomotion activity by regulating the dopaminergic and glutamatergic systems, increase the predation risk, instigate neurological disorders, disbalance neurotransmission, and produce histopathological alterations in the brain and liver tissues, similar to those described in mammals. Hence, this drugs-related multidimensional harm to fish should be thoroughly investigated in line with environmental protection policies before it is too late. At the same time, selected fish species (e.g., Danio rerio, zebrafish) can be employed as models to study toxic and binge-like effects of psychoactive, illicit compounds.

Occurrence, source, and ecological risk of pharmaceuticals and illicit drugs in surface water in Las Vegas, USA

Occurrence, source, and ecological risk of pharmaceuticals and illicit drugs in surface water in Las Vegas, USA

Determination of pollutants, antibiotics, and drugs in surface water in Italy as required by the third EU Water Framework Directive Watch List: method development, validation, and assessment.

In this paper, we report a study concerning the quantification of new emerging pollutants in water as a request from the third European Watch List mechanism. The EU Watch List compound was investigated by an internal method that was validated in terms of detection limits, linearities, accuracy, and precision in accordance with quality assurance criteria, and it was used to monitor several rivers from 11 Italian regions. The methodology developed was satisfactorily validated from 5 to 500 ng L-1 for the emerging pollutants studied, and it was applied to different river waters sampled in Italy, revealing the presence of drugs and antibiotics. Rivers were monitored for 2 years by two different campaigns conducted in 2021 and 2022. A total of 19 emerging pollutants were investigated on 45 samples. The most detected analytes were O-desmethylvenlafaxine and venlafaxine. About azole compounds, sulfamethoxazole, fluconazole, and Miconazole were found. About antibiotics, ciprofloxacin and amoxicillin were found in three and one samples, respectively. Moreover, statistical analyses have found a significant correlation between O-desmethylvenlafaxine with venlafaxine, sulfamethoxazole with venlafaxine, and fluconazole with venlafaxine.

A green method for the determination of illicit drugs in wastewater and surface waters-based on a semi-automated liquid-liquid microextraction device

Liquid-phase microextraction (LPME) is a simple, low-cost, and eco-friendly technique that enables the detection of trace concentrations of organic contaminants in water samples. In this work, a novel customized microextraction device was developed for the LPME extraction and preconcentration of nine illicit drugs in surface water and influent and effluent wastewater samples, followed by analysis by GC–MS without derivatization. The customized device was semi-automated by coupling it with a peristaltic pump to perform the collection of the upper layer of the organic phase. The extraction parameters affecting the LPME efficiency were optimized. The optimized conditions were: 100 µL of a toluene/DCM/EtAc mixture as extractor solvent; 30min of extraction time under vortex agitation (500rpm) and a solution pH of 11.6. The limits of detection and quantification ranged from 10.5ng L−1 (ethylone) to 22.0ng L−1 (methylone), and from 34.9ng L−1 to 73.3ng L−1 for these same compounds, respectively. The enrichment factors ranged from 39.7 (MDMA) to 117 (cocaethylene) and the relative recoveries ranged from 80.4% (N-ethylpentylone) to 120% (cocaine and cocaine-d3). The method was applied to real surface water, effluent, and influent wastewater samples collected in Salvador City, Bahia, Brazil. Cocaine was the main drug detected and quantified in wastewater samples, and its concentration ranged from 312ng L−1 to 1,847ng L−1. Finally, the AGREE metrics were applied to verify the greenness of the proposed method, and an overall score of 0.56 was achieved, which was considered environmentally friendly.

Psychotropic drugs and the environment: a comprehensive analysis of surface water concentrations and associated risks

IntroductionFor most countries it is currently unknown to what degree concentrations of psychotropic drugs in surface water exceed environmental threshold concentrations (ETCs) [MOU1] for ecosystems and what risk mitigation could be applied. ETCs are defined as per-compound threshold concentrations above which detrimental effects on reproduction, growth, and mortality of aquatic organisms cannot be excludeObjectivesTo quantify levels of antidepressants, antipsychotics, mood stabilizers, and benzodiazepines in surface water, investigate their sources and assess whether these levels exceed ETCs.Methods: DesignCross-sectional analysis of measured and modeled data. Environmental levels were compared to ETCs to evaluate their risks for the aquatic environment. Finally, sources of psychotropic drugs were investigated.SettingAll available Dutch water monitoring data from all regional and national monitoring campaigns of 2019, the last year before the COVID-19 pandemic.ExposuresConcentrations of aripiprazole, carbamazepine and its metabolites, clozapine, diazepam, (es)citalopram, fluoxetine, haloperidol, nortriptyline, olanzapine, oxazepam, temazepam, quetiapine, sertraline, valproic acid, and venlafaxine.Main outcomes and measuresThe main outcomes were measured and modeled concentrations of the aforementioned agents in surface water. As a secondary outcome, where possible, average risk quotients (RQs) were calculated by dividing the measured or modeled concentrations by the ETC. An RQ > 1 was interpreted as a risk to the environment.ResultsPsychotropic drug samples (n=1201; 14-520 measurements per drug) showed the highest average concentrations for oxazepam (0.91 μg/L; RQ = 1.89) and carbamazepine (0.74 μg/L; RQ = 1.48), with individual measurements exceeding ETCs. For other drugs, measured concentrations did not reach the detection limit (amisulpride, (es)citalopram, quetiapine, and venlafaxine) or did not exceed the ETC (fluoxetine). Furthermore, households contributed most to psychotropics in surface water. Finally, psychotropics were cleared less efficiently from a wastewater treatment plant than other medications.ConclusionsPsychotropic drugs are present in surface water, are primarily emitted by households, and may put organisms at risk. We signal a need to reduce concentrations of several psychotropic agents in the environment. Our findings set the stage for policies and research aimed at curtailing emissions of psychotropic drugs into the environment and highlight a need for responsible prescribing and waste measures.Disclosure of InterestNone Declared

Residues of Selected Anticonvulsive Drugs in Surface Waters of the Elbe River Basin (Czech Republic)

Anticonvulsants are pharmaceuticals used for epilepsy treatment, pain syndromes therapy and for various psychiatric indications. They enter the aquatic environment mainly through wastewater and were found to cause both biochemical and behavioral changes in aquatic biota. Because the consumption of anticonvulsive drugs is quite high, their monitoring in the aquatic environment is needed. The Elbe River basin is the fourth largest in Europe; the Elbe flows into the North Sea and therefore its contamination is of international importance. The aim of the present study was to determine the presence and concentrations of anticonvulsant pharmaceuticals (carbamazepine, lamotrigine and gabapentin) and their analogues (gabapentin-lactam) in water samples obtained from the Elbe River and its tributaries located in the Czech Republic, as well as to evaluate their correlations with flow rates. The results of this study show that the selected drugs are present in the surface water of the Elbe River in tens to hundreds of ng/L, with the highest measured concentrations for gabapentin. Our results also indicate that the further the sampling point from the Elbe spring is, the higher the concentrations of monitored pharmaceuticals are. Moreover, small tributaries are significantly more contaminated due to their low flow rates with the exceptions of streams flowing from preserved natural sites. The results of the monitoring highlight the importance of building wastewater treatment plants at the municipalities where they are still not present with focus on technology that would be able to decompose substances with negative removal efficiency.

Residues of Cardiovascular and Lipid-Lowering Drugs Pose a Risk to the Aquatic Ecosystem despite a High Wastewater Treatment Ratio in the Megacity Shanghai, China

The residues of pharmaceuticals in surface waters of megacities and ecotoxicological implications are of particular concern. In this study, we combined field investigations and model simulations to explore the contamination of cardiovascular and lipid-lowering drugs, one group of the most prescribed medications globally, in surface waters of a typical megacity, Shanghai, with a high wastewater treatment ratio (≈96%). Among 26 target substances, 19 drugs were detected with aqueous concentrations ranging from 0.2 (ketanserin) to 715 ng/L (telmisartan). Of them, angiotensin II receptor antagonists, telmisartan and irbesartan, were dominant besides β-blockers. Spatial distribution analysis demonstrated their much higher levels in tributaries compared to the mainstream. The results of model simulations and field investigation revealed relatively low concentrations of cardiovascular and lipid-lowering drugs in surface waters of Shanghai compared to other cities in highly developed countries, which is associated with low per capita usage in China. Ecotoxicological studies in zebrafish embryos further revealed developmental effects, including altered hatching success and heart rate, by irbesartan, telmisartan, lidocaine, and their mixtures at ng/L concentrations, which are typical levels in surface waters. Overall, the present results suggest that the high wastewater treatment ratio was not sufficient to protect fish species in the aquatic ecosystem of Shanghai. Exposure to cardiovascular and lipid-lowering drugs and associated risks will further increase in the future due to healthcare improvements and population aging.

Lab-In-Syringe with Bead Injection Coupled Online to High-Performance Liquid Chromatography as Versatile Tool for Determination of Nonsteroidal Anti-Inflammatory Drugs in Surface Waters

We report on the hyphenation of the modern flow techniques Lab-In-Syringe and Lab-On-Valve for automated sample preparation coupled online with high-performance liquid chromatography. Adopting the bead injection concept on the Lab-On-Valve platform, the on-demand, renewable, solid-phase extraction of five nonsteroidal anti-inflammatory drugs, namely ketoprofen, naproxen, flurbiprofen, diclofenac, and ibuprofen, was carried out as a proof-of-concept. In-syringe mixing of the sample with buffer and standards allowed straightforward pre-load sample modification for the preconcentration of large sample volumes. Packing of ca. 4.4 mg microSPE columns from Oasis HLB® sorbent slurry was performed for each sample analysis using a simple microcolumn adapted to the Lab-On-Valve manifold to achieve low backpressure during loading. Eluted analytes were injected into online coupled HPLC with subsequent separation on a Symmetry C18 column in isocratic mode. The optimized method was highly reproducible, with RSD values of 3.2% to 7.6% on 20 µg L−1 level. Linearity was confirmed up to 200 µg L−1 and LOD values were between 0.06 and 1.98 µg L−1. Recovery factors between 91 and 109% were obtained in the analysis of spiked surface water samples.

Advanced Oxidation Process for Degradation of Carbamazepine from Aqueous Solution: Influence of Metal Modified Microporous, Mesoporous Catalysts on the Ozonation Process

Carbamazepine (CBZ), a widely used pharmaceutical compound, is one of the most detected drugs in surface waters. The purpose of this work was to identify an active and durable catalyst, which, in combination with an ozonation process, could be used to remove CBZ and its degradation products. It was found that the CBZ was completely transformed after ozonation within the first minutes of the treatment. However, the resulting degradation products, 1-(2-benzaldehyde)-4-hydro-(1H,3H)-quinazoline-2-one (BQM) and 1-(2-benzaldehyde)-(1H,3H)-quinazoline-2,4-dione (BQD), were more resistant during the ozonation process. The formation and degradation of these products were studied in more detail and a thorough catalytic screening was conducted to reveal the reaction kinetics of both the CBZ and its degradation products. The work was performed by non-catalytic ozonation and with six different heterogeneous catalysts (Pt-MCM-41-IS, Ru-MCM-41-IS, Pd-H-Y-12-EIM, Pt-H-Y-12-EIM, Pd-H-Beta-300-EIM and Cu-MCM-41-A-EIM) operating at two temperatures 20 °C and 50 °C. The influence of temperature on degradation kinetics of CBZ, BQM and BQD was studied. The results exhibited a notable difference in the catalytic behavior by varying temperature. The higher reactor temperature (50 °C) showed a higher activity of the catalysts but a lower concentration of dissolved ozone. Most of the catalysts exhibited higher removal rate for BQM and BQD compared to non-catalytic experiments in both temperatures. The Pd-H-Y-12-EIM catalyst illustrated a higher degradation rate of by-products at 50 °C compared to other catalysts.

Coupling of nanofiltration and UV, UV/TiO2 and UV/H2O2 processes for the removal of anti-cancer drugs from real secondary wastewater effluent

The detection of anti-cancer drugs in surface waters at ng/L indicates that most wastewater treatment processes currently applied are not effective enough to remove these resilient compounds from wastewater. Therefore alternative treatment processes should be tested to avoid discharges in the environment of drugs that have been linked to genotoxic effects. The innovative contribution of this study stands in coupling nanofiltration with advanced oxidation processes to treat real secondary wastewater effluents spiked with 4 widely consumed anti-cancer drugs. Direct photolysis was found to be extremely effective to degrade etoposide and paclitaxel from the secondary effluent as well as from the highly concentrated retentate produced by nanofiltration. The two drugs were not detected after 10 min of exposure that corresponds to higher than 98% removals given the method detection limits by direct injection. This is equivalent to pseudo-first order degradation rate constants higher than 0.46 min−1, which, to the best of the author's knowledge, has not yet been reported for paclitaxel in the literature. However, none of the tested oxidation processes (UV, UV/TiO2 and UV/H2O2) using the reactor setup, exposure times and concentrations of TiO2 and H2O2 tested, were able to degrade cyclophosphamide or ifosfamide effectively. Compared to literature data, this is probably related to the low amount of photons received by the treated media. Finally important aggregation of catalyst particles was observed in secondary effluent, and photocatalysis had no advantage compared to the other two processes tested.

Dual enantioselective LC–MS/MS method to analyse chiral drugs in surface water: Monitoring in Douro River estuary

This work presents the development of an enantioselective method to quantify chiral drugs (CDs) in surface water and its application in the Douro River estuary monitoring. Different classes of CDs were targeted, including 23 compounds, namely beta-blockers, antidepressants, one beta2-adrenergic agonist, non-steroidal anti-inflammatory drugs, stimulants, and some illicit drugs as cocaine (COC) and its metabolites, and amphetamines. The analytical method was based on an innovative application of solid phase extraction (SPE), followed by liquid chromatography-tandem mass spectrometry (LC–MS/MS) using a triple quadrupole analyzer. The ground-breaking approach of SPE consists in the use of Oasis® MCX cartridges to pre-concentrate 500 mL of water samples, allowing the simultaneous extraction of acidic, basic and neutral analytes, rather than the conventional recovery of basic compounds only. Two chiral columns were used for enantiomeric separation in reverse elution mode, a Chirobiotic™V and a Pirkle type Whelk-O®1, for basic and acidic compounds, respectively. The method validation demonstrated good linearity (r2 > 0.99), selectivity and sensitivity, with method detection limits between 0.01 and 2.66 ng L−1 and method quantification limits between 0.02 and 5.71 ng L−1. The developed method was successfully applied to monitor daily variations along one week in surface waters collected in 5 locations of the Douro River estuary. Tramadol (TRM) and its metabolite N-desmethyltramadol (NDT), presented high concentrations near the affluent of a tributary river, while the second eluted enantiomer of O-desmethyltramadol (ODT) was found at high concentrations at the mouth of the Douro River. The metabolite NDT was quantified at higher concentrations than TRM. Venlafaxine (VNF) was found at high concentrations near the affluent of the same tributary river, but its metabolite, O-desmethylvenlafaxine (ODV), was found at concentrations 3 times higher. COC was found every day at all sampling points along the estuary, with slight variations.

Analysis of the presence of anti-inflammatories drugs in surface water: A case study in Beberibe river - PE, Brazil.

The contamination of water by drug residues has occurred all over the world, arousing interest of the scientific community due to possible deleterious effects that can cause to human health and to environment. Conventional treatment of water does not remove drug residues as they are not legislated. Knowledge about the concentrations of exposure of drug residues in aquatic matrices generates subsidies for these compounds to become candidates for future regulation. Beberibe river watershed, due to urbanization, has been affected by domestic effluents causing problems in the quality of water bodies. An old point of abstraction for public supply was abandoned some years ago and the uptake was installed upstream at a new point without presence of domestic effluents. In this context, the present study analyzed the presence of anti-inflammatories drugs in two points of Beberibe river, being Point 1 in a preserved area, not presenting urbanization in its surroundings, and Point 2 in an area that suffers with intense urbanization. During 6 months of surface water collection, contamination by diclofenac and paracetamol were evaluated. The analyzes were performed with using Shimadzu HPLC equipment, with an ULTRA C18 column with reverse phase analysis (5 μm; 4.6 × 250 mm) and UV detection (SPD - 20 A) for wavelengths of 285 nm. Diclofenac had higher concentrations than paracetamol, being 0.193 and 0.042 mg L-1, respectively. The highest levels of concentration were presented in Point 2, probably due to anthropogenic interference. In addition, it was observed that the highest concentrations were detected during drought periods.

Magnetic quaternary chitosan hybrid nanoparticles for the efficient uptake of diclofenac from water

The occurrence of pharmaceuticals in the environment and the water cycle, even at trace levels, has been a matter of great discussion in the literature in the recent years. Despite the clinical relevance of diclofenac (DCF), several studies indicate that it is one of the most frequently detected anti-inflammatory drugs in surface waters, with potential harmful impact on environment and human health. Herein, novel magnetic hybrid nanosorbents composed of magnetite cores encapsulated within a siliceous network highly enriched in a quaternary chitosan (HTCC) were successfully prepared and tested in magnetically assisted removal of sodium diclofenac from aqueous solutions. The DCF adsorption by the produced core–shell nanoparticles was assessed based on several experimental parameters. It was found that under optimal conditions, the modelling of the equilibrium data was best fit with Langmuir and Toth models where the maximum adsorption capacity of DCF was 240.4 mg/g. These results indicate that these hybrid biosorbents are among the most effective magnetic systems for the removal of this pharmaceutical from water. Through the strategy proposed in this work, novel hybrid magnetic nanoparticles containing a cationic surface charge in a broad pH range, from acidic to neutral pH values, is reported. Therefore, these materials may provide a new way of removing a wider class of other anionic contaminants from water.

Development and application of the diffusive gradients in thin films technique for simultaneous measurement of methcathinone and ephedrine in surface river water

In this study, a passive sampling technique, diffusive gradients in thin films (DGT) was developed to simultaneously measure two drugs, methcathinone (MC) and ephedrine (EPH) in surface water. Four types of binding gels and four types of filter membranes were tested for the optimal configuration. XAD18 agarose binding gel and agarose diffusive gel, together with polyethersulfone filter membrane were used for measuring MC and EPH in the DGT device. 5% NH3 in acetonitrile was used as the elution solvent, with the elution efficiency for MC and EPH higher than 71%. At 25°C, the diffusion coefficients of MC and EPH in the diffusive gel were 7.60×10−6cm2s−1 and 6.62×10−6cm2s−1, respectively. The DGT was effective in a wide range of pH (4–11) and ionic strength (NaCl: 0.001–0.5M). The DGT device was deployed in Beijing urban surface water for successive 7days to measure the time-weighted concentrations of MC and EPH. Results showed that EPH was detected in all samples, while MC was below its detection limit. DGT concentrations were comparable to the concentrations determined by SPE. This study demonstrated that the developed DGT method was effective to monitor the two drugs in surface water in situ.

Determination of endocrine disrupting chemicals and antiretroviral compounds in surface water: A disposable sorptive sampler with comprehensive gas chromatography – Time-of-flight mass spectrometry and large volume injection with ultra-high performance liquid chromatography–tandem mass spectrometry

Many rural dwellers and inhabitants of informal settlements in South Africa are without access to treated water and collect untreated water from rivers and dams for personal use. Endocrine disrupting chemicals (EDCs) have been detected in surface water and wildlife of South Africa. EDCs are often present in complex environmental matrices at ultra-trace levels complicating detection thereof. We report a simplified multi-residue approach for the detection and quantification of EDCs, emerging EDCs, and antiretroviral drugs in surface water. A low cost (less than one US dollar), disposable, sorptive extraction sampler was prepared in-house. The disposable samplers consisted of polydimethylsiloxane (PDMS) tubing fashioned into a loop which was then placed in water samples to concentrate EDCs and emerging pollutants. The PDMS samplers were thermally desorbed directly in the inlet of a GC, thereby eliminating the need for expensive consumable cryogenics. Comprehensive gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-TOFMS) was used for compound separation and identification. Linear retention indices of EDCs and emerging pollutants were determined on a proprietary Crossbond® phase Rtx®-CLPesticides II GC capillary column. In addition, large volume injection of surface water into an ultra-performance liquid chromatograph tandem mass spectrometer (UPLC–MS/MS) was used as complementary methodology for the detection of less volatile compounds. Large volume injection reduced tedious and costly sample preparation steps. Limits of detection for the GC method ranged from 1 to 98pg/l and for the LC method from 2 to 135ng/l. Known and emerging EDCs such as pharmaceuticals, personal care products and pesticides, as well as the antiretroviral compounds, efavirenz and nevirapine, were detected in surface water from South Africa at concentration levels ranging from 0.16ng/l to 227ng/l.

Pharmaceuticals and illicit drugs in surface, drinking and swimming pool waters in the Province of Modena: preliminary investigation

Introduction Pharmaceuticals and illicit drug residues are common contaminants of the aquatic environments and appear to be widespread, with consumers being the major source. Even if environmental levels are low, risks for human health cannot be excluded. Methods We present the results on the environmental levels of a group of pharmaceuticals and illicit drugs in surface waters, drinking and pool waters in the Province of Modena (Italy). We tested drugs of abuse (cocaine, opioids, amphetamines and cannabis derivatives), and/or their metabolites and 31 pharmaceuticals which have been previously found in significant concentrations in the environment in Italy. Surface waters of Panaro River were sampled upstream, before receiving the input of waters from the sewage treatment plant of Modena, and then downstream. Drinking waters were collected from three different points in water supplies in the Province and one swimming pool water sample was also investigated, because human release of body fluids may be relevant in swimming pool settings. Pharmaceuticals and illicit drug residues were measured by (HPLC–MS/MS), after solid phase extraction (SPE). Results Surface water from the Panaro River, before receiving wastewaters, shows the presence, at very low levels, of 9 out of 31 investigated pharmaceutical substances: cocaine and its metabolites were the most detected among illicit drugs. High levels of both pharmaceuticals and illicit drugs were observed in surface waters, immediately after receiving wastewaters from the sewage treatment plant. Pharmaceuticals were rarely detected in drinking water samples, while in swimming pool water the anti-inflammatory pharmaceuticals ibuprofen and ketoprofen were observed. Illicit drugs were found at trace levels both in drinking and in swimming pool waters. Conclusions Future research is needed to characterize potential health risks from long-term, low-level exposure to these substances, particularly for sensitive subpopulations.

Biological and photochemical degradation of cytostatic drugs under laboratory conditions

Cytostatic drugs, used in chemotherapy, have emerged as new environmental contaminants due to their recurrent presence in surface waters and genotoxic effects. Yet, their degradability and environmental fate is largely unknown. The aim of this study was to determine the degradation kinetics of 16 cytostatic drugs, prioritized according to their usage and occurrence in hospital and wastewater treatment plants (WWTP) effluents, through the following laboratory scale processes: hydrolysis, aerobic biodegradation, UV-C photolysis, UV-C/H2O2 and simulated solar radiation. Some drugs were unstable in milli-Q water (vincristine, vinblastine, daunorubicin, doxorubicin and irinotecan); others were photodegraded under UV-C light (melphalan and etoposide) but some others were found to be recalcitrant to biodegradation and/or UV-C, making necessary the use of advanced oxidation processes (AOPs) such as UV-C/H2O2 for complete elimination (cytarabine, ifosfamide and cyclophosphamide). Finally, radiation in a solar box was used to simulate the fate of cytostatic drugs in surface waters under natural radiation and complete removal was not observed for any drug. The degradation process was monitored using liquid chromatography coupled to high resolution mass spectrometry and pseudo-first order kinetic degradation constants were calculated. This study provides new data on the degradability of cytostatic compounds in water, thus contributing to the existing knowledge on their fate and risk in the environment.

Occurrence of illicit drugs in surface waters in China

Illicit drugs have been recognized as a group of emerging contaminants. In this work, occurrence of common illicit drugs and their metabolites in Chinese surface waters was examined by collecting samples from 49 lakes and 4 major rivers across the country. Among the drugs examined, methamphetamine and ketamine were detected with highest frequencies and concentration levels, consistent with the fact that these are primary drugs of abuse in China. Detection frequencies and concentrations of other drugs were much lower than in European lakes and rivers reported in the literature. In most Chinese surface waters methamphetamine and ketamine were detected at concentrations of several ng L−1 or less, but in some southern lakes and rivers, these two drugs were detected at much higher concentrations (up to several tens ng L−1). Greater occurrence of methamphetamine and ketamine in southern surface waters was attributed to greater abuse and more clandestine production of the two drugs in southern China.