Drug Residues In Water Research Articles

Fe3O4@SiO2@MPA-TAPA-COF as a novel sorbent in magnetic solid-phase extraction coupling with UPLC-MS/MS for determining 12 sulfonamides in water and milk

This study aimed to design and synthesize a novel adsorbent Fe3O4@SiO2@MPA-TAPA-COF material for the first time and used as an adsorbent of MSPE. It had significant potential for the pretreatment of trace analytes. The MSPE was coupled with ultra performance liquid chromatography–tandem mass spectrometry (UPLC-MS/MS) for the rapid extraction and detection of 12 sulfonamides (SAs) from water and milk samples for the first time. Several experimental parameters were optimized, including adsorbent dosage and the effects of pH, ionic strength, adsorption time, and desorption conditions. Under the optimized pretreatment and instrumental conditions, good linearity of 0.1–100 μg·L−1 with a correlation coefficient 0.9994–0.9999, low limits of detection (0.004–0.044 μg·L−1) and limits of quantitation (0.013–0.136 μg·L−1) were obtained. Moreover, the recoveries of sulfonamides in water and milk samples were in the range of 60.88 %-102.94 %, and the relative standard deviations not exceeding 9.62 %. Finally, the magnetic Fe3O4@SiO2@MPA-TAPA-COF material possessed the magnetic separation and high adsorption affinity for extracting SAs from real samples. This study holds great significance in enhancing the monitoring of SAs drug residues in water and milk.

Ultrasensitive detection of ornidazole–antibiotic drug residues in water using NiMOFs functionalized MWCNT modified electrode

Nitroimidazole-based drugs are widely used as an antibiotic for the treatment of anaerobic bacterial and parasite illnesses. The widespread use of these drugs in animal feed and the consequent environmental pollution have become significant concerns in recent years. Simple, sensitive, and rapid detection of the antibody in various real samples is demanding research interest. Herein, we report a Nickel-metal organic framework functionalized Multiwalled Carbon nanotubes modified glassy carbon electrode (MWCNT@NiMOFs) as an ultrasensitive and rapid voltammetric sensor for the detection of ornidazole (ORDZ) in a neutral pH solution. The MWCNT@NiMOFs were prepared using a microwave-assisted solvothermal technique accompanied by an ultrasonication method. The designed MWCNT@NiMOFs offered a low charge transfer resistance (Rct) of 141 Ω along with excellent electrocatalytic activity, and high current density at the lowered cathodic peak potential (-0.62 V vs Ag/AgCl) for ORDZ detection. The surface adsorption capacity (Γs) in terms of surface excess and heterogeneous charge transfer rate constant (k0) of the MWCNT@NiMOFs were calculated to be 3.29 × 10-9 mol cm−2 and 5.33 × 10-3 cm s−1, respectively. Under an optimal working condition, differential pulse voltammetry measurements of ORDZ have shown concentration linearity in a window, 100 nm to 10 µM range with excellent sensitivity, 5.69 × 10-5A µM−1 cm−2, and detection limit, 26 nM (3.3/s). The designed MWCNT@NiMOFs offered appreciable reproducibility, and repeatability up to 30 days of storage time. The real-time quantitative evaluation of ORDZ in human urine and tap water specimens was done along with ∼ 100 % recovery values. Since the new approach is simple, selective, and separation-free, it can be extendable to a variety of real-time practical applications.

Evaluation of direct sample injection as a fast, no-sample handling, approach for the LC-MS/MS monitoring of pharmaceuticals in different water matrices

The determination of drug residues in water, particularly in environmental water, is a hot topic due to the usual presence of these emerging contaminants in the aquatic environment and their potential negative impact on water quality. The most widely approach applied at present for their determination is the use of a solid phase extraction (SPE) step followed by the LC-MS/MS measurement. This is due to the theoretical need to pre-concentrate the analytes and to produce “clean” sample extracts leading to less inferences in subsequent analysis. However, in LC-MS/MS based methods, the main interferences are not “visible” and are mostly due to matrix effects, which in fact are produced by unknown compounds that co-elute with the analytes and therefore not easily removed by SPE. As an alternative, an increasing trend is observed towards the use of direct injection (DI) of the samples, which is nowadays possible thank to the notable improvement in sensitivity of modern LC-MS/MS instrumentation.In this work, both approaches, SPE and DI, have been evaluated for the determination of 16 pharmaceuticals in three different types of water: groundwater, surface water and effluent wastewater. The study has been performed by using pharmaceutical reference standards and their corresponding isotope-labelled internal standards (ILIS) for efficient matrix effects correction. Both methodologies have been compared in terms of matrix effects, sensitivity, and suitability for the analysis of real-world water samples. Our data show that DI is an efficient alternative to SPE, with satisfactory analyte recoveries for most pharmaceuticals, matrix effects even lower than in SPE, and sufficient sensitivity for most of applications. In addition, the absence of sample treatment minimizes potential errors associated with this step, and there is a notable saving in the analysis time and costs. The analysis of Quality Control (QC) samples included in different sample batch sequences has been used to support the feasibility of using DI in this type of analysis.

Multiclass determination of drug residues in water and fish for bioaccumulation potential assessment

In this work, a wide-scope liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the quantitative determination of environmental levels of multiclass drugs and their metabolites in water and fish samples was developed. The method allowed the reliable determination of 44 drugs, covering a rather wide range of chemistries and physicochemical characteristics. In order to obtain a reliable and robust analytical protocol, different combinations of extraction and cleanup techniques were systematically examined. Aqueous samples were extracted using a simple Oasis HLB SPE enrichment protocol with pH-optimized sample percolation (pH 3). The extraction of cryo-homogenized biota samples was performed using double extraction with MeOH basified with 0.5% NH3, which allowed high extraction recoveries for all target analytes. The problem of the coextracted lipid matrix, which is known to be the key obstacle for reliable biota analysis, was systematically examined in a series of model cleanup experiments. A combination of cryo-precipitation, filtration, and HLB SPE cleanup was proposed as a protocol, which allowed reliable and robust analysis of all target compounds at low ng/g levels. At the final conditions, the method which was validated at three concentration levels showed high extraction recoveries (68–97%), acceptable matrix effects (12 to −32%), accuracies (81–129%), and reproducibilities (3–32%) for all analytes. The developed method was used to determine drug concentrations in river water and in feral freshwater fish, including whole fish and muscle tissue, from the Sava River (Croatia), in order to estimate their corresponding bioaccumulation potential. With respect to bioaccumulation potential in whole fish and fish muscle, the most relevant drugs were lisinopril, sertraline, terbinafine, torsemide, diazepam, desloratadine, and loratadine with estimated bioaccumulation factors ranging from 20 to 838 and from 1 to 431, respectively.

Electrooxidation and Development of a Highly Sensitive Electrochemical Probe for Trace Determination of the Steroid 11-Desoxycorticosterone Drug Residues in Water

Anabolic-androgenic steroids (AASs), a class of compounds frequently misused by competitors and unfortunately by the general population, have lately attracted international attention. Thus, extraordinary demands for developing low cost, precise, rapid, and facile protocols for detection and/or determination of AAS have arisen. Hence, the current strategy explores for the first time the redox features of 21-hydroxypregn-4-ene-3, 20-dione, namely, 11-desoxycorticosterone (DCS) AA drug steroid at a glassy-carbon electrode (GCE) in a wide pH range (pH 2.0–10.0) by adsorptive differential pulse-anodic stripping voltammetry (DP- ASV) and cyclic voltammetry (CV). At pH 2, DP-ASV and CV at the optimized pH 2–3 displayed an irreversible anodic peak at 0.4 V versus Ag/AgCl electrode. The dependency of the anodic peak current of the CV at 0.4 V at various concentrations and scan rate of the DCS drug was characteristic of an electrode-coupled electron transfer of EE type mechanism. At the optimized parameters, the proposed strategy allowed quantification of DCS in the concentration range 2.5 -13.19 nM (0.83-4.36 ng mL−1) with satisfactory limits of detection (LOD) and quantization (LOQ) of 9.3 × 10−1 nM (3.1 × 10−1 ng mL−1) and 3.1 nM (1.02 ng mL−1), respectively. A relative standard deviation (RSD) of ±3.93% (n = 5) at 4.0 ng mL−1 DCS was achieved. The established probe was fruitfully employed and validated for trace determination of DCS residues in environmental water. The interference of several common diverse species on DCS sensing was insignificant revealing good selectivity. The established probe exhibited good sensitivity, selectivity, precision, and accuracy, short analytical time, and low cost compared with the reported methods, for DCS determination.

Effective degradation of COVID-19 related drugs by biochar-supported red mud catalyst activated persulfate process: Mechanism and pathway

With the global spread of the COVID-19 pandemic, the water pollution caused by extensive production and application of COVID-19 related drugs has aroused growing attention. Herein, a novel biochar-supported red mud catalyst (RM-BC) containing abundant free hydroxyl groups was synthesized. The RM-BC activated persulfate process was firstly put forward to degrade COVID-19 related drugs, including arbidol (ARB), chloroquine phosphate, hydroxychloroquine sulfate, and acyclovir. Highly effective removal of these pharmaceuticals was achieved and even 100% of ARB was removed within 12 min at optimum conditions. Mechanism study indicated that SO4•− and HO• were the predominant radicals, and these radicals were responsible for the formation of DMPOX in electron spin resonance experiments. Fe species (Fe0 and Fe3O4) and oxygen-containing functional groups in RM-BC played crucial roles in the elimination of ARB. Effects of degradation conditions and several common water matrices were also investigated. Finally, the degradation products of ARB were identified by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and possible degradation pathways were proposed. This study demonstrated that RM-BC/PS system would have great potential for the removal of COVID-19 related drug residues in water by the catalyst synthesized from the solid waste.

Environmental impact of prescribing in family medicine - Example of simple urinary tract infection

As the pharmaceutical industry keeps growing, the presence and impact of drug residues in water is becoming increasingly well documented. These end up in wastewater after human consumption, and then in surface water if they are not sufficiently removed in wastewater treatment plants, harming aquatic organisms even in minute quantities. Antibiotics and NSAIDs are the most worrying for the environment. We would recommend here a reduction in their prescription in urinary tract infections, considering that spontaneous healing occurs in half of the cases. We indicate more natural alternatives, with a reasonable level of safety despite a low level of evidence.

Analysis of β-blocker timolol maleate drug residues in wastewater and biological fluids using differential pulse – anodic stripping voltammetry

ABSTRACT Drug residues in water represent one of the most serious environmental problems because of their high toxicity to the biological system. Thus, this study reports a low-cost strategy for fast and precise analysis of β- blocker timolol maleate (TM) using differential pulse anodic stripping voltammetry (DP ASV) at a bare glassy carbon electrode (GCE). At the optimised solution pH 7.2 and other analytical parameters (accumulation time, deposition potential, scan rate, and pulse amplitude), a well-defined oxidation peak was observed at 0.85 V vs Ag/AgCl electrode. The linear calibration range for TM at 0.85 V vs. Ag/AgCl electrode was found to be 5.0 × 10−7 – 1.3 × 10−4 mol L−1 (0.21–56.2 μg mL−1) (R 2 = 0.9947) with lower limits of detection (LOD) and quantitation (LOQ) of 2.7 × 10−7 (0.12) and 8.99 × 10−7 mol L−1 (0.39 μg mL−1), respectively. The developed assay was satisfactorily applied for trace determination of TM residues in biological fluids (urine), environmental water samples and eye drop with good recoveries (90.5 ± 0.66–106 ± 0.66%), demonstrating good accuracy and applicability of the proposed method as an effective and reliable electrochemical sensor for analysis of TM in complex matrices. Common organic and inorganic compounds did not interfere with TM in its determination. The established strategy was validated using the official HPLC method. Analysis results obtained by the present method were comparable to those obtained using the official method; indicating that the proposed method could be used as an alternative method for the routine quality control of the drug in complex matrices. Chromatographic methods are still more precise, while electrochemical sensors are promising for the analyte determination as they have reduced analytical time, low cost and reproducible. The proposed sensor also demonstrated excellent precision, selectivity, and reproducibility for TM determination.

Persistent and transgenerational effects of risperidone in zebrafish

Since behavior is the connection between the internal physiological processes of an animal and its interaction with the environment, a complete behavioral repertoire is crucial for fish survival and fitness, at both the individual and population levels. Thus, unintended exposure of non-target organisms to antipsychotic residues in the environment can impact their normal behavior, and some of these behavioral changes can be seen during the entire life of the animal and passed to subsequent generations. Although there are some reports related to transgenerational toxicology, little is known of the long-term consequences of exposure to pharmaceutical compounds such as risperidone. Here, we show that zebrafish exposed to risperidone (RISP) during embryonic and larval stages presented impaired anti-predatory behavior during adulthood, characterizing a persistent effect. We also show that some of these behavioral changes are present in the following generation, characterizing a transgenerational effect. This suggests that even short exposures to environmentally relevant concentrations, at essential stages of development, can persist throughout the whole life of the zebrafish, including its offspring. From an environmental perspective, our results suggested possible risks and long-term consequences associated with drug residues in water, whichcan affect aquatic life and endanger species that depend on appropriate behavioral responses for survival.

Simultaneous detection of antibiotics and other drug residues in the dissolved and particulate phases of water by an off-line SPE combined with on-line SPE-LC-MS/MS: Method development and application

Due to their widespread use in human and animal healthcare, antibiotics and other drug residues are ubiquitous in the aquatic environment. Given their potential impacts on ecosystem functioning and public health, the quantification of environmental drug residues has become a necessity. Various analysis techniques have been found to be suitable for reliable detection of such compounds. However, quantification can be difficult because these compounds are present at trace or ultra-trace levels. Consequently, the accuracy of environmental analyses depends on both the efficiency and the robustness of the extraction and quantification method. In this work, an off-line solid-phase extraction (SPE) combined with on-line SPE-LC-MS/MS was applied to the simultaneous extraction and quantification of 26 pharmaceutical products, including 18 antibiotics, dissolved in a water phase. Optimal conditions were determined and then applied to assess the contamination level of the targeted drug residues in water collected from four sites in Northern France: a river, the input and output of an aerated lagoon, and a wastewater treatment plant. Drug residues associated with suspended solid matter (SSM) were also quantified in this work using pressurized liquid extraction (PLE) combined with an on-line SPE-LC-MS/MS system in order to complete an assessment of the degree of total background pollution.

Inter-laboratory test on drug residues in water intended for human consumption

In June 2009, the Laboratory in hydrology of Nancy (Ansès-LHN, Nancy) conducted an exploratory inter-laboratory proficiency tests (ILT) test in collaboration with the AQUAREF network to identify laboratory practices and estimate inter-laboratory uncertainty for the compounds under study. There were a total of 12 compounds belonging to six families (hormones, antibiotics, non-steroidal anti-inflammatory drugs, beta blockers, antipsychotics and others) including one compound used in veterinary medicine. It was the first ILT conducted in France on water intended for human consumption. Thirty-one laboratories participated, 4 of which were located abroad.

Assessment of the health risks related to the presence of drug residues in water for human consumption: Application to carbamazepine

Pharmaceutical residues have been detected at low (usually ng/L) concentrations in drinking water sources. The detection of drugs in water intended for human consumption (WIHC) has raised questions of safety. In the absence of regulatory or other official guidance, water utilities are faced with a problem of which pharmaceutical residues should be monitored and the toxicological limits that should be required.In this essay, we define an approach for the assessment of health risks related to chemicals found in drinking water. We use the examples of carbamazepine and its main metabolite 10,11-epoxycarbamazepine to demonstrate our approach, which involves application of the following algorithm: (1) when there is human or animal toxicity data, a toxicity reference value (TRV) can be calculated; (2) when this is not applicable, an attempt should be made to derive the TRV using known information about the minimum therapeutic dose (MTD); and (3) when no applicable data is available, at all, a threshold of toxicological concern (TTC) should be estimated.In the case of carbamazepine, where relevant toxicological data exists, we derived a TRV, based on the known minimum therapeutic dose (MTD). For carbamazepine’s metabolite 10,11-epoxycarbamazepine, there is no toxicological data, so we applied the TTC approach. Using this approach, and combining our estimates with what is known about these chemicals’ margin of exposure (MOE), suggests that there is likely to be no appreciable risk to human health exposure to carbamazepine or its major metabolite, even given the inevitable uncertainties in exposure scenarios.

Peering into dirty waters: the potential and implications of a new approach to monitoring drug consumption

Peering into dirty waters: the potential and implications of a new approach to monitoring drug consumption

Electrochemical oxidation of drug residues in water by the example of tetracycline, gentamicine and aspirin®

Electro-chemical oxidation as a method to destroy drug residues like aspirin, tetracycline or gentamicine in water was investigated with C-anodes (modified by manganese oxides) and Pt anodes. The mechanism of aspirin and tetracycline oxidation and the influence of the biocide effect was observed using GC-MS and three different microbiological tests. In general, the biological availability increases with progressive oxidation of the antibiotics.

Combination of Aqueous and Non-Aqueous Capillary Electrophoresis with Electrospray Mass Spectrometry for the Determination of Drug Residues in Water

The work presented in this paper deals with the combination of capillary electrophoresis (CE) with electrospray mass spectrometry (MS) for the determination of drug residues in water. CE/MS methods have been developed based on either aqueous or non-aqueous ammonium acetate solutions as the carrier electrolyte for the separation of selected drugs. The different separation conditions were compared in terms of selectivity and detection limits; both aqueous and non-aqueous CE proved to be suitable for the present analytical task, exhibiting detection limits between 3 and 93 μg/dm3 (injected standard concentration) corresponding to concentrations between 5 and 19 ng/dm3 in the sample. A combination of liquid-liquid extraction and solid-phase extraction was investigated for sample pretreatment, yielding enrichment factors of 10000. The applicability of CE/MS was demonstrated for the analysis of several river water samples.

Determination of drug residues in water by the combination of liquid chromatography or capillary electrophoresis with electrospray mass spectrometry

Methods for the determination of drug residues in water have been developed based on the combination of liquid chromatography (LC) or capillary electrophoresis (CE) with mass spectrometry (MS). For HPLC–MS two types of interfaces (pneumatically assisted electrospray ionization interface or an atmospheric pressure chemical ionization interface, respectively) were employed and compared in terms of detection limits. 2 m M Ammonium acetate at pH 5.5 and a methanol gradient was used for the HPLC–MS allowing the separation of a number of drugs such as paracetamol, clofibric acid, penicillin V, naproxen, bezafibrate, carbamazepine, diclofenac, ibuprofen and mefenamic acid. A 20 m M ammonium acetate solution, pH 5.1 was employed for the separation of clofibric acid, naproxen, bezafibrate, diclofenac, ibuprofen and mefenamic acid by CE–MS. Sample pretreatment was performed by solid-phase extraction (SPE) for HPLC–MS or by a combination of liquid–liquid extraction and SPE for CE–MS. The applicability of both the HPLC–MS and CE–MS method was demonstrated for several river water samples.