Fate of pharmaceuticals--photodegradation by simulated solar UV-light

The fate of pharmaceuticals in surface waters under solar irradiation was investigated. Photodegradation of pharmaceuticals caused by sun irradiation may be of major significance in the natural elimination process. Based on a data compilation from the literature, the lipid lowering agent metabolite clofibric acid, the iodinated X-ray contrast media iomeprol, which contribute to the adsorbable organic halogen compounds, and the antiepileptic drug carbamazepine were selected. The irradiation experiments were carried out in batch experiments with simulated UV–sunlight. The photodegradation of the pharmaceuticals showed a pseudo-first-order kinetics. The objective of this investigation was to demonstrate that the extent of photoinduced degradation of pharmaceuticals can vary significantly for the different pharmaceuticals and it strongly depends on the water constituents present in solution. The influences of different initial pharmaceutical concentrations, the presence of other pharmaceuticals like carbamazepine or clofibric acid and the presence of natural organic matter on the photochemical degradation rate of pharmaceuticals in aqueous solutions were investigated. Analyses of the pharmaceuticals and their photodegradation products were carried out by high performance liquid chromatography with diode-array and fluorescence detection.     

The removal of microorganisms and organic micropollutants from wastewater during infiltration to aquifers after irrigation of farmland in the Tula Valley, Mexico

The Tula Valley receives untreated wastewater from Mexico City for agricultural irrigation, half of which infiltrates to aquifers from where drinking water is extracted. Samples of wastewater and infiltrated water from three areas of the valley were analyzed for microorganisms, organic micropollutants, and some basic parameters. Concentrations of microorganisms in the infiltrated water were generally very low but the incidence of fecal coliforms (present in 68% of samples), somatic bacteriophages (36%), Giardia spp. (14%), and helminth eggs (8%) suggested a health risk. Organic micropollutants, often present at high concentrations in the wastewater, were generally absent from the infiltrated water except carbamazepine which was in 55% of samples (up to 193 ng/L). There was no correlation between carbamazepine concentrations and the presence of microorganisms but highest concentrations of carbamazepine and boron coincided. A treatment such as nanofiltration would be necessary for the infiltrated water to be a safe potable supply.     

Uptake of carbamazepine by cucumber plants--a case study related to irrigation with reclaimed wastewater

Reclaimed wastewater is an important source of irrigation in semiarid and arid zones. Here we report data on carbamazepine (CBZ) uptake by cucumber plants in hydroponic culture and greenhouse experiments using different soil types irrigated with fresh water or reclaimed wastewater. Data obtained from the hydroponic culture experiments suggest that CBZ is mainly translocated by water mass flow, and thus it is concentrated and accumulated to the largest extent in the mature/older leaves. Carbamazepine concentration in cucumber fruits and leaves was negatively correlated with soil organic matter content. The concentrations of CBZ in the roots and stems were relatively low, and most CBZ in the plant (76-84% of total uptake) was detected in the leaves. A greenhouse experiment using fresh water and reclaimed wastewater spiked, or not, with CBZ at 1 μg L⁻¹ (typical concentration in effluents) revealed that CBZ can be taken up and bioaccumulated from its background concentration in reclaimed wastewater. Bioaccumulation factor (calculated as the ratio of CBZ concentration in the plant to that in the soil solution) for the fruits (0.8-1) was significantly lower than the value calculated for the leaves (17-20).This study emphasizes the potential uptake of active pharmaceutical compounds by crops in organic-matter-poor soils irrigated with reclaimed wastewater and highlights the potential risks associated with this agricultural practice.     

Electro-catalytic activity of CeOx modified graphite felt for carbamazepine degradation via E-peroxone process

•CeO_x/GF-EP process had the better degradation efficiency than GF-EP process. •CeO_x/GF-EP process had the flexible application in the pH range from 5.0 to 9.0. •CeO_x could enhance surface hydrophilicity and reduce the charge-transfer resistance. •The interfacial electron transfer process was revealed. E-peroxone (EP) was one of the most attractive AOPs for removing refractory organic compounds from water, but the high energy consumption for in situ generating H₂O₂ and its low reaction efficiency for activating O₃ under acidic conditions made the obstacles for its practical application. In this study, cerium oxide was loaded on the surface of graphite felt (GF) by the hydrothermal method to construct the efficient electrode (CeO_x/GF) for mineralizing carbamazepine (CBZ) via EP process. CeO_x/GF was an efficient cathode, which led to 69.4% TOC removal in CeO_x/GF-EP process with current intensity of 10 mA in 60 min. Moreover, CeO_x/GF had the flexible application in the pH range from 5.0 to 9.0, TOC removal had no obvious decline with decrease of pH. Comparative characterizations showed that CeO_x could enhance surface hydrophilicity and reduce the charge-transfer resistance of GF. About 5.4 mg/L H₂O₂ generated in CeO_x/GF-EP process, which was 2.1 times as that in GF-EP process. The greater ozone utility was also found in CeO_x/GF-EP process. More O₃ was activated into hydroxyl radicals, which accounted for the mineralization of CBZ. An interfacial electron transfer process was revealed, which involved the function of oxygen vacancies and Ce³⁺/Ce⁴⁺ redox cycle. CeO_x/GF had the good recycling property in fifth times’ use.     

Energy-efficient removal of carbamazepine in solution by electrocoagulation-electrofenton using a novel P-rGO cathode

In this study,carbamazepine(CBZ) decay in solution has been studied by coupling electrocoagulation with electro-Fenton(EC-EF) with a novel P-rGO/carbon felt(CF) cathode,aiming to accelerate the in-situ generation of ·OH,instead of adding Fe²⁺ and H₂ O₂.Firstly,the fabricated P-rGO and its derived cathode were characterized by XRD,SEM,AFM,XPS and electrochemical test(EIS,CV and LSV).Secondly,it was confirmed that the performance in removal efficiency and electric ...     

Carbamazepine degradation by heterogeneous activation of peroxymonosulfate with lanthanum cobaltite perovskite: Performance, mechanism and toxicity

The widely used carbamazepine(CBZ) is one of the most persistent pharmaceuticals and suffers insufficient removal efficiency by conventional wastewater treatment.A synthesized Co-based perovskite(LaCoO_3) was used to activate peroxymonosulfate(PMS) in order to degrade CBZ.Results showed that LaCoO_3 exhibited an excellent performance in PMS activation and CBZ degradation at neutral pH,with low cobalt leaching.The results of FT-IR and XPS verified the high structurally and chemically stability of LaCoO_3 in PMS activation.Electron spin resonance(ESR) analysis suggested the generation of radical species,such as sulfate radicals(SO_4·~-) and hydroxyl radicals(·OH).Radical quenching experiments further revealed the responsibility of SO_4·~-as the dominant oxidant for CBZ oxidation.Ten products were detected via the oxidation of CBZ,with the olefinic double bond attacked by SO_4·~-as the initial step.Hydroxylation,hydrolysis,cyclization and dehydration were involved along the transformation of CBZ.The toxicity of CBZ solution was significantly reduced after treating by PMS/LaCoO_3.     

Prenatal diagnosis of spina bifida aperta after first-trimester valproate exposure

In the context of a prospective study on the adverse effects of anti-epileptic drugs on fetal outcome, we evaluated our experience with prenatal diagnosis by ultrasonography and α- fetoprotein (AFP) determination in amniotic fluid. We compared these results with AFP values in maternal serum obtained prior to amniocentesis. From November 1985 to July 1990, amniocentesis at 16–18 weeks of gestation was performed in 267 pregnancies of 237 different women using anti-epileptic drugs. Among 92 pregnancies with maternal valproic acid use, five (including one concordantly affected monozygotic twin-pair) were terminated because of a spina bifida aperta, all prenatally diagnosed by AFP determination and acetylcholinesterase electrophoresis in amniotic fluid. The maternal serum AFP level was raised (⩾ 2.5 multiples of the median (MOM) for singleton pregnancies and ⩾ 4.5 MOM for twin pregnancies) in only two of these five affected pregnancies. We emphasize that maternal serum AFP levels may be unreliable for prenatal screening for fetal neural tube defects in women taking valproate and recommend that amniocentesis and fetal ultrasound examination should be offered directly.     

The photocatalytic degradation of carbamazepine and prediction by artificial neural networks

The three layer artificial neural network model was applied to predict the degradation efficiency for carbamazepine in photocatalytic oxidation under UV radiation. Titania–zirconia was employed as a catalyst for the photooxidation. The catalyst was prepared using titanium isopropoxide and zirconium oxychloride by sol–gel method and characterized by transmission electron microscopy and BET analysis. Different process parameters such as, initial concentration of carbamazepine, pH of the solution, catalyst concentration and time of UV irradiation were employed as the input to the artificial neural network model and the output of the network was degradation efficiency of carbamazepine. The multilayer feed-forward networks with the Levenberg–Marquardt (trainlm) backpropagation training algorithm was used for the network training. The smallest mean square error was obtained for three-layer network with ‘logsig’ transfer function and five neurons in the hidden layer gave optimal results. A comparison between the predicted values and selective experimental data of degradation efficiency showed a high correlation coefficient (R²) of 0.997.     

Performance and mechanism of carbamazepine removal by FeS-S2O82– process: experimental investigation and DFT calculations

● Synergistic removal of carbamazepine (CBZ) was obtained in the FeS-S₂O₈^2– process. ● SO₄^•− and •OH were identified as the main radicals in the FeS-S₂O₈^2– process. ● Heterogeneous oxidation would be dominant first, followed by homogeneous reaction. ● Degradation pathway of CBZ was well elucidated by experiments and DFT calculations. As persulfate (S₂O₈^2–) is being increasingly used as an alternative oxidizing agent, developing low-cost and eco-friendly catalysts for efficient S₂O₈^2– activation is potentially useful for the treatment of wastewater containing refractory organic pollutant. In this study, the degradative features and mechanisms of carbamazepine (CBZ) were systematically investigated in a novel FeS- S₂O₈^2– process under near-neutral conditions. The results exhibited that CBZ can be effectively eliminated by the FeS-S₂O₈^2– process and the optimal conditions were: 250 mg/L FeS, 0.5 mmol/L S₂O₈^2–, and pH = 6.0. The existence of Cl⁻ (1 and 50 mmol/L) has little influence on the CBZ elimination, while both HCO₃⁻ and HPO₄²⁻ (1 and 50 mmol/L) significantly suppressed the CBZ removal in the FeS-S₂O₈^2– process. CBZ could be degraded via a radical mechanism in the FeS-S₂O₈^2– process, the working radical species (i.e., SO₄^•− and •OH) were efficiently formed via the promoted decomposition of S₂O₈^2– by the surface Fe²⁺ on the FeS and the dissolved ferrous ions in solution. Based on the identified oxidized products and Fukui index calculations, a possible degradation pathway of CBZ was speculated. More importantly, a two-stage oxidation mechanism of CBZ elimination was speculated in the FeS-S₂O₈^2– process, the activation of S₂O₈^2– by the surface-active Fe^(II) of FeS dominated in the initial 5 min, while homogeneous oxidation reactions played more essential parts than others in the following reaction stage (5–60 min). Overall, this study demonstrated that the FeS-S₂O₈^2– process is capable of removing CBZ from water efficiently.     

Immunoassays as high-throughput tools: Monitoring spatial and temporal variations of carbamazepine, caffeine and cetirizine in surface and wastewaters

Carbamazepine (CBZ), caffeine and cetirizine were monitored by enzyme-linked immunosorbent assays (ELISAs) in surface and wastewaters from Berlin, Germany. This fast and cost-efficient method enabled to assess the spatial and temporal variation of these anthropogenic markers in a high-throughput screening. CBZ and cetirizine were detected by the same antibody, which selectively discriminates between both compounds depending on the pH value used in the incubation step. To our best knowledge, this is the first dual-analyte immunoassay working with a single antibody.The frequent sampling with 487 samples being processed allowed for the repeated detection of unusually high concentrations of CBZ and caffeine. ELISA results correlate well with the ones obtained by liquid chromatography tandem mass spectrometry (LC-MS/MS). Caffeine concentrations found in surface waters were elevated by combined sewer overflows after stormwater events. During the hay fever season, the concentrations of the antihistamine drug cetirizine increased in both surface and wastewaters.Caffeine was almost completely removed during wastewater treatment, while CBZ and cetirizine were found to be more persistent. The maximum concentrations of caffeine, CBZ and cetirizine found in influent wastewater by LC-MS/MS were 470, 5.0 and 0.49 μg L⁻¹, while in effluent wastewater the concentrations were 0.22, 4.5 and 0.51 μg L⁻¹, respectively. For surface waters, concentrations up to 3.3, 4.5 and 0.72 μg L⁻¹ were found, respectively.