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1.
Environ Res ; 251(Pt 1): 118565, 2024 Jun 15.
Article in English | MEDLINE | ID: mdl-38431073

ABSTRACT

This study endeavors to develop cost-effective environmentally friendly technology for removing harmful residual pharmaceuticals from water and wastewater by utilizing the effective adsorption of pistachio shell (PS) biochar and the degradation potency of laccase immobilized on the biochar (L@PSAC). The carbonatization and activation of the shells were optimized regarding temperature, time, and NH4NO3/PS ratio. This step yielded an optimum PS biochar (PSAC) with the highest porosity and surface area treated at 700 °C for 3 h using an NH4NO3/PS ratio of 3% wt. The immobilization of laccase onto PSAC (L@PSAC) was at its best level at pH 5, 60 U/g, and 30 °C. The optimum L@PSAC maintained a high level of enzyme activity over two months. Almost a complete removal (>99%) of diclofenac, carbamazepine, and ciprofloxacin in Milli-Q (MQ) water and wastewater was achieved. Adsorption was responsible for >80% of the removal and the rest was facilitated by laccase degradation. L@PSAC maintained effective removal of pharmaceuticals of ≥60% for up to six treatment cycles underscoring the promising application of this material for wastewater treatment. These results indicate that activated carbon derived from the pistachio shell could potentially be utilized as a carrier and adsorbent to efficiently remove pharmaceutical compounds. This enzymatic physical elimination approach has the potential to be used on a large-scale.


Subject(s)
Charcoal , Laccase , Water Pollutants, Chemical , Water Purification , Water Pollutants, Chemical/chemistry , Charcoal/chemistry , Laccase/chemistry , Water Purification/methods , Adsorption , Pistacia/chemistry , Pharmaceutical Preparations/chemistry , Enzymes, Immobilized/chemistry , Wastewater/chemistry , Waste Disposal, Fluid/methods , Diclofenac/chemistry , Diclofenac/isolation & purification , Carbamazepine/chemistry , Carbamazepine/isolation & purification
2.
J Environ Manage ; 362: 121331, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38833931

ABSTRACT

This study introduces an innovative LED-IoT photoreactor, representing a significant advancement in response to the demand for sustainable water purification. The integration of LED-IoT installations addresses the challenge of intermittent sunlight availability, employing LEDs with a spectrum mimicking natural sunlight. Passive Infra-Red (PIR) sensors and Internet of things (IoT) technology ensure consistent radiation intensity, with the LED deactivating in ample sunlight and activating in its absence. Utilizing a visible light-absorbing photocatalyst developed through sol-gel synthesis and mild-temperature calcination, this research demonstrates a remarkable carbamazepine removal efficiency exceeding 95% under LED-IoT system illumination, compared to less than 90% efficiency with sunlight alone, within a 6-h exposure period. Moreover, the designed photocatalytic system achieves over 60% mineralization of carbamazepine after 12 h. Notably, the photocatalyst demonstrated excellent stability with no performance loss during five further cycles. Furthermore, integration with renewable energy sources facilitated continuous operation beyond daylight hours, enhancing the system's applicability in real-world water treatment scenarios. A notable application of the LED-IoT system at an operating sewage treatment plant showed nearly 80% efficiency in carbamazepine removal from sewage in the secondary settling tank after 6 h of irradiation, coupled with nearly 40% mineralization efficiency. Additionally, physicochemical analyses such as XPS and STA-FTIR confirm that the carbamazepine photooxidation process does not affect the surface of the photocatalyst, showing no adsorption for degradation products.


Subject(s)
Carbamazepine , Solar Energy , Water Pollutants, Chemical , Water Purification , Carbamazepine/chemistry , Carbamazepine/isolation & purification , Water Purification/methods , Water Pollutants, Chemical/chemistry , Sunlight , Waste Disposal, Fluid/methods , Catalysis
3.
Int J Mol Sci ; 23(1)2021 Dec 27.
Article in English | MEDLINE | ID: mdl-35008696

ABSTRACT

Enzymatic conversion of pharmaceutically active ingredients (API), using immobilized enzymes should be considered as a promising industrial tool due to improved reusability and stability of the biocatalysts at harsh process conditions. Therefore, in this study horseradish peroxidase was immobilized into sodium alginate capsules and then trapped into poly(vinyl chloride) electrospun fibers to provide additional enzyme stabilization and protection against the negative effect of harsh process conditions. Due to encapsulation immobilization, 100% of immobilization yield was achieved leading to loading of 25 µg of enzyme in 1 mg of the support. Immobilized in such a way, enzyme showed over 80% activity retention. Further, only slight changes in kinetic parameters of free (Km = 1.54 mM) and immobilized horseradish peroxidase (Km = 1.83 mM) were noticed, indicating retention of high catalytic properties and high substrate affinity by encapsulated biocatalyst. Encapsulated horseradish peroxidase was tested in biodegradation of two frequently occurring in wastewater API, sulfamethoxazole (antibiotic) and carbamazepine (anticonvulsant). Over 80% of both pharmaceutics was removed by immobilized enzyme after 24 h of the process from the solution at a concentration of 1 mg/L, under optimal conditions, which were found to be pH 7, temperature 25 °C and 2 mM of H2O2. However, even from 10 mg/L solutions, it was possible to remove over 40% of both pharmaceuticals. Finally, the reusability and storage stability study of immobilized horseradish peroxidase showed retention of over 60% of initial activity after 20 days of storage at 4 °C and after 10 repeated catalytic cycles, indicating great practical application potential. By contrast, the free enzyme showed less than 20% of its initial activity after 20 days of storage and exhibited no recycling potential.


Subject(s)
Carbamazepine/isolation & purification , Horseradish Peroxidase/metabolism , Polyvinyl Chloride/chemistry , Sulfamethoxazole/isolation & purification , Water Pollutants, Chemical/isolation & purification , Biocatalysis , Biodegradation, Environmental , Carbamazepine/chemistry , Enzyme Activation , Enzyme Stability , Enzymes, Immobilized/metabolism , Kinetics , Sulfamethoxazole/chemistry
4.
Molecules ; 26(23)2021 Dec 02.
Article in English | MEDLINE | ID: mdl-34885904

ABSTRACT

The transport of carbamazepine, ciprofloxacin and sulfamethoxazole in the different pores of activated carbon in an aqueous solution is a dynamic process that is entirely dependent on the intrinsic parameters of these molecules and of the adsorbent. The macroscopic processes that take place are analyzed by interfacial diffusion and reaction models. Modeling of the experimental kinetic curves obtained following batch treatment of each solute at 2 µg/L in tap water showed (i) that the transport and sorption rates were controlled by external diffusion and intraparticle diffusion and (ii) that the effective diffusion coefficient for each solute, with the surface and pore diffusion coefficients, were linked by a linear relationship. A statistical analysis of the experimental data established correlations between the diffusional parameters and some geometrical parameters of these three molecules. Given the major discontinuities observed in the adsorption kinetics, the modeling of the experimental data required the use of traditional kinetic models, as well as a new kinetic model composed of the pseudo first or second order model and a sigmoidal expression. The predictions of this model were excellent. The solubility of each molecule below 60 °C was formulated by an empirical expression.


Subject(s)
Carbamazepine/analysis , Charcoal/chemistry , Ciprofloxacin/analysis , Sulfamethoxazole/analysis , Water Pollutants, Chemical/analysis , Adsorption , Carbamazepine/isolation & purification , Ciprofloxacin/isolation & purification , Diffusion , Porosity , Solubility , Sulfamethoxazole/isolation & purification , Water Pollutants, Chemical/isolation & purification , Water Purification
5.
Anal Bioanal Chem ; 412(12): 2721-2730, 2020 May.
Article in English | MEDLINE | ID: mdl-32103309

ABSTRACT

Carbamazepine is an antiepileptic drug with a narrow therapeutic index, which requires an efficient method for blood level monitoring. Finger-prick dried blood spot (DBS) collection is an alternative microsampling technique, which is less invasive than conventional venipuncture. Paper-based molecularly imprinted-interpenetrating polymer networks (MI-IPN) were developed as blood collection devices, which allowed for selective on-spot microextraction of carbamazepine from DBS. A hybrid of homogeneous polystyrene and silica gel polymer was synthesized and coated on a Whatman® Grade 1 filter paper. Proteins and other interferences in the blood samples were eliminated by using the MI-IPN collection devices, and the resulting DBS extracts were suitable for direct injection into the capillary electrophoretic instrument. The lower limit of quantitation of 4 µg/mL in capillary blood was achieved by the sweeping-micellar electrokinetic chromatography method using a KCl-containing matrix, which was sufficient for the therapeutic drug monitoring purposes. Method accuracies were in the range of 88.4 ± 4.5% to 94.5 ± 2.7% with RSD values ≤ 5.1%. The developed paper-based MI-IPN provided superior extraction efficiencies (92.2 ± 2.5%) in comparison with commercially available DBS collection cards, i.e., Whatman® 903 protein saver card (59.8 ± 2.8%) and GenCollect™ 2.0 card (47.2 ± 1.4%). The paper-based MI-IPN devices for DBS collection and on-spot extraction were characterized by simple fabrication, low costs, disposability, and reduction in sample preparation steps, and their further developments might open new perspectives in clinical applications, such as in therapeutic drug monitoring. Graphical abstract.


Subject(s)
Anticonvulsants/blood , Blood Specimen Collection/methods , Carbamazepine/blood , Dried Blood Spot Testing/methods , Electrophoresis, Capillary/methods , Molecularly Imprinted Polymers/chemistry , Solid Phase Microextraction/methods , Anticonvulsants/isolation & purification , Carbamazepine/isolation & purification , Drug Monitoring , Humans , Paper , Tandem Mass Spectrometry
6.
J Sep Sci ; 43(5): 886-895, 2020 Mar.
Article in English | MEDLINE | ID: mdl-31849166

ABSTRACT

Pharmaceuticals constitute one of the most important emerging classes of environmental pollutants. A three-phase solvent system of water, water containing 0.1% of formic acid and acetonitrile was successfully used to separate, by liquid chromatography with mass spectrometry (LC-MS), polarity-matched pharmaceuticals, that is, carbamazepine, clarithromycin, and erythromycin, as well as amoxicillin and metformin. Despite of polarity similarities, these pharmaceuticals were completely resolved in the analytical run time of 15 min. The optimized three-phase solvent system based-method was validated for the simultaneous analysis of six matched-polarity pharmaceuticals in wastewater samples. Good linearity (coefficient of determination more than 0.993) and precision (relative standard deviation less than 15.66%) were achieved. Recovery of analytes from the wastewater was between 0.70 and 1.18. Limits of detections ranged from 0.0001 to 0.5114 µg/L. No significant matrix effect, evaluated by post extraction addition, was observed in the electrospray ionization (ESI) source. Then, this methodology has been successfully applied to environmental study of pharmaceutical residues occurring in influent and effluent wastewater samples, from the main wastewater treatment plant in Potenza (Basilicata, Southern Italy).


Subject(s)
Amoxicillin/isolation & purification , Carbamazepine/isolation & purification , Clarithromycin/isolation & purification , Erythromycin/isolation & purification , Metformin/isolation & purification , Water Pollutants, Chemical/isolation & purification , Amoxicillin/chemistry , Carbamazepine/chemistry , Chromatography, Liquid , Clarithromycin/chemistry , Erythromycin/chemistry , Metformin/chemistry , Particle Size , Solvents/chemistry , Surface Properties , Tandem Mass Spectrometry , Wastewater/chemistry , Water Pollutants, Chemical/chemistry
7.
Anal Bioanal Chem ; 411(8): 1525-1536, 2019 Mar.
Article in English | MEDLINE | ID: mdl-30710206

ABSTRACT

A molecularly imprinted polymer (MIP) was designed in order to allow the selective solid-phase extraction of carbamazepine (CBZ), an anticonvulsant and mood-stabilizing drug, at ultra-trace level from aqueous environmental samples. A structural analog of CBZ was selected as a dummy template and different synthesis conditions were screened. The selectivity of the resulting imprinted polymers was evaluated by studying the retention of CBZ in a solvent similar to the one used for the synthesis. The presence of imprinted cavities in the polymers was then demonstrated by comparing the elution profiles (obtained by using MIP and a non-imprinted polymer, NIP, as a control) of the template, of CBZ, and of a structural analog of CBZ. Then, the extraction procedure was further optimized for the treatment of aqueous samples on the two most promising MIPs, with special attention being paid to the volume and composition of the percolation and washing solutions. The best MIP provided a highly selective retention in tap water with 81% extraction recovery for CBZ in the elution fraction of the MIP and only 14% for NIP. The repeatability of the extraction procedure was demonstrated for both tap and river waters (RSD below 4% in river water) for the drugs CBZ, oxcarbamazepine, and one metabolite (carbamazepine 10,11-epoxide). A MIP capacity of 1.15 µmol g-1 was determined. Finally, an analytical procedure involving the MIP was developed allowing the detection of CBZ at a concentration level of only a few nanograms per liter in river water. The selectivity provided by the MIP resulted in a 3000-fold increase of the signal-to-noise ratio in LC/MS analysis as compared to the use of conventional sorbent. Graphical abstract.


Subject(s)
Carbamazepine/isolation & purification , Molecular Imprinting/methods , Polymers/chemistry , Solid Phase Extraction/methods , Water Pollutants, Chemical/isolation & purification , Carbamazepine/analogs & derivatives , Carbamazepine/analysis , Chromatography, High Pressure Liquid , Environmental Monitoring/methods , Rivers/chemistry , Tandem Mass Spectrometry , Water Pollutants, Chemical/analysis
8.
J Sep Sci ; 41(18): 3547-3552, 2018 Sep.
Article in English | MEDLINE | ID: mdl-30074301

ABSTRACT

We investigated cuttlefish bone powder for the solid-phase extraction of naproxen, ibuprofen, and carbamazepine. The basic principles controlling the extraction are presented to aid in the choice of the nature and quantity of the extracting phase according to the sample matrix and the solute properties, based on the mechanisms of phase retention. Their retention mechanism is based on hydrogen bonding and electrostatic interactions. The results show a significant recovery rate for the three drugs, selectivity, and low cost. The method has successfully reduced the amount of tested pharmaceuticals with recoveries >87% at pH 4.


Subject(s)
Bone and Bones/chemistry , Carbamazepine/isolation & purification , Ibuprofen/isolation & purification , Naproxen/isolation & purification , Powders/chemistry , Solid Phase Extraction , Adsorption , Animals , Carbamazepine/chemistry , Decapodiformes , Ibuprofen/chemistry , Molecular Structure , Naproxen/chemistry , Particle Size , Surface Properties
9.
J Sep Sci ; 39(8): 1500-8, 2016 Apr.
Article in English | MEDLINE | ID: mdl-26899307

ABSTRACT

A surface carbamazepine-imprinted polymer was grafted and synthesized on the SiO2 /graphene oxide surface. Firstly SiO2 was coated on synthesized graphene oxide sheet using the sol-gel technique. Prior to polymerization, the vinyl group was incorporated on to the surface of SiO2 /graphene oxide to direct selective polymerization on the surface. Methacrylic acid, ethylene glycol dimethacrylate and ethanol were used as monomer, cross-linker and porogen, respectively. Nonimprinted polymer was also prepared for comparison. The properties of the molecularly imprinted polymer were characterized using field-emission scanning electron microscopy and Fourier-transform infrared spectroscopy. The surface molecularly imprinted polymer was utilized as an adsorbent of dispersive solid-phase extraction for separation and preconcentration of carbamazepine. The effects of the different parameters influencing the extraction efficiency, such as sample pH were investigated and optimized. The specificity of the molecular imprinted polymer over the nonimprinted polymer was examined in absence and presence of competitive drugs. The carbamazepine calibration curve showed linearity in the ranges 0.5-500 µg/L. The limits of detection and quantification under the optimized conditions were 0.1 and 0.3 µg/L, respectively. The within-day and between-day relative standard deviations (n = 3) were 3.6 and 4.3%, respectively. Furthermore, the relative recoveries for spiked biological samples were above 85%.


Subject(s)
Carbamazepine/isolation & purification , Graphite/chemistry , Molecular Imprinting , Oxides/chemistry , Polymers/chemistry , Silicon Dioxide/chemistry , Solid Phase Extraction , Carbamazepine/chemistry , Particle Size , Polymers/chemical synthesis , Surface Properties
10.
Environ Sci Technol ; 48(22): 13197-206, 2014 Nov 18.
Article in English | MEDLINE | ID: mdl-25353977

ABSTRACT

Adsorption of three selected pharmaceuticals and personal care products (PPCPs) (ketoprofen (KEP), carbamazepine (CBZ), and bisphenol A (BPA)) by two reduced graphene oxides (rGO1 and rGO2) and one commercial graphene was examined under different solution conditions. Single-walled carbon nanotubes (SWCNTs), multiwalled carbon nanotubes (MWCNTs), and powdered graphite were also investigated for comparison. All adsorption isotherms followed the order of SWCNTs > rGO1 > rGO2 > MWCNTs > graphene > graphite, consistent with the orders of their surface areas and micropore volumes. After surface area normalization, adsorption affinities of the three PPCPs onto graphenes were lower than onto graphite, suggesting incomplete occupation for adsorption sites because of the aggregation of graphene sheets and the presence of oxygen-containing functional groups. The observed pH effects on adsorption correlated well with the pH-regulated distribution of the protonated neutral species of the three PPCPs. Increasing ionic strength from 0 to 20 mM increased KEP adsorption due to the electrostatic screening by Na(+) and Ca(2+). Both humic acid (HA) and sodium dodecylbenzenesulfonate (SDBS) suppressed PPCPs adsorption to all adsorbents, but their impacts onto graphenes were lower than those onto CNTs because of their lower adsorption by graphenes. More severe HA (or SDBS) effect was found on negatively charged KEP at the tested solution pH 6.50 due to the electrostatic repulsion between the same charged KEP and HA (or SDBS). The findings of the present study may have significant implications for the environmental fate assessment of PPCPs and graphene.


Subject(s)
Graphite/chemistry , Household Products/analysis , Nanotubes, Carbon/chemistry , Pharmaceutical Preparations/isolation & purification , Adsorption , Benzenesulfonates/chemistry , Benzhydryl Compounds/isolation & purification , Carbamazepine/isolation & purification , Humic Substances/analysis , Hydrogen-Ion Concentration , Ketoprofen/isolation & purification , Osmolar Concentration , Oxidation-Reduction , Phenols/isolation & purification , Solutions , Spectrophotometry, Ultraviolet , Temperature , X-Ray Diffraction
11.
J Sep Sci ; 37(9-10): 1094-102, 2014 May.
Article in English | MEDLINE | ID: mdl-24596023

ABSTRACT

In this study, we investigate the separation of a variety of mixtures of drugs, metabolites, and related analogs including representatives of the carbamazepine, methylated xanthine, steroid hormone, nicotine, and morphine families using several automated chromatographic method development screening systems including ultra high performance liquid chromatography, core-shell HPLC, achiral supercritical fluid chromatography (SFC), and chiral SFC. Of the 138 column and mobile phase combinations examined for each mixture, a few chromatographic conditions afford the best overall performance, with a single achiral SFC method (4.6 × 250 mm, 3.0 µm GreenSep Ethyl Pyridine, 25 mM isobutylamine in methanol/CO2) affording good separation for all samples. Four of these mixtures were also resolved by achiral SFC on the Luna HILIC and chiral SFC Chiralpak IB columns using methanol or ethanol with 25 mM isobutylamine as polar modifiers. Modifications of standard chromatography screening conditions afforded fast separation methods (from 1 to 5 min) for baseline resolution of all components of each of these challenging sets of closely related compounds.


Subject(s)
Carbamazepine/isolation & purification , Gonadal Steroid Hormones/isolation & purification , Morphine Derivatives/isolation & purification , Nicotine/isolation & purification , Xanthine/isolation & purification , Carbamazepine/chemistry , Carbamazepine/metabolism , Chromatography, High Pressure Liquid , Chromatography, Supercritical Fluid , Gonadal Steroid Hormones/chemistry , Gonadal Steroid Hormones/metabolism , Molecular Structure , Morphine Derivatives/chemistry , Morphine Derivatives/metabolism , Nicotine/chemistry , Nicotine/metabolism , Xanthine/chemistry , Xanthine/metabolism
12.
Environ Technol ; 35(9-12): 1055-63, 2014.
Article in English | MEDLINE | ID: mdl-24701901

ABSTRACT

The fate and removal of six selected endocrine disrupting compounds in a lab-scale anaerobic/aerobic (A/O) sequencing batch reactor (SBR), operating at 5 days, solids retention time (SRT) were investigated. A carbamazepine (CBZ), acetaminophen (ATP), diltiazem (DTZ), butyl benzyl phthalate (BBP), estrone and progesterone mix was spiked as model endocrine disrupting compounds (EDC) into domestic wastewater obtained from a nearby sewage treatment plant. The influent, effluent and sludge samples from the SBR unit were analysed by using an LC/MS/MS instrument equipped with electrospray ionization. More than 80% removal was observed for all the EDCs tested. It was found that biodegradation is the most important mechanism for BBP, ATP and progesterone. Biodegradation constants were calculated according to the simplified Monod model for these compounds. The DTZ seemed to have lower rate of biodegradation. The CBZ appeared totally resistant to biodegradation. However, it presented a high rate of sorption onto the sludge and was thereby treated. This contradicts with the literature studies.


Subject(s)
Bioreactors/microbiology , Endocrine Disruptors/isolation & purification , Water Pollutants, Chemical/isolation & purification , Acetaminophen/analysis , Acetaminophen/isolation & purification , Acetaminophen/metabolism , Adsorption , Carbamazepine/analysis , Carbamazepine/isolation & purification , Carbamazepine/metabolism , Diltiazem/analysis , Diltiazem/isolation & purification , Diltiazem/metabolism , Endocrine Disruptors/analysis , Endocrine Disruptors/metabolism , Estrone/analysis , Estrone/isolation & purification , Estrone/metabolism , Phthalic Acids/analysis , Phthalic Acids/isolation & purification , Phthalic Acids/metabolism , Progesterone/analysis , Progesterone/isolation & purification , Progesterone/metabolism , Sewage/analysis , Wastewater/analysis , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/metabolism
13.
Water Sci Technol ; 67(6): 1396-402, 2013.
Article in English | MEDLINE | ID: mdl-23508167

ABSTRACT

Carbamazepine (CBZ), nonbiodegradable pharmaceutical residue, has become an emerging pollutant in several aquatic environments. The effectiveness of the mixture of soil and fly ash (FA) in adsorbing CBZ from aqueous solution has been studied as well as agitation time, FA content, initial CBZ concentration and desorption as a function of FA content. The adsorption kinetics fits a hyperbolic or pseudo-second-order model. The maximum adsorbed amounts for natural soil and a mixture of soil/FA ranged from 77 to 158 mg kg(-1). Rate constants were considered relatively low (4.15-15.59 × 10(-4) kg mg(-1) min). The logarithmic form of the Freundlich equation gave a linearity and the Kf constants increased with the increase of FA content in adsorbent mixtures and with the affinity between the adsorbent surface and adsorbed solute. The mean removed amounts of CBZ by adsorption batch experiments in a soil mixture with 30% FA content were up to 92.8% for coal FA and 33% in natural soil. This work proved that the mixture of the coal FA and soil can be used as an efficient adsorbent material for removal of CBZ from water.


Subject(s)
Anticonvulsants/isolation & purification , Carbamazepine/isolation & purification , Coal Ash/chemistry , Soil/chemistry , Water Pollutants, Chemical/isolation & purification , Adsorption , Kinetics , Thermodynamics
14.
J Environ Sci (China) ; 25(12): 2384-95, 2013 Dec 01.
Article in English | MEDLINE | ID: mdl-24649668

ABSTRACT

Due to their widespread use, clofibric acid (CA) and carbamazepine (CBZ) have been frequently detected simultaneously at relatively high concentrations in aquatic environments. In this study, agricultural waste rice straw was employed as a potentially low-cost, effective and easy-to-operate biosorbent (RSB) to remove CA and CBZ. The adsorption of both pharmaceuticals followed pseudo second-order kinetics, and intraparticle diffusion was an important rate-limiting step. The adsorption isotherms of both drugs were fit well with Freundlich model. The adsorption of CA onto RSB was exothermic and was more likely to be dominated by physical processes, while the adsorption of CBZ was endothermic. Solution pH was determined to be the most important factor for CA adsorption, such that the adsorption capacity of CA onto RSB increased with the decline of solution pH. In the lower range of solution pH below 3.1, the CA removal efficiency was enhanced with the increase of biosorbent dosage. The CBZ removal efficiency was enhanced with the increase of RSB dosage without pH control. The maximum adsorption capacities were 126.3 mg/g for CA and 40.0 mg/g for CBZ.


Subject(s)
Carbamazepine/isolation & purification , Clofibric Acid/isolation & purification , Oryza/chemistry , Water Pollutants, Chemical/isolation & purification , Adsorption , Agriculture , Feasibility Studies , Hydrogen-Ion Concentration , Kinetics , Temperature , Thermodynamics
15.
Analyst ; 137(17): 4037-44, 2012 Sep 07.
Article in English | MEDLINE | ID: mdl-22814299

ABSTRACT

An analysis method for aqueous samples by the direct combination of C18/SCX mixed mode thin-film microextraction (TFME) and desorption electrospray ionization mass spectrometry (DESI-MS) was developed. Both techniques make analytical workflow simpler and faster, hence the combination of the two techniques enables considerably shorter analysis time compared to the traditional liquid chromatography mass spectrometry (LC-MS) approach. The method was characterized using carbamazepine and triclosan as typical examples for pharmaceuticals and personal care product (PPCP) components which draw increasing attention as wastewater-derived environmental contaminants. Both model compounds were successfully detected in real wastewater samples and their concentrations determined using external calibration with isotope labeled standards. Effects of temperature, agitation, sample volume, and exposure time were investigated in the case of spiked aqueous samples. Results were compared to those of parallel HPLC-MS determinations and good agreement was found through a three orders of magnitude wide concentration range. Serious matrix effects were observed in treated wastewater, but lower limits of detection were still found to be in the low ng L(-1) range. Using an Orbitrap mass spectrometer, the technique was found to be ideal for screening purposes and led to the detection of various different PPCP components in wastewater treatment plant effluents, including beta-blockers, nonsteroidal anti-inflammatory drugs, and UV filters.


Subject(s)
Spectrometry, Mass, Electrospray Ionization , Wastewater/analysis , Water Pollutants, Chemical/analysis , Carbamazepine/analysis , Carbamazepine/isolation & purification , Kinetics , Membranes, Artificial , Solid Phase Microextraction , Triclosan/analysis , Triclosan/isolation & purification , Water Pollutants, Chemical/isolation & purification
16.
J Sep Sci ; 35(21): 2970-7, 2012 Nov.
Article in English | MEDLINE | ID: mdl-22997153

ABSTRACT

A simple, accurate, and sensitive microextraction by packed sorbent-gas chromatography-mass spectrometry method has been developed for the simultaneous quantification of four antiepileptic drugs; oxcarbazepine, carbamazepine, phenytoin, and alprazolam in human plasma and urine as a tool for drug monitoring. Caffeine was used as internal standards for the electron ionization mode. An original pretreatment procedure on biological samples, based on microextraction in packed syringe using C(18) as packing material gave high extraction yields (69.92-99.38%), satisfactory precision (RSD < 4.7%) and good selectivity. Linearity was found in the 0.1-500 ng/mL range for these drugs with limits of detection (LODs) between 0.0018 and 0.0036 ng/mL. Therefore, the method has been found to be suitable for the therapeutic drug monitoring of patients treated with oxcarbazepine, carbamazepine, phenytoin, and alprazolam. After validation, the method was successfully applied to some plasma samples from patients undergoing therapy with one or more of these drugs. A comparison of the detection limit with similar methods indicates high sensitivity of the present method over the earlier reported methods. The present method is applied for the analysis of these drugs in the real urine and plasma samples of the epileptic patients.


Subject(s)
Anticonvulsants/analysis , Anticonvulsants/isolation & purification , Gas Chromatography-Mass Spectrometry/methods , Solid Phase Microextraction/methods , Alprazolam/blood , Alprazolam/isolation & purification , Alprazolam/urine , Anticonvulsants/blood , Anticonvulsants/urine , Carbamazepine/analogs & derivatives , Carbamazepine/blood , Carbamazepine/isolation & purification , Carbamazepine/urine , Epilepsy/blood , Epilepsy/drug therapy , Epilepsy/urine , Humans , Oxcarbazepine , Phenytoin/blood , Phenytoin/isolation & purification , Phenytoin/urine
17.
J Environ Qual ; 41(5): 1674-80, 2012.
Article in English | MEDLINE | ID: mdl-23099959

ABSTRACT

This study presents findings on an assessment of the effect of continuous and batch feeding strategies on the removal of selected pharmaceuticals from synthetic wastewater. Six mesocosm-scale constructed wetlands, including three horizontal subsurface flow constructed wetlands and three sand filters, were set up at the campus of Nanyang Technological University, Singapore. The findings showed that ibuprofen and diclofenac removal in the wetlands was significantly ( < 0.05) enhanced in the batch versus continuous mode. In contrast, naproxen and carbamazepine showed no significant differences ( > 0.05) in elimination under either feeding strategy. Our results also clearly showed that the presence of plants exerts a stimulatory effect on pharmaceutical removal for ibuprofen, diclofenac, and naproxen in batch and continuous mode. Estimation of the quantitative role of this stimulatory effect on pharmaceutical elimination of batch operation as compared with the effect of the presence of the higher plant alone showed that batch operation may account for 40 to 87% of the contribution conferred by the aquatic plant. The findings of this study imply that where maximal removal of pharmaceutical compounds is desired, periodic draining and filling might be the preferred operational strategy for full-scale, subsurface flow constructed wetlands.


Subject(s)
Pharmaceutical Preparations/isolation & purification , Water Pollutants, Chemical/isolation & purification , Water Purification/methods , Wetlands , Carbamazepine/isolation & purification , Diclofenac/isolation & purification , Ibuprofen/isolation & purification , Naproxen/isolation & purification
18.
Water Sci Technol ; 66(9): 1856-63, 2012.
Article in English | MEDLINE | ID: mdl-22925856

ABSTRACT

Emerging wastewater treatment processes such as membrane bioreactors (MBRs) have attracted a significant amount of interest internationally due to their ability to produce high quality effluent suitable for water recycling. It is therefore important that their efficiency in removing hazardous trace organic contaminants be assessed. Accordingly, this study investigated the removal of trace organic chemical contaminants through a full-scale, package MBR in New South Wales, Australia. This study was unique in the context of MBR research because it characterised the removal of 48 trace organic chemical contaminants, which included steroidal hormones, xenoestrogens, pesticides, caffeine, pharmaceuticals and personal care products (PPCPs). Results showed that the removal of most trace organic chemical contaminants through the MBR was high (above 90%). However, amitriptyline, carbamazepine, diazepam, diclofenac, fluoxetine, gemfibrozil, omeprazole, sulphamethoxazole and trimethoprim were only partially removed through the MBR with the removal efficiencies of 24-68%. These are potential indicators for assessing MBR performance as these chemicals are usually sensitive to changes in the treatment systems. The trace organic chemical contaminants detected in the MBR permeate were 1 to 6 orders of magnitude lower than guideline values reported in the Australian Guidelines for Water Recycling. The outcomes of this study enhanced our understanding of the levels and removal of trace organic contaminants by MBRs.


Subject(s)
Bioreactors , Organic Chemicals/metabolism , Amitriptyline/isolation & purification , Amitriptyline/metabolism , Carbamazepine/isolation & purification , Carbamazepine/metabolism , Diazepam/isolation & purification , Diazepam/metabolism , Diclofenac/isolation & purification , Diclofenac/metabolism , Fluoxetine/isolation & purification , Fluoxetine/metabolism , Gemfibrozil/isolation & purification , Gemfibrozil/metabolism , Omeprazole/isolation & purification , Omeprazole/metabolism , Organic Chemicals/isolation & purification , Pharmaceutical Preparations/isolation & purification , Pharmaceutical Preparations/metabolism , Sulfamethoxazole/isolation & purification , Sulfamethoxazole/metabolism , Trimethoprim/isolation & purification , Trimethoprim/metabolism , Waste Disposal, Fluid/methods , Water Pollutants, Chemical/isolation & purification , Water Pollutants, Chemical/metabolism
19.
Environ Technol ; 33(13-15): 1747-53, 2012.
Article in English | MEDLINE | ID: mdl-22988636

ABSTRACT

This study compared several pretreatment methods for inhibiting BrO3(-) formation during ozonation of tap water, from the DTU (Technical University of Denmark) campus, including H2O2 addition (peroxone), pH depression, and NH4+ and Cl2/NH4+ addition. At the same time, the inhibition of atrazine and carbamazepine removal was evaluated for each pretreatment. The required delivered O3 dose to achieve 90% removal of atrazine in the tap water from the DTU campus was 3.5 mg/L, which produced 130-170 microg/L BrO3(-). Peroxone did not reduce the required O3 dose for contaminant removal; however, it limited BrO3(-) formation to below the drinking water limit of 10 microg/L. Depression of solution pH to 6.0, reduced BrO3(-) formation to half, but it was still well above the water limit. Pretreatment with NH4+ also reduced BrO3(-) formation by approximately 50%, though it reduced atrazine degradation to 65%. Pretreatment with Cl2/NH4+ reduced BrO3(-) formation close to the 10 microg/L limit; however, atrazine removal did not exceed 75%. Carbamazepine was completely removed under all the tested experimental conditions with the 3.5 mg/L O3 dose.


Subject(s)
Bromates/chemistry , Ozone/chemistry , Water Purification/methods , Atrazine/isolation & purification , Bromides/chemistry , Carbamazepine/isolation & purification , Denmark , Drinking Water/chemistry , Hydrogen Peroxide/chemistry , Hydrogen-Ion Concentration , Kinetics , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/isolation & purification
20.
Environ Sci Technol ; 45(16): 6800-5, 2011 Aug 15.
Article in English | MEDLINE | ID: mdl-21744850

ABSTRACT

Carbamazepine (CBZ) is an environmentally recalcitrant compound highly stable in soil and during wastewater treatment. In this study, we examined the mechanisms by which the white-rot fungus Pleurotus ostreatus metabolizes CBZ in liquid culture using a physiological approach. P. ostreatus PC9 was grown in media known to support different levels of a multiplicity of enzyme systems such as cytochrome P450 (CYP450) and manganese peroxidase (MnP). When both CYP450 and MnP systems were active, 99% of the added CBZ was eliminated from the solution and transformed to 10,11-epoxycarbamazepine. High removal of CBZ was also obtained when either MnP or CYP450 was active. When both CYP450 and MnP were inactivated, only 10 to 30% of the added CBZ was removed. In this latter system, removal of CBZ might be partially attributed to the activity of versatile peroxidase. P. ostreatus was able to eliminate CBZ in liquid culture even when CBZ was added at an environmentally relevant concentration (1 µg L(-1)). On the basis of our study, we suggest that two families of enzymes are involved in the oxidation of CBZ in liquid culture: MnP in a Mn(2+)-dependent or independent manner and CYP450. Our study also highlights the potential of using P. ostreatus for bioremediation systems.


Subject(s)
Carbamazepine/metabolism , Cytochrome P-450 Enzyme System/metabolism , Peroxidases/metabolism , Pharmaceutical Preparations/metabolism , Pleurotus/enzymology , Biodegradation, Environmental/drug effects , Biotransformation/drug effects , Carbamazepine/isolation & purification , Culture Media/pharmacology , Pharmaceutical Preparations/isolation & purification , Pleurotus/drug effects , Pleurotus/metabolism
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