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1.
J Environ Manage ; 358: 120822, 2024 May.
Article En | MEDLINE | ID: mdl-38599088

Contamination by wastewater has been traditionally assessed by measuring faecal coliforms, such as E. coli and entereococci. However, using micropollutants to track wastewater input is gaining interest. In this study, we identified nine micropollutant indicators that could be used to characterize water quality and wastewater treatment efficiency in pond-based wastewater treatment plants (WWTPs) of varying configuration. Of 232 micropollutants tested, nine micropollutants were detected in treated wastewater at concentrations and frequencies suitable to be considered as indicators for treated wastewater. The nine indicators were then classified as stable (carbamazepine, sucralose, benzotriazole, 4+5-methylbenzotriazole), labile (atorvastatin, naproxen, galaxolide) or intermediate/uncertain (gemfibrozil, tris(chloropropyl)phosphate isomers) based on observed removals in the pond-based WWTPs and correlations between micropollutant and dissolved organic carbon removal. The utility of the selected indicators was evaluated by assessing the wastewater quality in different stages of wastewater treatment in three pond-based WWTPs, as well as selected groundwater bores near one WWTP, where treated wastewater was used to irrigate a nearby golf course. Ratios of labile to stable indicators provided insight into the treatment efficiency of different facultative and maturation ponds and highlighted the seasonal variability in treatment efficiency for some pond-based WWTPs. Additionally, indicator ratios of labile to stable indicators identified potential unintended release of untreated wastewater to groundwater, even with the presence of micropollutants in other groundwater bores related to approved reuse of treated wastewater.


Groundwater , Wastewater , Water Pollutants, Chemical , Wastewater/chemistry , Wastewater/analysis , Groundwater/chemistry , Water Pollutants, Chemical/analysis , Environmental Monitoring , Waste Disposal, Fluid/methods , Water Quality , Triazoles/analysis , Water Purification/methods , Gemfibrozil/analysis
2.
Environ Res ; 216(Pt 3): 114659, 2023 01 01.
Article En | MEDLINE | ID: mdl-36328221

Photochemical transformation of pharmaceuticals plays an important role in their natural attenuation, especially in lagoon-based wastewater treatment plants and surface waters receiving substantial sunlight. In this study, the photodegradation of five important pharmaceuticals was studied in samples obtained from a wastewater treatment plant and surface water sources. Batch photodegradation studies for a mixture of pharmaceuticals (diclofenac, sulfamethoxazole, acetaminophen, carbamazepine and gemfibrozil) were carried out in a photochemical reactor. Multiple aliquots of samples removed from the reactor during the experiment were analyzed through high-performance liquid chromatography (HPLC) coupled to a photodiode array (PDA) detector. Intermediate products formed due to photodegradation were identified by ultra-high-performance liquid chromatography coupled with a time-of-flight mass spectrometry (UHPLC-MS/MS). Diclofenac and sulfamethoxazole were found to undergo direct photodegradation due to strong light absorption, whereas the indirect route of photosensitized degradation in the presence of dissolved organic matter (DOM) and model humic acid was significant for acetaminophen, carbamazepine, and gemfibrozil. The reactive radicals such as hydroxyl (OH•), singlet oxygen (1O2) and excited states of DOM (*DOM) were predominantly responsible for the indirect photodegradation of acetaminophen, gemfibrozil and carbamazepine, respectively. Computational analysis revealed that chlorine and carbon atoms belonging to the benzene ring of diclofenac were more reactive to radical attack. Sulfamethoxazole photodegradation occurred through oxidation of the NH2 group. Acetaminophen was more susceptible to electrophilic radical attack at the O-11, and N-7 positions and carbon atoms ortho to the phenolic oxygen and the amine group. The double bonds between C-7, C-8 and C-13 were the most reactive sites for carbamazepine that participated in the phototransformation pathway. Organic matter plays a critical role in the photodegradation of emerging contaminants. The coupling of DFT calculations with UHPLC-MS/MS analysis provided insights on key functional groups participating in the phototransformation pathway. Thus, both parent pharmaceuticals and the photodegradation intermediates should be considered during wastewater treatment.


Wastewater , Water Pollutants, Chemical , Photolysis , Wastewater/chemistry , Gemfibrozil/analysis , Tandem Mass Spectrometry , Diclofenac , Acetaminophen , Water Pollutants, Chemical/analysis , Sulfamethoxazole , Carbon , Carbamazepine/analysis , Pharmaceutical Preparations
4.
Mar Pollut Bull ; 146: 509-520, 2019 Sep.
Article En | MEDLINE | ID: mdl-31426188

Ten pharmaceutically active compounds (PhACs) were determined in northern Taiwan estuarine waters and Taiwan Strait (TS) seawater. The ecological risk of these PhACs was assessed using risk quotient (RQ), which is the ratio of the measured maximum concentration to the predicted no-effect concentration. Six PhACs were detected within the estuarine waters. Caffeine concentration (130-718 ng l-1) was the highest among the analyzed PhACs. The distribution of PhACs in the Danshuei River Estuary generally exhibited addition behavior, except that caffeine showed conservative behavior. Carbamazepine, gemfibrozil, caffeine, and ketoprofen were detected in TS seawaters. Their concentrations follow the sequence: gemfibrozil > ketoprofen > caffeine > carbamazepine. The caffeine concentrations in TS seawaters were 2-3 orders of magnitude lower than those in Danshuei estuarine waters. With few exceptions for caffeine, erythromycin, and sulfadiazine posing low risk in some estuarine waters, most of the RQ values were <0.01, suggesting no adverse effects on aquatic organisms.


Environmental Monitoring , Pharmaceutical Preparations/analysis , Water Pollutants, Chemical/analysis , Aquatic Organisms , Carbamazepine/analysis , Erythromycin/analysis , Estuaries , Gemfibrozil/analysis , Rivers , Seawater , Taiwan
5.
J Hazard Mater ; 358: 216-221, 2018 09 15.
Article En | MEDLINE | ID: mdl-29990809

Pharmaceuticals are a group of ubiquitous emerging pollutants, many of which have been shown to undergo efficient photolysis in the environment. Photochemically produced reactive intermediates (PPRIs) sensitized by the pharmaceuticals in sunlit natural waters may induce photodegradation of coexisting compounds. In this study, the roles of coexisting contaminants on the phototransformation of pharmaceuticals were unveiled with the fibrate drugs gemfibrozil (GMF), fenofibrate (FNF), and fenofibric acid (FNFA) as model compounds. GMF undergoes initial concentration dependent photodegradation due to the involvement of singlet oxygen (1O2) initiated self-sensitized photolysis, and undergoes pH dependent photodegradation due to dissociation and hydroxyl radical (OH) generation. The decarboxylated intermediates of GMF and coexisting FNFA significantly accelerated the photodegradation of GMF. The promotional effects of the decarboxylated intermediates are attributed to generation of PPRIs, e.g. 1O2, superoxide (O2-), that subsequently react with GMF. Besides, FNFA can also promote the photodegradation of GMF through the electron transfer reaction from ground state GMF to excited state FNFA, leading to the formation of decarboxylated intermediates. The formed intermediates can subsequently also facilitate GMF photodegradation. The results presented here provided valuable novel insights into the effects of coexisting contaminants on the photodegradation of pharmaceuticals in polluted waters.


Fenofibrate/analogs & derivatives , Gemfibrozil/analysis , Light , Pharmaceutical Preparations/analysis , Photolysis , Water Pollutants, Chemical/analysis , China , Fenofibrate/analysis , Fenofibrate/radiation effects , Gemfibrozil/radiation effects , Hydrogen-Ion Concentration , Models, Theoretical , Molecular Structure , Pharmaceutical Preparations/radiation effects , Rivers/chemistry , Water Pollutants, Chemical/radiation effects
6.
Chemosphere ; 192: 75-80, 2018 Feb.
Article En | MEDLINE | ID: mdl-29100124

Gemfibrozil, a common lipid regulator, enters aquatic environments through treated municipal wastewater effluent that fails to remove it completely from effluent streams. When exposed to gemfibrozil concentrations of 50, 500, 5,000, and 50,000 ng L-1, Daphnia magna showed increased lipid reserves by 14-21% (significant at 500 ng L-1), increased length by 9-13% (significant at 50 ng L-1), increased mass by 6-13% (significant at 50 ng L-1) and increased neonate production by 57-74% (significant at 50 ng L-1). Gemfibrozil-exposed Daphnia held under conditions where food availability was low, grew and reproduced as well as those in the control. Taken together, these results suggest that gemfibrozil exposure within environmentally relevant concentration ranges is not toxic to Daphnia magna but has the potential to be beneficial to the species under these conditions.


Daphnia/drug effects , Daphnia/physiology , Energy Metabolism/drug effects , Food , Gemfibrozil/analysis , Gemfibrozil/toxicity , Animals , Daphnia/growth & development , Daphnia/metabolism , Reproduction/drug effects , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/toxicity
7.
Sci Rep ; 7: 45931, 2017 04 12.
Article En | MEDLINE | ID: mdl-28401920

Fibrates, which are widely used lipidaemic-modulating drugs, are emerging environmental pollutants. However, fibrate concentrations in the environment have not been thoroughly surveyed. Here, we determined concentrations of the most commonly used fibrates and their metabolites in source water and drinking water samples from ten drinking water treatment plants in Shanghai and Zhejiang, China, using solid-phase extraction and liquid chromatography-tandem mass spectrometry. All the target compounds were detected in at least some of the source water samples, at concentrations ranging from 0.04 ng/L (fenofibrate) to 1.53 ng/L (gemfibrozil). All the compounds except fenofibrate were also detected in at least some of the drinking water samples, at recoveries ranging from 35.5% to 91.7%, suggesting that these compounds are poorly removed by typical drinking water treatment processes. In a peroxisome proliferator-activated receptor α agonistic activity assay, the target compounds showed no significant activity at nanogram per litre concentrations; therefore, our results suggest that the fibrate concentrations in drinking water in Shanghai and Zhejiang, China do not significantly affect human health. However, because of the increasing westernization of the Chinese diet, fibrate use may increase, and thus monitoring fibrate concentrations in aquatic environments and drinking water in China will become increasingly important.


Drinking Water/analysis , Fenofibrate/analysis , Gemfibrozil/analysis , Water Pollutants, Chemical/analysis , China , Chromatography, Liquid , Drinking Water/chemistry , Environmental Monitoring/methods , Fenofibrate/isolation & purification , Gemfibrozil/isolation & purification , Humans , Solid Phase Extraction , Tandem Mass Spectrometry , Water Pollutants, Chemical/isolation & purification , Water Purification/methods
8.
Chemosphere ; 170: 124-133, 2017 Mar.
Article En | MEDLINE | ID: mdl-27987461

Gemfibrozil (GFZ) is a relatively persistent pollutant in surface-water environments and it is rather recalcitrant to biological degradation. The GFZ photochemical lifetimes are relatively short in shallow waters with low levels of dissolved organic carbon (DOC), but they can reach the month-year range in deep and high-DOC waters. The main reason is that GFZ undergoes negligible reaction with singlet oxygen or degradation sensitised by the triplet states of chromophoric dissolved organic matter, which are the usually prevalent photochemical pathways in deep and high-DOC sunlit waters. Nitrate and nitrite scarcely affect the overall GFZ lifetimes, but they can shift photodegradation from direct photolysis to the OH process. These two pathways are the main GFZ phototransformation routes, with the direct photolysis prevailing in shallow environments during summer. Under these conditions the GFZ photochemical lifetimes are also shorter and the environmental significance of photodegradation correspondingly higher. The direct photolysis of GFZ under UVB irradiation yielded several transformation intermediates deriving from oxidation or cleavage of the aliphatic lateral chain. A quinone derivative (2,5-dimethyl-1,4-benzoquinone), a likely oxidation product of the transformation intermediate 2,5-dimethylphenol, is expected to be the most acutely and chronically toxic compound arising from GFZ direct photolysis. Interestingly, literature evidence suggests that the same toxic intermediate would be formed upon OH reaction.


Benzoquinones/analysis , Cyclohexenes/analysis , Gemfibrozil/analysis , Water Pollutants, Chemical/analysis , Environment , Half-Life , Hydroxyl Radical/chemistry , Kinetics , Models, Chemical , Models, Theoretical , Nitrates/analysis , Nitrites/analysis , Oxygen/chemistry , Photochemical Processes , Photolysis , Ultraviolet Rays , Water
9.
J Sep Sci ; 39(11): 2087-96, 2016 Jun.
Article En | MEDLINE | ID: mdl-27060926

A rapid and sensitive bioassay was established and validated to simultaneously determine gemfibrozil, morphine, morphine-3ß-glucuronide, and morphine-6ß-glucuronide in mouse cerebrum, epencephalon, and hippocampus based on ultra-high performance liquid chromatography and tandem mass spectrometry. The deuterated internal standard, M6G-d3, was mixed with the prepared samples at 10 ng/mL as the final concentration. The samples were transferred into the C18 solid-phase extraction columns with gradient elution for solid-phase extraction. The mobile phase consisted of methanol and 0.05% formic acid (pH 3.2). Multiple reaction monitoring has been applied to analyze gemfibrozil (m/z 249.0 → 121.0) in anion mode, and M6G-d3 (m/z 465.1 → 289.1), morphine (m/z 286.0 → 200.9), and M3G and M6G (m/z 462.1 → 286.1) in the positive ion mode. The method has a linear calibration range from 0.05 to 10 ng for gemfibrozil, morphine, and M3G and M6G with correlation coefficients >0.993. The lower limit of quantitation for all four analytes was 0.05 ng/mL, relative standard deviation of intra- and interday precision was less than 10.5%, and the relative error of accuracy was from -8.2 to 8.3% at low, medium, and high concentrations for all the analytes. In conclusion, gemfibrozil can influence the morphine antinociception after coronary heart disease induced chronic angina by the change in one of morphine metabolites', M3G, distribution in mouse brain.


Brain/metabolism , Gemfibrozil/analysis , Morphine/analysis , Solid Phase Extraction , Animals , Chromatography, High Pressure Liquid , Gemfibrozil/administration & dosage , Gemfibrozil/metabolism , Male , Mice , Mice, Inbred ICR , Molecular Structure , Morphine/administration & dosage , Morphine/metabolism , Tandem Mass Spectrometry
10.
Mater Sci Eng C Mater Biol Appl ; 62: 605-13, 2016 May.
Article En | MEDLINE | ID: mdl-26952464

Functionalized magnetic carbonaceous nanomaterials, which are important materials with many practical and research applications in biomedical, pharmaceutical and biological fields, have recently attracted much attention. In this study, a magnetic mesoporous carbon coated with ß-cyclodextrin (MMC@ß-CD) was synthesized for the first time from natural pericarpium granati (PG). The as-obtained MMC@ß-CD has high surface areas (203 m(2)g(-1)), large pore volumes (0.16 cm(3)g(-1)), relatively broad mesoporous sizes (6.8 nm) and a high saturation magnetization of 26.2 emu g(-1), which is sufficient for magnetic separation by an external magnetic field. The MMC@ß-CD was used as an innovative adsorbent for magnetic solid-phase extraction of lopid via host-guest interaction prior to spectrofluorometric analysis. The proposed method was successfully applied to analyze lopid in human serum and pharmaceutical wastewater samples with recoveries in the range of 85.0-103.5% for the spiked samples. Overall, this work not only provides an inexpensive and eco-friendly method to fabricate MMC@ß-CD (or MMC) from PG, but also develops a highly selective approach for capture of lopid in biological samples and environmental substances.


Carbon/chemistry , Fluorometry , Gemfibrozil/blood , Wastewater/chemistry , Water Pollutants, Chemical/analysis , beta-Cyclodextrins/chemistry , Gemfibrozil/analysis , Gemfibrozil/isolation & purification , Humans , Lythraceae/metabolism , Magnetics , Microscopy, Electron, Scanning , Microscopy, Electron, Transmission , Porosity , Solid Phase Extraction , Spectroscopy, Fourier Transform Infrared , Surface Properties , Thermogravimetry , X-Ray Diffraction
11.
Talanta ; 134: 387-393, 2015 Mar.
Article En | MEDLINE | ID: mdl-25618684

A magnetic solid phase extraction method based on ß-cyclodextrin (ß-CD) grafted graphene oxide (GO)/magnetite (Fe3O4) nano-hybrid as an innovative adsorbent was developed for the separation and pre-concentration of gemfibrozil prior to its determination by spectrofluorometry. The as-prepared ß-CD/GO/Fe3O4 nano-hybrid possesses the magnetism property of Fe3O4 nano-particles that makes it easily manipulated by an external magnetic field. On the other hand, the surface modification of GO by ß-CD leads to selective separation of the target analyte from sample matrices. The structure and morphology of the synthesized adsorbent were characterized using powder X-ray diffraction, Fourier transform infrared spectroscopy, and field emission scanning electron microscopy. The experimental factors affecting the extraction/pre-concentration and determination of the analyte were investigated and optimized. Under the optimized experimental conditions, the calibration graph was linear in the range between 10 and 5000 pg mL(-1) with a correlation coefficient of 0.9989. The limit of detection and enrichment factor for gemfibrozil were 3 pg mL(-1) and 100, respectively. The maximum sorption capacity of the adsorbent for gemfibrozil was 49.8 mg g(-1). The method was successfully applied to monitoring gemfibrozil in human serum and pharmaceutical wastewaters samples with recoveries in the range of 96.0-104.0% for the spiked samples.


Ferrosoferric Oxide/chemistry , Gemfibrozil/analysis , Graphite/chemistry , Hypolipidemic Agents/analysis , Water Pollutants, Chemical/analysis , beta-Cyclodextrins/chemistry , Adsorption , Drug Industry , Gemfibrozil/blood , Humans , Hypolipidemic Agents/blood , Industrial Waste , Magnetic Phenomena , Nanostructures/chemistry , Oxides/chemistry , Solid Phase Extraction , Wastewater/analysis
12.
Environ Sci Pollut Res Int ; 22(8): 5864-76, 2015 Apr.
Article En | MEDLINE | ID: mdl-25352396

This paper provides data on the occurrence of selected human pharmaceuticals (carbamazepine, clofibric acid, diclofenac, fenofibrate, fenoprofen, gemfibrozil, ibuprofen, ketoprofen, and naproxen) including steroid hormones (17ß-estradiol, 17α-ethinylestradiol, and estrone) in influents/effluents to/from the four principal wastewater treatment plants (WWTPs) serving the city of Rome (Italy), in two different sampling campaigns. Target compounds were also analyzed in the receiving River Tiber and River Aniene. Analytical determination was carried out by LC-MS/MS after sample cleanup and concentration by off-line solid-phase extraction (SPE). The aim of the study was to increase the information currently available on the presence and persistence of pharmaceuticals in Italian urban wastewaters and to evaluate the environmental impact of the pharmaceutical residues discharged through effluents into the receiving rivers. Results indicated that after the treatment processes, most of pharmaceuticals were not completely eliminated, as average removal efficiencies were in the 14-100% wide range during both sampling periods, with higher yields in spring than in winter. Levels detected in overall samples ranged from 5 to 2,230 ng/L in influents and from 5 to 1,424 ng/L in effluents. Carbamazepine, diclofenac, ibuprofen, and gemfibrozil showed the highest persistence to removal. Concentrations in the receiving waters were about one order of magnitude lower than in effluents, with a tendency to increase progressively through the urban tract of the river. Finally, an environmental risk analysis showed that carbamazepine, gemfibrozil, and estrone can pose a high risk at the concentrations detected in effluents and a medium risk in rivers, highlighting their potential hazard for the health of the aquatic ecosystem.


Environmental Monitoring/methods , Pharmaceutical Preparations/analysis , Rivers/chemistry , Waste Disposal, Fluid/methods , Water Pollutants, Chemical/analysis , Carbamazepine/analysis , Chromatography, Liquid , Diclofenac/analysis , Environmental Monitoring/statistics & numerical data , Estrone/analysis , Gemfibrozil/analysis , Humans , Ibuprofen/analysis , Ketoprofen/analysis , Naproxen/analysis , Risk Assessment , Rome , Seasons , Solid Phase Extraction , Tandem Mass Spectrometry
13.
Mar Pollut Bull ; 85(2): 391-9, 2014 Aug 30.
Article En | MEDLINE | ID: mdl-24439316

This study provides a first estimate of the sources, distribution, and risk presented by emerging organic contaminants (EOCs) in coastal waters off southwestern Taiwan. Ten illicit drugs, seven nonsteroidal anti-inflammatory drugs (NSAIDs), five antibiotics, two blood lipid regulators, two antiepileptic drugs, two UV filters, caffeine, atenolol, and omeprazole were analyzed by solid-phase extraction and liquid chromatography coupled to tandem mass spectrometry (SPE-LC-MS/MS). Thirteen EOCs were detected in coastal waters, including four NSAIDs (acetaminophen, ibuprofen, ketoprofen, and codeine), three antibiotics (ampicillin, erythromycin, and cefalexin), three illicit drugs (ketamine, pseudoephedrine, and MDMA), caffeine, carbamazepine, and gemfibrozil. The median concentrations for the 13 EOCs ranged from 1.47 ng/L to 156 ng/L. Spatial variation in concentration of the 13 EOCs suggests discharge into coastal waters via ocean outfall pipes and rivers. Codeine and ampicillin have significant pollution risk quotients (RQ>1), indicating potentially high risk to aquatic organisms in coastal waters.


Seawater/chemistry , Water Pollutants, Chemical/analysis , Anti-Bacterial Agents/analysis , Anti-Bacterial Agents/chemistry , Anti-Inflammatory Agents, Non-Steroidal/analysis , Anti-Inflammatory Agents, Non-Steroidal/chemistry , Aquatic Organisms/drug effects , Caffeine/analysis , Caffeine/chemistry , Carbamazepine/analysis , Carbamazepine/chemistry , Chromatography, Liquid , Environmental Monitoring/methods , Gemfibrozil/analysis , Gemfibrozil/chemistry , Humans , Ketamine/analysis , Ketamine/chemistry , N-Methyl-3,4-methylenedioxyamphetamine/analysis , N-Methyl-3,4-methylenedioxyamphetamine/chemistry , Population Density , Pseudoephedrine/analysis , Pseudoephedrine/chemistry , Risk , Rivers/chemistry , Solid Phase Extraction , Taiwan , Tandem Mass Spectrometry , Water Pollutants, Chemical/chemistry
14.
Environ Pollut ; 182: 1-8, 2013 Nov.
Article En | MEDLINE | ID: mdl-23892012

The fate and exposure risks of pharmaceutically active compounds (PhACs) and endocrine disrupting chemicals (EDCs) in marine environments are not well-understood. In this study we developed a multi-residue analytical method for quantifying concentrations of forty target compounds in seawater from Singapore. Analyses of samples (n = 24) from eight sites showed the occurrence of several compounds, including gemfibrozil (<0.09-19.8 ng/L), triclosan (<0.55-10.5 ng/L), carbamazepine (<0.28-10.9 ng/L) and ibuprofen (<2.2-9.1 ng/L). A 3D hydrodynamic model for Singapore was used to predict residence time (tR). Principal Components Analysis revealed a strong relationship between tR and contaminant concentrations. While source emissions are undoubtedly important, proximate distance to a wastewater treatment plant had little influence on concentrations. The site with the greatest tR, which exhibited the highest concentrations, is adjacent to Singapore's largest protected wetland reserve. The results highlight an important linkage between hydrodynamic behavior and contaminant exposure risks in complex coastal marine ecosystems.


Endocrine Disruptors/analysis , Pharmaceutical Preparations/analysis , Seawater/chemistry , Water Pollutants, Chemical/analysis , Carbamazepine/analysis , Carbamazepine/chemistry , Endocrine Disruptors/chemistry , Environmental Monitoring , Gemfibrozil/analysis , Gemfibrozil/chemistry , Hydrodynamics , Ibuprofen/analysis , Ibuprofen/chemistry , Singapore , Triclosan/analysis , Triclosan/chemistry , Waste Disposal Facilities , Waste Disposal, Fluid , Wastewater/chemistry , Water Pollutants, Chemical/chemistry
15.
Article En | MEDLINE | ID: mdl-23708373

A spectrofluorometric method has been developed and validated for the determination of gemfibrozil. The method is based on the excitation and emission capacities of gemfibrozil with excitation and emission wavelengths of 276 and 304 nm respectively. This method allows de determination of the drug in a self-nanoemulsifying drug delivery system (SNEDDS) for improve its intestinal absorption. Results obtained showed linear relationships with good correlation coefficients (r(2)>0.999) and low limits of detection and quantification (LOD of 0.075 µg mL(-1) and LOQ of 0.226 µg mL(-1)) in the range of 0.2-5 µg mL(-1), equally this method showed a good robustness and stability. Thus the amounts of gemfibrozil released from SNEDDS contained in gastro resistant hard gelatine capsules were analysed, and release studies could be performed satisfactorily.


Drug Delivery Systems , Emulsions/chemistry , Gemfibrozil/analysis , Gemfibrozil/chemistry , Nanoparticles/chemistry , Spectrometry, Fluorescence/methods , Calibration , Solutions
16.
Environ Sci Technol ; 46(10): 5583-9, 2012 May 15.
Article En | MEDLINE | ID: mdl-22494162

The cholesterol-lowering pharmaceutical gemfibrozil is a relevant environmental contaminant because of its frequency of detection in U.S. wastewaters at concentrations which have been shown to disrupt endocrine function in aquatic species. The treatment of gemfibrozil solutions with sodium hypochlorite yielded a 4'-chlorinated gemfibrozil analog (chlorogemfibrozil). In the presence of bromide ion, as is often encountered in municipal wastewater, hypobromous acid generated through a halogen exchange reaction produced an additional 4'-brominated gemfibrozil product (bromogemfibrozil). Standards of chloro- and bromogemfibrozil were synthesized, isolated and characterized using mass spectrometry and NMR spectroscopy. Mass spectrometry was used to follow the in situ halogenation reaction of gemfibrozil in deionized water and wastewater matrices, and to measure levels of gemfibrozil (254 ± 20 ng/L), chlorogemfibrozil (166 ± 121 ng/L), and bromogemfibrozil (50 ± 11 ng/L) in advanced primary wastewater treatment effluent treated by chlorination. Chlorogemfibrozil demonstrated a significant (p < 0.05) reduction in the levels of 11-ketotestosterone at 55.1 µg/L and bromogemfibrozil demonstrated a significant (p < 0.05) reduction in the levels of testosterone at 58.8 µg/L in vivo in Japanese medaka in a 21 day exposure. These results indicated that aqueous exposure to halogenated degradates of gemfibrozil enhanced the antiandrogenicity of the parent compound in a model fish species, demonstrating that chlorination may increase the toxicity of pharmaceutically active compounds in surface water.


Gemfibrozil/analysis , Gemfibrozil/toxicity , Halogenation/drug effects , Waste Disposal, Fluid , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/toxicity , Adsorption/drug effects , Animals , Gemfibrozil/chemistry , Oryzias/metabolism , Particulate Matter/chemistry , Testosterone/analogs & derivatives , Testosterone/metabolism , Time Factors
17.
J Environ Manage ; 102: 18-25, 2012 Jul 15.
Article En | MEDLINE | ID: mdl-22425875

In this work, the distribution and the ecotoxicological risk of sixteen pharmaceutically active compounds belonging to seven different therapeutic groups (five anti-inflammatory drugs, two antibiotics, an anti-epileptic drug, a ß-blocker, a nervous stimulant, four estrogens and two lipid regulators) have been studied in sewage sludge from wastewater treatment plants. Only three of the sixteen pharmaceutical compounds were never detected in sludge while eleven of the studied pharmaceuticals were still detected in compost. Mean concentration levels of the pharmaceutically active compounds ranged between 24.9 and 4105 µg/kg dm, 14.5-944 µg/kg dm, 3.29-636 µg/kg dm and 9.19-974 µg/kg dm in primary, secondary, digested sludge and compost, respectively. An increase in the concentration levels of most of the pharmaceuticals was observed from summer to winter (mean values in primary and secondary sludge were 304 and 85.1 µg/kg dm in summer and 435 and 175 µg/kg dm in winter, respectively) probably due to an increase of their consumption during the coldest season and a reduction of the microbial activity under colder temperatures. The highest ecotoxicological risk, in digested sludge and compost, was due to the estrogenic compound 17ß-estradiol. The ecotoxicological risk significantly decreased after the application of digested sludge or compost to the soils (risk quotient values ranged between 0.04 and 252 in digested sludge and 0.002-37.8 in compost and decreased to 8·10(-4)-1.92 in digested sludge-amended soil and 1·10(-4)-0.23 in compost-amended soil).


Environmental Pollutants/analysis , Environmental Pollution/analysis , Estradiol/analysis , Sewage/chemistry , Soil/chemistry , Anti-Bacterial Agents/analysis , Anti-Bacterial Agents/toxicity , Anti-Inflammatory Agents, Non-Steroidal/analysis , Anti-Inflammatory Agents, Non-Steroidal/toxicity , Caffeine/analysis , Caffeine/toxicity , Carbamazepine/analysis , Carbamazepine/toxicity , Clofibric Acid/analysis , Clofibric Acid/toxicity , Environmental Pollutants/toxicity , Estradiol/toxicity , Gemfibrozil/analysis , Gemfibrozil/toxicity , Propranolol/analysis , Risk Assessment , Spain , Time Factors
18.
Environ Toxicol Chem ; 31(3): 550-5, 2012 Mar.
Article En | MEDLINE | ID: mdl-22180293

Pharmaceuticals and personal care products (PPCPs) have emerged as a group of potential environmental contaminants of concern. The occurrence of gemfibrozil, a lipid-regulating drug, was studied in the influent and effluent at a wastewater treatment plant (WWTP) and groundwater below a land application site receiving treated effluent from the WWTP. In addition, the sorption of gemfibrozil in two loam soils and sand was assessed, and biological degradation rates in two soil types under aerobic conditions were also determined. Results showed that concentrations of gemfibrozil in wastewater influent, effluent, and groundwater were in the range of 3.47 to 63.8 µg/L, 0.08 to 19.4 µg/L, and undetectable to 6.86 µg/L, respectively. Data also indicated that gemfibrozil in the wastewater could reach groundwater following land application of the treated effluent. Soil-water distribution coefficients for gemfibrozil, determined by the batch equilibrium method, varied with organic carbon content in the soils. The sorption capacity was silt loam > sandy loam > sand. Under aerobic conditions, dissipation half-lives for gemfibrozil in sandy loam and silt loam soils were 17.8 and 20.6 days, respectively; 25.4 and 11.3% of gemfibrozil was lost through biodegradation from the two soils over 14 days.


Gemfibrozil/analysis , Groundwater/chemistry , Hypolipidemic Agents/analysis , Soil Pollutants/analysis , Water Pollutants, Chemical/analysis , Biodegradation, Environmental , Environmental Monitoring , Soil/chemistry , Waste Disposal, Fluid
19.
Chemosphere ; 85(9): 1472-80, 2011 Nov.
Article En | MEDLINE | ID: mdl-21955351

A variety of emerging chemicals of concern are released continuously to surface water through the municipal wastewater effluent discharges. The ability to rapidly determine bioaccumulation of these contaminants in exposed fish without sacrificing the animal (i.e. in vivo) would be of significant advantage to facilitate research, assessment and monitoring of their risk to the environment. In this study, an in vivo solid phase micro-extraction (SPME) approach was developed and applied to the measurement of a variety of emerging contaminants (carbamazepine, naproxen, diclofenac, gemfibrozil, bisphenol A, fluoxetine, ibuprofen and atrazine) in fish. Our results indicated in vivo SPME was a potential alternative extraction technique for quantitative determination of contaminants in lab exposures and as well after exposure to two municipal wastewater effluents (MWWE), with a major advantage over conventional techniques due to its ability to non-lethally sample tissues of living organisms.


Environmental Monitoring/methods , Water Pollutants, Chemical/analysis , Animals , Atrazine/analysis , Atrazine/isolation & purification , Benzhydryl Compounds , Carbamazepine/analysis , Carbamazepine/isolation & purification , Diclofenac/analysis , Diclofenac/isolation & purification , Fishes , Fluoxetine/analysis , Fluoxetine/isolation & purification , Gemfibrozil/analysis , Gemfibrozil/isolation & purification , Ibuprofen/analysis , Ibuprofen/isolation & purification , Naproxen/analysis , Naproxen/isolation & purification , Phenols/analysis , Phenols/isolation & purification , Solid Phase Extraction , Solid Phase Microextraction , Waste Disposal, Fluid , Water Pollutants, Chemical/isolation & purification
20.
Water Res ; 45(13): 4019-27, 2011 Jul.
Article En | MEDLINE | ID: mdl-21665241

Urban watersheds are susceptible to numerous pollutant sources and the identification of source-specific indicators can provide a beneficial tool in the identification and control of input loads, often times needed for a water body to achieve designated beneficial uses. Differentiation of wastewater flows from other urban wet weather flows is needed in order to more adequately address such environmental concerns as water body nutrient impairment and potable source water contamination. Anthropogenic compounds previously suggested as potential wastewater indicators include caffeine, carbamazepine, N,N-diethyl-meta-toluamide (DEET), gemfibrozil, primidone, sulfamethoxazole, and TCEP. This paper compares the suitability of a variety of anthropogenic compounds to sucralose, an artificial sweetener, as wastewater indicators by examining occurrence data for 85 trace organic compounds in samples of wastewater effluents, source waters with known wastewater point source inputs, and sources without known wastewater point source inputs. The findings statistically demonstrate the superior performance of sucralose as a potential indicator of domestic wastewater input in the U.S. While several compounds were detected in all of the wastewater effluent samples, only sucralose was consistently detected in the source waters with known wastewater discharges, absent in the sources without wastewater influence, and consistently present in septic samples. All of the other compounds were prone to either false negatives or false positives in the environment.


Sucrose/analogs & derivatives , Water Pollutants, Chemical/analysis , Caffeine/analysis , Carbamazepine/analysis , DEET/analysis , Gemfibrozil/analysis , Phosphines/analysis , Primidone/analysis , Sucrose/analysis , Sulfamethoxazole/analysis
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