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1.
Bull Environ Contam Toxicol ; 112(3): 48, 2024 Mar 09.
Artigo em Inglês | MEDLINE | ID: mdl-38459992

RESUMO

This study aimed on the development of a SPE-UHPLC-MS/MS method for the simultaneous determination of pesticide residues in drinking water samples. A chemometric approach was applied to optimize the efficiency of the SPE pretreatment procedure. This study involved (i) the application of a Full Factorial Design for the screening of the significant factors, (ii) the application of a Central Composite Design for the determination of the optimal conditions and (iii) the evaluation and validation of the significance of the statistically proposed models. Oasis HLB cartridges were used for the extraction. The optimum sample volume was 300 mL and the elution solvent 3 mL of the mixture of methanol:ethylacetate 70:30 v/v. The method was validated according to the international guidelines. Recoveries were ranged from 63 to 116% and the detection limits were between 0.1 and 1.5 pg mL- 1. The validated method could be used in routine analysis for pesticides screening.


Assuntos
Praguicidas , Praguicidas/análise , Espectrometria de Massas em Tandem/métodos , Cromatografia Líquida de Alta Pressão/métodos , Quimiometria , Extração em Fase Sólida/métodos , Água
2.
Environ Monit Assess ; 193(5): 249, 2021 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-33829338

RESUMO

This study presents the development of an analytical method for the simultaneous determination of multiclass illicit drugs (cocainoids, opiates, amphetamines, and cannabinoids) and psychoactive pharmaceuticals (anxiolytics, hypnotics, antipsychotics, antidepressants, and antiparkinsonian), in municipal wastewater. The analytical method was validated in terms of specificity, linearity, precision, and accuracy. The recoveries (%) for the majority of the analytes ranged between 70 and 120%, while the method showed good repeatability (2.4-29.2%). The limits of detection (LOD) of the method ranged between 0.8 and 9.4 ng L-1. The method was implemented on influent and effluent samples from Thessaloniki (N. Greece) wastewater treatment plant (WWTP), and it revealed the daily presence of benzoylecgonine (BEG) (84.0-202.2 ng L-1), methadone (12.3-17.5 ng L-1), 11-Nor-9-carboxy-Δ9-tetrahydrocannabinol (THC-COOH) (80.3-171.9 ng L-1), morphine (144.2-264.3 ng L-1), and 6-monoacetylmorphine (6-MAM) (5.8-12.0 ng L-1) in the influent samples of WWTP. Clozapine (101.6-315.5 ng L-1), quetiapine (33.5-109.7 ng L-1), and fluoxetine (20.9-124.4 ng L-1) were pharmaceutical psychotics with the highest concentration in the influents. Back calculation estimated that the daily consumption of cocaine, heroin, cannabis, and methadone was 36-95, 86-164, 2300-5400, and 8-12 mg day-1 per 1000 inhabitants, respectively. The consumption was estimated between 7-16 and 15 mg day-1 per 1000 inhabitants for methyl diethanolamine (MDEA) and 3,4-methylenedioxymethamphetamine (MDMA), respectively.


Assuntos
Drogas Ilícitas , Poluentes Químicos da Água , Cromatografia Líquida , Monitoramento Ambiental , Grécia , Extração em Fase Sólida , Espectrometria de Massas em Tandem , Águas Residuárias/análise , Poluentes Químicos da Água/análise
3.
J Pharm Biomed Anal ; 199: 114053, 2021 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-33819696

RESUMO

A fast fabric phase sorptive extraction method is presented herein for the rapid isolation of selected beta-blocker drugs from human serum and urine. Among many high efficiency sol-gel sorbent coated FPSE membranes, sol-gel CW20 M coated FPSE membrane was identified as the best FPSE membrane for the target beta-blocker drugs possessing logP values ranging from 0.1 (highly polar) to 3.1 (moderately polar). Due to the engineered affinity towards the analytes via complementary intermolecular interactions and high mass transfer rate of the analytes from the bulk sample solution to the FPSE membrane, the extraction is accomplished in relatively short time (15 min) while its high permeability permits the direct extraction of biological samples without any other pretreatment. The advantages of the fabricated extraction membrane were exploited for the determination of six beta-blockers (namely atenolol, nadolol, metoprolol, oxprenolol, labetalol and propranolol) in biological matrices in combination with UHPLC-ESI-MS/MS. Important parameters including extraction time, sample volume, sorbent size, elution solvent, etc. affecting the performance of the extraction were systematically investigated. The linearity of the method was evaluated in the range of 50-5000 ng mL-1 by constructing weighted (1/X) matrix-matched calibration curves. The intra-day and inter-day trueness were ranged between - 17.2 to 13.3% and - 10.8 to 12.6%, respectively. The intra-day and inter-day precision were less than 11.5 and 14.5 %, respectively. The proposed analytical scheme was successfully applied to the determination of the target drugs in human serum and urine.


Assuntos
Espectrometria de Massas em Tandem , Cromatografia Líquida de Alta Pressão , Humanos
4.
J Hazard Mater ; 403: 123819, 2021 02 05.
Artigo em Inglês | MEDLINE | ID: mdl-33264914

RESUMO

The objectives of the present study were: a) to evaluate the photocatalytic degradation of two benzodiazepine pharmaceuticals, alprazolam and diazepam, using Photo-Fenton, b) to optimize the experimental parameters through a central composite experimental design, c) to assess their mineralization and toxicity variations and d) to identify the transformation products during the process and to propose transformation pathways. Response Surface Methodology proved to be a useful tool for the optimization of the degradation process as the statistical coefficients (R2 = 0.967 for alprazolam and R2 = 0.929 for diazepam) showed satisfactory values confirming the adequate correlation between the predicted models and experimental values. Two sets of experimental conditions were proposed taking into consideration criteria related to the reaction rate and the minimum use of iron. Toxicity of the system varied with time after the treatment, indicating the gradual production of transformation products which differ in their toxic potential. Fifteen and twenty-three photocatalytic degradation products were identified for ALP and DZP respectively using LC-(ESI)MS/MS. In the case of ALP, the main degradation reactions included, phenyl-group removal and the opening of the 7-membered ring, while for DZP, degradation occurred through hydroxylation, formation of benzophenone and the opening of the 7-membered cyclic group.


Assuntos
Preparações Farmacêuticas , Poluentes Químicos da Água , Alprazolam/toxicidade , Diazepam/toxicidade , Peróxido de Hidrogênio , Oxirredução , Espectrometria de Massas em Tandem , Poluentes Químicos da Água/análise
5.
Environ Geochem Health ; 42(9): 2747-2769, 2020 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-31933038

RESUMO

The presence of phosphorus (P) and heavy metals (HMs) in surface sediments originating from lakes Volvi, Kerkini, and Doirani (N. Greece), as well as their fractionation patterns, were investigated. No statistically significant differences in total P content were observed among the studied lakes, but notable differences were observed among sampling periods. HM contents in all lakes presented a consistent trend, i.e., Mn > Cr > Zn > Pb > Ni > Cu > Cd, while the highest concentrations were recorded in Lake Kerkini. Most of the HMs exceeded probable effect level value indicating a probable biological effect, while Ni in many cases even exceeded threshold effects level, suggesting severe toxic effects. P was dominantly bound to metal oxides, while a significant shift toward the labile fractions was observed during the spring period. The sum of potentially bioavailable HM fractions followed a downward trend of Mn > Cr > Pb > Zn > Cu > Ni > Cd for most lakes. The geoaccumulation index Igeo values of Cr, Cu, Mn, Ni, and Zn in all lakes characterized the sediments as "unpolluted," while many sediments in lakes Volvi and Kerkini were characterized as "moderately to heavily polluted" with regard to Cd. The descending order of potential ecological risk [Formula: see text] was Cd > Pb > Cu > Ni > Cr > Zn > Mn for all the studied lakes. Ni and Cr presented the highest toxic risk index values in all lake sediments. Finally, the role of mineralogical divergences among lake sediments on the contamination degree was signified.


Assuntos
Sedimentos Geológicos/análise , Lagos/análise , Metais Pesados/análise , Fósforo/análise , Poluentes Químicos da Água/análise , Fracionamento Químico , Monitoramento Ambiental , Sedimentos Geológicos/química , Grécia , Lagos/química , Metais Pesados/química , Metais Pesados/toxicidade , Fósforo/química , Medição de Risco , Estações do Ano , Poluentes Químicos da Água/química , Poluentes Químicos da Água/toxicidade
6.
Addiction ; 115(1): 109-120, 2020 01.
Artigo em Inglês | MEDLINE | ID: mdl-31642141

RESUMO

BACKGROUND AND AIMS: Wastewater-based epidemiology is an additional indicator of drug use that is gaining reliability to complement the current established panel of indicators. The aims of this study were to: (i) assess spatial and temporal trends of population-normalized mass loads of benzoylecgonine, amphetamine, methamphetamine and 3,4-methylenedioxymethamphetamine (MDMA) in raw wastewater over 7 years (2011-17); (ii) address overall drug use by estimating the average number of combined doses consumed per day in each city; and (iii) compare these with existing prevalence and seizure data. DESIGN: Analysis of daily raw wastewater composite samples collected over 1 week per year from 2011 to 2017. SETTING AND PARTICIPANTS: Catchment areas of 143 wastewater treatment plants in 120 cities in 37 countries. MEASUREMENTS: Parent substances (amphetamine, methamphetamine and MDMA) and the metabolites of cocaine (benzoylecgonine) and of Δ9 -tetrahydrocannabinol (11-nor-9-carboxy-Δ9 -tetrahydrocannabinol) were measured in wastewater using liquid chromatography-tandem mass spectrometry. Daily mass loads (mg/day) were normalized to catchment population (mg/1000 people/day) and converted to the number of combined doses consumed per day. Spatial differences were assessed world-wide, and temporal trends were discerned at European level by comparing 2011-13 drug loads versus 2014-17 loads. FINDINGS: Benzoylecgonine was the stimulant metabolite detected at higher loads in southern and western Europe, and amphetamine, MDMA and methamphetamine in East and North-Central Europe. In other continents, methamphetamine showed the highest levels in the United States and Australia and benzoylecgonine in South America. During the reporting period, benzoylecgonine loads increased in general across Europe, amphetamine and methamphetamine levels fluctuated and MDMA underwent an intermittent upsurge. CONCLUSIONS: The analysis of wastewater to quantify drug loads provides near real-time drug use estimates that globally correspond to prevalence and seizure data.


Assuntos
Monitoramento Ambiental/métodos , Drogas Ilícitas , Análise Espaço-Temporal , Detecção do Abuso de Substâncias/métodos , Águas Residuárias/química , Anfetamina/análise , Cromatografia Líquida , Cocaína/análogos & derivados , Cocaína/análise , Humanos , Internacionalidade , Metanfetamina/análise , N-Metil-3,4-Metilenodioxianfetamina/análise , Espectrometria de Massas em Tandem
7.
Molecules ; 25(1)2019 Dec 31.
Artigo em Inglês | MEDLINE | ID: mdl-31906217

RESUMO

An automated flow method for the determination of hydrazine based on the concept of zone-fluidics has been developed. The analyte reacts under flow conditions with p-dimethylamino benzaldehyde (25 mmol L-1) in micellar medium (100 mmol L-1 SDS) to form a stable derivative (460 nm). Micelles mediated catalysis excludes the use of highly acidic environment typical for this kind of reaction. Following careful examination of chemical and instrumental variables, the method allows the determination of hydrazine at the low micromolar level (0.3-10 µmol L-1) in water samples. Real sample analyses (drinking and boiler feed water) resulted in satisfactory results in terms of accuracy with the percent recoveries being in the range of 82-114%.


Assuntos
Hidrazinas/análise , Poluentes Químicos da Água/análise , Benzaldeídos/química , Catálise , Confiabilidade dos Dados , Limite de Detecção , Micelas , Dodecilsulfato de Sódio/química , Temperatura , Fatores de Tempo , Água/química
8.
Environ Sci Pollut Res Int ; 25(27): 26766-26779, 2018 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-28875392

RESUMO

The scope of this study was the development, optimization and validation of an analytical method for the determination of selected heavy metals and trace elements (As, Hg, Se, Cd, Cu, Pb, Mn, Fe, Ni, Zn, Cr) in milk powder, using microwave-assisted digestion. A statistical experimental design approach using central composite design (CCD) was carried out, to investigate the effects of three independent pretreatment variables (final digestion temperature (°C), HNO3 concentration (in % w/v), microwave hold time) on the heavy metal recovery of spiked undigested milk powder sample and to calculate the variable factor values which produce the optimum recovery. CCD results revealed that the optimum digestion conditions, with respect to maximum recovery were as follows: temperature 190 °C, HNO3 56.8% w/v, and digestion time of 8.47 min. The method was fully validated. Recoveries for all metals ranged between 92 and 108% while intra-day repeatability was below 6.59% (rsd). A certified reference material (ERM BD 150) that included 8 out of the total 11 heavy metals of the present study (Hg, Se, Cd, Cu, Pb, Mn, Ni, and Zn) was used to test the accuracy of the method where acceptable recovery values ranging between 96 and 107% were obtained. High heavy metal recoveries, short digestion time, and low acid consumption were the advantages of the pretreatment method. The analytical process was successfully applied for the determination of heavy metals in different milk samples from the Greek market. Heavy metal concentrations for Ni, Cr, Pb, Cd, Se, Mn, and Cu measured in this study reached 307, 102, 8.01, 5.96, 60.2, 519, and 438 µg/kg wet weight (ww), respectively. Zn and Fe were found at concentrations ranging 3.21-8.39 and 0.170-10.1 mg/kg ww, respectively. Risk assessment based on the WHO tolerable daily intake levels and the calculated target hazard quotients revealed that the consumption of the selected milk samples is considered safe.


Assuntos
Poluentes Ambientais/análise , Contaminação de Alimentos/análise , Metais Pesados/análise , Leite/química , Adulto , Animais , Monitoramento Ambiental , Grécia , Humanos , Micro-Ondas , Medição de Risco
9.
Environ Geochem Health ; 39(3): 611-634, 2017 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-27240845

RESUMO

In the present study, an investigation of the mineralogy and morphology, the heavy metal content and the health risk of urban road dusts from the second largest city of Greece was conducted. For this reason road dust samples from selected sites within the city core area were collected. No differences were observed in the mineralogy of road dusts coming from different sampling sites, and they were mainly consisted of quartz and calcite, while an elevated amorphous content was detected. Morphologically road dusts presented Ca-rich, Fe-rich and silicates particles with various shapes and sizes. The mean concentrations of Cd, Cr, Cu, Mn, Ni, Pb and Zn in road dust were 1.76, 104.9, 662.3, 336.4, 89.43, 209 and 452.8 µg g-1, respectively. A series of spatial distribution patterns revealed that the hotspot areas were tended to associate with major road junctions and regions with high traffic. Combination of pollution indexes and statistical analyses (correlation analysis, cluster analysis and principal component analysis) revealed that road dusts have a severe influence by anthropogenic activities. In attempt to identify the source of metals through geostatistical and multivariate statistical analyses, it was concluded as follows: Cr, Cu, Fe and Zn mainly originated from tire/break wear and vehicle abrasions, while Cd, Mn and Pb were mainly related to fuel/oil leakage from automobiles along with oil lubricants and vehicle abrasion. Hazard quotient values for children based on total metal concentrations for the road dust ingestion route were lower than safe level (=1). However, the fact that the Hazard Index value for Pb (0.459) which is a particularly toxic metal, was close to safe level, renders essential further investigation in order to provide more reliable characterizations of potential health risks.


Assuntos
Cidades , Poeira/análise , Metais Pesados/análise , Meios de Transporte , Carbonato de Cálcio/análise , Monitoramento Ambiental , Grécia , Humanos , Quartzo/análise , Medição de Risco
10.
Environ Sci Pollut Res Int ; 23(16): 16620-30, 2016 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-27178297

RESUMO

This study focused on (a) the development of a screening methodology, in order to determine the main experimental variables affecting chlorinated and brominated disinfection by-product (DBP) formation in water during chlorination experiments and (b) the application of a central composite design (CCD) using response surface methodology (RSM) for the mathematical description and optimization of DBP formation. Chlorine dose and total organic carbon (TOC) were proven to be the main factors affecting the formation of total chlorinated DBPs, while chlorine dose and bromide concentration were the main parameters affecting the total brominated THMs. Longer contact time promoted a rise in chlorinated DBPs' concentration even in the presence of a minimal amount of organic matter. A maximum production of chlorinated DBPs was observed under a medium TOC value and it reduced at high TOC concentrations, possibly due to the competitive production of brominated THMs. The highest concentrations of chlorinated THMs were observed at chlorine dose 10 mg L(-1) and TOC 5.5 mg L(-1). The formation of brominated DBPs is possible even with a minimum amount of NaOCl in the presence of high concentration of bromide ions. Brominated DBPs were observed in maximum concentrations using 8 mg L(-1) of chlorine in the presence of 300 µg L(-1) bromides.


Assuntos
Desinfetantes/química , Desinfecção/métodos , Trialometanos/química , Poluentes Químicos da Água/química , Purificação da Água/métodos , Brometos/química , Halogenação , Modelos Químicos
11.
J Chromatogr A ; 1377: 46-54, 2015 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-25543304

RESUMO

In the present report, a simple and cost-effective method for the determination of twelve US EPA priority polycyclic aromatic hydrocarbons (PAHs) in honey samples after salting-assisted liquid-liquid extraction and UHPLC with fluorescence detection is proposed. The sample treatment is based on the usage of hydrophilic acetonitrile as extraction solvent and its phase separation under high salinity conditions. Due to the high sugar content of the samples the phase separation is promoted effortlessly. Several parameters affecting the extraction efficiency and method sensitivity including the concentration of the honey samples, the type and volume of the extraction solvent, the type and quantity of the inorganic salt, extraction time and centrifugation time was systematically investigated. The method was validated in-house according to the Commission Decision 2002/657/EC guidelines. The limit of detection (LOD) of the method lay between 0.02 and 0.04ngmL(-1) (corresponding to 0.08 and 0.16ngg(-1)) which are close to the quality criteria established by European Regulation (EC) 836/2011 concerning the PAHs in foodstuffs. The mean analytical bias (expressed as relative recoveries) in all spiking levels was acceptable being in the range of 54-118% while the relative standard deviation (RSD) was lower than 19%. The proposed method has been satisfactorily applied for the analysis of the selected PAHs residues in various honey samples obtained from Greek region.


Assuntos
Acetonitrilas/química , Técnicas de Química Analítica , Cromatografia Líquida/normas , Tecnologia de Alimentos/métodos , Mel/análise , Extração Líquido-Líquido , Hidrocarbonetos Policíclicos Aromáticos/análise , Cloreto de Sódio/química , Interações Hidrofóbicas e Hidrofílicas , Peso Molecular
12.
Environ Sci Pollut Res Int ; 21(12): 7252-62, 2014 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-24691934

RESUMO

The development and application of an analytical methodology for the pretreatment and determination of 253 multiclass pesticides, in lake sediment samples, using liquid chromatography coupled with mass spectrometry (LC-MS/MS) are described in this work. Sediments of lakes Volvi, Doirani, and Kerkini, located in northern Greece, were collected in two-time periods (fall/winter 2010 and spring/summer 2011) and analyzed, applying the developed analytical methodology. Microwave-assisted extraction (MAE) was applied to extract the pesticide residues from lake sediment samples. Analytical results were stored, categorized, and visualized using geographical information systems, in order to assess and observe spatial and temporal variations of the pollution. Main pesticides that were detected included the following: amitrole, tebuconazole, phoxim, diniconazole, sethoxydim, temephos, tetrachlorvinphos, pendimethalin, boscalid, disulfoton sulfone, lenacil, propiconazole, cycloxydim, pyridaben, and terbuthylazine. Amitrole, diniconazole, and tebuconazole were found to be common in all three lakes. Lakes Kerkini and Doirani exhibited increased concentrations during the first sampling period (winter 2010) with predominant pesticide classes, triazines/triazoles and organophosphates. Pollution is mainly located near the populated villages of the lakes and the nearby cultivations. During the second sampling period, pesticide concentrations appear lower and located in sediments near the center of the lake. Lake Volvi exhibits increased pesticide concentrations during the second sampling period, temporal and spatial variations and different pesticide profile pattern. Increased pollution occurs near the center of the lake during the first sampling period, mainly comprised by triazines/triazoles and organophosphates. During the second sampling period, the majority of the sediment samples demonstrated a different pesticide profile dominated by unclassified pesticides and triazines/triazoles. Mineralogical analysis of the samples demonstrates that sediments are mainly composed of clay, mud, and sand particles, and they present spatial variations. Near the center of the lakes, sediments appear to be more fine-grained with higher clay content and are more likely to adsorb pesticides.


Assuntos
Sedimentos Geológicos/química , Lagos/análise , Resíduos de Praguicidas/análise , Poluentes Químicos da Água/análise , Cromatografia Líquida , Monitoramento Ambiental/métodos , Grécia , Micro-Ondas , Estações do Ano , Espectrometria de Massas em Tandem
13.
Environ Sci Pollut Res Int ; 21(12): 7239-51, 2014 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-24696214

RESUMO

The present work describes the application of an analytical procedure, utilizing ultra performance liquid chromatography (UPLC) coupled with mass spectrometry instrumentation, for the determination of 253 multiclass pesticides, classified in six different groups. Solid phase extraction was applied for the isolation and pre-concentration of target compounds in water samples. Surface waters of the lakes located in Northern Greece (Volvi, Doirani, and Kerkini), were collected in two time periods (fall/winter 2010 and spring/summer 2011) and analyzed, applying the developed analytical methods. Spatial distribution of detected pesticides was visualized using interpolation methods and geographical information systems (GIS). Pesticides with maximum concentrations were amitrole, propoxur, simazine, chlorpyrifos, carbendazim, triazophos, disulfoton-sulfone, pyridaben, sebuthylazine, terbuthylazine, atrazine, atrazine-desethyl, bensulfuron-methyl, metobromuron, metribuzin, rotenone, pyriproxyfen, and rimsulfuron. In Lake Kerkini, mainly carbamates and triazines were determined at elevated concentrations, near the coastal point of the NW side of the lake. Seasonal variations were strong among the applied pesticide classes and determined concentrations, indicating the contribution of pesticide application patterns and rainfall. Lake Doirani exhibited organophosphate pesticides at higher concentrations mainly at coastal points, while triazines emerged as the main pollutant during spring sampling. Lake Volvi exhibited the highest pesticide concentrations, mostly triazines and ureas at the central part of the lake. The occurrence of extreme values and nonconstant seasonal variations indicated that the concentrations were increased disproportionately during the second sampling, as a result of the varying contribution of pollution sources right after the application period. In all cases, the total concentration of pesticides increased during the second sampling period.


Assuntos
Lagos/análise , Resíduos de Praguicidas/análise , Poluentes Químicos da Água/análise , Cromatografia Líquida , Monitoramento Ambiental/métodos , Grécia , Estações do Ano , Extração em Fase Sólida , Espectrometria de Massas em Tandem/métodos
14.
Chemosphere ; 93(9): 1818-25, 2013 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-23871596

RESUMO

The aims of this study were (a) to evaluate the degradation of acetamiprid with the use of Fenton reaction, (b) to investigate the effect of different concentrations of H2O2 and Fe(2+), initial pH and various iron salts, on the degradation of acetamiprid and (c) to apply response surface methodology for the evaluation of degradation kinetics. The kinetic study revealed a two-stage process, described by pseudo- first and second order kinetics. Different H2O2:Fe(2+) molar ratios were examined for their effect on acetamiprid degradation kinetics. The ratio of 3 mg L(-1) Fe(2+): 40 mg L(-1) H2O2 was found to completely remove acetamiprid at less than 10 min. Degradation rate was faster at lower pH, with the optimal value at pH 2.9, while Mohr salt appeared to degrade acetamiprid faster. A central composite design was selected in order to observe the effects of Fe(2+) and H2O2 initial concentration on acetamiprid degradation kinetics. A quadratic model fitted the experimental data, with satisfactory regression and fit. The most significant effect on the degradation of acetamiprid, was induced by ferrous iron concentration followed by H2O2. Optimization, aiming to minimize the applied ferrous concentration and the process time, proposed a ratio of 7.76 mg L(-1) Fe(II): 19.78 mg L(-1) H2O2. DOC is reduced much more slowly and requires more than 6h of processing for 50% degradation. The use to zero valent iron, demonstrated fast kinetic rates with acetamiprid degradation occurring in 10 min and effective DOC removal.


Assuntos
Peróxido de Hidrogênio/química , Ferro/química , Praguicidas/química , Piridinas/química , Águas Residuárias/química , Poluentes Químicos da Água/química , Concentração de Íons de Hidrogênio , Cinética , Modelos Químicos , Neonicotinoides , Oxirredução , Praguicidas/análise , Piridinas/análise , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/análise
15.
Artigo em Inglês | MEDLINE | ID: mdl-23394897

RESUMO

An ultra high pressure liquid chromatographic method coupled with diode array detector (UHPLC-DAD) has been developed and validated for the fast separation and determination of three major methylxanthines, i.e., caffeine, theophylline and theobromine, in various herbal beverages. Isocratic elution using 0.1vol% formic acid/CH3OH (92.5:7.5, v/v) enabled the completion of the separation cycle in less than 3min using a flow rate of 0.7mL/min and a column temperature of 50°C. Validation of the method included linearity (0.5-50mg/L), limits of detection (12-35µg/L) and quantification (40-120µg/L), precision, matrix effect and accuracy. The percent recoveries ranged between 90 and 108%.


Assuntos
Bebidas/análise , Cromatografia Líquida de Alta Pressão/métodos , Chá/química , Xantinas/análise , Camellia sinensis/química , Camomila/química , Modelos Lineares , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , Xantinas/química
16.
J Sep Sci ; 35(18): 2422-9, 2012 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-22893549

RESUMO

A simple vortex-assisted liquid-liquid microextraction protocol followed by GC-MS is proposed for the determination of 12 organophosphate pesticides residues in environmental water samples and wines. The sample pretreatment employs the usage of low-density organic solvent. The parameters affecting the extraction efficiency (type and volume of organic extraction solvent, sample pH, ionic strength, extraction time, and centrifugation speed) were carefully examined. A mild emulsification process was involved by the addition of 40 µL toluene into 10 mL sample followed by sequential vortex-based agitation and manual shaking for 3 min. Following the extraction, the pesticide-rich organic solvent was recovered by centrifugation at 4000 rpm for 5 min. A fraction of the floated toluene was then collected and analyzed by GC-MS in SIM mode. Under the optimized conditions, the enrichment factor ranged between 65 and 389. Satisfactory linearity was observed for all pesticides tested with correlation coefficients higher than 0.9945 while the LODs were in the range of 2-11 ng L(-1) . The main advantages of the proposed method are the simplicity of operation, rapidity, low cost, and high sensitivity.


Assuntos
Microextração em Fase Líquida , Compostos Organofosforados/análise , Praguicidas/análise , Poluentes Químicos da Água/química , Vinho/análise , Cromatografia Gasosa-Espectrometria de Massas
17.
J AOAC Int ; 90(6): 1677-81, 2007.
Artigo em Inglês | MEDLINE | ID: mdl-18193747

RESUMO

Residues of organophosphorus insecticides (diazinon, methyl parathion, fenitrothion, malathion, and parathion) were determined in 13 different vegetable matrixes by headspace solid-phase microextraction performed with a polydimethyl-siloxane fiber (100 microm). Determination was carried out by gas chromatography with a nitrogen-phosphorus detector. Limits of detection and quantification were < 0.005 and 0.017 mg/kg, respectively; thus, the limits of maximum residue levels (MRLs) required by European regulations can be verified without difficulty. Pesticide residues were found in 38% of the 125 fresh commercial samples (imported and domestic) that were analyzed. Residues of methyl parathion and parathion, which were withdrawn in Greece in 2003, were detected in 36.8 and 4% of all samples, respectively. The MRLs were exceeded overall by 1%.


Assuntos
Inseticidas/análise , Compostos Organofosforados/análise , Verduras/química , Cromatografia Gasosa , Exposição Ambiental , Grécia , Indicadores e Reagentes , Padrões de Referência
18.
J Environ Qual ; 35(4): 1181-92, 2006.
Artigo em Inglês | MEDLINE | ID: mdl-16738404

RESUMO

Laboratory studies were conducted to determine the effect of pH and redox conditions, as well as the effect of Fe, Mn, Ca, Al, and organic matter, on the release of ortho-phosphates in lake sediments taken from Lakes Koronia and Volvi (Northern Greece). Results were evaluated in combination with experiments to determine P fractionation in the sediment. The study revealed the major effect of redox potential and pH on the release of P from lake sediments. Both lakes showed increased release rates under reductive conditions and high pH values. The fractionation experiments revealed increased mobility of the reductive P fraction as well as of the NaOH-P fraction, indicating participation of both fractions in the overall release of sediment-bound P, depending on the prevailing environmental conditions. The results were assessed in combination with the release patterns of Fe, Mn, Ca, Al, and organic matter, enabling the identification of more specific processes of P release for each lake. The basic release patterns included the redox induced reductive dissolution of P-bearing metal oxides and the competitive exchange of phosphate anions with OH- at high pH values. The formation of an oxidized surface microlayer under oxic conditions acted as a protective film, preventing further P release from the sediments of Lake Volvi, while sediments from Lake Koronia exhibited a continuous and increased tendency to release P under various physicochemical conditions, acting as a constant source of internal P loading.


Assuntos
Água Doce/química , Sedimentos Geológicos/microbiologia , Fósforo/metabolismo , Poluentes Químicos da Água/metabolismo , Monitoramento Ambiental , Geografia , Sedimentos Geológicos/análise , Concentração de Íons de Hidrogênio , Metais/análise , Metais/química , Compostos Orgânicos/análise , Compostos Orgânicos/química , Oxirredução , Fatores de Tempo , Movimentos da Água , Poluentes Químicos da Água/análise
19.
Environ Monit Assess ; 93(1-3): 55-67, 2004.
Artigo em Inglês | MEDLINE | ID: mdl-15074609

RESUMO

The general profile of the pollution of drinking water, originating from groundwater, by nitrates, chloride and arsenic, in the Prefecture of Thessaloniki, was studied in this project. Samples (tap water) were collected from 52 areas-villages of the Prefecture, during a period of 6 months. The analytical results were related to certain points on the map of the area, thus producing coloured representations of the Prefecture, according to the concentration of the corresponding pollutant. The statistical analysis of the data led to some conclusions concerning the causes of pollution and the relation of the concentrations to certain physico-chemical parameters. Nitrate concentration of samples collected from two specific regions were especially high, sometimes above the highest permitted level. A limited number of samples (13.5%) contained arsenic concentrations above the imminent EC drinking water limit (10 ppb). The majority of the tap water samples, collected from areas along the seashore contained increased concentrations of chloride ions, which is a clear indication of seawater intrusion into the related aquifers.


Assuntos
Arsênio/análise , Cloretos/análise , Sistemas de Informação Geográfica , Nitratos/análise , Poluentes da Água/análise , Abastecimento de Água , Monitoramento Ambiental/métodos , Grécia , Solo
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