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1.
Biosens Bioelectron ; 79: 894-900, 2016 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-26800205

RESUMO

Nitromethane (CH3NO2) is an important organic chemical raw material with a wide variety of applications as well as one of the most common pollutants. Therefore it is pretty important to establish a simple and sensitive detection method for CH3NO2. In our study, a novel amperometric biosensor for nitromethane (CH3NO2) based on immobilization of electrochemically-reduced graphene oxide (rGO), chitosan (CS) and hemoglobin (Hb) on a glassy carbon electrode (GCE) was constructed. Scanning electron microscopy, infrared spectroscopy and electrochemical methods were used to characterize the Hb-CS/rGO-CS composite film. The effects of scan rate and pH of phosphate buffer on the biosensor have been studied in detail and optimized. Due to the graphene and chitosan nanocomposite, the developed biosensor demonstrating direct electrochemistry with faster electron-transfer rate (6.48s(-1)) and excellent catalytic activity towards CH3NO2. Under optimal conditions, the proposed biosensor exhibited fast amperometric response (<5s) to CH3NO2 with a wide linear range of 5 µM~1.46 mM (R=0.999) and a low detection limit of 1.5 µM (S/N=3). In addition, the biosensor had high selectivity, reproducibility and stability, providing the possibility for monitoring CH3NO2 in complex real samples.


Assuntos
Técnicas Biossensoriais/métodos , Quitosana/química , Grafite/química , Hemoglobinas/química , Metano/análogos & derivados , Nanocompostos/química , Nitroparafinas/análise , Óxidos/química , Animais , Bovinos , Técnicas Eletroquímicas/métodos , Metano/análise , Nanocompostos/ultraestrutura , Oxirredução , Reprodutibilidade dos Testes
2.
J Occup Environ Hyg ; 13(5): 356-71, 2016.
Artigo em Inglês | MEDLINE | ID: mdl-26698920

RESUMO

Exposure control systems performance was investigated in an aircraft painting hangar. The ability of the ventilation system and respiratory protection program to limit worker exposures was examined through air sampling during painting of F/A-18C/D strike fighter aircraft, in four field surveys. Air velocities were measured across the supply filter, exhaust filter, and hangar midplane under crossflow ventilation. Air sampling conducted during painting process phases (wipe-down, primer spraying, and topcoat spraying) encompassed volatile organic compounds, total particulate matter, Cr[VI], metals, nitroethane, and hexamethylene diisocyanate, for two worker groups: sprayers and sprayer helpers ("hosemen"). One of six methyl ethyl ketone and two of six methyl isobutyl ketone samples exceeded the short term exposure limits of 300 and 75 ppm, with means 57 ppm and 63 ppm, respectively. All 12 Cr[VI] 8-hr time-weighted averages exceeded the recommended exposure limit of 1 µg/m3, 11 out of 12 exceeded the permissible exposure limit of 5 µg/m3, and 7 out of 12 exceeded the threshold limit value of 10 µg/m3, with means 38 µg/m3 for sprayers and 8.3 µg/m3 for hosemen. Hexamethylene diisocyanate means were 5.95 µg/m3 for sprayers and 0.645 µg/m3 for hosemen. Total reactive isocyanate group--the total of monomer and oligomer as NCO group mass--showed 6 of 15 personal samples exceeded the United Kingdom Health and Safety Executive workplace exposure limit of 20 µg/m3, with means 50.9 µg/m3 for sprayers and 7.29 µg/m3 for hosemen. Several exposure limits were exceeded, reinforcing continued use of personal protective equipment. The supply rate, 94.4 m3/s (200,000 cfm), produced a velocity of 8.58 m/s (157 fpm) at the supply filter, while the exhaust rate, 68.7 m3/s (146,000 cfm), drew 1.34 m/s (264 fpm) at the exhaust filter. Midway between supply and exhaust locations, the velocity was 0.528 m/s (104 fpm). Supply rate exceeding exhaust rate created re-circulations, turbulence, and fugitive emissions, while wasting energy. Smoke releases showing more effective ventilation here than in other aircraft painting facilities carries technical feasibility relevance.


Assuntos
Poluentes Ocupacionais do Ar/análise , Aeronaves , Cromo/análise , Isocianatos/análise , Exposição Ocupacional/prevenção & controle , Pintura , Material Particulado/análise , Butanonas/análise , California , Etano/análogos & derivados , Etano/análise , Metais/análise , Metil n-Butil Cetona/análise , Militares , Nitroparafinas/análise , Exposição Ocupacional/análise , Ventilação
3.
J Chromatogr A ; 1424: 118-26, 2015 Dec 11.
Artigo em Inglês | MEDLINE | ID: mdl-26603996

RESUMO

In this paper, heart-cutting two-dimensional GC/MS (GC-GC/MS) method in combination with a simple sample collection procedure was developed for the determination of 6 nitroalkanes in mainstream cigarette smoke. The method could remove large amounts of impurities on-line in the first polar column by heart-cuts and separate from the left interferences in a second mid-polar column. And the target compounds could be focused at the inlet of the second column by cryo-concentration. Compared to conventional GC/MS, GC-GC/MS achieved a lower noise level and sensitivity at least an order of magnitude higher. Furthermore, the GC-GC/MS method could avoid the false negative and false positive results that appeared in the compared conventional GC/MS analysis. By trapping the vapor phase of 20 cigarettes smoke, the LODs and LOQs of the nitroalkanes were 1.3 to 9.8 and 4.3 to 32.6ng/cigarette, respectively, and all linear correlation efficiencies were larger than 0.999. The validation results also indicate that the method has high accuracy (spiked recoveries between 84% and 102%) and good repeatability (RSD between 7.2% and 9.4%). The developed method was applied to analyze 1 Kentucky reference cigarette (3R4F) and 10 Chinese commercial brands of cigarettes. The research results indicated that nitromethane, nitroethane, 2-nitropropane and 1-nitro-n-pentane were detected in mainstream cigarette smoke, but 1-nitro-n-butane and 2-nitropropane, which were reported by one previous study, were not detected in all cigarette samples.


Assuntos
Nicotiana/química , Fumaça/análise , Etano/análogos & derivados , Etano/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Limite de Detecção , Metano/análogos & derivados , Metano/análise , Nitroparafinas/análise , Propano/análogos & derivados , Propano/análise , Produtos do Tabaco
4.
J Sep Sci ; 38(19): 3383-9, 2015 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-26255649

RESUMO

Chloropicrin (trichloronitromethane) is a widely used soil fumigant and an old chemical warfare agent. The metabolism of chloropicrin is not well known in mammals but nitromethane has been shown to be one of its main metabolites. Here, a fast and simple headspace gas chromatography with mass spectrometry method was applied for the measurement of nitromethane from aqueous samples. The analytical method was validated using stable isotope labeled internal standard and a small sample volume of 260 µL. No conventional sample preparation steps were needed. The method was accurate (relative standard deviations ≤1.5%) and linear (R(2) = 0.9996) within the concentration range of 0.1-6.0 µg/mL. This method was used to measure nitromethane in in vitro incubations with human and pig liver cell fractions containing enzymes for xenobiotic metabolism, exposed to chloropicrin. The results indicate that the presence of glutathione is necessary for the formation of nitromethane from chloropicrin. Also, nitromethane was formed mostly in liver cytosol fractions, but not in microsomal fractions after the incubation with chloropicrin. Our results suggest that although nitromethane is not the unequivocal biomarker of chloropicrin exposure, this method could be applied for screening the elevated levels in humans after chloropicrin exposure.


Assuntos
Hidrocarbonetos Clorados/análise , Técnicas de Diluição do Indicador , Metano/análogos & derivados , Nitroparafinas/análise , Animais , Biomarcadores/análise , Substâncias para a Guerra Química/análise , Substâncias para a Guerra Química/farmacocinética , Substâncias para a Guerra Química/toxicidade , Feminino , Fumigação , Cromatografia Gasosa-Espectrometria de Massas/métodos , Humanos , Hidrocarbonetos Clorados/farmacocinética , Hidrocarbonetos Clorados/toxicidade , Técnicas In Vitro , Fígado/efeitos dos fármacos , Fígado/metabolismo , Metano/análise , Metano/farmacocinética , Metano/toxicidade , Nitroparafinas/farmacocinética , Nitroparafinas/toxicidade , Praguicidas/análise , Praguicidas/farmacocinética , Praguicidas/toxicidade , Sus scrofa
5.
Chemosphere ; 119: 540-546, 2015 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-25112580

RESUMO

The deterioration of water quality, especially organic pollution in Tai Lake and the Qiantang River, have recently received attention in China. The objectives of this study were to evaluate the formation of halonitromethanes (HNMs) using multiple regression models for chlorination and chloramination and to identify the key factors that influence the formation of HNMs in Tai Lake and the Qiantang River. The results showed that the total formation of HNMs (T-HNMs) during chlorination and chloramination could be described using the following models: (1) [Formula: see text] =(10)(5.267)(DON)(6.645)(Br(-))(0.737)(DOC)(-)(5.537)(Cl2)(0.333)(t)(0.165) (R(2)=0.974, p<0.01, n=33), and (2) T-HNMNH2Cl=(10)(-)(2.481)(Cl2)(0.451)(NO2(-))(0.382)(Br(-))(0.630)(t)(0.640)(Temp)(0.581) (R(2)=0.961, p<0.05, n=33), respectively. The key factors that influenced the T-HNM yields during chlorination were dissolved organic nitrogen (DON), bromide and dissolved organic carbon (DOC). The nitrite and bromide concentrations and the reaction time mainly affected the T-HNM yields during chloramination. Additional analysis indicated that the bromine incorporation factors (BIFs) for trihalogenated HNMs generally decreased as the chlorine/chloramine dose, temperature and reaction time decreased and increased as the bromide concentration increased.


Assuntos
Desinfetantes , Desinfecção/métodos , Hidrocarbonetos Halogenados/análise , Lagos/química , Metano/análogos & derivados , Modelos Químicos , Nitroparafinas/análise , Rios/química , Poluentes Químicos da Água/análise , Brometos/análise , China , Cloraminas/análise , Cloro/análise , Desinfetantes/análise , Halogenação , Metano/análise , Análise Multivariada , Análise de Regressão , Qualidade da Água
6.
Talanta ; 132: 334-8, 2015 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-25476316

RESUMO

During the past decade, the number of terrorism acts has increased and the need for efficient explosive detectors has become an urgent worldwide necessity. A prototype, Nebulex™, was recently developed in our laboratory. Basically, it couples the solubilization of an analyte from the atmosphere by a nebulization process and in-situ detection. This article presents the development and integration of an electrochemical sensor for the detection of nitromethane, a common chemical product that can be used to make an improvised explosive device. A gold screen-printed electrode was used in a flow-cell and a detection limit of 4.5 µM was achieved by square wave voltammetry. The detection method was also determined to be selective toward nitromethane over a large panel of interfering compounds. Detection tests with the Nebulex™ were thus carried out using a custom-made calibrated nitromethane vapor generator. Detection times of less than one minute were obtained for nitromethane contents of 8 and 90 ppmv. Further measurements were performed in a room-measurement configuration leading to detection times in the range of 1-2 min, clearly demonstrating the system's efficiency under quasi-real conditions.


Assuntos
Técnicas Eletroquímicas , Substâncias Explosivas/análise , Ouro/química , Metano/análogos & derivados , Nitroparafinas/análise , Calibragem , Carbono , Eletrodos , Humanos , Limite de Detecção , Metano/análise , Terrorismo/prevenção & controle , Fatores de Tempo
7.
J Chromatogr A ; 1365: 45-53, 2014 Oct 24.
Artigo em Inglês | MEDLINE | ID: mdl-25257930

RESUMO

When iodide and natural organic matter are present in raw water, the formation of iodo-trihalomethanes (Iodo-THMs), haloacetonitriles (HANs), and halonitromethanes (HNMs) pose a potential health risk because they have been reported to be more toxic than their brominated or chlorinated analogs. In the work, simultaneous analysis of Iodo-THMs, HANs, and HNMs in drinking water samples in a single cleanup and chromatographic analysis was proposed. The DVB/CAR/PDMS fiber was found to be the most suitable for all target compounds, although 75µm CAR/PDMS was better for chlorinated HANs and 65µm PDMS/DVB for brominated HNMs. After optimization of the SPME parameters (DVB/CAR/PDMS fiber, extraction time of 30min at 40°C, addition of 40% w/v of salt, (NH4)2SO4 as a quenching agent, and desorption time of 3min at 170°C), detection limits ranged from 1 to 50ng/L for different analogs, with a linear range of at least two orders of magnitude. Good recoveries (78.6-104.7%) were obtained for spiked samples of a wide range of treated drinking waters, demonstrating that the method is applicable for analysis of real drinking water samples. Matrix effects were negligible for the treated water samples with total organic carbon concentration of less than 2.9mg/L. An effective survey conducted by two drinking water treatment plants showed the highest proportion of Iodo-THMs, HANs, and HNMs occurred in treated water, and concentrations of 13 detected compounds ranged between the ng/L and the µg/L levels.


Assuntos
Acetonitrilas/análise , Água Potável/química , Metano/análogos & derivados , Nitroparafinas/análise , Trialometanos/análise , Poluentes Químicos da Água/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Halogenação , Metano/análise , Microextração em Fase Sólida/métodos , Purificação da Água
8.
Biosci Biotechnol Biochem ; 78(8): 1320-3, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-25130732

RESUMO

(2-Nitroethyl)benzene was identified as a major component of the flower scent of the Japanese loquat Eriobotrya japonica [Rosales: Rosaceae], together with p-methoxybenzaldehyde and methyl p-methoxybenzoate. The corresponding volatiles from chopped leaves did not contain these three compounds. This is the first time that 1-nitro-2-phenyl-ethane has been demonstrated to be a natural product among Japanese plants, although two Japanese millipedes are known to possess the same aromatics.


Assuntos
Derivados de Benzeno/análise , Eriobotrya/química , Flores/química , Nitroparafinas/análise , Odorantes/análise , Derivados de Benzeno/química , Nitroparafinas/química , Volatilização
9.
Ind Health ; 50(6): 540-7, 2012.
Artigo em Inglês | MEDLINE | ID: mdl-23047081

RESUMO

During the rice harvesting season in Thailand, large amounts of fresh paddy are sent to rice mills immediately after harvesting due to a lack of proper farm storage space. At certain levels of moisture content, rice grains may generate hazardous gases, which can replace oxygen (O(2)) in the confined spaces of underground rice mill pits. This phenomenon has been observed in a fatal accident in Thailand. Our study aimed to investigate the type of gases and their air concentrations emitted from the paddy piles at different levels of moisture content and duration of piling time. Four levels of moisture content in the paddy piles were investigated, including dry paddy group (< 14% wet basis (wb)), wet paddy groups (22-24, 25-27 and 28-30%wb). Our measurements were conducted in 16 experimental concrete pits 80 × 80 cm wide by 60 cm high. Gases emitted were measured with an infrared spectrophotometer and a multi-gas detector every 12 h for 5 days throughout the experiment. The results revealed high levels of carbon dioxide (CO(2)) (range 5,864-8,419 ppm) in all wet paddy groups, which gradually increased over time. The concentration of carbon monoxide (CO), methane (CH(4)), nitromethane (CH(3)NO(2)) and nitrous oxide (N(2)O) in all wet paddy groups increased with piling time and with moisture content, with ranges of 11-289; 2-8; 36-374; and 4-26 ppm, respectively. The highest levels of moisture content in the paddy piles were in the range 28-30%wb. Nitrogen dioxide (NO(2)) concentrations were low in all paddy groups. The percentage of O(2) in the wet paddy groups decreased with piling time and moisture content (from 18.7% to 4.1%). This study suggested that hazardous gases could be emitted in moist paddy piles, and their concentrations could increase with increasing moisture content and piling time period.


Assuntos
Indústria de Processamento de Alimentos , Gases/análise , Oryza , Dióxido de Carbono/análise , Monóxido de Carbono/análise , Monitoramento Ambiental , Humanos , Metano/análogos & derivados , Metano/análise , Nitroparafinas/análise , Óxido Nitroso/análise , Tailândia/epidemiologia , Água
11.
J Chromatogr A ; 1248: 1-8, 2012 Jul 27.
Artigo em Inglês | MEDLINE | ID: mdl-22717036

RESUMO

Halonitromethanes (HNMs) are a class of nitrogenous disinfection by-products (N-DBPs) that have so far received little attention and focused largely on trichloronitromethane. By contrast, trihalomethanes (THMs) are the most commonly regulated DBPs and have been the subject of much study. This paper reports the first miniaturized system for the simultaneous determination of the nine known HNMs and four THMs in tap and swimming pool water. Micro liquid-liquid extraction (MLLE) is an adaptation of EPA Method 551.1 using ethyl acetate instead of methyl tert-butyl ether as extractant and large injected sample volumes (30 µL) in combination with programmed temperature vaporizer-gas chromatography-mass spectrometry for improved sensitivity and selectivity. Because extraction is done with a few microlitres of organic solvent (200 µL) and practically all extract is injected into the instrument, MLLE can be regarded as a virtually solvent-free sample preparation technique. The proposed method provided an extraction efficiency of ∼85%, average limits of detection (tribromonitromethane excluded) of 30 ng/L and relative standard deviations of ∼6.0%. The influence of various dechlorinating agents on the stability of the thirteen target analytes in treated water was evaluated; the only salt allowing both types of compounds to be efficiently preserved was (NH(4))(2)SO(4), but only for 1 day at 4 °C. Therefore, acidifying the sample at pH ∼3.4-the optimum value for MLLE-at the time of collection is recommended in order to ensure that both HNMs and THMs retain their integrity for 2 days during storage at 4 °C.


Assuntos
Desinfetantes/isolamento & purificação , Microextração em Fase Líquida/métodos , Metano/análogos & derivados , Nitroparafinas/isolamento & purificação , Trialometanos/isolamento & purificação , Poluentes Químicos da Água/isolamento & purificação , Água/análise , Desinfetantes/análise , Desinfecção , Cromatografia Gasosa-Espectrometria de Massas/métodos , Halogenação , Limite de Detecção , Metano/análise , Metano/isolamento & purificação , Éteres Metílicos , Nitroparafinas/análise , Piscinas , Trialometanos/análise , Poluentes Químicos da Água/análise
12.
Talanta ; 94: 342-7, 2012 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-22608458

RESUMO

Deep Raman spectroscopy has been utilized for the standoff detection of concealed chemical threat agents from a distance of 15 m under real life background illumination conditions. By using combined time and space resolved measurements, various explosive precursors hidden in opaque plastic containers were identified non-invasively. Our results confirm that combined time and space resolved Raman spectroscopy leads to higher selectivity towards the sub-layer over the surface layer as well as enhanced rejection of fluorescence from the container surface when compared to standoff spatially offset Raman spectroscopy. Raman spectra that have minimal interference from the packaging material and good signal-to-noise ratio were acquired within 5 s of measurement time. A new combined time and space resolved Raman spectrometer has been designed with nanosecond laser excitation and gated detection, making it of lower cost and complexity than picosecond-based laboratory systems.


Assuntos
Sulfato de Bário/análise , Substâncias para a Guerra Química/análise , Substâncias Explosivas/análise , Metano/análogos & derivados , Nitratos/análise , Nitroparafinas/análise , Análise Espectral Raman/métodos , Humanos , Lasers , Metano/análise , Razão Sinal-Ruído , Fatores de Tempo
13.
Environ Sci Technol ; 45(8): 3657-64, 2011 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-21417331

RESUMO

The application of UV disinfection in water treatment is increasing due to both its effectiveness against protozoan pathogens, and the perception that its lack of chemical inputs would minimize disinfection byproduct formation. However, previous research has indicated that treatment of nitrate-containing drinking waters with polychromatic medium pressure (MP), but not monochromatic (254 nm) low pressure (LP), UV lamps followed by chlorination could promote chloropicrin formation. To better understand this phenomenon, conditions promoting the formation of the full suite of chlorinated halonitromethanes and haloacetonitriles were studied. MP UV/postchlorination of authentic filter effluent waters increased chloropicrin formation up to an order of magnitude above the 0.19 µg/L median level in the U.S. EPA's Information Collection Rule database, even at disinfection-level fluences (<300 mJ/cm(2)) and nitrate/nitrite concentrations (1.0 mg/L-N) relevant to drinking waters. Formation was up to 2.5 times higher for postchlorination than for postchloramination. Experiments indicated that the nitrating agent, NO(2)(•), generated during nitrate photolysis, was primarily responsible for halonitromethane promotion. LP UV treatment up to 1500 mJ/cm(2) did not enhance halonitromethane formation. Although MP UV/postchloramination enhanced dichloroacetonitrile formation with Sigma-Aldrich humic acid, formation was not significant in field waters. Prechlorination/MP UV nearly doubled chloropicrin formation compared to MP UV/postchlorination, but effects on haloacetonitrile formation were not significant.


Assuntos
Acetonitrilas/síntese química , Halogenação , Metano/análogos & derivados , Nitroparafinas/síntese química , Raios Ultravioleta , Poluentes Químicos da Água/síntese química , Purificação da Água/métodos , Acetonitrilas/análise , Desinfetantes/análise , Desinfetantes/química , Desinfetantes/efeitos da radiação , Desinfecção/métodos , Água Doce/química , Hidrocarbonetos Clorados/análise , Hidrocarbonetos Clorados/síntese química , Metano/análise , Metano/síntese química , Nitroparafinas/análise , Processos Fotoquímicos , Poluentes Químicos da Água/análise , Abastecimento de Água/análise
14.
J Hazard Mater ; 185(2-3): 756-62, 2011 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-20965653

RESUMO

The aim of this paper is to provide new experimental data of the minimum ignition energy (MIE) of gaseous nitromethane/air mixtures to discuss the explosion pressure and the flame temperature as a function of nitromethane concentration. Observations on the influence of nitromethane concentration on combustion pressure and temperature through the pressure and temperature measure system show that peak temperature (the peak of combustion temperature wave) is always behind peak pressure (the peak of the combustion pressure wave) in arrival time, the peak combustion pressure of nitromethane increases in the range of its volume fraction 10-40% as the concentration of nitromethane increases, and it slightly decreases in the range of 40-50%. The maximum peak pressure is equal to 0.94 MPa and the minimum peak pressure 0.58 MPa. Somewhat similar to the peak pressure, the peak combustion temperature increases with the volume fraction of nitromethane in the range of 10-40%, and slightly decreases in 40-50%. The maximum peak temperature is 1340 °C and the minimum 860 °C. The combustion temperature rise rate increases with the concentration of nitromethane in 10-30%, while decreases in 30-50% and its maximum value of combustion temperature rise rate in 10-50% is 4200 °C/s at the volume fraction of 30%. Influence of the concentration of nitromethane on the combustion pressure rise rate is relatively complicated, and the maximum value of rise rate of combustion pressure wave in 10-50% is 11 MPa/s at the concentration 20%.


Assuntos
Ar , Explosões , Gases , Metano/análogos & derivados , Nitroparafinas/análise , Metano/análise , Pressão
15.
Artigo em Chinês | MEDLINE | ID: mdl-22335170

RESUMO

OBJECTIVE: To establish a gas chromatography method for detecting the concentration of 1,1-dichloro-1-nitroethane in air of workplaces. METHOD: 1,1-dichloro-1-nitroethane in air of workplaces was collected by activated charcoal tube, absorbed using carbon disulfide and analyzed by Gas Chromatography (FID) with FFAP capillary column. RESULTS: The linear rang of 1,1-dichloro-1-nitroethane in this method was 4.0-858.2 microg/ml, the linear regression formula was Y = 283X-1076, the correlation coefficient was 0.9999, the lowest detection concentration was 0.4 mg/m3 (3L sampling air), the relative standard deviation (RSD) was 1.8%-4.1%, the desorption efficiency was 88.5%-90.6%, the breakthrough volume was > 0.7 mg, the sampling efficiency was 100%, the samples could be kept at ambient temperature for at least 7 days. CONCLUSION: The indicators of this method were conformed to the requirements of "Guide for establishing occupational health standards--Determination methods of air chemicals in workplace". This method could be used to detect 1,1-dichloro-1-nitroethane in air of workplaces.


Assuntos
Poluentes Ocupacionais do Ar/análise , Cromatografia Gasosa/métodos , Etano/análogos & derivados , Nitroparafinas/análise , Etano/análise , Local de Trabalho
16.
Biosens Bioelectron ; 26(3): 991-5, 2010 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-20833016

RESUMO

A novel amperometric biosensor for nitromethane (CH(3)NO(2)) based on immobilization of graphene (GR), chitosan (CS), hemoglobin (Hb) and room temperature ionic liquid (IL) on a glassy carbon electrode (GCE) was developed for the first time. The surface morphologies of a set of representative membranes were characterized by means of scanning electron microscopy (SEM). The electrochemical performance of the biosensor was evaluated by cyclic voltammetry (CV) and chronoamperometry. A pair of stable and well-defined redox peaks of Hb with a formal potential of -0.240 V was observed at the GR-CS/Hb/GR/IL/GCE. The effects of phosphate buffer pH, scan rate, and temperature on the biosensor were investigated to provide optimum analytical performance. Moreover, several electrochemical parameters, e.g., the heterogeneous electron transfer rate constant (k(s)), were calculated in detail. The presence of both GR and IL not only dramatically facilitated the electron transfer of Hb, but also greatly enhanced electrocatalytic activity towards CH(3)NO(2). The apparent Michaelis-Menten constant was down to 0.16 µM, indicating that the biosensor possessed high affinity to CH(3)NO(2). Besides this, the proposed biosensor exhibited fast amperometric response (<5s), low detection limit (6.0 × 10(-10)M), and excellent long-time storage stability for the determination of CH(3)NO(2).


Assuntos
Técnicas Biossensoriais/métodos , Metano/análogos & derivados , Nitroparafinas/análise , Materiais Biocompatíveis , Técnicas Biossensoriais/instrumentação , Técnicas Biossensoriais/estatística & dados numéricos , Quitosana , Condutividade Elétrica , Técnicas Eletroquímicas , Transporte de Elétrons , Grafite , Hemoglobinas , Metano/análise , Microscopia Eletrônica de Varredura , Oxirredução , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , Propriedades de Superfície , Temperatura
17.
J Occup Health ; 52(3): 194-7, 2010.
Artigo em Inglês | MEDLINE | ID: mdl-20379077

RESUMO

OBJECTIVES: The purpose of this research was to develop a determination method for nitromethane (NM) in workplace air for risk assessment. METHODS: A suitable sampler and appropriate desorption condition were selected by a recovery test in which a spiked sampler was used. The characteristics of the proposed method, such as recovery, detection limit, and reproducibility, and the storage stability of the sample were examined. RESULTS: A sampling tube containing bead-shaped activated carbon was chosen as the sampler. NM in the sampler was desorbed with acetone and analyzed by a gas chromatograph equipped with a flame ionization detector. The recoveries of NM from the spiked sampler were 81-97% and 80-98% for personal exposure monitoring and working environment measurement, respectively. On the first day of storage in a refrigerator, the recovery from the spiked samplers exceeded 90%; however, it decreased dramatically with increasing storage time. In particular, the decrease was more remarkable for the smaller spiked amounts. The overall LOQ was 2 microg/sample. The relative standard deviation, which represents the overall reproducibility, was 1.1-4.0%. CONCLUSIONS: The proposed method enables 4-hour personal exposure monitoring of NM at concentrations equaling 0.001-2 times the threshold limit value-time-weighted average (TLV-TWA: 20 ppm) proposed by the American Conference of Governmental Industrial Hygienists, as well as 10-minute working environment measurement at concentrations equaling 0.02-2 times TLV-TWA. Thus, the proposed method will be useful for estimating worker exposure to NM.


Assuntos
Poluição do Ar em Ambientes Fechados/análise , Metano/análogos & derivados , Nitroparafinas/análise , Cromatografia Gasosa , Metano/análise , Exposição Ocupacional/análise , Medição de Risco , Local de Trabalho/normas
18.
Water Res ; 44(1): 105-14, 2010 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-19793604

RESUMO

Halonitromethanes (HNMs) are highly cyto- and genotoxic nitrogenous disinfection by-products (DBPs) that have been detected in some water distribution systems. In this study, a systematic investigation was conducted to examine the formation potential of HNMs in drinking waters under different oxidation conditions. Formation potential tests of samples obtained from various drinking water sources showed that ozonation-chlorination produced the highest HNM yields followed by in the order of chlorination, ozonation-chloramination, and chloramination. Similar or higher HNM yields were observed in the treated waters (i.e., after conventional water treatment) than in the raw waters, indicating that hydrophilic natural organic matter (NOM) components that are not effectively removed by conventional treatment processes are likely the main precursors of HNMs. This was further confirmed by examining HNM formation potentials of NOM fractions obtained with resin fractionation. Hydrophilic NOM fractions (HPI) showed significantly higher HNM yields than hydrophobic (HPO) and transphilic (TPH) fractions. The correlation analysis of HNM formation potentials during ozonation-chlorination with various water quality parameters showed the best correlation between the HNM yields and the ratio of dissolved organic carbon to dissolved organic nitrogen concentrations in the water samples tested.


Assuntos
Metano/análogos & derivados , Nitroparafinas/química , Poluentes Químicos da Água/química , Halogenação , Metano/análise , Metano/química , Nitroparafinas/análise , Ozônio/química , Poluentes Químicos da Água/análise , Abastecimento de Água
19.
Am J Ind Med ; 40(1): 107-13, 2001 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-11439403

RESUMO

BACKGROUND: Two workers from a headlight subassembly plant developed severe peripheral neuropathy. These workers had extensive, but brief (1-2 months) dermal and inhalational exposure to nitromethane, a solvent. METHODS: Environmental sampling was performed for nitromethane and ethyl cyanoacrylate. Medical records, including electrodiagnostic studies, were reviewed. Literature on nitromethane, ethyl cyanoacrylate, and other exposures in the workplace was reviewed. RESULTS: Electromyography and nerve conduction studies performed on these patients were consistent with a severe, axonal neuropathy. No etiology was discovered despite an extensive medical evaluation. Environmental sampling revealed exposure to nitromethane at the threshold limit value. CONCLUSIONS: The history of acute onset of severe peripheral neuropathy temporally associated with exposure to nitromethane is suggestive of a toxic neuropathy. While it cannot be definitively concluded that these two workers developed peripheral neuropathy secondary to exposures at work, occupational exposure to nitromethane appears to be the most likely etiology.


Assuntos
Metano/efeitos adversos , Nitroparafinas/efeitos adversos , Exposição Ocupacional/efeitos adversos , Doenças do Sistema Nervoso Periférico/induzido quimicamente , Solventes/efeitos adversos , Adulto , Cianoacrilatos/efeitos adversos , Cianoacrilatos/análise , Eletromiografia , Feminino , Humanos , Masculino , Metano/análogos & derivados , Metano/análise , Nitroparafinas/análise , Exposição Ocupacional/análise , Doenças do Sistema Nervoso Periférico/fisiopatologia , Solventes/análise , Níveis Máximos Permitidos
20.
Anal Chem ; 73(9): 2004-11, 2001 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-11354482

RESUMO

A novel approach based on fluorescence quenching is presented for the analysis of nitrated explosives. Seventeen common explosives and their degradation products are shown to be potent quenchers of pyrene, having Stern-Volmer constants that generally increase with the degree of nitration. Aromatic explosives such as 2,4,6-trinitrotoluene (2,4,6-TNT) are more effective quenchers than aliphatic or nitramine explosives. In addition, nitroaromatic explosives are found to have unique interactions with pyrene that lead to a wavelength dependence of their Stern-Volmer constants. This phenomenon allows for their differentiation from other nitrated explosives. The fluorescence quenching method is then applied to the determination of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazine(HMX), 2,4,6-TNT, nitromethane, and ammonium nitrate in various commercial explosive samples. The samples are separated by capillary liquid chromatography with post-column addition of the pyrene solution and detection by laser-induced fluorescence. The indirect fluorescence quenching method shows increased sensitivity and selectivity over traditional UV-visible absorbance as well as the ability to detect a wider range of organic and inorganic nitrated compounds.


Assuntos
Poluentes Atmosféricos/análise , Explosões , Espectrometria de Fluorescência , Algoritmos , Azocinas/análise , Cromatografia Líquida , Eletroforese Capilar , Compostos Heterocíclicos com 1 Anel/análise , Metano/análogos & derivados , Metano/análise , Nitratos/análise , Nitroparafinas/análise , Pirenos/química , Espectrofotometria Ultravioleta , Triazinas/análise , Trinitrotolueno/análise , Trinitrotolueno/química
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