When nitrated polynuclear aromatic hydrocarbons (NPAH) were recognised as long‐term toxic compounds and were also identified in several anthropogenic emissions and among the by‐products of photochemical smog they became objects of investigation in ambient air in both polluted and clean environments. In Italy the first investigations focussing on atmospheric NPAH were performed in the early eighties and encompassed both the canyon streets and dwelling areas of Rome. Because NPAH were indicated as markers of vehicle emission, new investigations were performed in other cities and also in rural and (nominally) unpolluted locations. In general, the first measurements of NPAH were episodic and could not be assumed to be strictly representative of the sites investigated. In contrast, nowadays consistent data bases on NPAH have been built up and are discussed in the technical literature, so that both neat concentrations and the yearly timed variation of the most important NPAH congeners have been measured in Italian air. Although concentrations of NPAH in air are usually much lower than those of PAH, owing to their very high potency in inducing mutations and tumours NPAH are regarded as having an important health impact on populations living in Italian urban areas. In this regard the genotoxicity of atmospheric aerosols is partly associated with nitrofluoranthenes and nitropyrenes whereas nitronaphthalenes and methylnitronaphthalenes seem to contribute to that of the gaseous organic fraction. Several civic and regional administrations are introducing control of atmospheric NPAH among ways of improving air quality in cities. 相似文献
Inhalable aerosols collected in downtown Milan during a whole‐year field campaign (from November 2000 to October 2001) were investigated to determine amounts of n‐alkanes, polynuclear aromatic hydrocarbons (PAH), including benzo[a]pyrene (BaP), nitrated PAH (NPAH), and monocarboxylic n‐alkanoic acids. Combustion processes including vehicle emission were confirmed as the most important sources affecting air quality, whereas release of organic material from biota contributed a few percent. The occurrence of in‐situ reactions in the atmosphere promoted by oxidants modified, to some extent, the composition of both PAH and NPAH fractions, by reducing the amount of BaP present in the aerosols and increasing that of NPAH. 相似文献
The objective of this study was to develop an efficient and sensitive analytical protocol for the determination of nitrated polycyclic aromatic hydrocarbons (NPAHs) in aerosol samples. The separation of 16 NPAH (mono-and dinitro-PAH) was achieved by reversed-phase high-performance liquid chromatography (HPLC) followed by on-line reduction of the NPAHs to their corresponding amino polycyclic aromatic hydrocarbons (APAHs) and quantification by fluorescence detection. The main factors affecting the on-line reduction efficiency, such as the flow rate, the temperature, the position and packing of the reduction column were evaluated and optimised. The optimal conditions obtained were: packing of the reduction column with Pt-Al(2)O(3); a reduction column oven temperature of 90 degrees C; a flow rate of 0.8 mL min(-1). The resulting detection limits of the method ranged between 0.06 (2 NN) and 1.25 microg L(-1) (1.8 DNN), with an uncertainty of about 6%. The lifetime of the reduction column was identical to that of a typical analytical column. This analytical method was applied to particulate matter samples collected during December 2005 and August 2006 in Strasbourg (Alsace, eastern France). The NPAH concentrations observed for this urban site showed that the compounds are more abundant during winter (average of 534 pg m(-3)) than during summer (average of 118 pg m(-3)). 1-Nitropyrene was the predominant NPAH species, independent of season. 相似文献
An extraction procedure based on the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) approach has been developed and used for analysis of particle-bound nitrated and oxygenated PAH derivatives (NPAH and OPAH, respectively). Several analytical conditions, for example GC injection temperature and MS detection settings, were optimized. This analytical procedure enabled simultaneous GC–NICIMS quantification of 32 NPAH and 32 OPAH (or other oxygenated compounds), including typical components of secondary organic aerosol (SOA) formed by photooxidation of PAH (e.g. 2-formyl-trans-cinnamaldehyde and 6H-dibenzo[b,d]pyran-6-one). The QuEChERS-like approach was optimized, including the nature of the extraction solvent, the sorbent used for clean-up, and extraction time. The final extraction procedure was based on brief mechanical agitation (vortex mixing for 1.5 min), with 7 mL acetonitrile as solvent. Because dispersive solid-phase extraction (d-SPE) did not provide satisfactory results, SPE using SiO2 was selected for sample purification. Identical results were obtained when the QuEChERS-like and traditional pressurised solvent extraction (PLE) procedures were compared for analysis of fortified ambient air particle samples. The procedure was validated by analysis of two aerosol standard reference materials (NIST SRM 1649b (urban dust) and SRM 2787 (fine particulate matter, <10 μm)). For numerous NPAH and OPAH, this is the first report of their quantification in both SRMs. Compared with other extraction methods, including PLE, the QuEChERS-like procedure resulted in increased productivity and reduced extraction cost. This paper shows that QuEChERS-like extraction procedures can be suitably adapted for molecular chemical characterization of aerosol samples and could be extended to other categories of compound.
An ultra-performance liquid chromatographic-atmospheric pressure chemical ionization time-of-flight mass spectrometric (UPLC-APCIToFMS)
method for rapid analysis of twelve nitrated polycyclic aromatic hydrocarbons (NPAHs) and nine oxygenated polycyclic aromatic
hydrocarbons (OPAHs) in particle samples has been developed. The extraction step using pressurized liquid extraction was optimized
by experimental design methods and the concentrated extracts were analyzed without further clean-up. Matrix effects resulting
in suppression or enhancement of the response during the ionization step were not observed. The suitability of the developed
method is demonstrated by analysis of six different particle samples including standard reference materials, atmospheric particles
collected by a high-volume sampler at an urban background site, and a soot sample from a burner. Results from these measurements
showed clear differences between the different kinds of samples. Concentrations from reference materials are in good agreement
with those from previous studies. Additionally a clear seasonal trend could be observed in atmospheric NPAH and OPAH concentrations
found in real samples, with higher concentrations in winter. 相似文献
A high-performance liquid chromatography (HPLC) method for the analysis of nitrated polcyclic aromatic hydrocarbons (NPAHs) is reported. NPAH mixtures were pre-concentrated using solid-phase extraction and well resolved on a C(18) column. They were detected using an indirect method involving the quenching of the emission from the fluorophores 5,6,7,8-tetrahydronaphthol (5,6,7,8-THN-1-OH), 7-amino-4-methyl coumarin (Coumarin 120, COU-120) and 3-hydroxy-4-(2-hydroxy-4-sulfo-1-naphthylazo)2-naphthalene carboxylic acid (Calcon carboxylic acid, CCA). Linear calibration curves were obtained in the range 1.1 x 10(-9) to 1.1 x 10(-8) mol/L. Using COU 120 as the fluorophore, the detection limit was 2.9 x 10(-10) mol/L for 1-nitronaphthalene and 2.1 x 10(-11) mol/L for 2-nitrofluorene. Recoveries of NPAHs from spiked tap water samples were between 88 and 100%. 相似文献
A method for determination of nitrated polycyclic aromatic hydrocarbons (NPAHs) in diesel soot by high-performance liquid chromatography-mass spectrometry with atmospheric pressure chemical ionization (APCI) and detection by ion-trap following ultrasonic extraction is described. The determination of 1-nitropyrene that it is the predominant NPAH in diesel soot was emphasized. Vaporization and drying temperatures of the APCI interface, electronic parameters of the MS detector and the analytical conditions in reversed-phase HPLC were optimized. The patterns of fragmentation of representative NPAHs were evaluated by single and multiple fragmentation steps and negative ionization led to the largest signals. The transition (247-->217) was employed for quantitative analysis of 1-nitropyrene. Calibration curves were linear between 1 and 15 microgL(-1) with correlation coefficients better than 0.999. Typical detection limit (DL) of 0.2 microgL(-1) was obtained. Samples of diesel soot and of the reference material (SRM-2975, NIST, USA) were extracted with methylene chloride. Recoveries were estimated by analysis of SRM 2975 and were between 82 and 105%. DL for 1-nitropyrene was better than 1.5 mg kg(-1), but the inclusion of an evaporation step in the sample processing procedure lowered the DL. The application of the method to diesel soot samples from bench motors showed levels 相似文献
Particulate matter 2.5 (PM2.5), collected from ambient air in Fukuoka City, was analyzed by gas chromatography combined with multiphoton ionization mass spectrometry using an ultraviolet femtosecond laser (267 nm) as the ionization source. Numerous parent polycyclic aromatic hydrocarbons (PPAHs) were observed in a sample extracted from PM2.5, and their concentrations were determined to be in the range from 30 to 190 pg/m3 for heavy PPAHs. Standard samples of nitrated polycyclic aromatic hydrocarbons (NPAHs) were examined, and the limits of detection were determined to be in the picogram range. The concentration of NPAH adsorbed on PM2.5 in the air was less than 900–1300 pg/m3.
The accelerated growth of aquaculture has resulted in a series of harmful effects to human health. The widespread and unrestricted use of antibiotics in this industry, to prevent bacterial infections, leads to remaining amounts in the aquatic environment. This has resulted in the emergence of antibiotic-resistant bacteria in aquaculture environments, in the increase in antibiotic resistance in fish pathogens as well as in the transfer of these resistance determinants to human pathogens. Moreover, the use of large amounts of antibiotics may lead to the presence of residual antibiotics in fish tissue and fish products. Fluoroquinolones, tetracyclines, penicillins, sulphonamides and other antibiotics, exhibiting activity against both Gram-positive and Gram-negative bacteria, are widely used for the treatment and prevention of diseases in fish. An extended and comprehensive review on the recent analytical methodologies concerning antibiotic residues in fish reported in the literature is provided in the present article. Emphasis is given on sample preparation regarding isolation and purification, chromatographic conditions and method validation according to legislation. Results of published assays are comparatively presented and criticised. 相似文献
Methods of stripping voltammetry, quartz microgravimetry, and x-ray-fluorescence analysis are employed to explore the copper displacement process on thin electrodeposited layers of pure cobalt and nickel and on deposits of these metals with inclusions of copper. The displacement reaction proceeds at a considerable rate on cobalt in the sulfate and sulfosalicylate solutions and virtually does not proceed on nickel in both the sulfate or sulfate-chloride solutions. An estimate of the rate of the copper displacement reaction following a change in the concentration of copper ions in the solution and in the pH of the sulfosalicylate solution is given. A decrease in the contact exchange rate is facilitated by a decrease in the concentration of copper ions in solution and their participation in the formation of complexes. 相似文献
Calibration methods for microdialysis sampling were studied in the muscle and adipose tissue of rats. Both the delivery method and the no-net-flux method were used to determine the extraction efficiency (EE) of acetaminophen and caffeine in both tissues. There was no concentration dependence of the EE either in vitro or in vivo for either acetaminophen or caffeine. The EEs determined by the delivery and no-net-flux methods were not different. However, the EEs of both caffeine and acetaminophen determined in vitro were significantly higher than those determined in the muscle and adipose. This indicates that mass transfer in the tissue is the rate-determining factor for the EE in vivo. The relative difference between the EE in vitro and the EE in the muscle was smaller than the difference between the EE in vitro and the EE in the adipose. In addition, the EE in the muscle decreased more than the EE in the adipose after the animal was euthanized. This indicated that exchange between the extracellular fluid and plasma is the rate-determining step in mass transport relative to microdialysis sampling. This has a more significant effect on the EE in the muscle than the EE in the adipose. Both the delivery and no-net-flux methods can be used to calibrate microdialysis probes in the muscle and adipose. 相似文献
The density and surface tension of water in small pores of silicas have been investigated. These physical properties of water
in the pores were calculated from a comparison of pore volumes and pore radii which were estimated from adsorption and desorption
isotherms of nitrogen and water. Below a pore radius of about 5 nm both the density and the surface tension of water in the
pores were smaller than those of the bulk liquid and decreased with a decrease in pore size. The density of water in the pores
decreased with an increase in the concentration of surface hydroxyl groups. Similarly the surface tension of water in the
pores is influenced by the surface hydroxyl groups. Anomalous changes in the density and surface tension of the water in the
pores are attributed to the interaction of water molecules with surface hydroxyl groups and hydrogen-bond formation among
water molecules.
Received: 20 April 1999 Accepted in revised form: 17 November 1999 相似文献
The measurement of nitric oxide (NO) in exhaled air is used in diagnostics and monitoring the pathologies not only in the respiratory system but also in the oral cavity. It has shown a huge increase in its level in asthma and diseases of the oral cavity. It seems reasonable to undertake research on the impact of inflammation on the level of NO in exhaled air. The aim of the study is to make an evidence-based review of the application of NO levels in exhaled air in the diagnosis of inflammation and treatment monitoring on the basis of selected measuring devices. Methods and Results: This paper presents an example of the application of NO measurement in exhaled air in individual human systems. Selected measuring devices, their non-invasiveness, and their advantages are described. Discussion: The usefulness of this diagnostic method in pathologies of the oral cavity was noted. Conclusions: Measuring the level of NO in exhaled air seems to be a useful diagnostic method. 相似文献
Four different spruce sulphite pulp samples were used for the preparation of carboxymethylcellulose (CMC). The characteristics
of the unreacted fibre and particle residuals obtained in the CMC-preparation were used to establish a correlation between
the hemicellulose in the pulp and the intrinsic viscosity, i.e.,␣cellulose chain length and the occurence of unreacted residuals.
It was shown that the residual particles in the CMC consisted of fibres, fibre fractions and gel particles of different degrees
of substitution. The results suggested that pulps with long cellulose chains, i.e., pulps with high intrinsic viscosities,
resulted in particles that were more substituted and more swollen. These pulps also resulted in more substituted hemicelluloses
in the CMC and more substituted residuals. It was also suggested that galactoglucomannan in the cellulose pulps is favourable
for the swelling which results in more substituted hemicelluloses in the CMC and more swollen residuals. The amount of residuals
was influenced mainly by the characteristics of the cellulose in the pulp. It is therefore believed that a combination of
high viscosity and a suitable combination of hemicelluloses is the most favourable way of eliminating the occurrence of undissolved
residuals in CMC. 相似文献
The aim of this work was to elucidate soy proteins–xanthan gum interactions at a molecular level by studying protein composition at the air–water interface of foams and in the solutions used to make them and to see if the different properties of heat denatured protein were reflected in the proportions in which they were present at the interface or in the ability to interact with xanthan. To this end SDS-PAGE and densitometry was employed. Initial protein concentration and xanthan influenced the composition of proteins in the solutions used to make the foams. The increase in NSP concentration of solutions (0.5–6 wt.%) in the absence of xanthan promoted the formation of aggregates of low molecular weight (160 kDa), the association of A an B polypeptides and a decrease in and ′ subunits. As DSP concentration of solutions increased, an increase in the proportion of aggregates of high molecular weight (above 200 kDa) and B-polypeptide was observed. On addition of xanthan (0.025 and 0.05%) to protein solutions (0.5 and 2%), the formation of aggregates of high molecular weight was favoured for both NSP and DSP. In the absence of xanthan, no preferential adsorption of soy polypeptides was observed at the air–water interface of NSP foams. However in DSP foams, there was a preferential adsorption of B-polypeptides. Xanthan present in NSP foams (0.5 or 2%), caused an increase in the proportion of aggregates of high molecular weight at the interface as compared with the composition of solutions used to make the foams. An increase in proportion of AB-polypeptides (for 0.5% NSP and 0.025% xanthan) and B-polypeptides together with polypeptides of molecular weight lower than 14 kDa (for 0.5% NSP and 0.05% xanthan) was also observed at the interface in NSP foams. On the contrary, the presence of xanthan in DSP foams caused a decrease in the proportion of aggregates of high molecular weight and a concomitant increase in B-polypeptide. The B-11S polypeptide predominated the interface of DSP foams probably for its hydrophobicity and basic characteristics. 相似文献
Abstract The accumulation, persistence and fate of systemic pesticide aldicarb was melencholy evaluated in orange crops. The concentration of this pesticide and its two toxic metabolites, aldicarb sulfoxide and aldicarb sulfone was determined in leaves, rind and pulp of three orange varieties (Satsuma, Navelina and Clemetina de Nules) and in the top soil of the orange groves. The groves were located in two different places in the Valencia Community (Spain). The analysis showed that the aldicarb concentration was lower than those of aldicarb sulfoxide and aldicarb sulfone. In all cases, the residues persisted at least 160 days in vegetable samples and between 157 and 227 days in soil samples. Residue concentrations measured in the soil samples were highly variable but a relation with the organic matter content can be observed. The residue levels found in vegetal products were higher in leaves than in rind, and in rind than in pulp. The maximum residue values were obtained between 47 and 70 days after the application. One hundred days after treatment (Security period) the residue levels of total fruit were lower than the maximum residue level of 0.2 mg/kg established by law. 相似文献
Severn Sound is a heavily used recreational and beating area in the southeast corner of Georgian Bay, Lake Huron, Canada. Because of the concern over the possible release of tributyltin species (TBT) from antifouling paints on boat hulls and marinas, surveys were carried out in 1989 and 1992 to determine the presence of this species and its degradation products dibutyltin (DBT) and monobutyltin (MBT) in this area. Many fish (pike and young–of–the–year spottail shiners) and sediment samples collected in 1989 contained detectable levels of TBT. A maximum concentration of TBT was recorded in northern pike in the spring to be 240 ng Sn g?1. Maximum levels occurred in marinas during the beginning of the boating season and significantly reduced during the summer and early autumn, although the maximum value of TBT in sediment (392 ng Sn g?1) was observed in the summer of 1989. The seasonal variation of TBT levels was further substantiated in the subsequent 1992 study, in which sediments from three areas in a marina were sampled at monthly intervals from May to October. TBT levels were much higher in May and then generally decreased with time. Mussels (Elliptio complanta) caged in the marina for three months also contained TBT. DBT was frequently detected in the sediments but less frequently in fish and mussels. MBT was generally below detection limits. Plants (macrophytes and cladophora) contained very small amounts of butyltin compounds. 相似文献
Pistacia species contain oleoresins with bioactive triterpenes. In this study triterpenes, including minor components, were identified and quantified in both neutral and acidic fractions of Pistacia terebinthus var. Chia resin, grown exclusively in Chios island (Greece), collected traditionally, as well as using stimulating agents (liquid collection). It was proved that these two resin samples were composed of several different minor triterpenes, while major constituents were similar but in different proportions. Compounds that differentiated two resin samples of P. lentiscus and P. terebinthus var. Chia, both traditionally collected, were detected, in order to identify the nature of resins present in archaeological materials. In the traditionally collected resin, 37 triterpenes were identified, 12 in the acidic and 25 in the neutral fraction. In the liquid collection resin 10 compounds were identified in the acidic and 23 in the neutral fraction, while 16 compounds were not contained in the traditionally collected resin. The main triterpenes in both resin samples collected traditionally and using stimulating agents were: isomasticadienonic acid (23.6 and 26.3% w[sol ]w of the triterpenic fraction, respectively), 28-norolean-17-en-3-one (16.3 and 17.5% w[sol ]w of the triterpenic fraction, respectively) and masticadienonic acid (5.8 and 6.0% w[sol ]w of the triterpenic fraction). In this study the qualitative and quantitative composition of triterpenes was compared in the Pistacia lentiscus and P. terebinthus var. Chia resin samples collected with the traditional and new liquid techniques, and also triterpenes in resins of P. terebinthus obtained by the traditional technique and using stimulating agents. The aim of the study was also to examine whether the collection technique influenced the triterpenes contained in P. terebinthus var. Chia resin samples. 相似文献
