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PubMed2005

Effect of controlled atmosphere storage, modified atmosphere packaging and gaseous ozone treatment on the survival of Salmonella Enteritidis on cherry tomatoes.

In recent years, outbreaks of infections associated with raw and minimally processed fruits and vegetables have been reported. The objective of this study was to analyse the growth/survival of Salmonella Enteritidis at spot-inoculated or stem-injected cherry tomatoes during passive modified atmosphere packaging (MAP), controlled atmosphere (CA) and to compare the results with those of air storage at 7 and 22 degrees C. During MAP, the gas composition equilibrated to 6% O2/4% CO2. CO2 level was maintained as 5% through the term of CA storage at 7 and 22 degrees C. The results demonstrate that S. Enteritidis can survive and/or grow during the storage of tomatoes depending on the location site of the pathogen on fruit, suspension cell density and storage temperature. During MAP, CA and air storage, S. Enteritidis with initial population of 7.0 log10 cfu/tomato survived on tomato surfaces with an approximate decrease of 4.0-5.0 log10 cfu/tomato in population within the storage period; however, in the case of initial population of 3.0 log10 cfu/tomato, cells died completely on day 4 during MAP storage and on day 6 during both CA and air storage. The death rate of S. Enteritidis on the surfaces of tomatoes that were stored in MAP was faster than that of stored in air and in CA. Storage temperature was effective on the survival of S. Enteritidis for the samples stored at ambient atmosphere; cells died completely on day 6 at 7 degrees C and on day 8 at 22 degrees C. Stem scars provided protective environments for Salmonella; an approximate increase of 1.0 log10 cfu/tomato in stem-scar population was observed during MAP, CA and air storage at 22 degrees C within the period of 20 days. Cells survived with no significant change in number at 7 degrees C. During the research, the effect of ozone treatment (5-30 mg/l ozone gas for 0-20 min) was also considered for surface sanitation before storage. Gaseous ozone treatment has bactericidal effect on S. Enteritidis, inoculated on the surface of the tomatoes and can be used for surface sanitation of S. Enteritidis on tomatoes before storage at different conditions. Ten mg/l ozone gas treatment with different time intervals of 5 and 15 min was found to be effective respectively on low and high dose inoculum levels of S. Enteritidis attached for 1 h. Another variable considered during ozone treatment was the 4 h attachment time.

Colony Count, Microbial↗
PubMed1997

PLATIN (plant-atmosphere interaction) I: A model of plant-atmosphere interaction for estimating absorbed doses of gaseous air pollutants.

A PLant-ATmosphere INteraction model (PLATIN) was developed for estimating air pollutant absorbed doses under ambient conditions. PLATIN is based on the canopy energy balance combined with a gas transport submodel. The model has three major resistance components: (1) a turbulent atmospheric resistance Rah(zm) that describes the atmospheric transport properties between a measurement height above the canopy and the conceptual height z=d+z0m which represents the sink for momentum according to the big-leaf concept; (2) a quasilaminar layer resistance R(b,A) that quantifies the way in which the transfer of sensible heat and matter (e.g. latent heat, ozone) differs from momentum transfer; (3) a canopy or surface resistance R(c,A) that describes the influences of the plant/soil system on the exchange processes. Soil water content is simulated by a Force-Restore model. By a simple interception submodel precipitation and dew are partitioned into intercepted water and water reaching the soil surface. PLATIN can be run in a prognostic or a diagnostic mode. It is also intended for on-line use in air quality monitoring networks.

Journal Article↗
PubMed2002

Atmospheric chemistry of HFE-7500 [n-C3F7CF(OC2H5)CF(CF3)2]: reaction with OH radicals and Cl atoms and atmospheric fate of n-C3F7CF(OCHO*)CF(CF3)2 and n-C3F7CF(OCH2CH2O*)CF(CF3)2 radicals.

Relative rate techniques were used to measure k(OH + HFE-7500) = (2.6+/-0.6) x 10(-14), k(Cl + HFE-7500) = (2.3+/-0.7) x 10(-12), k[Cl + n-C3F7CF(OC(O)H)CF(CF3)2] = (9.7+/-1.4) x 10(-15), and k[Cl + n-C3F7CF(OC(O)CH3)CF(CF3)2] < 6 x 10(-17) cm3 molecule(-1) s(-1) at 295 K [HFE-7500 = n-C3F7-CF(OC2H5)CF(CF3)2]. From the value of k(OH + HFE-7500) an estimate of 2.2 years for the atmospheric lifetime of HFE-7500 is obtained. Two competing loss mechanisms for n-C3F7-CF(OCHO.CH3)CF(CF3)2 radicals were identified in 700 Torr of N2/O2 diluent at 295 K; reaction with O2 and decomposition via C-C bond scission with kO2/k(decomp) = 0.013+/-0.006 Torr(-1). The Cl atom initiated oxidation of HFE-7500 in N2/O2 diluent gives n-C3F7CF(OC(O)CH3)CF(CF3)2 as the major product and n-C3F7CF(OC(O)H)CF(CF3)2 as a minor product. The atmospheric oxidation of HFE-7500 gives n-C3F7-CF(OC(O)CH3)CF(CF3)2 and n-C3F7CF(OC(O)H)CF(CF3)2 as oxidation products. The results are discussed with respect to the atmospheric chemistry and environmental impact of HFE-7500.

Air Pollutants↗
PubMed2003

A model evaluation of the NO titration technique to remove atmospheric oxidants for the determination of atmospheric organic compounds.

Chemical artifact is a problem in the sampling of atmospheric organic species for a relatively long sampling period. In this study, we evaluated a technique for the removal of atmospheric oxidants with added NO during gas and aerosol sampling by theoretical approach using a Regional Atmospheric Chemistry Mechanism (RACM) model. The elimination of O3 in the sample air is regulated predominantly by the reaction of NO and O3 in all simulated cases. We found that, without any oxidant scavenger, OH and NO3 concentrations in the sampler can be kept high even when wall loss processes of radicals are taken into account The relatively high concentration of OH is mainly due to the production of HO(x) in the sample air via the decomposition of HO2NO2 and O3-olefin reactions, whereas NO3 is produced by the decomposition of N2O5. Addition of NO with appropriate concentrations was found to effectively reduce both OH and NO3 concentrations in the sampling devices. This study demonstrates that scavenging of OH and NO3 as well as O3 is important for the study of chemical speciation of organic compounds and that NO addition is a useful technique to eliminate these oxidants.

Aerosols↗
PubMed1986

Development and validation of personal monitoring methods for low levels of acrylonitrile in workplace atmosphere: I. Test atmosphere generation and solvent desorption methods.

The purpose of this study was to optimize monitoring methods and to investigate new technology for the determination of low levels of acrylonitrile (0.05 to 5 ppm) in workplace atmospheres. In the first phase of the study, a dynamic atmosphere generation system was developed to produce low levels of acrylonitrile in simulated workplace atmospheres. Various potential sorbents were investigated in the second phase, and the candidate methods were compared in a laboratory validation study over a concentration range from 0.05 to 5 ppm acrylonitrile in the presence of potential interferences and under relative humidity conditions from 30% to 95% RH. A collection tube containing 600 mg Pittsburgh coconut base charcoal was found to be the optimum tube for sampling for a full 8-hr shift. No breakthrough was observed over the concentrations and humidities tested. The recovery was 91.3% with a total relative precision of +/- 21% over the test range, and the recovery was not affected by storage for up to five weeks.

Acrylonitrile↗
PubMedDate not supplied

Interpretation of atmospheric pollution phenomena in relationship with the vertical atmospheric remixing by means of natural radioactivity measurements (radon) of particulate matter.

In this paper the results of seasonal monitoring campaign for primary (benzene and carbon monoxide) and secondary (nitrogen dioxide and ozone) pollutants and for the natural radioactivity of the particulate matter in the urban area of Rome, are reported to investigate acute atmospheric pollution episodes. Comparing the daily concentration trends of primary and secondary pollutants with those of the natural radioactivity, considered as index of the vertical diffusion in the low boundary layer, it has been evidenced that the acute pollution episodes in Rome occur in the winter period for the high atmospheric stability (primary pollution) and in the summer period for the strong diurnal atmospheric remixing (secondary pollution).

Air Movements↗
PubMed2006

Atmospheric pressure photoionization-mass spectrometry and atmospheric pressure chemical ionization-mass spectrometry of neurotransmitters.

A group of five neurotransmitters with different properties was analyzed using atmospheric pressure photoionization (APPI) and atmospheric pressure chemical ionization-mass spectrometry (APCI-MS). The sensitivity of the techniques for the analytes was tested in six solvents and in positive and negative ion modes. APPI was found to be superior in sensitivity for all the compounds in both positive and negative ion modes. In positive ion mode, water/methanol/formic acid was found to be the best solvent, whereas in negative ion mode, water/methanol/ammonium hydroxide performed best. Detection limits using APPI were between 2.5-250 fmol, depending on the compound. The sensitivity was best for the neurosteroids dehydroepiandrosterone and beta-estradiol, and acetylcholine (LOD 2.5-10 fmol).

Atmospheric Pressure↗
PubMed2004

An atmospheric pressure chemical ionization study of the positive and negative ion chemistry of the hydrofluorocarbons 1,1-difluoroethane (HFC-152a) and 1,1,1,2-tetrafluoroethane (HFC-134a) and of perfluoro-n-hexane (FC-72) in air plasma at atmospheric pressure.

A report is given on the ionization/dissociation behavior of the title compounds within air plasmas produced by electrical corona discharges at atmospheric pressure: both positive and negative ions were investigated at different temperatures using atmospheric pressure chemical ionization mass spectrometry (APCI-MS). CHF(2)CH(3) (HFC-152a) undergoes efficient ionic oxidation to C(2)H(5)O(+), in which the oxygen comes from water present in the plasma. In contrast, CF(3)CH(2)F (HFC-134a) does not produce any characteristic positive ion under APCI conditions, its presence within the plasma being revealed only as a neutral ligand in ion-molecule complexes with ions of the background (H(3)O(+) and NO(+)). Analogously, the perfluorocarbon FC-72 (n-C(6)F(14)) does not produce significant positive ions at 30 degrees C: at high temperature, however, it undergoes dissociative ionization to form many product ions including C(3)F(6)(+), C(2)F(4)(+), C(n)F(2n+1)(+) and a few families of oxygen containing cations (C(n)F(2n+1)OH(2)(+), C(n)F(2n)OH(+), C(n)F(2n-1)O(+), C(n)F(2n-1)O(2)H(2)(+), C(n)F(2n-2)O(2)H(+)) which are suggested to derive from C(n)F(2n+1)(+) in a cascade of steps initiated by condensation with water followed by steps of HF elimination and H(2)O addition. Negative ions formed from the fluoroethanes CHF(2)CH(3) and CF(3)CH(2)F (M) include complexes with ions of the background, O(2)(-)(M), O(3)(-)(M) and some higher complexes involving also water, and complexes of the fluoride ion, F(-)(H(2)O), F(-)(M) and higher complexes with both M and H(2)O also together. The interesting product O(2)(-)(HF) is also formed from 1,1-difluoroethane. In contrast to the HFCs, perfluoro-n-hexane gives stable molecular anions, M(-), which at low source temperature or in humidified air are also detected as hydrates, M(-)(H(2)O). In addition, in humidified air F(-)(H(2)O)(n) complexes are also formed. The reactions leading to all major positive and negative product ions are discussed also with reference to available thermochemical data and relevant literature reports. The effects on both positive and negative APCI spectra due to ion activation via increasing V(cone) are also reported and discussed: several interesting endothermic processes are observed under these conditions. The results provide important information on the role of ionic reactions in non-thermal plasma processes.

Air↗
PubMed2004

Atmospheric pressure chemical ionization and atmospheric pressure photoionization for simultaneous mass spectrometric analysis of microbial respiratory ubiquinones and menaquinones.

An atmospheric pressure photoionization (APPI) source and an atmospheric pressure chemical ionization (APCI) source were compared for the selective detection of microbial respiratory ubiquinone and menaquinone isoprenologues using tandem mass spectrometry. Ionization source- and compound mass-dependent parameters were optimized individually for both sources, using the available quinone standards. Detection levels for the two ion sources were determined with ubiquinone-6 (UQ6) and menaquinone-4 (MK4, vitamin K2) standards using flow injection analysis and selected reaction monitoring (SRM). With APPI the calculated lower limit of detection (LLOD) was 1.7 fmol microl(-1) for UQ6 and 2.2 fmol microl(-1) for MK4 at a signal-to-noise ratio of 3. These LLODs were at least three times lower than with APCI. The selectivity of detection afforded by SRM detection reduced complex mixture analysis to 3 min per sample by eliminating the need for chromatographic separations. The detection method was successfully applied to quinone quantification in a variety of environmental samples and cell cultures. Adequate amounts of respiratory quinones can be extracted and quantified from samples containing as low as 2 x 10(7) cells.

Atmospheric Pressure↗
PubMed2004

Comparison of electrospray ionization, atmospheric pressure chemical ionization, and atmospheric pressure photoionization for the analysis of dinitropyrene and aminonitropyrene LC-MS/MS.

The only relevant source for human exposure to dinitropyrenes is diesel engine emissions. Due to this specificity, dinitropyrenes may be used as biomarkers for monitoring human exposure to diesel engine emissions. Only few analytical methods have been described for the quantitation of dinitropyrenes and their metabolites, aminonitropyrenes, and diaminopyrenes. Therefore, for dinitropyrenes, aminonitropyrenes, and diaminopyrenes were selected as model compounds for the development of a sensitive HPLC-MS/MS method (high performance liquid chromatography coupled to triple quadrupole mass spectrometry) was to quantify polyaromatic amines and nitroarenes in biological matrices was developed optimal methods by comparing electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and atmospheric pressure photoionization (APPI) sources. Dinitropyrene was not effectively ionized and diaminopyrene yielded mainly [M(.)](+) ions by electrospray ionization. With APCI and APPI, precursor ions of diaminopyrene and aminonitropyrene were [M + H](+) and [M(.)](-) for dinitropyrene. Precursor ions with [M - 30(.)](-) for dinitropyrene and [M - 30 + H](+) for aminonitropyrene were observed. Reversed and normal phase HPLC-MS/MS with ESI, APCI and APPI were optimized separately with respect to unequivocal analyte identification and sensitivity. Normal phase HPLC coupled to APPI-MS/MS gave the highest precision and sensitivity for aminonitropyrene (6%/0.2 pg on column) and dinitropyrene (9%/0.5 pg on column). The limit of detection in spiked rat plasma was 5 pg/100 microL for aminonitropyrene (accuracy 82%) and 10 pg/100 microL for dinitropyrene (accuracy 105%). In plasma of rats treated with dinitropyrene by oral administration, no detectable levels of dinitropyrene but higher aminonitropyrene levels compared with intratracheal instillation were observed. These findings clearly demonstrate that dinitropyrene was absorbed after oral and intratracheal application and that a reduction of nitro groups occurs to a high extent in the reductive environment of the intestine. To our knowledge, this is the first time that aminonitropyrene was observed in plasma after intratracheal or oral administration directly demonstrating the reductive metabolism of dinitropyrene in vivo.

Air Ionization↗
PubMed1999

Capillary column supercritical fluid chromatography-atmospheric pressure ionisation mass spectrometry interface performance of atmospheric pressure chemical ionisation and electrospray ionisation.

A supercritical fluid chromatography interface probe for atmospheric pressure ionisation mass spectrometry (API-MS) with the advantage of convenient switch between ionisation modes [atmospheric pressure chemical ionisation (APCI) and electrospray ionisation (ESI)] has recently been reported [P.J.R. Sjöberg, K.E. Markides, J. Chromatogr. A, 785 (1997) 101]. In order to obtain a stable ion signal and a low minimum detectable quantity, the design of the spray devise has to be optimised. For easy optimisation in the APCI mode, the corona needle was mounted directly on the interface probe. To compensate for the adiabatic cooling of the expanding mobile phase in the APCI mode, a heated region around the restrictor tip was used. In comparison, ESI required no additional heat, which might also prevent fragmentation for thermolabile compounds. As the mobile phase used was neat CO2, a low flow of make-up liquid was utilised in the ESI mode for transfer of the analytes from the expanding CO2 gas to the liquid phase before ionisation. The low make-up liquid flow in the ESI mode was sufficient for preventing the restrictor from becoming blocked. Factors that influence the ion signal intensity and stability have been studied. In APCI mode, corona needle position, nebuliser gas flow and gas additives were studied and in ESI mode, spray capillary assembly dimension and position, liquid flow-rate and composition were studied. The achievable detection limits were in the 50-0.1 pg (i.e., 290 fmol-140 amol) range. The detection limit in APCI mode was improved by a factor of about 20-25 compared to an earlier design [L.N. Tyrefors, R.X. Moulder, K.E. Markides, Anal. Chem. 65 (1993) 2835].

Atmospheric Pressure↗
PubMed2002

Comparison of electrospray, atmospheric pressure chemical ionization, and atmospheric pressure photoionization in the identification of apomorphine, dobutamine, and entacapone phase II metabolites in biological samples.

The applicability of different ionization techniques, electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and a novel atmospheric pressure photoionization (APPI), were tested for the identification of the phase II metabolites of apomorphine, dobutamine, and entacapone in rat urine and in vitro incubation mixtures (rat hepatocytes and human liver microsomes). ESI proved to be the most suitable ionization method; it enabled detection of 22 conjugates, whereas APCI and APPI showed only 12 and 14 conjugates, respectively. Methyl conjugates were detected with all ionization methods. Glucuronide conjugates were ionized most efficiently with ESI. Only some of the glucuronides detected with ESI were detected with APCI and APPI. Sulfate conjugates were detected only with ESI. MS/MS experiments showed that the site of glucuronidation or sulfation could not be determined, since the primary cleavage was a loss of the conjugate group (glucuronic acid or SO3), and no site-characteristic product ions were formed. However, it may be possible to determine the site of methylation, since methylated products are more stable than glucuronides or sulfates. Furthermore, the loss of CH3 is not necessarily the primary cleavage, and site characteristic products may be formed. Identification and comparison of conjugates formed from the current model drugs were successfully analyzed in different biological specimens of common interest to biomedical research. A fairly good relation was obtained between the data from in vivo and in vitro models of drug metabolism.

Animals↗
PubMed2005

Comparison of atmospheric pressure chemical ionization, electrospray ionization, and atmospheric pressure photoionization for the determination of cyclosporin A in rat plasma.

Atmospheric pressure chemical ionization was compared with electrospray ionization and atmospheric pressure photoionization (APPI) as an interface of high-performance liquid chromatography (HPLC)-tandem mass spectrometry (MS/MS) for the determination of cyclosporin A (CsA) in biological fluids in support of in vivo pharmacodynamic studies. These ion sources were investigated in terms of their suitability and sensitivity for the detection of CsA. The effects of the eluent flow rate and composition as well as the nebulizer temperatures on the photoionization efficiency of CsA in the positive ion mode under normal-phase HPLC conditions were explored. The ionization mechanism in the APPI environment with and without the use of the dopant was studied using two test compounds and a few solvent systems employed for normal-phase chromatography. The test compounds were observed to be ionized mainly by proton transfer with the self-protonated solvent molecules produced through photon irradiation. Furthermore, ion suppression due to sample matrix interference in the normal-phase HPLC-APPI-MS/MS system was monitored by the postcolumn infusion technique. The applicability of these proposed HPLC-API-MS/MS approaches for the determination of CsA at low nanogram per milliliter levels in rat plasma was examined. These proposed methods were then compared with respect to specificity, linearity, detection limit, and accuracy.

Air Ionization↗
PubMed2006

Comparison of atmospheric pressure photoionization, atmospheric pressure chemical ionization, and electrospray ionization mass spectrometry for analysis of lipids.

In this work, we compare the quantitative accuracy and sensitivity of analyzing lipids by atmospheric pressure photoionization (APPI), atmospheric pressure chemical ionization (APCI), and electrospray ionization (ESI) LC/MS. The target analytes include free fatty acids and their esters, monoglyceride, diglyceride, and triglyceride. The results demonstrate the benefits of using LC/APPI-MS for lipid analysis. Analyses were performed on a Waters ZQ LC/MS. Normal-phase solvent systems were used due to low solubility of these compounds in aqueous reversed-phase solvent systems. By comparison, APPI offers lower detection limits, generally highest signal intensities, and the highest S/N ratio. APPI is 2-4 times more sensitive than APCI and much more sensitive than ESI without mobile-phase modifiers. APPI and APCI offer comparable linear range (i.e., 4-5 decades). ESI sensitivity is dramatically enhanced by use of mobile phase modifiers (i.e., ammonium formate or sodium acetate); however, these ESI adduct signals are less stable and either are nonlinear or have dramatically reduced linear ranges. Analysis of fish oils by APPI shows significantly enhanced target analyte intensities in comparison with APCI and ESI.

Atmospheric Pressure↗
PubMed2001

Effect of eluent on the ionization efficiency of flavonoids by ion spray, atmospheric pressure chemical ionization, and atmospheric pressure photoionization mass spectrometry.

The effect of nine different eluent compositions on the ionization efficiency of five flavonoids was studied using ion spray (IS), atmospheric pressure chemical ionization (APCI), and the novel atmospheric pressure photoionization (APPI), in positive and negative ion modes. The eluent composition had a great effect on the ionization efficiency, and the optimal ionization conditions were achieved in positive ion IS and APCI using 0.4% formic acid (pH 2.3) as a buffer, and in negative ion IS and APCI using ammonium acetate buffer adjusted to pH 4.0. For APPI work, the eluent of choice appeared to be a mixture of organic solvent and 5 mM aqueous ammonium acetate. The limits of detection (LODs) were determined in scan mode for the analytes by liquid chromatography/mass spectrometry using IS, APCI and APPI interfaces. The results show that negative ion IS with an eluent system consisting of acidic ammonium acetate buffer provides the best conditions for detection of flavonoids in mass spectrometry mode, their LODs being between 0.8 and 13 microM for an injection volume of 20 microl.

Journal Article↗
PubMed2002

Liquid chromatography/mass spectrometry in anabolic steroid analysis--optimization and comparison of three ionization techniques: electrospray ionization, atmospheric pressure chemical ionization and atmospheric pressure photoionization.

The applicability of liquid chromatography/tandem mass spectrometry (LC/MS/MS) for the detection of the free anabolic steroid fraction in human urine was examined. Electrospray ionization (ESI), atmospheric pressure chemical ionization and atmospheric pressure photoionization methods were optimized regarding eluent composition, ion source parameters and fragmentation. The methods were compared with respect to specificity and detection limit. Although all methods proved suitable, LC/ESI-MS/MS with a methanol-water gradient including 5 mM ammonium acetate and 0.01% acetic acid was found best for the purpose. Multiple reaction monitoring allowed the determination of steroids in urine at low nanogram per milliliter levels. LC/MS/MS exhibited high sensitivity and specificity for the detection of free steroids and may be a suitable technique for screening for the abuse of anabolic steroids in sports.

Anabolic Agents↗
PubMed2005

Atmospheric particle evolution during a nighttime atmospheric mercury depletion event in sub-Arctic at Kuujjuarapik/Whapmagoostui, Québec, Canada.

During a field experiment at Kuujjuarapik/Whapmagoostui (55.31 degrees N, 77.75 degrees W), Quebec, we observed increases of concentrations of particles with diameters larger than 0.3 microm in the ambient air during a nighttime atmospheric mercury depletion event (AMDE). These increases were strongly correlated with decreases of ozone and atmospheric mercury, and we also observed a change in the particle size distribution during this AMDE. Assuming that these phenomena imply either a chemical link or an association through transport, we also studied the nature of this AMDE. We hypothesize that the observed AMDE was a result of an influx of already depleted air masses and that it was not a product of local chemical reactions.

Journal Article↗
PubMed2002

Surface-assisted reduction of aniline oligomers, N-phenyl-1,4-phenylenediimine and thionin in atmospheric pressure chemical ionization and atmospheric pressure photoionization.

Reduction of the oligomers formed from on-line electropolymerization of aniline, the compound N-phenyl-1,4-phenylenediimine, and the thiazine dye thionin was observed in both an atmospheric pressure chemical ionization and an atmospheric pressure photoionization source. The reduction, which alters the mass of these analytes by 2 Da, was shown to occur by means of a surface-assisted process which involves reactive species, possibly hydrogen radicals, generated from protic solvents in the ionization plasma. Reduction was minimized by limiting protic solvents, by using a high heated nebulizer temperature, and by using a clean, heated nebulizer probe liner. The expected generality of this reduction process, and the possibility of similar reduction processes in other plasma ionization sources are discussed in relation to the use of these ion sources for on-line electrochemistry/mass spectrometry experiments.

Journal Article↗