Chemical characteristics of aerosol insecticide deposition in indoor surfaces

We investigated the deposition rate of aerosol insecticide on through woollen surfaces inside a test chamber. Compared to floor surface, the deposition rate of aerosol insecticide active ingredient on table of 1 m high was up to 2.07 times for piperonyl butoxide, 1.64 times for tetramethrin and 2.95 times for permethrin represented by 0.51, 0.37 and 0.23 μg cm^?2 for the three molecules, respectively. Application of the household used cleaning to the woollen table surface decrease these concentrations by 61.32%, 45.01% and 59.80% for the three pesticides respectively, this cleaning procedure still not efficient for the floor surfaces. Moreover, indoor conditions permit the removal of 46.42%, 21.92% and 14.35% of the table surface deposition rate after one week, for the three pesticides, respectively. These conditions ensure the removal of only 28.72%, 20.69% and 24.05% of the three deposit molecules respectively on floor surface.     

Detecting trace pesticides in real time using single particle aerosol mass spectrometry

Pesticides are toxic substances and may cause unintentional harm if improperly used. The ubiquitous nature of pesticides, with frequent use in agriculture and the household, and the potential for harm that pesticides pose to non-target organisms such as wildlife, humans, and pets, demonstrate the need for rapid and effective detection and identification of these compounds. In this study, single particle aerosol mass spectrometry (SPAMS) was used to rapidly detect compounds from four classes of pesticides commonly used in agricultural and household applications. These include permethrin (pyrethroid class), malathion and dichlorvos (organophosphate class), imidacloprid (chloronicotinyl class), and carbaryl (carbamate class). Analytical standards of each compound were diluted and aerosolized using a nebulizer to create particles for analysis in the SPAMS instrument. The resultant dual-polarity time-of-flight mass spectra were then analyzed to identify the characteristic peaks of the compound in each sample. In addition, samples of commercial products containing pesticides, a commercial insecticide spray, containing permethrin, and a canine flea collar, containing carbaryl, were analyzed in their original form using SPAMS without any significant sample preparation. The characteristic mass spectral peaks of the active pesticides in these samples were identified using the mass spectra obtained earlier from the pesticide analytical standards. By successfully identifying pesticides in analytical standards and in commercial products, it is demonstrated herein that the SPAMS system may be capable of pesticide detection in numerous environmental and agricultural situations.     

A simple and fast method for the determination of active ingredient in antiperspirant cosmetics by neutron activation analysis

Antiperspirant cosmetics are tested for their active ingredient (aluminium chlorohydroxide) by conventional analytical techniques. Aluminium has been determined by instrumental neutron activation analysis in all antiperspirant products and package forms available in the Greek market in order to develop a simple and fast method for its quantitation. Our results show that neutron activation analysis could be established as an official method for the determination of active ingredient in antiperspirant cosmetics. The proposed method is compared with the existing official methods and an alternative sampling method for aerosol package is presented.     

Sample preparation for gas chromatographic analysis of organic solvents in aerosol cans

Summary A method for the sampling of chemical products from aerosol cans is described. An aerosol can is frozen in liquid nitrogen, followed by puncturing the can and allowing the propellant to distill off. The conditions for the smaple preparation have been optimized. Solvent content in the products were analysed by headspace gas chromatography-mass spectrometry.     

乙苯光氧化产生二次有机气溶胶的化学成分及反应机理分析

在自制的烟雾腔内,研究羟基自由基(OH·)启动的乙苯的光氧化反应和一系列后续反应,产生了二次有机气溶胶. 采用空气动力学直径粒谱分析仪分析了气溶胶粒子的尺寸分布;并用自制的气溶胶飞行时间质谱仪快速、实时地测量了单个二次有机气溶胶粒子的分子组分. 初步探讨了这些组分的可能反应机理.     

Headspace analysis of chlorinated organic solvents in aerosol cans by gas chromatography

Summary A gas chromatographic (GC) method for the analysis of chlorinated solvents in chemical products in aerosol cans is described. Conditions for the sampling of chemical products from aerosol cans were optimized, so that the recovery of the solvents was better than 90%. Chlorinated solvents were identified by headspace GC—electron capture detection (ECD) as well as by GC — mass spectrometry. Headspace analysis employing the standard additions method and GC-ECD was used for the quantitation of chlorinated solvents. Analysis of 159 acrosol products, for various uses, revealed that 9% of these did not comply with the Danish Aerosol Regulations. The results of the study further indicated that aerosol products for haircare, paints and paint removers, and many others, can be formulated without chlorinated solvents.     

Heterogeneous reaction of suspended phosmet particles with NO3 radicals

As an organophosphorous insecticide, phosmet is widely used for plant protection as well as against the ectoparasites on productive livestock. It emits into the atmosphere in both gas and particulate phases via spray drift from treatments and postapplication emissions, but its degradation in the atmosphere is not well-known up to now. In this study, the heterogeneous reaction of phosmet absorbed on the azelaic acid particles with NO(3) radicals is investigated in real-time using a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). Two primary products and their nitro-substituted derivates are observed. The apparent reaction rate of phosmet particles with NO(3) radicals is also obtained by a relative rate method with isoprene and 1,4-cyclohexadiene as the reference compounds. The concentrations of the reference substance and phosmet particles are synchronously detected with an atmospheric gas analysis mass spectrometer and the VUV-ATOFMS. Under the experimental conditions, the average apparent reaction rate obtained is (1.92 ± 0.09) × 10(-12) cm(3) molecule(-1) s(-1), and the corresponding atmospheric lifetime toward NO(3) radicals is roughly estimated to be ~0.3 h.     

Surface-catalyzed chlorine and nitrogen activation: mechanisms for the heterogeneous formation of ClNO, NO, NO2, HONO, and N2O from HNO3 and HCl on aluminum oxide particle surfaces

It is well-known that chlorine active species (e.g., Cl(2), ClONO(2), ClONO) can form from heterogeneous reactions between nitrogen oxides and hydrogen chloride on aerosol particle surfaces in the stratosphere. However, less is known about these reactions in the troposphere. In this study, a potential new heterogeneous pathway involving reaction of gaseous HCl and HNO(3) on aluminum oxide particle surfaces, a proxy for mineral dust in the troposphere, is proposed. We combine transmission Fourier transform infrared spectroscopy with X-ray photoelectron spectroscopy to investigate changes in the composition of both gas-phase and surface-bound species during the reaction under different environmental conditions of relative humidity and simulated solar radiation. Exposure of surface nitrate-coated aluminum oxide particles, from prereaction with nitric acid, to gaseous HCl yields several gas-phase products, including ClNO, NO(2), and HNO(3), under dry (RH < 1%) conditions. Under humid more conditions (RH > 20%), NO and N(2)O are the only gas products observed. The experimental data suggest that, in the presence of adsorbed water, ClNO is hydrolyzed on the particle surface to yield NO and NO(2), potentially via a HONO intermediate. NO(2) undergoes further hydrolysis via a surface-mediated process, resulting in N(2)O as an additional nitrogen-containing product. In the presence of broad-band irradiation (λ > 300 nm) gas-phase products can undergo photochemistry, e.g., ClNO photodissociates to NO and chlorine atoms. The gas-phase product distribution also depends on particle mineralogy (Al(2)O(3) vs CaCO(3)) and the presence of other coadsorbed gases (e.g., NH(3)). These newly identified reaction pathways discussed here involve continuous production of active ozone-depleting chlorine and nitrogen species from stable sinks such as gas-phase HCl and HNO(3) as a result of heterogeneous surface reactions. Given that aluminosilicates represent a major fraction of mineral dust aerosol, aluminum oxide can be used as a model system to begin to understand various aspects of possible reactions on mineral dust aerosol surfaces.     

Resolution of overlapped peaks in liquid chromatography by use of derivative spectrophotometry and multivariate analysis and its application in the determination of active components in insecticide formulations

Two procedures for the determination of active components in insecticide formulations have been devised. The first is based in the use of derivative spectra of the components obtained by a diode-array spectrophotomer around the maxima signal of the chromatographic peak. In the second method, mixtures are resolved by the partial least-squares (PLS) regression method from standard spectra of the pure components; spectra of the components were also registered around the maxima signal of the peak. Both procedures have been applied to the analysis of diverse mixtures of active components (piperonyl butoxide, neopynamine and fenitrothion) in insecticide formulations with satisfactory results.     

Ozonolysis and photolysis of alkene-terminated self-assembled monolayers on quartz nanoparticles: implications for photochemical aging of organic aerosol particles

Photolysis of alkene-terminated self assembled monolayers (SAM) deposited on Degussa SiO(2) nanoparticles is studied following oxidation of SAM with a gaseous ozone/oxygen mixture. Infrared cavity ring-down spectroscopy is used to observe gas-phase products generated during ozonolysis and subsequent photolysis of SAM in real time. Reactions taking place during ozonolysis transform alkene-terminated SAM into a photochemically active state capable of photolysis in the tropospheric actinic window (lambda > 295 nm). Formaldehyde and formic acid are the observed photolysis products. Photodissociation action spectra of oxidized SAM and the observed pattern of gas-phase products are consistent with the well-established Criegee mechanism of ozonolysis of terminal alkenes. There is strong evidence for the presence of secondary ozonides (1,3,4-trioxalones) and other peroxides on the oxidized SAM surface. The data imply that photolysis plays a role in atmospheric aging of primary and secondary organic aerosol particles.     

A routine gas chromatographic method for the analysis of chlorofluorocarbons in aerosol cans

Summary A gas chromatographic (GC) method for the routine analysis of fully halogenated chlorofluorocarbons (CFCs) in aerosol cans is described. The identification of CFCs by GC was found to be in full agreement with those by GC-mass-spectrometery. The method has been applied to the analysis of CFCs in 448 aerosol products. The most commonly used fully halogenated CFC propellants in aerosol cans were found to be CFC11, CFC12 and CFC114.     

Syntheses of Racemic and Scalemic cis‐Chrysanthemic Acid from β,γ‐Unsaturated Cyclohexanol

2,2,5,5‐Tetramethylcyclohexane‐1,3‐dione is a valuable starting‐material precursor of cis‐chrysanthemic acid. The (1S)‐stereoisomer is a precursor of pyrethrin I, the most active natural insecticide from Chrysanthemum cinerariifolium, whereas the (1R)‐stereoisomer is efficiently transformed to deltamethrin, the most active commercially available pyrethroid insecticide. Several intermediates have been identified and used with variable success for that purpose.     

Chemical Composition and Reaction Mechanisms for Secondary Organic Aerosol from Photooxidation of Toluene

A laboratory study was carried out to investigate the secondary organic aerosol (SOA) products from photooxidation of the aromatic hydrocarbon toluene. The experiments were conducted by irradiating toluene/CH₃ONO/NO/air mixtures in a home‐made smog chamber. The aerosol time‐of‐flight mass spectrometer (ATOFMS) was used to measure the size and the chemical composition of individual secondary organic aerosol particles in real‐time. According to a large number of single aerosol diameters and mass spectra, we obtained the size distribution and chemical composition of SOA statistically. Expeperimental results showed that aerosol created by toluene photooxidation is predominantly in the form of fine particles, which have diameters less than 2.5 μm (i.e. PM2.5), and the predominant components of aerosol are furane, methyl glyoxylic acid, phenol, benzaldehyde, benzyl alcohol, cresol, 3‐hydroxy‐2,4‐dioxo‐pentanal, methyl nitrophenol, and 5‐hydroxy‐4,6‐dioxo‐2‐heptenal. The possible reaction mechanisms leading to these products were also discussed.     

Conversion of viscous liquid malathion into free flowing solids through co-inclusion in urea for multiple benefits

In current investigation, malathion—a thick viscous liquid insecticide was successfully converted into free flowing solids through co-inclusion in urea for multiple benefits. Resulting fertilizer—insecticide amalgamation offer steep reduction in toxicity/odor and improved handling/formulation characteristics. Malathion (MA), a widely used organophosphate insecticide was accommodated in urea host lattice in presence of long chain rapidly complexing agent (RCA). MA is entrapped in cavities of hexagonal urea and is accordingly not accessible either to the surface/environment for inhalation or for dermal contact. Therefore, personnel engaged in handling of hazardous insecticide will not be exposed after its containment in urea lattice. Insects will be exposed to insecticide only after malathion urea co-inclusion complex (MAUCIC) comes in contact with water in soil/crops following switching on of water distribution/sprinkling system in the fields. Since, MA is engulfed in urea channels, steep reduction in petroleum like skunk odor of MA was observed. Rheological studies revealed better flow properties of MAUCIC in comparison to viscous liquid malathion. This also results in reduced cost of transportation/packaging. Minimum amount of RCA required for co-inclusion of MA in urea was determined calorimetrically. Formation of MAUCIC was characterized by FTIR, DSC, XRD and ¹H-NMR studies. Thermal studies revealed increase in heat of decomposition with corresponding increase in proportion of RCA in MAUCICs. MAUCIC complex revealed uniform formulation composition and improved dissolution profile of MA. Studies reveal fertilizer–insecticide amalgamation to be a useful technique for formulation of viscous insecticide into free flowing products with improved handling characteristics.     

Cholesterol ozonolysis: kinetics, mechanism, and oligomer products

Fine particles of cholesterol were reacted with ozone under pseudo-first-order conditions in an aerosol bag reactor. Gas-phase ozone was monitored using an ozone meter. Particle size distribution functions were determined using a scanning mobility particle sizer, which selected particle sizes for introduction into a photoionization aerosol mass spectrometer (PIAMS). PIAMS was used to determine the concentration of cholesterol in the aerosol as a function of reaction time. Dilution corrected rate coefficients were used to calculate the reactive uptake coefficient for ozone onto cholesterol particles as (2.8 +/- 0.4) x 10(-6). Uptake was found to be independent of particle diameter for the sizes studied (100 and 200 nm), suggesting that the uptake is surface mediated. The reaction products were also collected on filters and analyzed by electrospray ionization (ESI) mass spectrometry with both direct infusion and liquid chromatography sample introduction. The main primary reaction products contained one, two, or three oxygens added to the cholesterol moiety. Secondary oligomeric products were also observed, consisting of covalently bound dimers and trimers. Tandem mass spectrometry was used to confirm the expected structures of these compounds. The dimers appear to be acyl hydroperoxides, consistent with a previously reported mechanism for the reaction in a nonparticipating solvent. Finally, the magnitude of the uptake coefficient confirms that cholesterol is suitable as a local source tracer for source apportionment of ambient organic aerosol.     

Low‐Molecular Weight and Oligomeric Components in Secondary Organic Aerosol from the Photooxidation of p‐Xylene

A laboratory study was performed to investigate the composition of secondary organic aerosol (SOA) products from photooxidation of the aromatic hydrocarbon p‐xylene. The experiments were conducted by irradiating p‐xylene/CH₃ONO/NO/air mixtures in a home‐made smog chamber. The aerosol time‐of‐flight mass spectrometer (ATOFMS) was used to measure the size and the chemical composition of individual secondary organic aerosol particles in real‐time. According to a large number of single aerosol diameters and mass spectra, the size distribution and chemical composition of SOA were determined statistically. Experimental results showed that aerosol created by p‐xylene photooxidation is predominantly in the form of fine particles, which have diameters less than 2.5 μm (i.e. PM2.5), and aromatic aldehyde, unsaturated dicarbonys, hydroxyl dicarbonys, and organic acid are major product components in the SOA after 2 hours photooxidation. After aging for more than 8 hours, about 10% of the particle mass consists of oligomers with a molecular mass up to 600 daltons. The possible reaction mechanisms leading to these products are also proposed.     

Enzymatic kinetic resolution and chemoenzymatic dynamic kinetic resolution of delta-hydroxy esters. An efficient route to chiral delta-lactones

A successful kinetic resolution of a racemic mixture of delta-hydroxy esters 1 was obtained via lipase-catalyzed transesterification (E value up to 360). The combination of the enzymatic kinetic resolution with a ruthenium-catalyzed alcohol racemization led to an efficient dynamic kinetic resolution (ee up to 99% and conversion up to 92%). The synthetic utility of this procedure was illustrated by the practical syntheses of delta-lactones (R)-6-methyl- and (R)-6-ethyl-tetrahydropyran-2-one and (S)-5-(tert-butyldimethylsiloxy)heptanal. The former are important building blocks in the synthesis of natural products and biologically active compounds, and the latter is a key intermediate in the synthesis of widely used commercial insecticide Spinosyn A.     

Photo-oxidation of Isoprene with Organic Seed: Estimates of Aerosol Size Distributions Evolution and Formation Rates

ondary organic aerosol (SOA) formation from OH-initiated photo-oxidation of isoprene in the presence of organic seed aerosol. The dependence of the size distributions of SOA on both the level of pre-existing particles generated in situ from the photo-oxidation of trace hydrocarbons of indoor atmosphere and the concentration of precursor, has been investi-gated. It was shown that in the presence of high-level seed aerosol and low-level isoprene (typical urban atmospheric conditions), particle growth due to condensation of secondary organic products on pre-existing particles dominated; while in the presence of low-level seed aerosol and comparatively high-level isoprene (typical atmospheric conditions in rural re-gion), bimodal structures appeared in the size distributions of SOA, which corresponded to new particle formation resulting from homogeneous nucleation and particle growth due to condensation of secondary organic products on the per-existing particles respectively. The effects of concentrations of organic seed particles on SOA were also investigated. The particle size distributions evolutions as well as the corresponding formation rates of new particles indifferent conditions were also estimated.     

Mass Spectrometry Study of OH-initiated Photooxidation of Toluene

The composition of products formed from photooxidation of the aromatic hydrocarbon toluene was investigated. The OH-initiated photooxidation experiments were conducted by irradiating toluene/CH₃ONO/NO/air mixtures in a smog chamber, the gaseous products were detected under the supersonic beam conditions by utilizing vacuum ultraviolet pho-toionization mass spectrometer using synchrotron radiation in real-time. And an aerosol time-of-flight mass spectrometer was used to provide on-line measurements of the individ-ual secondary organic aerosol particle resulting from irradiating toluene. The experimen-tal results demonstrated that there were some differences between the gaseous products and that of particle-phase, the products of glyoxal, 2-hydroxyl-3-oxo-butanal, nitrotoluene, and methyl-nitrophenol only existed in the particle-phase. However, furane, methylglyoxal, 2-methylfurane, benzaldehyde, cresol, and benzoic acid were the predominant photooxidation products in both the gas phase and particle phase.     

Mass spectral evidence that small changes in composition caused by oxidative aging processes alter aerosol CCN properties

Oxidative processing (i.e., "aging") of organic aerosol particles in the troposphere affects their cloud condensation nuclei (CCN) activity, yet the chemical mechanisms remain poorly understood. In this study, oleic acid aerosol particles were reacted with ozone while particle chemical composition and CCN activity were simultaneously monitored. The CCN activated fraction at 0.66 +/- 0.06% supersaturation was zero for 200 nm mobility diameter particles exposed to 565 to 8320 ppmv O3 for less than 30 s. For greater exposure times, however, the particles became CCN active. The corresponding chemical change shown in the particle mass spectra was the oxidation of aldehyde groups to form carboxylic acid groups. Specifically, 9-oxononanoic acid was oxidized to azelaic acid, although the azelaic acid remained a minor component, comprising 3-5% of the mass in the CCN-inactive particles compared to 4-6% in the CCN-active particles. Similarly, the aldehyde groups of alpha-acyloxyalkylhydroperoxide (AAHP) products were also oxidized to carboxylic acid groups. On a mass basis, this conversion was at least as important as the increased azelaic acid yield. Analysis of our results with K?hler theory suggests that an increase in the water-soluble material brought about by the aldehyde-to-carboxylic acid conversion is an insufficient explanation for the increased CCN activity. An increased concentration of surface-active species, which decreases the surface tension of the aqueous droplet during activation, is an interpretation consistent with the chemical composition observations and K?hler theory. These results suggest that small changes in particle chemical composition caused by oxidation could increase the CCN activity of tropospheric aerosol particles during their atmospheric residence time.