Novel Approaches to the Sampling of Atmospheric Aerosols and Determination of Chemical Composition

The Earth s climate is a highly dynamic and complex system in which atmospheric aerosols have been increasingly recognized to play a key role. Aerosol particles affect the climate through a multitude of processes, directly by absorbing and reflecting radiation and indirectly by changing the properties of clouds. Because of the complexity, quantification of the effects of aerosols continues to be a highly uncertain science. Better understanding of the effects of aerosols requires more information on aerosol chemistry. Before the determination of aerosol chemical composition by the various available analytical techniques, aerosol particles must be reliably sampled and prepared. Indeed, sampling is one of the most challenging steps in aerosol studies, since all available sampling techniques harbor drawbacks. In this study, novel methodologies were developed for sampling and determination of the chemical composition of atmospheric aerosols. In the particle-into-liquid sampler (PILS), aerosol particles grow in saturated water vapor with further impaction and dissolution in liquid water. Once in water, the aerosol sample can then be transported and analyzed by various off-line or on-line techniques. In this study, PILS was modified and the sampling procedure was optimized to obtain less altered aerosol samples with good time resolution. A combination of denuders with different coatings was tested to adsorb gas phase compounds before PILS. Mixtures of water with alcohols were introduced to increase the solubility of aerosols. Minimum sampling time required was determined by collecting samples off-line every hour and proceeding with liquid-liquid extraction (LLE) and analysis by gas chromatography-mass spectrometry (GC-MS). The laboriousness of LLE followed by GC-MS analysis next prompted an evaluation of solid-phase extraction (SPE) for the extraction of aldehydes and acids in aerosol samples. These two compound groups are thought to be key for aerosol growth. Octadecylsilica, hydrophilic-lipophilic balance (HLB), and mixed phase anion exchange (MAX) were tested as extraction materials. MAX proved to be efficient for acids, but no tested material offered sufficient adsorption for aldehydes. Thus, PILS samples were extracted only with MAX to guarantee good results for organic acids determined by liquid chromatography-mass spectrometry (HPLC-MS). On-line coupling of SPE with HPLC-MS is relatively easy, and here on-line coupling of PILS with HPLC-MS through the SPE trap produced some interesting data on relevant acids in atmospheric aerosol samples. A completely different approach to aerosol sampling, namely, differential mobility analyzer (DMA)-assisted filter sampling, was employed in this study to provide information about the size dependent chemical composition of aerosols and understanding of the processes driving aerosol growth from nano-size clusters to climatically relevant particles (>40 nm). The DMA was set to sample particles with diameters of 50, 40, and 30 nm and aerosols were collected on teflon or quartz fiber filters. To clarify the gas-phase contribution, zero gas-phase samples were collected by switching off the DMA every other 15 minutes. Gas-phase compounds were adsorbed equally well on both types of filter, and were found to contribute significantly to the total compound mass. Gas-phase adsorption is especially significant during the collection of nanometer-size aerosols and needs always to be taken into account. Other aims of this study were to determine the oxidation products of β-caryophyllene (the major sesquiterpene in boreal forest) in aerosol particles. Since reference compounds are needed for verification of the accuracy of analytical measurements, three oxidation products of β-caryophyllene were synthesized: β-caryophyllene aldehyde, β-nocaryophyllene aldehyde, and β-caryophyllinic acid. All three were identified for the first time in ambient aerosol samples, at relatively high concentrations, and their contribution to the aerosol mass (and probably growth) was concluded to be significant. Methodological and instrumental developments presented in this work enable fuller understanding of the processes behind biogenic aerosol formation and provide new tools for more precise determination of biosphere-atmosphere interactions.

Otimização de metodologia para determinação de hidrocarbonetos policíclicos aromáticos pela técnica de extração por líquido pressurizado e sua aplicação a diferentes solos brasileiros

Os hidrocarbonetos policíclicos aromáticos (HPA) representam hoje grande preocupação à comunidade científica devido a sua comprovada ação cancerígena e mutagênica, assim tornam-se necessárias metodologias mais eficientes para suas determinações. O presente trabalho desenvolveu a técnica de extração por líquido pressurizado com a etapa de clean-up simultânea a extração, com sílica e alumina como adsorventes dentro da cela do equipamento ASE-350. A metodologia desenvolvida foi comparada com a tradicional extração por Sohxlet através de material de referência certificado. A extração por Soxhlet, apesar de eficiente, mostrou-se dispendiosa pelo gasto enorme de tempo, solvente e adsorventes quando comparada a extração por líquido pressurizado. De maneira geral a extração por líquido pressurizado apresentou-se mais vantajosa que a tradicional extração por Soxhlet. A eficiência da metodologia desenvolvida também foi testada através de quatro diferentes tipos de solos brasileiros fortificados com solução padrão de HPA. Os solos utilizados foram dos seguintes locais: Nova Lima MG, Lavras MG, Casimiro de Abreu RJ e Luiz Eduardo Magalhães BA. Todos possuíam características granulométricas e químicas diferentes entre si. Dois solos foram classificados em latossolos vermelhos, um em vermelho-amarelo e um em planossolo. Houve diferença significativa na eficiência de recuperação de alguns HPA quando comparados os quatro tipos de solos, já para outros HPA não evidenciou-se influência da tipologia do solo

Determination of 266 pesticide residues in apple juice by matrix solid-phase dispersion and gas chromatography-mass selective detection

A macro matrix solid-phase dispersion (MSPD) method was developed to extract 266 pesticides from apple juice samples prior to gas chromatography-mass selective detection (GC-MSD) determination. A 10 g samples was mixed with 20 g diatomaceous earth. The mixture was transferred into a glass column. Pesticide residues were leached with a 160 mL hexane-dichloromethane (1:1) at 5 mL/min. Two hundred and sixty-six pesticides were divided into three groups and detected by GC-MSD under selective ion monitoring. The proposed method takes advantage of both liquid-liquid extraction and conventional MSPD methods. Application was illustrated by the analysis of 236 apple juice samples produced in Shaanxi province China mainland this year. (C) 2004 Elsevier B.V. All rights reserved.

Analysis of organchlorine compounds in water by solid phase microextraction and gas chromatography

In this work, both,solid phase microextraction (SPME) and solid phase extraction(SPE) were used to enrich organochlorine compounds in water samples and analyzed by gas chromatography with electron capture detector. The operating conditions of SPME have been studied and different kinds of solid phase were compared. Linear alkybenzene sulfonate(LAS) was added to the samples to investigate its effect on the analysis. The results indicated that polyacrylate was better than other commercial solid phases in extraction of moderated polar organic compounds and the sensitivity of SPME was higher than SPE. LAS affect much in liquid-liquid extraction and headspace SPME; but it has little effect on SPE and direct-SPME method. The applications showed that SPME was a fast and effective method in sample preparation.

Influence of isooctanol on the interfacial activity and mass transfer of ytterbium(III) using 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester as an acidic extractant

BACKGROUND: Introducing an adduct into an extractant system is an effective method of improving extraction performance. The effect of additives upon extraction is very important, especially in the case of interfacial behaviour. In most work published in the literature, there is little data on the interfacial behaviour of extractants and modifiers. As the mass transfer must pass through an interface, the influence of isooctanol on the interfacial activity and mass transfer of ytterbium(III) using 2-ethylhexylphosphonic acid mono-2-ethlhexyl ester has been investigated.RESULTS: With increasing amounts of isooctanol, the interfacial tension and surface excess (Gamma(max)) of the 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester(HEHEHP)-isooctanol system decreased, and the area of the absorbed HEHEHP molecule (Amin) increased. The interfacial activity of the HEHEHP-isooctanol system varied significantly depending on ionic strength and temperature and the mass transfer flux decreased with increasing isooctanol content.

Separation of yttrium from heavy lanthanide by CA-100 using the complexing agent

The selective extraction of yttrium front heavy lanthanide by liquid-liquid extraction using CA-100 in the presence of the complexing agent, such as EDTA, DTPA, and HEDTA was investigated. The extraction of heavy lanthanide in the present of the complexing agent was Suppressed when compared to that of Y because of the masking effect, but the selective extraction of Y was enhanced. All complexing agents formed 1: 1 complex with rare earth elements (RE), and only free rare earth ions could take part in the extraction. The condition for separation was obtained by exploring the effects of the complexing agent concentration, the extractant concentration, pH and the equilibration time on the extraction of the heavy rare earth elements.

Determination of Hg(II) in waters by on-line preconcentration using Cyanex 923 as a sorbent - Cold vapor atomic absorption spectrometry

Using a solid phase extraction mini-column home-made from a neutral extractant Cyanex 923, inorganic Hg could be on-line preconcentrated and simultaneously separated from methyl mercury. The preconcentrated Hg (11) was then eluted with 10% HNO3 and subsequently reduced by NaBH4 to form Hg vapor before determination by cold vapor atomic absorption spectrometry (CVAAS). Optimal conditions for and interferences on the Hg preconcentration and measurement were at 1% HCl, for a 25 mL sample uptake volume and a 10 mL min(-1) sample loading rate. The detection limit was 0.2 ng L-1 and much lower than that of conventional method (around 15.8 ng L-1). The relative standard deviation (RSD) is 1.8% for measurements of 40 ng L-1 of Hg and the linear working curve is from 20 to 2000 ng L-1 (with a correlation coefficient of 0.9996). The method was applied in determination of inorganic Hg in city lake and deep well water (from Changchun, Jilin, China), and recovery test results for both samples were satisfactory.

Selective separation of yttrium by CA-100 in the presence of a complexing agent

The selective separation of Y from yttrium solution containing small heavy rare earth (HRE) impurities (Ho, Er, Tm, Yb, Lu) by liquid-liquid extraction using CA-100 in the presence of a water-soluble complexing agent of ethylenediaminetetraacetic acid (EDTA) was experimentally studied at 298K. Experiments were carried Out in two feeds, Feed-I: [RE](f) = 4.94 x 10(-3) M, Y = 98.5%, HRE (Ho, Er, Tm, Yb, Lu) = 1.5%; Feed-II: [RE](f) = 4.94 x 10(-3) M, Y = 99.9%, HRE (Ho, Er, Tm, Yb, Lu) = 0.1%, as a function of equilibrium pH (pH(eq)), the concentration ratio of [EDTA]:[HRE impurities]. It was shown that the extraction of HRE in the presence of EDTA was suppressed when compared to that of Y because of the masking effect, while the selective extraction of Y was enhanced and the separation factors increased to maximum at appropriate condition for Feed-I: Y/Ho = 1.53, Y/Er = 3.09, Y/Tm = 5.61, Y/Yb = 12.04, Y/Lu = 27.51 at pH 4.37 and [EDTA]:[HRE impurities] = 4: 1, for Feed-II: Y/Ho = 1.32, Y/Er = 1.91, Y/Tm = 2.00, Y/Yb = 3.05, Y/Lu = 3.33 at pH 4.42 and [EDTA]: [HRE impurities] = 8:1. The separation and purification of Y by this method was discussed.

Separation of scandium, yttrium and lanthanum in high-performance centrifugal partition chromatography with S-octyl phenyloxy acetic acid

Separation of scandium(III), yttrium(III) and lanthanum(III) was performed by high-performance centrifugal partition chromatography (HPCPC) employing the stationary phase of S-octyl phenyloxy acetic acid (CA-12). The liquid-liquid extraction behavior of CA-12 for Sc(III), Y(III) and La(III), the acidity of aqueous phase, and the operation conditions of HPCPC were examined. The retention volume (V-R) increased with the order of Y(III), La(III) and Sc(III) accompanied with the elution of the mobile phase in different pH, which is lowered from 4.6 to 2.1.

Determination of sulpiride by capillary electrophoresis with end-column electrogenerated chemiluminescence detection

Background: Capillary electrophoresis (CE) with tris(2,2'-bipyridyl)ruthenium(II) [Ru(bpy)(3)(2+)]-electro-generated chemiluminescence (ECL) detection is a promising method for clinical analysis. In this study, a method combining CE with Ru(bpy)(3)(2+) ECL (CE-ECL) detection that can be applied to amine-containing clinical species was developed, and the performance of CE-ECL as a quantitative method for determination of sulpiride in human plasma or urine was evaluated. Methods: Sulpiride was separated by capillary zone electrophoresis in uncoated fused-silica capillaries [510 cm x 25 mum (i.d.)] filled with phosphate buffer (pH 8.0 and a driving voltage of +15 kV, with end-column Ru(bpy)(3)(2+) ECL detection. A platinum disc electrode was used as working electrode. Sulpiride in human plasma or urine samples (100 muL) was extracted by a double-step liquid-liquid extraction procedure, dried under nitrogen at 35 degreesC in a water bath, and reconstituted with 100 muL of filtered water. The extraction solvent was ethyl acetate-dichloromethane (5:1 by volume). Results: Under optimum conditions (pH 8.0 phosphate buffer, injection for 6 s at 10 kV, and +1.2 V as detection potential), separation of sulpiride was accomplished within 4 min. The calibration curve was linear over a concentration range of 0.05-25.0 mumol/L, and the limit of detection was 2.9 x 10(-8) mol/L for sulpiride. Intra- and interday CVs for ECL intensities were <6%. Extraction recoveries of sulpiride were 95.6-101% with CVs of 2.9-6.0%. The method was,clinically validated for patient plasma and urine samples. Conclusions: CE combined with Ru(bpy)(3)(2+) ECL is reproducible, precise, selective, and enables the analysis of sulpiride in human plasma and urine. It thus is of value for rapid and efficient analysis of amine-containing analytes of clinical interest.

Grignard Reaction - Synthesis of Substituted Benzoic Acids

A convenient preparation of substituted benzoic acids from Grignard additions to solid carbon dioxide. Students create a library of carboxylic acids by using differentially substituted, commercially available aryl bromides, which can be used as the starting materials for a multistep synthesis. This is a modification and improvement of a very popular undergraduate organic chemistry experiment.

Room-temperature ionic liquids as replacements for organic solvents in multiphase bioprocess operations

Organic solvents are widely used in a range of multiphase bioprocess operations including the liquid-liquid extraction of antibiotics and two-phase biotransformation reactions. There are, however, considerable problems associated with the safe handling of these solvents which relate to their toxic and flammable nature. In this work we have shown for the first time that room-temperature ionic liquids, such as 1-butyl-3-methylimidazolium hexafluorophosphate, [bmim][PF6], can be successfully used in place of conventional solvents for the liquid-liquid extraction of erythromycin-A and for the Rhodococcus R312 catalyzed biotransformation of 1,3-dicyanobenzene (1,3-DCB) in a liquid-liquid, two-phase system. Extraction of erythromycin with either butyl acetate or [bmim][PF6] showed that values of the equilibrium partition coefficient, K, up to 20-25 could be obtained for both extractants. The variation of K with the extraction pH was also similar in the pH range 5-9 though differed significantly at higher pH values. Biotransformation of 1,3-DCB in both water-toluene and water-[bmim][PF6] systems showed similar profiles for the conversion of 1,3-DCB initially to 3-cyanobenzamide and then 3-cyanobenzoic acid. The initial rate of 3-cyanobenzamide production in the water-[bmim][PF6] system was somewhat lower, however, due to the reduced rate of 1,3-DCB mass transfer from the more viscous [bmim] [PF,] phase. it was also shown that the specific activity of the biocatalyst in the water-[bmim][PF6] system was almost an order of magnitude greater than in the water-toluene system which suggests that the rate of 3-cyanobenzamide production was limited by substrate mass transfer rather than the activity of the biocatalyst. (C) 2000 John Wiley & Sons, Inc.

Development and validation of a method for the confirmation of halofuginone in chicken liver and eggs using electrospray tandem mass spectrometry

A method is described for the quantitative confirmation of halofuginone (HFG) residues in chicken liver and eggs. This method is based on LC coupled to positive ion electrospray MS-MS of the tissue extracts, prepared by trypsin digestion of the tissues followed by liquid-liquid extraction and final clean-up using Solid Phase Extraction (SPE). The [M+H](+) ion at m/z 416 is monitored along with four transitions at m/z 398, 138, 120 and 100. The method has been validated according to the draft EU criteria for the analysis of veterinary drug residues at 15, 30 and 45 mug kg (-1) in liver and 5, 15 and 50 mug kg (-1) in eggs. The new analytical limits, CCalpha and CCbeta were calculated for liver and were 35.4 and 43.6 mug kg (-1), respectively. (C) 2003 Elsevier Science B.V. All rights reserved.

DETECTION OF CLENBUTEROL RESIDUES IN BOVINE LIVER, MUSCLE, RETINA AND URINE USING GAS-CHROMATOGRAPHY MASS-SPECTROMETRY

A gas chromatographic/mass spectrometric method is described for the detection of clenbuterol residues in liver, muscle, urine and retina. Tissue samples are first digested using protease and any clenbuterol present is extracted using a simple liquid/liquid extraction procedure. The dried extracts are then derivatized using methylboronic acid and the derivatives are subjected to gas chromatography/mass spectrometry on a magnetic sector instrument. The detection limit of the assay is 0.05 ng g-1 clenbuterol in liver, muscle or urine using a 10 g sample size, and 4 ng g-1 in retina using a 0.5 g sample size. The assay is made very specific by using selected ion monitoring of three ions at a resolution of 3500 and by ion ratio measurements. The precision and reproducibility of the assay are enhanced by the use of a deuterated internal standard, with a typical coefficient of variation of 3%.

Development and validation of a method for the confirmation of nicarbazin in chicken liver and eggs using LC-electrospray MS-MS according to the revised EU criteria for veterinary drug residue analysis

A method is described for the quantitative confirmation of 4,4'-dinitrocarbanilide (DNC), the marker residue for nicarbazin in chicken liver and eggs. The method is based on LC coupled to negative ion electrospray MS-MS of tissue extracts prepared by liquid-liquid extraction. The [M-H](-) ion at m/z 301 is monitored along with two transition ions at m/z 137 and 107 for DNC and the [M-H](-) ion at m/z 309 for the internal standard, d(8)-DNC. The method has been validated according to the new EU criteria for the analysis of veterinary drug residues at 100, 200 and 300 mug kg(-1) in liver and at 10, 30 and 100 mug kg(-1) in eggs. Difficulties concerning the application of the new analytical limits, namely the decision limit (CC) and the detection capability (CC) to the determination of DNC in both liver and eggs are discussed.