Determination of alkylselenide compounds in air by gas chromatography—atomic absorption spectrometry

Dimethylselenide, dimethyldiselenide and diethylselenide are sampled from air by cryogenic trapping and determined by gas chromatography with electrothermal atomicabsorption spectrometric detection. Important considerations in the optimization of sensitivity and selectivity of this approach are discussed. Molecular absorption at the selenium atomic absorption wavelength is reduced by the addition of 10% hydrogen to the argon flow in the graphite oven. Detection limits down to 0.2 ng m^-3 allow the ready detection of the methyl compounds in rural air with a precision of about 10% at the nanogram level.     

Determination of soluble and insoluble nickel compounds in airborne particulate matter by graphite furnace atomic absorption spectrometry and inductively coupled plasma mass spectrometry

An extraction procedure for the determination of soluble and insoluble nickel and its compounds in ambient air dust was investigated employing a special device for the generation of test aerosols and using water-soluble NiCl2, partly water-soluble NiCO3 and water-insoluble NiO as model compounds. Additionally, results of the separation and determination of different nickel species down to some ng/m3 in ambient aerosols are discussed. The extraction was carried out with a solution containing 0.01 mol/L EDTA in order to determine partly water-soluble compounds such as NiCO3 and water-soluble, non-toxic nickel compounds in one step. Airborne dust was sampled on filters at locations close to two metallurgical plants in Northrhine-Westphalia (Germany), and first results on the nickel concentration (mean (median) values over a period of 4 months: 8.6+/-6.5 ng/m3 (6.7 ng/m3) and 27.7+/-36 ng/m3 (10.8 ng/m3), respectively) in the collected dust are presented. For EDTA-soluble nickel compounds the maximum and mean fractions of total nickel were found to be 77.1% and 18.6+/-12%, respectively.     

Determination of soluble and insoluble nickel compounds in airborne particulate matter by graphite furnace atomic absorption spectrometry and inductively coupled plasma mass spectrometry

An extraction procedure for the determination of soluble and insoluble nickel and its compounds in ambient air dust was investigated employing a special device for the generation of test aerosols and using water-soluble NiCl₂, partly water-soluble NiCO₃ and water-insoluble NiO as model compounds. Additionally, results of the separation and determination of different nickel species down to some ng/m³ in ambient aerosols are discussed. The extraction was carried out with a solution containing 0.01 mol/L EDTA in order to determine partly water-soluble compounds such as NiCO₃ and water-soluble, non-toxic nickel compounds in one step. Airborne dust was sampled on filters at locations close to two metallurgical plants in Northrhine-Westphalia (Germany), and first results on the nickel concentration (mean (median) values over a period of 4 months: 8.6 ± 6.5 ng/m³ (6.7 ng/m³) and 27.7 ± 36 ng/m³ (10.8 ng/m³), respectively) in the collected dust are presented. For EDTA-soluble nickel compounds the maximum and mean fractions of total nickel were found to be 77.1% and 18.6 ± 12%, respectively.     

Determination of alkyl lead compounds in air by gas chromatography and atomic absorption spectrometry

Alkyl lead compounds are condensed from a 70-l street air sample in a series of four traps at-72°C, separated by gas chromatography and determined by atomic absorption spectrometry with electrothermal atomization. Total atmospheric alkyl lead averaged 14 ng Pb m^-3. Vehicular exhaust fumes are an insignificant contributor to this total. Tetraethyllead, the only alkyl lead compound used in southern Ontario gasoline, is unstable in air. Besides decomposing, it reacts to give other alkyl lead compounds, which can be determined by the technique described. Evaporation of gasoline is almost exclusively the source of alkyl lead compounds in street air.     

Determination of bismuth in atmospheric particulate matter by hydride generation and atomic absorption spectrometry

The particulates are collected on Whatman 41 cellulose filters and decomposed with sulfuric acid and hydrogen peroxide; bismuth is then measured by hydride generation/atomic absorption spectrometry. The detection limis is 0.08 ng m^?3 if 500 m³ of air is filtered through an 11-cm filter. Generally, the precision is better than 10%. The concentrations found in Ghent, Belgium varied between 0.1 and 0.8 ng m^?3. Bismuth was also determined in NBS Orchard leaves (SRM 1571); a value of 98.5 ± 15 ng g^?1 was found.     

Determination of tin in atmospheric particulate matter by hydride generation and atomic absorption spectrometry

A procedure is described for the determination of tin in atmospheric particulate matter collected on Whatman 41 cellulose filters. The samples are decomposed with sulfuric acid and nitric acid, followed by hydrofluoric acid to dissolve residual silicates. The analytical parameters for the hydride generation and the subsequent atomic absorption spectrometric measurements are optimized. Severe memory effects encountered with an automatic generator system are avoided when a manual apparatus is used. The precision of the entire method is within 10%. The detection limit is 0.20 ng m^?3 tin if 500 m³ of air is filtered. The concentrations found in residential and industrial areas varied between 1.8 and 47.5 ng m^?3.     

Speciation of organotin compounds in water by gas chromatography/atomic absorption spectrometry

Summary A reproducible and interference-free method is presented for simultaneous determination of individual tri-, di- and monoalkyltin species present in aqueous systems. The ionic methyltin and butyltin compounds are extracted from water into pentane as diethyldithiocarbamate complexes at pH 5. The organic phase is then evaporated to dryness under reduced pressure, after which derivatization withn-pentyl (Pe) Grignard reagent is carried out in a microvolume ofn-octane to form pentylated alkyltin compounds R _n SnPe_(4-n) (R = Methyl, Me or Butyl, Bu). The quantitation is subsequently performed by gas chromatography with quartz furnace atomic absorption spectrometric detection (GC-AAS). Absolute detection limits range between 0.16 ng and 0.40 ng Sn for the various organotin species, allowing speciation in natural water down to the 4-10 ng 1^–1 level.

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Speziation von organischen Zinnverbindungen in Wasser durch GC/AAS

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Dedicated to Prof. Dr. G. Tölg on the occasion of his 60th birthday     

Determination of basic azaarenes and polynuclear aromatic hydrocarbons in airborne particulate matter by gas chromatography

Polynuclear aromatic hydrocarbons (PAH) and their nitrogen analogs, basic azaarenes, are extracted from samples of airborne particulate matter by toluene with ultrasonic treatment. The basic azaarenes are extracted from the toluene phase with phosphoric acid, re-extracted from the phosphoric acid phase (adjusted to pH 14 with potassium hydroxide) with dichloromethane, and determined by capillary gas chromatography (g.c.) with a nitrogen-sensitive detector. The PAH in the toluene phase are isolated by means of semipreparative high-performance liquid chromatography and liquid-liquid extraction and determined by g.c. with a flame-ionization detector. Eleven basic azaarenes were identified; their concentration were one to two orders of magnitude lower than those of PAH. Results from the determination of the concentrations of basic azaarenes and PAH in the atmosphere in a busy street and in a suburban residential area of Copenhagen are presented and discussed.     

Determination of methylmercury in organic matrices with gas chromatography/ atomic absorption spectrometry

Determinations of methylmercury in biological tissues by gas chromatography with electron-capture detection are often disturbed by electron-capturing compounds simultaneously eluting with the organo-mercury compound.Identification and quantification of methylmercury is improved by interfacing the gas chromatograph to the gas cell of a flameless atomic absorption spectrometer. The construction of the transfer line used is described.     

Determination of polycyclic aromatic sulfur heterocycles in diesel particulate matter and diesel fuel by gas chromatography with atomic emission detection

The sulfur content of diesel fuel is of environmental concern because sulfur can facilitate the formation of diesel particulate matter (DPM) and sulfur dioxide (SO2) in the exhaust can poison catalytic converters. The US Environmental Protection Agency (EPA) has established more stringent regulations to reduce the sulfur content of diesel fuels in the near future. In this study, various types of organosulfur compounds in DPM extracts and the corresponding fuels have been determined by gas chromatography with atomic emission detection. The diesel fuels used have sulfur contents of 2284 and 433 ppm, respectively, and are labeled as high-sulfur and low-sulfur diesel fuels. The compounds identified are mainly polycyclic aromatic sulfur heterocycles (PASHs). In the fuels tested, trimethylbenzothiophenes (TMBTs), dibenzothiophenes (DBTs), and 4-methyldibenzothiophene (4-MDBT) were the most abundant sulfur compounds, while larger PASH compounds were more abundant in DPM extracts. The high-sulfur diesel fuel contained a larger proportion of PASHs with one or two rings (lighter PASHs). In DPM, the concentrations of total organic sulfur and individual PASHs are higher for the high-sulfur diesel fuel, and the relative percentage of one or two-ring PASHs is higher as well. The influence of engine load on the DPM composition was also examined. With increasing load, the PASH concentration in DPM decreased for lighter PASHs, increased for heavier PASHs, and had a bell-shaped distribution for PASHs in between.     

Determination of water-soluble and insoluble compounds in size classified airborne particulate matter

The elemental composition of water soluble and acid soluble size-fractionated airborne particulate matter (APM) was investigated. PM2.5 and PM2.5-10 samples were collected every three days from October 2006 to October 2007 in Buenos Aires, Argentina. The collection was performed on Nucleopore® filters using a GENT sampler. Samples containing fine and coarse particles were subjected to an aqueous leaching to obtain information on the dissolution behaviors of ions, metal and metalloids. Key elements namely, Al, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Pb, Se, Ti and Zn were determined in each fraction by inductively coupled plasma optical emission spectrometry (ICP OES). In the aqueous fractions, Cl⁻, SO₄²⁻, Na⁺ and NH₄⁺ were determined by high performance liquid chromatography (HPLC). A (6:2:5) mixture of nitric, hydrochloric and perchloric acids was used for leaching metals from the residual filters. For validation of the extraction procedure, the ICP OES measurements the Standard Reference Material NIST 1648 (Urban particulate matter) was subjected to the same analytical procedure that the samples loaded with APM. Total analyte concentration varied from 333.2 μg g^− 1 (equivalent to 3.7 ng m^− 3) for Ti to 692 mg g^− 1 (equivalent to 2.47 μg m^− 3) for Ca.     

Environmental analysis using gas chromatography — atomic absorption spectrometry

The combination of gas chromatography and atomic absorption spectrophotometry offers high sensitivity and specificity in the analysis of volatile organometallic species, and has been applied to alkyl derivatives of As, Pb, Se and Sn in environmental samples of air, water, sediment and biological tissues. Techniques of sample introduction and detector design are discussed with regard to the sensitivity attainable.     

Organic mercury speciation in fish by capillary gas chromatography interfaced with atomic absorption spectrometry

Summary A rapid method for the speciation of mercury in fish has been described. Organomercurials in benzene extract were separated by glass capillary gas chromatography and detected by atomic absorption spectrometry. Spiked alkylmercury in fish yielded 95% recovery with one single extraction with benzene. The absolute detection limit was about 1.0×10^–10 g mercury. The method can be applied to the determination of 0.04 ppm of mercury in a 0.5 g sample.

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Speziation von organischem Quecksilber in Fisch mit Hilfe der Capillar-Gas-Chromatographie in Verbindung mit AAS

     

Speciation of organotin compounds in water and sediments by gas chromatography/atomic absorption spectrometry (GC-AAS)

A commercially available atomic absorption detector coupled to a wide-bore column-containing gas Chromatograph (GC-AAS) was utilized to detect organotin compounds. Speciation was performed by pentane extraction of the organotin species as the corresponding sodium diethyldithiocarbamate complexes, enrichment by rotary evaporation, derivatization with Grignard reagent and finally the extracted water and sediment samples were separated and detected on the GC-AAS system.     

Determination of fatty acids in airborne particulate matter, dust and soot by mass chromatography

Extracts from mixture airborne particulate matter, dust taken from an air filter and some soots were fractioned by alumina column chromatography. The solution eluted with ethanol-actic acid (9:1) contained fatty acids and other polar substances. After heating the solution with a small amount of sulphuric acid, the esters of the fatty acids formed were extracted and separated from other polar substances by column chromatography. Identification and quantification were performed by mass chromatography at the molecular ion masses of the esters. Fatty acids from octanoic to tetratriacontanoic acid were determined in these samples and dotriacontanoic, tritricontanoic and tetratriacontanoic acids were found for the first time.     

Determination of mercury in airborne particulate matter collected on glass fiber filters using high-resolution continuum source graphite furnace atomic absorption spectrometry and direct solid sampling

A study has been undertaken to assess the capability of high-resolution continuum source graphite furnace atomic absorption spectrometry for the determination of mercury in airborne particulate matter (APM) collected on glass fiber filters using direct solid sampling. The main Hg absorption line at 253.652 nm was used for all determinations. The certified reference material NIST SRM 1648 (Urban Particulate Matter) was used to check the accuracy of the method, and good agreement was obtained between published and determined values. The characteristic mass was 22 pg Hg. The limit of detection (3σ), based on ten atomizations of an unexposed filter, was 40 ng g^− 1, corresponding to 0.12 ng m^− 3 in the air for a typical air volume of 1440 m³ collected within 24 h. The limit of quantification was 150 ng g⁻¹, equivalent to 0.41 ng m⁻³ in the air. The repeatability of measurements was better than 17% RSD (n = 5). Mercury concentrations found in filter samples loaded with APM collected in Buenos Aires, Argentina, were between < 40 ng g⁻¹ and 381 ± 24 ng g⁻¹. These values correspond to a mercury concentration in the air between < 0.12 ng m⁻³ and 1.47 ± 0.09 ng m⁻³. The proposed procedure was found to be simple, fast and reliable, and suitable as a screening procedure for the determination of mercury in APM samples.     

Determination of 40 currently used pesticides in airborne particulate matter (PM 10) by microwave-assisted extraction and gas chromatography coupled to triple quadrupole mass spectrometry

A confirmatory and sensitive procedure has been developed for the determination of 40 currently used pesticides (CUPs) in airborne particulate matter (PM 10) at trace level. The proposed method includes extraction of PM 10-bound pesticides by microwave-assisted extraction (MAE) followed by a gel permeation chromatography (GPC) clean-up and determination by GC-MS/MS. The injection mode and the main parameters in MS/MS were optimized. The matrix effect was also evaluated. Recoveries ranged from 70 to 120% except for pyrimethanil and pirimicarb. The limit of quantification (LOQ) ranged from 1.32 to 39.47 pg m(-3), when air volumes of 760 m(3) were collected. The method was applied to 38 samples collected from a rural station belonging to the atmospheric monitoring network of the Regional Valencia Government (Spain) during April-June 2010. Eighteen out of 40 pesticides investigated were found in at least one sample (bifenthrin, chlorothalonil, chlorpyriphos-e, chlorpyriphos-m, clorpropham, diazinon, dicofol, diphenylamine, fipronil, fludioxonil, folpet, malathion, metalaxyl, penconazole, quinoxyfen, triadimefon, trifluralin, and vinclozoline), with concentrations ranging from 1.32 to 625.80 pg m(-3).     

Speciation of butyltin compounds by ion chromatography coupled to electrothermal atomic absorption spectrometry

A new method for the determination of butyltin species by ion-exchange chromatography linked with graphite-furnace electrothermal atomic absorption spectrometry (ETAAS) is presented. The separation is achieved on a strong cation-exchange column with a 0.18 mol dm^?3 solution of diammonium citrate at pH 6.5 with a step change to pH 4.0 in 60:40 methanol/water solvent. ETAAS detection is performed on-line using an oxidizing matrix modifier. Mono-, di- and tri-butyltin may be determined in a single experiment with detection limits of (respectively) 0.5, 1.1 and 0.8 ng (Sn). Applications to actual samples are reported.     

Determination of mercury species in gas condensates by on-line coupled high-performance liquid chromatography and cold-vapor atomic absorption spectrometry

A method for the speciation of mercury in gas condensates is reported. Mercury(II) chloride (HgCl₂), methylmercury chloride (MeHgCl), phenylmercury acetate (PhHgAc) and diphenylmercury (Ph₂Hg) are separated by reversed-phase high-performance liquid chromatography (HPLC) using gradient elution. Prior to the determination, the organic ligands and the matrix were destroyed by oxidation with K₂Cr₂O₇. Mercury is detected with cold-vapor atomic absorption spectrometry (CVAA), where the mercury compounds are reduced to metallic mercury by a treatment with NaBH₄. In a continuous-flow system the concentrations of the reagents used are optimized using a modified simplex algorithm. Detection limits for mercury are at the 10 ng ml^?1 level. Analysis of multi-compound mixtures indicates that chemical reactions between HgCl₂ and Ph₂Hg and between MeHgCl and Ph₂Hg take place. The method developed was applied to the speciation of mercury in gas condensates and did not require use of any solvent extraction or chemical derivatization steps. In the gas condensates, mercury(II) compounds were found to be present at the 100 ng ml^?1 level.     

Determination of Sb, Ni and V in slurry from airborne particulate material collected on filter by graphite furnace atomic absorption spectrometry

A microdigestion procedure performed directly in the autosampler cup is proposed. Small quartz filter pieces loaded with the particulate material are transferred to the cup. The sample is digested by a mixture of nitric, sulfuric and hydrofluoric acid (1:1:1) under sonication. After the addition of a boric acid solution the elements are determined by graphite furnace atomic absorption spectrometry using the autosampler to deliver the slurry into the furnace. A mixture of palladium and magnesium nitrates was used as a modifier for Sb. Spiking studies showed recoveries close to 100% using aqueous analytical curves for Ni and Sb. For V, an analytical curve in the blank slurry, obtained by submitting an unloaded filter to the same procedure, was used. The method was applied to two standard reference materials, Coal Fly Ash (NIST 1633a) and Urban Particulate (NIST 1648) and the concentrations showed good agreement with the certified or recommended values using aqueous analytical solutions.