Determination of ultra-trace levels of gold in size-segregated atmospheric particulate samples by laser induced fluorescence: towards an aerosol tracer

A method is described for measuring the gold content of integral and size-segregated samples of atmospheric particulate matter. After acid digestion and a liquid/ liquid extraction, the sample are analysed by Two-Colour Laser Induced Fluorescence in a graphite furnace. An absolute instrumental detection limit of 1 fg is achieved. Assuming a sampled volume of 1 m(3), this corresponds to an atmospheric concentration of 50 fg m(-3). Due to blank limited noise, the above limits increase to 20 fg and 1 pg m(-3), respectively. Results of the analysis of filter samples as well as of size-segregated impactor samples are presented.     

A multi-residue method for characterization and determination of atmospheric pesticides measured at two French urban and rural sampling sites

The extensive use of pesticides to protect agricultural crops can result in the transfer of these compounds into the atmosphere and their diffusion towards urban areas. Precise evaluation of the geographic impact of this type of pollution is important environmentally. In this paper, analytical methods for the sampling, characterization, and determination of agricultural pesticides in air were developed; the methods were then applied in the Paris and Champagne regions. Sixteen pesticides belonging to nine chemical families were monitored. Sampling was carried out in urban (Paris) and rural (Aube district) sites, utilizing either a high-volume pump (12.5 m³ h^–1) (urban site) or a low-volume pump (2.3 m³ h^–1) for the rural site. Quartz filters and polyurethane foams (PUF) were used for sampling in all cases. After extracting the samples and concentrating the recovered solutions, high-performance liquid chromatography (HPLC) analysis with UV detection was performed. Identification of the pesticides was confirmed by applying to the HPLC measurements a novel UV-detection procedure based on the normalized absorbance variation with wavelength (Noravawa procedure). The presence of metsulfuron methyl, isoproturon, linuron, deltamethrin (and/or malathion), and chlorophenoxy acids (2,4-D and MCPP) was found at the urban sampling site at levels ranging from about 1 to 1130 ng m^–3 of air, depending on the compound and sampling period. On the rural sampling site residues of isoproturon, deltamethrin (and/or malathion), MCPP, and 2,4-D were generally detected at higher levels (19–5130 ng m^–3) than on the urban site, as expected. The effects of the weather conditions and agricultural activity on the atmospheric concentrations of pesticides are discussed, as are long-range atmospheric transfer processes for these pesticides.     

Analysis of anthropogenic and biogenic lipids in the aerosol of a coastal area in East Mediterranean Sea

Summary The concentrations of lipids were determined in atmospheric particle samples, collected seasonally, in an urban coastal area of the Island of Crete. Lipid compound classes, such as n-alkanes, hopanes and steranes, PAH, fatty alcohols, fatty acids and fatty acids selts, were determined by GC-FID and GC-MS analysis. The concentrations ranged between 56–215 ng/m³ for n-alkanes, 10–52 ng/m³ for PAH, 2–31 ng/m³ for fatty alcohols, 13–279 ng/m³ for fatty acids and 24–220 ng/m³ for fatty acid salts. -Oxocarboxylic acids were also determined as salts, indicating the atmospheric oxidation of unsaturated fatty acids.     

Supported liquid membrane extraction of W(VI) ions using tri-n-octylamine as carrier

Study of the extraction of W(VI) ions using supported liquid membrane has been carried out. The carrier used for this metal ion transport, is tri-n-octylamine (TOA) dissolved in xylene. The liquid was supported in microporous polypropylene film. The parameters studied are effect of carrier concentration in the membrane, acid concentrations in the feed solution, concentration of stripping agent on transport of W(VI) ions and of temperature on the transport properties of these supported liquid membranes. The optimum conditions of transport for these metal ions determined are, TOA concentration, 0.66 mol·dm^–3 (TOA); HF concentration in the feed solution, 0.01 mol·dm^–3 and concentration of NaOH used as stripping agent 2.5 mol·dm^–3. The maximum flux and permeability determined under optimum conditions are 3.06·10^–5 mol·m^–2·s^–1 and 8.44·10^–11 mol· ·m²·s^–1 at 25±2°C and 4.21·10^–5 mol·m^–2·s^–1 and 11.55·10^–11 mol·m²·s^–1 at 65°C, respectively. The diffusion coefficients for the metal ion carrier complex in the membrane have also been determined. Under the optimum conditions the value for the metal ion carrier complex is 0.14·10^–11 mol·m²·s^–1. Mechanism of transport and the complex formed in the presence of HF have also been discussed. The transport process involves two carrier amine molecules and two protons.     

Comparison of INAA and RNAA Methods with Thermal-Ionization Mass Spectrometry for Iridium Determinations in Atmospheric Tracer Studies

The sensitivity and precision of instrumental neutron activation analysis (NAA), radiochemical neutron activation analysis (RNAA), and thermal ionization mass spectrometry (TIMS) are compared for the determination of Ir in ambient size-fractionated aerosol particulate samples. The results of the TIMS analyses indicated high analytical precision (0.2% at >50 pg Ir), but the sensitivity of detection was limited by blank values (300–500 fg). The sensitivities for INAA and RNAA were comparable, i.e., 60 to 90 fg in size-segregated particulate samples.     

Separation of 99mTc from 99Mo by Using TOPO — Kerosene Supported Liquid Membrane

Transport of ^99mTcO₄ ^– ions across TOPO-kerosene based supported liquid membrane was investigated at different concentrations of phosphoric acid as a feed solution and different concentrations of TOPO in the membrane, where 0.9% NaCl aqueous solution was used as a stripping solution. The flux of TcO₄ ^– ions across this liquid membrane varied with the concentration of both H₃PO₄ and TOPO. The best permeability coefficient was obtained at concentrations, [H₃PO₄] = 3 mole·l^–1 and [TOPO] = 0.5 mole·l^–1 (P = 2.08·10^–9 m²·s^–1). The results were utilized for the separation of ^99mTc from ⁹⁹Mo, where a selective and effective separation was obtained since no ⁹⁹Mo transport across this liquid membrane was noticed while a high rate of ^99mTc transport took place.     

Extraction procedures for chemical speciation of arsenic in atmospheric total suspended particles

An arsenic chemical speciation study was performed in 2000, using air filters on which total suspended particles (TSP) were collected, from the city of Huelva, a medium size city with huge industrial influence in SW Spain. Different procedures for extraction of the arsenic species were performed using water, NH₂OH.HCl, and H₃PO₄ solutions, with either microwave or ultrasonic radiation. The best optimised extraction methods were use of 100 mmol L^–1 NH₂OH.HCl and 10 mmol L^–1 H₃PO₄ and microwave radiation for 4 min. High-performance liquid chromatography coupled with hydride generation and atomic fluorescence spectrometry (HPLC–HG–AFS) was employed for determination of the arsenic species. The results from 12 TSP air filters collected on a monthly basis showed extraction was quantitative (94% with NH₂OH.HCl and 86% H₃PO₄). Only inorganic arsenic species (arsenite and arsenate) were detected. The mean arsenite concentration was 1.2±0.3 ng m^–3 (minimum 0.3 ng m^–3, maximum 1.8 ng m^–3). The mean arsenate concentration was 10.4±1.8 ng m^–3, with greater monthly variations than arsenite (minimum 2.1 ng m^–3, maximum 30.6 ng m^–3). The high level of arsenic species in the TSP samples can be related to a copper smelter located in the region.     

Extraction of Pd(II) ions using tri-n-octylamine xylene base supported liquid membranes

Membranes, based on tri-n-octylamine (TOA) xylene liquid, supported in hydrophobic microporous films have been used to study the transport of Pd(II) ions, after extraction into the membrane. Various parameters, such as the effect of hydrochloric acid concentration in the feed solution, TOA concentration in the membrane phase, effect of stripping agent like nitric acid concentration, and temperature on the flux of Pd(II) ions across the liquid membranes have been investigated. The optimum conditions of transport for these metal ions determined are, TOA concentration, 1.25 mol·dm^–3, HCl concentration in the feed solution, 5 mol·dm^–3, and concentration of nitric acid used as a stripping, agent 5 mol·dm^–3. The maximum values of the flux and permeability determined under the optimum condition are 23·10^–6 mol·m^–2·s^–1 and 2.40·10³ m²·s^–1 at 25°C. The results obtained have been used to elucidate the mechanism of palladium transport.     

Extraction and stripping study of strontium ions across D2EHPA-TBP-kerosene oil based supported liquid membranes

A Sr ion transport study across D2EHPA-TBP kerosene oil based liquid membranes supported on microporous polypropylene film has been performed. The parameters studied were the effect of di(2-ethylhexyl)phosphoric acid (D2EHPA) and TBP concentration variation in the membrane liquid, HNO₃ concentration variation in the stripping phase and citric acid concentration variation in the feed solution. The optimum conditions of transport are 0.3 mol/dm³ D2EHPA, 0.1 mol/dm³ TBP, 0.01 mol/dm³ citric acid in feed and 2 mol/dm³ HNO₃ in the stripping phase. The mechanism of transport observed is counter-ion coupled transport. The coupling ions are protons. The maximum flux for Sr ion transport observed is 5.33·10^–5 mol·m^–2·s^–1 and maximum permeability under optimum conditions observed is 8.08·10^–11 m^–2·s^–1.     

Radon measurements in groundwater

A device was developed for the collection, containment, and bubbling of radon from groundwater samples to facilitate concentration measurements in the field without the need for fragile glassware. Wellwater supplies were collected in high-potential areas of New York State in a comparison of the device with traditional methods (liquid scintillation and laboratory-based Lucas-cell counters). Waterborne radon levels to 4100 Bq L^–1 reveal the potential contribution to indoor air from everyday water use in a home, as levels of 1500 Bq L^–1 contribute about 150 Bq m^–3 (the EPA-recommended limit) to indoor-air radon levels. With a Geographic Information System (GIS), spatial coordinates from each site are used to correlate concentrations with bedrock geology.     

Nitric acid transport across TBP—Kerosene oil supported liquid membranes

HNO₃ transport across tri-n-butyl phosphate kerosene oil supported liquid membrane with or without uranyl ion transport has been studied. Parameters studied are the effect of TBP in the membrane, nitric acid in the feed solution and nitrate ion concentration in the feed solution. The flux of protons for 1 to 10 mol·dm^–3 HNO₃ solution is in the range of (0–25)·10^–4 mol·m^–2·s^–1 and for the TBP concentration range of 0.359 to 3.59 mol·dm^–3, the flux determined is (8.9 to 22)·10^–4 mol·m^–2·s^–1. From the experimental data and using theoretical equations the complex under transport through the membrane appears to be 2TBP·HNO₃ both in the presence and absence of uranyl ions. The diffusion coefficient for H⁺ ions through the membrane as a function of TBP concentration varies from (53 to 6)·10^–12 m²·s^–1, based on experimental flux and permeability data. The values of this coefficient supposing 2TBP·HNO₃ as diffusing species, based on viscosity data and theoretical estimation varies from (82.50 to 3.30)·10^–12 m²·s^–1. The value of distribution coefficient varies in the reverse direction from 0.06 to 1.46 at the same TBP concentration.     

Simultaneous determination of lead-210, gross beta and gross alpha activities of air filters by pulse shape discrimination liquid scintillation counting

A chemical procedure for transferring deposited solid matter from a cellulose filter into the liquid scintillation cocktail has been described. The influence of chemical and color quenching on alpha and beta detection efficiency, as well as on misclassification of beta and alpha pulses was corrected by an external standard method. Under the chosen pulse shape discrimination level (PSD), the alpha and beta detection efficiencies were above 85% and spillovers of alpha and beta pulses were below 10% and 2% respectively. Determination limits for samples containing up to 200 mg of mineral matter were 0.015 mBq m^–3 for alpha, 0.055 mBq.m^–3 for²¹⁰Pb and 0.055 mBq.m^–3 for beta activity (counting time 12000 s and volume of filtered air 1000 m³). The method has been applied for routine monitoring of²¹⁰Pb as well as for gross alpha and beta activities of longer-living radionuclides (T_1/2.>11 hrs) in suspended air matter.     

Nitrate ion transport across TBP-kerosene oil supported liquid membranes coupled with uranyl ions

The role of nitrate ions in uranyl ions transport across TBP-kerosene oil supported liquid membranes (SLM) at varied concentrations of HNO₃ and NaNO₃ has been studied. It has been found that nitrate ions move faster compared to uranyl ions at the uranium feed solution concentrations studied. The nitrate to uranyl ions flux ratio vary from 355 to 2636 under different chemical conditions. At low uranium concentration the nitrate ions transport as HNO₃ · TBP, in addition to as UO₂(NO₃)₂ · 2TBP type complex species. The flux of nitrate ions is of the order of 12.10 · 10^–3 mol · m^–2 · s^–1 compared to that of uranium ions (4.56 · 10^–6 mol · m^–2 · s^–1). The permeability coefficient of the membrane for nitrate ions varies with chemical composition of the feed solution and is in the order of 2.5 · 10^–10 m^–2 · s^–1. The data is useful to estimate the nitrate ions required to move a given amount of uranyl ions across such an SLM and in simple solvent extraction.     

Determination of atmospheric iodine species using a system of specifically prepared filters and IDMS

Summary A system was developed which allowed the determination of four different atmospheric iodine species by preparing glass microfibre filters, which were arranged in consecutive order, in a specific way. Particulate iodine was collected by a particle filter, HI and I₂ by a NaOH impregnated filter, HOI was adsorbed on a TBAH impregnated filter and organoiodine was adsorbed on a filter loaded with activated charcoal. These behaviours were checked by extensive model experiments. Two or more filters of the same type were used in series to show the degree of collection of one iodine species. Two European samples, one of continental and one of marine origin, and two Antarctic samples were analysed by this filter system using isotope dilution mass spectrometry (IDMS) for quantification. The distribution pattern for the different iodine species is similar for the two European samples. Organoiodine is found to be the most abundant species whereas in Antarctica the HI/I₂ fraction is up to nearly 50% of the total iodine. The particulate iodine fraction is higher in Europe than in Antarctica, which is due to the low particle concentration in the remote area of Antarctica. The higher HI/I₂ and HOI fractions found at the North Sea compared with the continental sample indicate that the ocean is a primary source of these species. Concentrations in the range of (0.3–3.1) ng I/m³ were analysed for particulate iodine, (0.4–1.3) ng I/m³ for HI/I₂, (0.2–1.8) ng I/m³ for HOI and (0.4–7.6) ng I/m³ for organoiodine. The detection limits varied with the variances of the blank values of the different filters and lay between 0.02 ng I/m³ and 0.24 ng I/m³ using sample volumes of 70 m³ air.     

Validation of a simplified field-adapted procedure for routine determinations of methyl mercury at trace levels in natural water samples using species-specific isotope dilution mass spectrometry

A field-adapted procedure based on species-specific isotope dilution (SSID) methodology for trace-level determinations of methyl mercury (CH₃Hg⁺) in mire, fresh and sea water samples was developed, validated and applied in a field study. In the field study, mire water samples were filtered, standardised volumetrically with isotopically enriched CH₃²⁰⁰Hg⁺, and frozen on dry ice. The samples were derivatised in the laboratory without further pre-treatment using sodium tetraethyl borate (NaB(C₂H₅)₄) and the ethylated methyl mercury was purge-trapped on Tenax columns. The analyte was thermo-desorbed onto a GC-ICP-MS system for analysis. Investigations preceding field application of the method showed that when using SSID, for all tested matrices, identical results were obtained between samples that were freeze-preserved or analysed unpreserved. For DOC-rich samples (mire water) additional experiments showed no difference in CH₃Hg⁺ concentration between samples that were derivatised without pre-treatment or after liquid extraction. Extractions of samples for matrix–analyte separation prior to derivatisation are therefore not necessary. No formation of CH₃Hg⁺ was observed during sample storage and treatment when spiking samples with ¹⁹⁸Hg²⁺. Total uncertainty budgets for the field application of the method showed that for analyte concentrations higher than 1.5 pg g^–1 (as Hg) the relative expanded uncertainty (REU) was approximately 5% and dominated by the uncertainty in the isotope standard concentration. Below 0.5 pg g^–1 (as Hg), the REU was >10% and dominated by variations in the field blank. The uncertainty of the method is sufficiently low to accurately determine CH₃Hg⁺ concentrations at trace levels. The detection limit was determined to be 4 fg g^–1 (as Hg) based on replicate analyses of laboratory blanks. The described procedure is reliable, considerably faster and simplified compared to non-SSID methods and thereby very suitable for routine applications of CH₃Hg⁺ speciation analysis in a wide range of water samples.     

Determination of aliphatic amines in air by membrane enrichment directly coupled to a gas chromatograph

Summary A method is described for the determination of shortchain aliphatic amines in ambient air based on impinger sampling in dilute H₂SO₄, selective enrichment across a PTFE gas membrane and quantification by gas chromatography. The enrichment step is carried out in a flow system directly connected to the chromatograph. The separation is performed on a packed column with nitrogen selective detection. The enrichment per sample volume was in the range 7.3 to 8.2 mL^–1 for C₁–C₆ amines. Detection limits were ca 3–10 nM with enrichment of a 2.9 mL liquid sample. After impinger sampling of 5 m³ air in 10 mL absorption solution, this corresponds, to 0.4–0.8 ng/m³ (ca 0.2–0.5 ppt by volume) in air.     

An improved apparatus for the determination of krypton-85 and xenon-133 in an emergency situation

A simple and portable apparatus was developed for measurements of⁸⁵Kr and¹³³Xe that would be released into the atmosphere in an emergency situation of nuclear facilities. The method is based on cryogenic adsorption of these gases on charcoal followed by chromatographic separation from other gases. The⁸⁵Kr and¹³³Xe recovered from atmospheric air are determined separately by liquid scintillation counting. It takes about 1 hour for the stepwise determination of⁸⁵Kr and¹³³Xe. The atmospheric concentration of 3·10^–3 Ci per m³ air (1.1·10² Bq/m³ air) is measurable for both nuclides with 20% counting error.     

Transport of titanium(IV) ions across di-2-ethylhexylphosphoric acid-CCl4 supported liquid membranes

Transport study for Ti(IV) ions using di-2-ethylhexylphosphoric acid (D2EHPA) (carrier)-CCl₄ (diluent) liquid supported membrane in microporous polypropylene hydrophobic film has been performed. The parameters studied are effects of carrier, H₂SO₄, stripping agent (NH₄F) concentrations and temperature variation on flux and permeability coefficients of the metal ion. The optimum concentrations of transport found are 2.04 mol·dm^–3 D2EHPA, 1.0 mol·dm^–3 H₂SO₄ in the feed and 1 mol·dm^–3 NH₄F as stripping agent. The maximum flux and permeability coefficient determined are 1.32·10^–5 mol·m^–2·s^–1 and 8.02·10^–12 mol·m^–2·s^–1, respectively. The transport of this metal ion is increased with increase in temperature. The mechanism of transport appears to be based on coupled counter ion transport phenomenon.     

Determination of selected polycyclic aromatic hydrocarbons and oxygenated polycyclic aromatic hydrocarbons in aerosol samples by high-performance liquid chromatography and liquid chromatography–tandem mass spectrometry

Fine and ultrafine particles are probably responsible for numerous health effects, but it is still unclear whether and to what extent the particle itself or organic compounds adsorbed or condensed on the particle are responsible for the effects observed. One important class of particle-bound substances are the polycyclic aromatic hydrocarbons (PAH) and their oxygenated derivatives. To improve the tools used for chemical characterization of particulate matter analytical methods for the determination of PAH and oxygenated PAH in aerosol samples of different origin have been developed and optimized. PAH on high-volume filters and on soot aerosols were analyzed by using accelerated solvent extraction for extraction and high-performance liquid chromatography with fluorescence detection for separation and quantification. Total PAH concentrations were in the range 0.3–9.3 ng m^–3. For analysis of selected oxygenated PAH on high-volume filters a liquid chromatography–tandem mass spectrometric method was developed and optimized. Preliminary investigations showed that oxygenated PAH at pg m^–3 concentrations can be determined.     

The lipid composition of the Western Mediterranean aerosol

Summary Marine remote aerosol samples collected in a fixed station situated at 1100 m above sea level in Mallorca Island (Western Mediterranean) have been analyzed for lipids, both neutral and acidic, by capillary gas chromatography (GC) and GC coupled to mass spectrometry. Higher plant and algal compounds are predominant. The former encompass distributions of even numbered C22–C32 n-alkan-1-ols (8–21 ng/m³) and n-aldehydes, C25–C32 odd numbered n-alkanes (3–6 ng/m³), and n-nonacosan-10-ol, -sitosterol (0–0.09 ng/m³), dehydroabietic acid and triterpenols. The latter are constituted by even numbered C14–C18 fatty acids (0.6–30 ng/m³) and cholest-5-en-3-ol (0–0.86 ng/m³). Pyrolytic polycyclic aromatic hydrocarbons are also found (86–410 pg/m³) whereas direct petrogenic inputs are not significant.