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.     

Radioanalytical Determination of Biogenic Volatile Iodine Emitted from Aqueous Environmental Samples

A reliable method using ¹²⁵I tracer for direct determination of volatile iodine formed in aqueous environmental samples was established. Soil solution, seawater and bacterial cell suspension were selected as model samples, and incubated with ¹²⁵I^–. Volatile inorganic and organic iodine species produced during incubation were collected in silver wool and activated charcoal traps, separately the efficiency of the traps, the storage conditions of ¹²⁵I^– stock solution and the procedures to expel the dissolved volatile iodine from the sample solutions were examined. Formation of biological volatile iodine was observed in all samples, and the dominant iodine species was found to be organic iodine. The advantages of this method are its simplicity, low cost and low detection limit.     

The collection and determination of atmospheric gaseous bromine and iodine

A procedure has been developed which allows for the isolation, collection and analysis of atmospheric gaseous iodine and bromine. Particulate matter is removed from the airstream to be sampled by electrostatic precipitation. The gaseous halogen species are adsorbed onto specially cleaned activated charcoal. After irradiation of the charcoal sample with thermal neutrons, the iodine and bromine are removed from the charcoal, isolated, and purified as the AgX precipitate. The amounts of gaseous iodine and bromine are then determined by β-counting. The system works well for air sheds with low particulate iodine and bromine concentrations relative to that in the gaseous phase. In air sheds where the particulate halogen predominates, the gas phase measurements are more uncertain.     

The determination of organic and inorganic lead compounds in urban air by atomic-absorption spectrometry with electrothermal atomization

A method for the simultaneous determination of inorganic and organic lead compounds in air is described, together with some results from its application at different sampling sites. Air-borne particulate lead is collected on a cellulose filter. Organic lead vapours are trapped in an iodine monochloride solution, placed behind the filter. A fraction of the cellulose filter is subjected to low-temperature ashing, after which the lead content in the residue is measured by electrothermal atomic-absorption spectrometry. The organolead material absorbed in the iodine monochloride solution, is determined by solvent extraction and electrothermal atomic-absorption spectrometry. For a 6-h sampling period, detection limits of the order of 10 ng m^-3 for inorganic and 8 ng m^-3 for organic lead materials may be obtained.     

Concept and validation of a novel approach for producing large batches of reference material of ambient aerosols on filters

A novel method for preparing reference material of aerosol particulate matter (PM) on filters was developed by using the concept of very high volume, multiport sampling, and this was subsequently applied to produce more than 300 well-characterised units. The dedicated sampler built for this purpose features a 0.94-m-diameter, vacuum-tight main chamber with a total of 349 monitor ports, each holding a 37-mm-diameter, cellulose acetate–nitrate ester (CA) membrane filter with a nominal pore size of 0.8 m. At a pressure difference of about 130 hPa across the filter cassettes, the total initial air flow rate was 350 m³ h^–1 (1.0 m³ h^–1 per filter). Investigations into the variability of filter parameters showed that the flow resistance of CA filters is mostly determined by and proportional to their blank mass, with a mean uncertainty of about 5%. Total suspended particulate matter (TSP) was sampled for a total of 50 h using 349 selected filters with a relatively narrow spread in blank mass. The mean TSP mass per filter thus produced was 3.35 mg. Corrected for small differences in blank mass of the filters, the normalised aerosol masses per filter of 96% of the samples exhibited normal distributions with standard deviations of only 2.1 and 3.4%, depending on details of the normalisation procedure. Within the limits of the technique, a variation of aerosol mass with radial distance from the centre of the sampler is not clearly evident. The results provide evidence that the multiport approach allows large batches of particulate matter on filters to be produced in a reliable manner.     

Evaluation of solid-phase microextraction with PDMS for air sampling of gaseous organophosphate flame-retardants and plasticizers

As an inexpensive, simple, and low-solvent consuming extraction technique, the suitability of solid-phase microextraction (SPME) with polydimethylsiloxane (PDMS) sorbent was investigated as a quantitative method for sampling gaseous organophosphate triesters in air. These compounds have become ubiquitous in indoor air, because of their widespread use as additive flame retardants/plasticizers in various indoor materials. Results obtained by sampling these compounds at controlled air concentrations using SPME and active sampling on glass fibre filters were compared to evaluate the method. A constant linear airflow of 10 cm s^–1 over the fibres was applied to increase the extraction rate. For extraction of triethyl phosphate with a 100-m PDMS fibre, equilibrium was achieved after 8 h. The limit of detection was determined to be less than 10 pg m^–3. The PDMS–air partition coefficients, K_fs, for the individual organophosphate triesters were determined to be in the range 5–60×10⁶ at room temperature (22–23°C). Air measurements were performed utilising the determined coefficients for quantification. In samples taken from a lecture room four different airborne organophosphate esters were identified, the most abundant of which was tris(chloropropyl) phosphate, at the comparatively high level of 1.1 g m^–3. The results from SPME and active sampling had comparable repeatability (RSD less than 17%), and the determined concentrations were also similar. The results suggest that the investigated compounds were almost entirely associated with the gaseous phase at the time and place sampled.     

Neutron activation analysis of iodine in soil

A simple pre-irradiation procedure for the separation of iodine from soil has been developed. A soil sample was heated in a quartz tube for 15 min at about 900 °C. The evaporated iodine was collected in activated charcoal, which was produced from phenol resin with low impurities. The charcoal, with sorbed iodine, was irradiated by neutrons and the¹²⁸I produced was measured. A successful elimination of the background radioactivity due to the matrix elements was possible with this separation procedure. The detection limit by this method for soil samples was about 0.1 mg/kg (dry). The method has been applied to analyze selected soil samples.     

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.     

The use of charcoal from agriculture waste in the speciation of iodine from well and river waters

The concentrations of iodine in fresh waters are known to be within the range of 0.5 to 35 ng·ml⁻¹, much lower than in oceanic waters. The iodine concentrations, particularly that of¹²⁹I which is significant from the radiation safety aspect, in public drinking waters have to be specified in order to verify the required level before distribution for domestic use. A modified version of an established method was used in the adsorption of iodine, iodate, total inorganic iodine and charcoal-adsorbable iodine using activated carbon prepared from oil palm kernel wastes. A thorough investigation of the physical properties of the activated carbon was carried out to determine its viability as an adsorbent for volatile species such as iodine. The iodine species were preconcentrated from water samples collected from wells in villages and from water intake points along rivers. The quantitative analysis of the species adsorbed was done by irradiating the activated charcoal loaded with the respective species in a neutron flux of 5.1·10¹² n·cm⁻²·s⁻¹ from a TRIGA MkII, nuclear reactor. Recovery experiments using spiked samples was done to provide quality assurance controls.     

Airborne gamma-ray emitters from Fukushima detected in New York State

An air-sampling network that operates continuously as part of New York State’s environmental surveillance program collected radionuclides emitted as a result of the Fukushima nuclear accident. Samples were collected, typically for 7 days each, by drawing ~600 m³ of air through a particulate-collecting filter followed in series by a canister containing activated charcoal. Additional air sampling was implemented at ~3-day intervals at two locations. Gamma-ray spectroscopy was used to confirm the detection of ¹³¹I, ¹³⁷Cs, ¹³⁴Cs, and ⁷Be in the particulate phase at all sites, with maximum concentrations near 1,260, 160, 160, and 5,200 μBq/m³, respectively. Gas-phase ¹³¹I, collected on activated charcoal, exhibited a maximum concentration of 3,400 μBq/m³ at the sites. Assessment of radionuclide levels in the air samples suggests that there were minimal health impacts from the airborne radionuclides as the activities contributed an insignificant amount to the annual human dose.     

Feinreinigung von Radiostrontiumproben mittels Ionen-Chromatographie

Summary An annular denuder system for simultaneous determination of gaseous and particulate pollutants in ambient air was developed. Inorganic acids (HCl, HNO₃) were collected in a NaF-coated denuder, while organic acids (HCOOH, CH₃COOH) were trapped in one coated with KOH. NH₃ was sampled with a H₃PO₄-coated denuder tube. Particulate H₂SO₄ was evaporated at elevated temperature (145°–155°C) and deposited on a NaF-coating together with HCl and HNO₃ originating from thermal decomposition of NH₄Cl and NH₄NO₃. NH₃ resulting from deammoniation of (NH₄)₂SO₄ as well as NH₃ remaining from NH₄Cl and NH₄NO₃ were collected in a H₃PO₄-coated denuder. The practical collection capacity of the tubes ranged from 0.35 to 1.0 mol calculated from an experimentally determined sorption efficiency of at least 90%. The precision, expressed as relative standard deviation, of sampling and analytical procedures was determined from duplicate measurements in ambient air. The reproducibility varied from 9% to 14% for the gaseous components, while that of the particulate compounds ranged from 12% to 23%. Aqueous extracts of the denuder coatings were analysed for ionic components by ion chromatography using conductivity detection. The minimum detectable concentration in air was found to be 1.5 to 14 nmol/m³ for the different compounds calculated for 1.6 m³ sample volume, based on 3-h measurements at a flow of 9 l/min.

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Bestimmung der atmosphärischen Konzentrationen von anorganischen und organischen gasförmigen Säuren, NH₃, teilchenförmigem SO ₄ ^2– , NO ₃ ^2– und Cl^– mit einem Ringspaltrohr-Diffusionsdenudersystem

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On leave from the Institute of Occupational Health, Helsinki, Finland     

Photochemical aspects of the behavior of the atmospheric radioiodine after the Chernobyl accident

A hybrid stable iodine/radioiodine (¹³¹I) atmospheric photochemistry box model, including 27 reactions, has been developed and solved using algorithmic programme with the application of the Runge-Kutta method of the order 4(5). This modelling offers a clearer view of relationship among aerosol-associated (inorganic iodine compounds, mostly I₂O₂), gaseous inorganic (mostly IONO₂, HOI) and organic (CH₃I) iodine compounds in ambient atmosphere. Summing up the data of the Chernobyl accident, the problem of the standardised method for atmospheric aerosol-associated and gaseous (inorganic and organic) radioiodine activity measurements in the case of the nuclear power plant accident is discussed.     

Iodine speciation in size fractionated atmospheric particles by isotope dilution mass spectrometry

An isotope dilution mass spectrometric method has been developed for the accurate and sensitive determination of iodide and iodate in aerosol particles of the atmosphere. The direct iodine speciation has been possible by the use of species specifically ¹²⁹I enriched spike solutions and separation of the isotope diluted species by anion exchange chromatography after water extraction of the filters. Size fractionated collection of aerosol particles by a six stage impactor system shows different distributions of iodide and iodate for particles of different size with specific patterns for anthropogenically influenced continental and unpolluted marine aerosols, respectively. The detection limit for particulate iodide and iodate has been (3–5) pg/m³ for sampling volumes of 3000 m³. Oil, used for heating plants, could be identified as one but not the only anthropogenic iodine source.Dedicated to Professor Dr. D. Klockow on the occasion of his 60th birthday     

Dry deposition of elemental iodine on skin,hair, and clothing from air

Hairless rats, clothes, human hair, filter paper and water were exposed to gaseous elemental iodine in a glass chamber for 60–120 minutes. The deposition of gaseous elemental iodine on skin and lung of rats, human hair, water, clothes and paper were investigated by measuring iodine content in the exposed material by epithermal neutron activation analysis (ENAA). For measurement of the iodine concentration in the chamber air, elemental iodine in the air was collected by continuously sucking air through an active charcoal column. The trapped iodine in the active charcoal was then determined by ENAA. The measured deposition velocity in the test chamber of gaseous elemental iodine on skin, clothing, hair and water ranges from 0.006 on filter paper and water to about 0.05 cm/s on skin and clothes. The variation of elemental iodine concentration in air of the glass chamber was investigated by collecting and analyzing air samples at various time intervals. The results show that the variation with time in the concentration of the iodine can be described by an exponential function.     

Development of a gas chromatography-mass spectrometry method for the determination of pesticides in gaseous and particulate phases in the atmosphere

A reliable multi-residue method for determining gaseous and particulate phase pesticides in atmospheric samples has been developed. This method, based on full scan gas chromatography–mass spectrometry (GC–MS), allowed the proper determination of sixteen relevant pesticides, in a wide range of concentrations and without the influence of interferences. The pesticides were benfluralin, bitertanol, buprofezin, chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl, ethalfluralin, fenthion, lindane, malathion, methidathion, propachlor, propanil, pyriproxifen, tebuconazol and trifluralin. Comparisons of two types of sampling filters (quartz and glass fibre) and four types of solid-phase cartridges (XAD-2, XAD-4, Florisil and Orbo-49P) showed that the most suitable supports were glass fibre filter for particulate pesticides and XAD-2 and XAD-4 cartridges for gaseous pesticides (>95% recovery). Evaluations of elution solvents for ultrasonic-assisted extraction demonstrated that isooctane is better than ethylacetate, dichloromethane, methanol or a mixture of acetone:hexane (1:1).Recovery assays and the standard addition method were performed to validate the proposed methodology. Moreover, large simulator chamber experiments allowed the best study of the gas-particle partitioning of pesticides for testing the sampling efficiency for the validation of an analytical multiresidue method for pesticides in air. Satisfactory analytical parameters were obtained, with a repeatability of 5 ± 1%, a reproducibility of 13 ± 3% and detection limits of 0.05–0.18 pg m⁻³ for the particulate phase and 26–88 pg m⁻³ for the gaseous phase. Finally, the methodology was successfully applied to rural and agricultural samples in the Mediterranean area.     

Study of the uptake of inorganic ions and organic acids at theα-alumina-electrolyte interface in a colloidal system by radiochemical techniques and microelectrophoresis

The interactions of the alumina-electrolyte in the presence of inorganic ions (copper, selenium) and/or organic acids (benzoic acid, glutamic acid, phenol) have been studied. The acid-based properties of-alumina have been determined in NaCl media (pzc=8.5±0.3). Three types of hydroxy groups with different acidity constants have been found. The adsorption of copper and selenium have been described by the formation of the surface complexes: (=Al¹–OH, CuCl) and (=Al¹, SeO₃)^–. The interaction of copper with the surface oxygen atoms is strong and so is the interaction of selenium with the surface aluminium atoms, which involves a shift of the iep of alumina. For the three organic acids studied (HX), the adsorption equilibrium is:=Alⁱ–OH+HX(=Alⁱ, X)+H₂O. The interaction of the X^– group and the aluminium atoms is strong following the order: glutamic acid > benzoic acid > phenol. The uptake of selenium is uninfluenced by the presence of organic acids with carboxylic, amino-acidic and phenolic groups. The uptake of copper is highly increased by the presence of organic acids but it is not influenced by the presence of the phenolic groups. Both of these behaviours can be extrapolated to inorganic ions of the same chemical structure.     

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.     

Radiochemical studies of iodine behaviour under conditions relevant to nuclear reactor accidents

Radiochemical methods are quite suitable for studying the behaviour of radioiodine under the dilute conditions relevant to nuclear reactor accidents. Species selective adsorbents are able to distinguish between various inorganic and organic gas-phase iodine species. A solvent extraction procedure for determining aqueous phase organic iodide, free iodine, I^– and IO ₃ ^– fractions has been investigated and found to be valuable, although large inaccuracies in the separation of I^– and IO ₃ ^– can occur for solutions of pH above 10. The extraction of potentially-volatile species in the aqueous phase gives a measure of iodine species volatility consistent with observed values of the partition coefficient. Indirect measurement suggest that the partition coefficient of HOI at room temperature exceeds 30,000.     

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.     

Removal of radioiodine from nuclear-fuel-reprocessing off-gases with silver-nitrate-impregnated silica gel

Silver-impregnated silica gels prepared by us have very good adsorption characteristics for both organic and inorganic radioiodine. Under the operating conditions applied, the adsorption capacity is up to 200 mg I g^–1 and the utilization of silver on the sorbent is higher than 90%. The adsorbent can be used to remove iodine from nuclear fuel reprocessing off-gases and from air cleaning systems of nuclear reactors.