Comparison of passive and active sampling methods for the determination of nitrogen dioxide in urban air

Three different methods for sampling and determination of nitrogen dioxide in urban air are compared: an NO/NO_x-monitor and an active (pumped) and a passive sampling method. For the latter two methods, sodium iodide is used as absorbent. For weekly averages the results from the passive sampler are within 10–20% of the results for the two other methods in the concentration range 15–30 μg NO₂/m³. The detection limit for the passive sampler is 1 μg NO₂/m³ (7 days), the precision is 5% and the accuracy is estimated to 20%. The active iodide method agrees very well with the NO/NO_x-monitor. Compared on 24 h basis for a period of 3 months, covering a concentration range of 5–45 μg NO₂/m³, the deviation between the two methods is within 5%, and the absorption capacity of the iodide reagent is excellent as the breakthrough is below 1%.     

Comparison of passive and active sampling methods for the determination of nitrogen dioxide in urban air

Three different methods for sampling and determination of nitrogen dioxide in urban air are compared: an NO/NO_x-monitor and an active (pumped) and a passive sampling method. For the latter two methods, sodium iodide is used as absorbent. For weekly averages the results from the passive sampler are within 10–20% of the results for the two other methods in the concentration range 15–30 μg NO₂/m³. The detection limit for the passive sampler is 1 μg NO₂/m³ (7 days), the precision is 5% and the accuracy is estimated to 20%. The active iodide method agrees very well with the NO/NO_x-monitor. Compared on 24 h basis for a period of 3 months, covering a concentration range of 5–45 μg NO₂/m³, the deviation between the two methods is within 5%, and the absorption capacity of the iodide reagent is excellent as the breakthrough is below 1%. Received: 3 December 1996 / Revised: 11 March 1997 / Accepted: 15 March 1997     

Determination of diphenylamine in contaminated air of agricultural buildings using active sampling on solid sorbents

This paper reports the results of a study carried out with solid sorbents in order to establish the optimum procedure for sampling and determination of diphenylamine (DPA), the most widely used post-harvest chemical in apples, in the indoor air of apple storage buildings. Different sorbents (Amberlite XAD-2, Amberlite XAD-4, Supelpak 2, Florisil, and the octadecyl silica bonded sorbent, C-18) were evaluated for their capacity to efficiently retain DPA under different air sampling and storage conditions, whereas a desorption study of all sorbents tested was also performed to optimise a simple extraction procedure using low volumes of organic solvents. In general all sorbents produced acceptable results for DPA air sampling whereas DPA was recovered easily by the use of low volumes of both ethyl acetate and acetone from all sorbents studied thus making DPA a suitable analyte to be used in methods of indoor air analysis for multi-organic pollutants. However, the best results (analytical features, recovery results, and stability results during storage) were obtained by the use of Supelpak 2 as a sorbent for DPA active sampling. Limits of Quantification (LOQs) for the GC-NPD system ranged from 1.0 to 2.0?µg?m^?3 for 120 and 60?L air sampled, respectively. The developed air sampling procedure and analytical methodology was applied with success in the field to measure DPA residues in indoor air of two apple storage plants in Greece and results were further used to calculate the occupational inhalation exposure to DPA and consequently risk characterisation. Since DPA was detected in indoor air (at concentrations ranged from 1.6 to 580?µg?m^?3), there is no zero occupational risk for workers. However, the inhalation exposure of workers to DPA estimated in this study is far below the Acceptable Operator Exposure Level recently reviewed by the European Union and far below the critical exposure level for haematotoxicity systemic effect observed in carcinogenicity studies in rats for long-term inhalation exposure to DPA.     

Investigation of the storage stability of selected volatile sulfur compounds in different sampling containers

The suitability of various sample containers (i.e. standard Tedlar sample bags, black/clear layered Tedlar sample bags and Silcosteel sample cylinders) was examined for a gaseous multicomponent standard containing methylmercaptan, ethylmercaptan, dimethyl sulfide, ethylmethyl sulfide, 2-propylmercaptan, 1-propylmercaptan, 2-butylmercaptan, diethyl sulfide and 1-butylmercaptan (1 mg/m3 each in nitrogen). In the black/clear layered Tedlar sample bags, significant losses (up to 10% for methylmercaptan as the most critical component) were observed after 2 days, whereas in the standard Tedlar sample bags the recovery of methylmercaptan was approximately 90% even after 1 week. The Silcosteel sample cylinders were suitable for sampling of volatile sulfur compounds with respect to the stability of the analytes, but the recoveries exceeded 100% especially for the higher boiling compounds, which was attributed to enrichment effects on parts of the sampling system.     

Comparison of solid-phase sorbents for the determination of fluoroquinolone antibiotics in wastewater

Three different SPE sorbents (weak cation exchange, mixed cation exchange, and hydrophobic-lipophilic balance polymers) were compared in terms of recovery, precision, and the effect of matrix components on analyte response for the determination of fluoroquinolones antibiotics. The influence of ethylenediaminetetraacetic acid disodium salt (Na2-EDTA) was as well tested. Two of the sorbents, hydrophilic-lipophilic balance (HLB) and weak cation exchange (WCX), turned out to be suitable for ultratrace analysis. HLB sorbent showed higher capacity for analyte trapping and better precision while weak cation exchange sorbent had a superior performance in terms of selectivity. In complex samples, the higher capacity of HLB was outweighed by the higher selectivity of WCX when considering the LODs of the methods.     

Assessment of different sorbents efficiency for solid phase extraction of aquatic humic acids

In the present study, a simple procedure for the isolation by solid-phase extraction (SPE) and quantification by UV-Vis spectrometry (400 nm) of the humic acids (HAs) in the natural waters was developed. Seven different sorbents: Porapak P (polystyrene-divinylbenzene copolymer), Florisil (chemical composition: 84.0% SiO₂, 15.5% MgO and 0.5% Na₂SO₄), Silica gel C18 (octadecyl silane), Strata X (surface modified polystyrene-divinylbenzene), Strata NH₂ (silica-based trifunctional amino ligand), Strata SAX (silica-based trifunctional quaternary amine) and Strata C18-E (silica-based trifunctional C18 with hydrophobic end-capping of silanols) were tested. The HAs, adsorbed on SPE cartridges, were eluted using: NaOH (0.1 M), sodium dodecyl sulphate (SDS) (20 g L⁻¹), and a 1:1 v/v mixture of SDS (20 g L⁻¹) and NaOH (0.1 M). The extraction efficiency was evaluated by comparing the HAs recovery levels. The repeatability of results was estimated by the relative standard deviation (RSD). The data confirmed that Porapak P, Silica gel C18, Florisil, Strata NH₂ and Strata X could be good alternatives for the traditional isolation of the aquatic HAs with XAD resin. The proposed method was applied for the determination of HAs in some waters sampled from the Western Romanian Plain. The content of HAs was correlated with the arsenic concentration and total organic carbon (TOC) level.      

Automated on-line preconcentration of palladium on different sorbents and its determination in environmental samples

The determination of noble metals in environmental samples is of increasing importance. Palladium is often employed as a catalyst in chemical industry and is also used with platinum and rhodium in motor car catalytic converters which might cause environmental pollution problems. Two different sorbents for palladium preconcentration in different samples were investigated: silica gel functionalized with 1,5-bis(di-2-pyridyl)methylene tbiocarbohydrazide (DPTH-gel) and [1,5-Bis(2-pyridyl)-3-sulphophenyI methylene thiocarbonohydrazide (PSTH) immobilised on an anion-exchange resin (Dowex lx8-200)]. The sorbents were tested in a micro-column, placed in the auto-sampler arm, at the flow rate 2.8 mL min(-1). Elution was performed with 4 M HCl and 4 M HNO3, respectively. Satisfactory results were obtained for two sorbents.     

Ionic liquids: solvents and sorbents in sample preparation

The applications of ionic liquids (ILs) and IL‐derived sorbents are rapidly expanding. By careful selection of the cation and anion components, the physicochemical properties of ILs can be altered to meet the requirements of specific applications. Reports of IL solvents possessing high selectivity for specific analytes are numerous and continue to motivate the development of new IL‐based sample preparation methods that are faster, more selective, and environmentally benign compared to conventional organic solvents. The advantages of ILs have also been exploited in solid/polymer formats in which ordinarily nonspecific sorbents are functionalized with IL moieties in order to impart selectivity for an analyte or analyte class. Furthermore, new ILs that incorporate a paramagnetic component into the IL structure, known as magnetic ionic liquids (MILs), have emerged as useful solvents for bioanalytical applications. In this rapidly changing field, this Review focuses on the applications of ILs and IL‐based sorbents in sample preparation with a special emphasis on liquid phase extraction techniques using ILs and MILs, IL‐based solid‐phase extraction, ILs in mass spectrometry, and biological applications.     

Novel multi-sorbent for sampling and determination of trace volatile organic sulfur compounds in ambient air

Novel adsorbent APSG-MW (average particle size 215?µm and specific surface 98 m²?g^?1) bonding multi-walled carbon nanotubes (MWCNTs) on silica gel are obtained. Then the sampling tubes filled with Tenax TA and APSG-MW are prepared and the adsorptive capacity of Tenax TA/APSG-MW for volatile organic sulfur compounds (VOSCs) is studied. The data show that the adsorption and desorption recoveries of multi-sorbent for VOSCs are satisfactory (>85%), and the breakthrough values are large (>16?L?g^?1) enough to absorb VOSCs in ambient air. The sampling precision of the sorbent tubes meets TO-17 criteria. The sampling tubes are successfully used to concentrate and analyze a sample of landfill air, and the major S compounds are identified.     

Gas chromatographic determination of formaldehyde in air using solid-phase microextraction sampling

Summary The optimization of in situ derivatization and preconcentration of formaldehyde in air using solid phase microextraction with gas chromatographic determination was investigated. A dimethylpolysiloxane coating (7 μm) solid-phase microextraction needle was used in the final procedure as a support for derivatizing reagents such as 2,4-dinitrophenylhydrazine and acetylacetone. Standard concentrations of formaldehyde in air were obtained using a headspace technique and equilibrium concentrations of formaldehyde in air were calculated using Henry's law. After derivatization on the fiber, the derivative was thermally desorbed in the injector of a gas chromatograph and analyzed using an electron capture detector. A detection limit of 0.17 mg m⁻³ was obtained. Calibration was done at 296 K. Reproducibility of the method was 9.6%. Some real air samples were also analyzed. The method is very convenient and ideal for the rapid determination of formaldehyde in air. Presented at: Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 3–5, 1997     

Selectivity and efficiency of different reversed-phase and mixed-mode sorbents to preconcentrate and isolate aroma molecules

A comparison of the ability of different sorbent systems, including mixed-mode resins and reversed-phase sorbents, to extract and isolate volatile molecules from hydroalcoholic medium has been carried out by means of the determination of liquid–solid distribution coefficients. Eighteen volatile compounds covering a wide range of physicochemical properties (acids, bases and neutrals) and chemical functionalities, and thirteen different sorbents have been tested. LiChrolut EN and Isolute ENV (both polymeric with high surface area) showed the highest retention capability for nearly all analytes at all pHs tested. Exceptions were 2,3,5-trimethylpyrazine, most efficiently extracted with Strata XC at acidic pH, and indole best retained with Oasis MCX and Strata XC at any pH. Although nearly all basic compounds were most selectively extracted with cationic mixed-mode resins at acid pHs and 3-mercaptohexyl acetate and m-cresol show maxima α at pH 10 with Oasis MAX, the α values obtained have been relatively low, which suggests that retention is not particularly driven by ionic forces. The study has also shown that selectivity depends on the pH, the exact kind of mixed-mode sorbent and on the polarity of the analyte. High selectivity towards ionogenic compounds can be obtained by combining retention in mixed mode, a rinsing with a non-polar solvent and further elution with a solvent containing a neutralizing agent. However, not all the ionogenic molecules seem to be retained in ionic mode in the conditions tested and the complete elution of some analytes can be difficult, which suggests that analyte-specific isolation procedures should be analyzed case by case.     

Active sampling followed by solid-phase microextraction for the determination of pyrethroids in indoor air

A method based on solid-phase enrichment followed by headspace (HS)-solid-phase microextraction (SPME) is optimized to determine pyrethroids in air. By active sampling, pyrethroids present in air are retained in 25 mg of activated florisil and then transferred from the solid sorbent to an SPME fiber in the HS mode. A small volume of solvent is added to the adsorbent to favor this process. The selection of the adsorbent, as well as the optimization of certain parameters affecting the SPME, is performed using an experimental design strategy. Linearity is studied by external calibration in a wide range of concentrations using gas chromatography coupled to three different detection systems: electron capture detection, micro-electron capture detection, and mass spectrometry. An analysis of variance with a lack-of-fit test is run to validate the calibration data. Breakthrough of the adsorbent was studied sampling from 0.5 to 10 m(3) air, demonstrating that 1 m(3) air could be sampled without losses of pyrethroids. Quantitative recoveries are obtained at three concentration levels, with adequate repeatability. Limits of detection of the method are estimated at the sub-ng/m(3) level in most cases, well below the regulatory limits. Finally, several real indoor samples are collected and analyzed by the proposed method. Identification and quantitation of all target analytes present in the room air are possible.     

PAH-losses from glass fiber filters under the conditions of different air volume sampling: results of field evaluations in occupational atmospheres

Summary The estimation of the occupational medical and toxicological risks to workers exposed to PAH depends on sampling these compounds, some of which are carcinogenic, with as little loss as possible in the air of the working environment.A sampling system for the collection of air samples for PAH in field investigations consisting of a glass fiber filter followed by a suction pump has been tested for its efficiency at various suction rates using n=19 specially selected reference substances. The variability of the suction rate obtainable with the pump employed is to be regarded as being of particular significance.A total of 60 determinations made in areas devoted to the manufacture of artificial coal and at road paving operations revealed greatly reduced and pumping rate-dependent recoveries, i.e. correspondingly high losses. With an air throughput of 22 500 l/h an average of 47.8% of the total of 19 PAH was recovered on the glass fiber filter; when a suction pump with a throughput of 2840 l/h was employed 28% of the PAH was not collected and the losses amounted to 15% at a pumping rate of 120 l/h. The losses of 5 PAH compounds chosen for their carcinogenicity were of the same order of magnitude with ca. 51%, 22% and 11%.The influence of the number of rings in the PAH, i. e., its increasing boiling point, plays a decisive role in its recovery rate. Thus, when sampling at a throughput of 120 l/h, the recovery rates of various members of the 4, 5, 6 and 7-ring PAH systems were on average 77.1%, 88.4%, 95.6% and 99.1%, respectively.Glass fiber filters are not suitable for use as the sole collection phase for PAH air sampling, particularly when pumps having a high throughput are employed. A combination of filters as the collection phase for particulate PAH followed by adsorbent tubes of Tenax or XAD-2 for gaseous PAH must be regarded as necessary for the collection of representative samples for determination of the total concentration of polycyclic aromatics.

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PAH-Verluste an Glasfaserfiltern unter den Bedingungen der Probenahme bei unterschiedlichen Luftdurchsätzen: Ergebnisse von Feldauswertungen in Arbeitsbereichen

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Dedicated to Prof. Dr. G. Hesse on the occasion of his 80th birthday     

Comparison of several solid-phase extraction sorbents for continuous determination of amines in water by gas chromatography-mass spectrometry

A semiautomatic method has been proposed for the determination of different types of amines in water samples including anilines, chloroanilines, N-nitrosamines and aliphatic amines. The analytes were retained on a solid-phase extraction sorbent column and after elution, 1 μL of the extract was analysed by gas chromatography coupled with electron impact ionization mass spectrometry. A systematic overview is given of the advantages and disadvantages of several sorbents (LiChrolut EN, Oasis HLB, RP-C₁₈, graphitized carbon black, fullerenes and nanotubes) in the retention of amine compounds and based on sensitivity, selectivity and reliability. The retention efficiency for the studied amines was higher (ca. 100%) with LiChrolut EN and Oasis HLB than it was with RP-C₁₈ and fullerenes (53 and 62%, respectively, on average). Detection limits of 0.5-16 ng L⁻¹ for the 27 amines studied were obtained when using a sorbent column containing 75 mg of LiChrolut EN for 100 mL of sample, the RSD being lower than 6.5%. The method was applied with good accuracy and precision in the determination of amines in various types of water including river, pond, tap, well, drinking, swimming pool and waste.     

Rapid determination of desorption efficiency, and analysis of solvent mixtures for occupational exposure studies

Summary An analytical procedure has been developed for simultaneous determination of solvent mixture vapors to enable evaluation of occupational exposure. To determine the desorption efficiency the volatile components of the solvent mixtures were generated from a glass tube filled with glass wool. This device is easy to prepare and use. These vapors were then collected in activated charcoal tubes and analyzed by capillary gas chromatography. The method was tested with a mixture of 22 solvents, including aliphatic and aromatic hydrocarbons, alcohols, ethers, esters, and ketones, all at low concentrations. All the components were detected. When a 99∶1 mixture of carbon disulfide-dimethylformamide was used for desorption the efficiency was>75% for most of the solvents.     

Comparison of different sampling heads applied for investigation of welding fume

Welding fume samples were collected in two Hungarian welding plants, where different types of steels were welded with metal active gas (MAG) welding. Welding fumes were sampled with “fixed point” and personal sampling techniques applying different sampling heads: Institute of Occupational Medicine (IOM) sampler and conical inhalable sampler (CIS) for the inhalable aerosol fraction and the Higgins-Dewell (HD) cyclone for the respirable fraction. When sampled, the welding fume samples were digested with the mixture of nitric acid and hydrogen peroxide in a closed vessel microwave digestion system. The Cr, Mn, Ni and Co contents of the solutions were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). Iron was analysed only by the ICP-AES method. Metal concentrations of the workplace air were calculated for the three samplers, and the results were compared to each other. The differences of the metal concentrations determined by the different inhalable sampling heads, which were paired during the sampling, proved not to be significant. Therefore, the IOM and CIS heads can be equally used for the sampling of welding fume. Finally, the distributions of metals were determined between the inhalable and respirable fractions. Metal concentrations in the respirable aerosol fraction were 57-98% of the concentrations in the inhalable fraction. These high rates of metals in the respirable aerosol call the attention to the increased health risk of the welding fume.     

Comparison of conventional filtration and a denuder-based methodology for sampling of particulate-phase mercury in ambient air

This paper compares the results of total atmospheric particulate-phase mercury determinations using samples collected by two methods. The conventional filtration method (FM) collects airborne particulate matter first, whereas the denuder-based method (DM) removes gaseous-phase mercury prior to particulate matter collection. In each case, particulate-phase mercury (PM) is collected on a quartz fiber disc held in a miniaturized device and is analyzed using a pyrolysis/gold amalgamation/thermal desorption/cold vapor atomic fluorescence spectrometry (CVAFS) technique. The results show that the concentrations of PM determined using the samples collected by DM are higher than those determined using the samples collected by FM. Evidence presented shows that the higher results are due to mercury-bearing gold particles flaking off from the gold-coated denuder surfaces in the denuder-based sampling system.