Study on air pollution monitoring in Korea using instrumental neutron activation analysis

Trace elements in airborne particulate matter collected monthly at suburban and rural areas in Korea were analyzed by instrumental neutron activation analysis (INAA). Neutron irradiation of the samples was done at the irradiation hole (neutron flux 1·10¹³ n·cm^–2·s^–1) of the TRIGA Mark-III Research Reactor in the Korea Atomic Energy Research Institute. For the verification of the analytical technique, two reference materials, NIST SRM-1648 and NIES CRM-8, were chosen for analysis. The accuracy and precision of the determinations of the 40 elements were compared with the reference values. We used this method (1) to analyze 30 trace elements in airborne particulate matter collected monthly with the high volume air sampler (PM-10) at two different locations and (2) to confirm the possibility of using this method as a routine monitoring tool to find out environmental pollution sources.     

Source identification and long-term monitoring of airborne particulate matter (PM<Subscript>2.5</Subscript>/PM<Subscript>10</Subscript>) in an urban region of Korea

Summary For the identification of air pollution sources, about 500 airborne particulate matter (PM_2.5and PM₁₀) samples were collected by using a Gent air sampler and a polycarbonate filter in an urban region in the middle of Korea from 2000 to 2003. The concentrations of 25 elements in the samples were measured by using instrumental neutron activation analysis (INAA). Receptor modeling was performed on the air monitoring data by using the positive matrix factorization (PMF2) method. According to this analysis, the existence of 6 to 10PMF factors, such as metal-alloy, oil combustion, diesel exhaust, coal combustion, gasoline exhaust, incinerator, Cu-smelter, biomass burning, sea-salt, and soil dust were identified.     

Analysis of urban dust (PM<Subscript>2</Subscript>/PM<Subscript>10-2</Subscript>) in Daejeon city by instrumental neutron activation analysis

Summary As part of an air pollution monitoring study, airborne particulate matter (PM₂/PM_10-2) samples were collected from 2000 to 2003 at two sampling sites in an urban region, Daejeon, the middle of Korea. Mass concentrations of both fine and coarse fractions and that of the black carbon in the fine particles were measured using the Gent stacked filter unit sampler and the smoke stain reflectometer, respectively. In the collected samples the concentrations of 24 elements were analyzed using instrumental neutron activation analysis. Monitored data were investigated for their temporal trends under different environmental conditions and their seasonal correlation patterns. Crustal enrichment factors were also estimated to establish the contribution between anthropogenic and crustal origin. Patterns for airborne particle matter (APM) and elemental concentrations, seasonal variation of some marker elements were investigated. The results can be applied for the investigation of further air pollution sources and for the evaluation of air quality.     

Determination of chemical elements in airborne particulate matter collected at Lembang, Indonesia by particle induced X-ray emission

Monitoring the air quality in ambient air is an important step for assessing the air pollution level in one region and its impact to the human health. In this study, the determination of chemical elements concentrations in airborne particulate matter collected in suburban area of Lembang, Indonesia was carried out. Samples were collected using a Gent stacked filter unit sampler in two size fractions of <2.5 μm (fine) and 2.5–10 μm (coarse). Sampling was conducted twice a week for 24 h from January 2008 to June 2009 and 123 pairs of samples were collected. Black carbon was determined by reflectance and chemical elements analysis were performed using particle induced X-ray emission (PIXE). PIXE as one of ion beam analysis techniques is suitable for analyzing particulate matter for its multielemental analysis with good limits of detection. Results showed that none of daily concentrations of PM_2.5 and PM₁₀ exceeded the 24 h Indonesian NAAQS for PM_2.5 and PM₁₀. Chemical elements such as Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Hg and Pb were determined and the correlation between these elements was reported in order to understand the anthropogenic sources of particulate matter.     

Analysis of 1-nitropyrene in air particulate matter standard reference materials by using two-dimensional high performance liquid chromatography with online reduction and tandem mass spectrometry detection

1-Nitropyrene (1-NP) is enriched in diesel exhaust particulate matter (DPM) relative to other sources of particulate matter (PM), and has been proposed as a marker for DPM. However, in ambient air, 1-NP concentrations are typically in the low pg/m(3) range. Therefore, collection of large volume air samples coupled with extensive sample clean-up procedures has been required to achieve adequate detection limits to measure 1-NP in ambient samples. We report here an improved LC-MS/MS method suitable for the detection and quantification of 1-NP in low volume ambient PM samples. The method involves ultrasonic extraction of ambient PM in organic solvent, concentration of the sample under reduced pressure, and two-dimensional HPLC analysis of the extract. 1-NP is isolated on the first HPLC column, then converted to 1-aminopyrene (1-AP) via online reduction in a column packed with a Pt/Rh catalyst. The 1-AP containing fraction from the first column is refocused on a trapping column, then eluted through a second HPLC column prior to MS/MS detection. Deuterated (d(9)) 1-NP (1-dNP) is added to each sample prior to extraction as an internal standard for quantification of 1-NP. The accuracy and precision of the assay, as applied to ambient particulate standard reference materials are 110+/-5.7% for SRM 1650b, 116+/-7.1% for SRM 2975, 108+/-5.8% for SRM 1649a, and 53+/-9.2% for SRM 1648. The analytical limit of detection was 152 fg on column, and analytical limit of quantitation 221 fg on column. To our knowledge, the sensitivity of this method is comparable with GC-NICI-MS methods while having the advantage of considerably less extensive sample preparation. This method is an approximately 10-fold improvement in sensitivity over HPLC methods utilizing fluorescence and/or chemiluminescence detection.     

Neutron activation analysis for identification of African mineral dust transport

A Gent stacked filter unit sampler was used to collect air particulate matter (APM) in separate coarse (PM_2.5–10) and fine (PM_2.5) size fractions, at a sub-urban site in Lisbon, Portugal. The sampling was done during the year 2001 and two daily samples were taken per week. The filters were analyzed for particulate mass by instrumental neutron activation analysis (INAA). The chemical analysis of APM levels and the study of the atmospheric dynamics by back-trajectories showed that most of the PM_2.5 and PM_2.5–10 peaks events were associated with air masses transport from the Saharan desert. High mineral load in ambient particulate matter levels were registered during the Saharan dust outbreaks. The accuracy of INAA to measure Fe, Sc and Sm was evaluated by NIST filter standards, revealing results with an agreement of ± 10%. This method constituted an important tool to identify these events.     

Development and validation of an ultra-high-performance liquid chromatography coupled to time-of-flight mass spectrometry method to quantify benzoic acid and long-chain monocarboxylic acids (C12–C28) in atmospheric aerosols

An ultra-high-performance liquid chromatography/time-of-flight mass spectrometry (with negative ion electrospray ionization) methodology was developed for the simultaneous quantification of benzoic acid and 15 long-chain monocarboxylic acids (MCAs) in ambient aerosols. A fast and quantitative pressurized fluid extraction procedure was optimized using experimental design and the extracts were analyzed without any further clean-up step. Chromatographic separation was achieved on a BEH-C18 column with a mobile phase consisting of 5 mM formic acid in water/acetonitrile (90:10, v/v) and methanol. Excellent precision and accuracies in the MS mass measurements were observed. The method was validated using actual samples spiked with a solution containing either standards or ¹³C-surrogates. Matrix effects were observed for the C₁₄ MCA only. It was then applied to air particulate reference materials and atmospheric samples collected by a low-volume sampler.     

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.     

Hydrogen peroxide-sodium hydrosulfite chemiluminescence system combined with high-performance liquid chromatography for determination of 1-hydroxypyrene in airborne particulates

In this research, a highly sensitive chemiluminescence method based on a sodium hydrosulfite (NaHSO₃)-hydrogen peroxide (H₂O₂) reaction for the determination of 1-hydroxypyrene (1-OHP) was developed. The response of this system was linear in the range from 0.5 to 50 pmol (R² = 0.9983). The limit of detection for 1-OHP was 100 fmol (S/N = 3). 1-OHP in airborne particulates was well separated from interfering compounds using an ODS column with 75% methanol as the mobile phase in isocratic mode. The proposed method was successfully applied to determine the 1-OHP in airborne particulates collected in Kanazawa, Japan. The average concentration of 1-OHP in the atmosphere was 2.0 pg/m³ (9.2 fmol/m³).     

Analysis of inorganic mercury species associated with airborne particulate matter/aerosols: method development

This paper describes a method for speciation of Hg associated with airborne particulate matter. This method uses a mini-sampler for sample collection and analysis, thermal desorption for separating Hg species, and inductively coupled plasma mass spectrometry (ICP–MS) for identification and quantification of Hg. Coal fly ash spiked with different Hg compounds (e.g. Hg⁰, HgCl₂, HgO, and HgS) was used for qualitative calibration. A standard reference material with a certified value for Hg concentration was used to evaluate the method. When the temperature of the furnace was programmed at a linear rate of increase of 50° min^–1, different Hg compounds could clearly be separated. Three airborne particulate matter samples were collected in parallel in Toronto, ON, Canada and analyzed using this method. Reproducible results were obtained and Hg⁰, HgCl₂, HgO, and HgS species from these samples were detected.     

Development of a KI Annular Denuder for NO2 Collection

Abstract

The use of a KI-coated annular denuder for eliminating NO₂ interference during sampling of airborne particulate matter on filter media is proposed. The performances of this novel diffusion sampler were evaluated in a series of practical tests concerning optimization of the sorption efficiency of NO₂. Results pointed out that a properly sized annular denuder under 1 m long could be able to remove HO₂ before collecting aerosols at laminar airflows as high as 15 1 min^?1.     

Atomic emission spectrometric analysis of airborne particulate matter by direct nebulization of suspensions into the inductively-coupled plasma

A method is described for the rapid, direct emission spectrometric determination of iron in airborne particulate matter collected on polystyrene fiber filters using a conventional high-volume sampler and a Japanese low-volume sampler. The suspension prepared by dissolving the filter material in xylene was directly nebulized into the inductivelycoupled plasma excitation source. An ultrasonic immersion device was used for stirring purposes. Particles within the size range 0.1–100 μm in diameter are collected on the high-volume filters, while the largest particles on low-volume filters do not exceed 10 μm in diameter. The difference in the particle size composition entailed the use of a separate set of standard suspensions for each sample type. Standard suspensions for calibration were prepared from NBS SRM-1648 (urban particulates) as originally received and from its ground powder for high-volume and low-volume samples, respectively. The relative standard deviation was usually below 5%, which is acceptable for large-scale air pollution survey work. The possibility of determining other major and minor elements in airborne particulate matter was also examined.     

Particle-size distribution of polycyclic aromatic hydrocarbons in urban air in southern Spain

The size distribution of polycyclic aromatic hydrocarbons (PAH) was determined for airborne particles from a large city with high vehicular traffic. The analytical method was optimised and validated using NIST standard reference material (SRM 1649a Urban Dust). The 16 priority PAH listed in the US-EPA were Soxhlet-extracted from filtered particulate matter and then fractionated using on-column chromatography. The aromatic fraction was quantified by gas chromatography-mass spectrometry. Real samples of particles collected in Seville (Spain) were analysed using the validated method. Values for the total concentration of PAH in the air, as well as the concentrations of each PAH in six particle-size ranges were obtained. Values of the PAH in TSP, PM₁₀, PM_2.5 and PM₁ were assessed.     

Rapid determination of trace polycyclic aromatic hydrocarbons in particulate matter using accelerated solvent extraction followed by ultra high performance liquid chromatography with fluorescence detection

A method has been developed for the trace analysis of polycyclic aromatic hydrocarbons, which are known as persistent organic pollutants and ubiquitous constituents of fine particulate matter that causes growing airborne pollution. The method, which was especially for samples of airborne particulate matter less than 2.5 μm in diameter, utilized accelerated solvent extraction and ultra high performance liquid chromatography with fluorescence detector. Four principal parameters of accelerated solvent extraction were optimized to obtain maximum extraction efficiency. Using the established synergetic programs of gradient elution and fluorescence wavelength switching, a rapid separation was achieved in 6.56 min with good linearity for 15 polycyclic aromatic hydrocarbons (coefficient of determination above 0.999). The limits of detection ranged from 0.833 to 10.0 pg/m³. The precision of the method expressed as inter‐day relative standard deviation ranged from 0.2 to 1%, which was calculated from nine repetitive measurements of 8.00 μg/L analytes. Average spiked recoveries ranged from 71.6 to 97.7%, with the exception of naphthalene. The rapid, sensitive, and accurate method can meet the pressing needs of health risk assessment and increasingly heavy daily tasks of air quality monitoring.     

Evaluation of a passive sampler for airborne formaldehyde

Summary A diffusive sampler for the large scale routine determination of airborne formaldehyde was developed. Formaldehyde is sampled in a badge-type passive sampler containing a 2,4-dinitrophenylhydrazine-coated filter paper as sampling layer. Formaldehyde is immediately converted to the corresponding hydrazone, which, after desorption with acetonitrile, is separated and quantified by gradient HPLC using UV detection at 345 nm. Calibration was done via an active sampling method and showed an excellent, time- and concentration-independent linear performance of the diffusive samplers. A detection limit of about 0.05 ml/m³·h (ppm·h) and a relative standard deviation of about 10% ensured a good analytical reliability. By testing the influence of air movements at the sampler surface, a minimum air velocity of 10 cm/s was found necessary to ensure representative sampling.     

Microwave assisted sample preparation for determining water-soluble fraction of trace elements in urban airborne particulate matter: evaluation of bioavailability

The feasibility of using two different microwave-based sample preparation methods was investigated to determine the total and water-soluble trace metal fraction in airborne particulate matter. The extraction techniques were then applied to urban particulate matter of different sizes in order to evaluate their bioavailability of associated trace metals. While a combination of HNO₃-HF-H₂O₂ was used for the total trace metal fraction of particulate matter, water was employed for the microwave-assisted extraction of water-soluble trace metal fractions. Inductively coupled plasma-mass spectrometry (ICP-MS) was used for the analysis of trace elements. The experimental protocol for the microwave assisted digestion was established using two different SRMs (1648, urban particulate matter and 1649a, urban dust). In the case of water-soluble trace metal fraction, the quantities extracted from the SRMs were compared between ultrasonic and microwave-assisted extractions, and there was a good agreement between the two extraction methods. Blanks values and limits of detection (LODs) for total and water-soluble trace metal concentrations were determined for three different filter substrates (Teflon, Zeflour, and Quartz). Subsequently, the proposed digestion method was evaluated for its extraction efficiency with these filter substrates. Finally, the real-world application of the proposed microwave-based sample preparation methods was demonstrated by analyzing trace elements in airborne particulate samples collected from different outdoor environments in Singapore. The solubility of 11 trace elements detected in the particulate samples is quantified.     

Air pollution monitoring of an urban dust in Daejeon city,Korea by using instrumental neutron activation analysis

For air pollution monitoring, about 1300 airborne particulate matter samples were collected by using a low volume air sampler and a polycarbonate filter at two sampling sites in an urban region, Daejeon, the middle of Korea from 2003 to 2006. Mass concentrations of the black carbon were measured using a smoke stain reflectometer. The concentrations of 24 elements in the collected samples were analyzed by using instrumental neutron activation analysis, and its temporal trends and enrichment factors were investigated under different environmental conditions. Analytical control was carried out by using certified reference materials.     

A liquid chromatography–atmospheric pressure photoionization tandem mass spectrometric method for the determination of azaarenes in atmospheric particulate matter

The development, optimization and validation of a liquid chromatography–atmospheric pressure photoionization tandem mass spectrometric (LC–APPI/MS/MS) method for the determination of 15 azaarenes (4-azafluorene, benzo[h] and -[f]quinoline, phenanthridine, acridine, 1-azafluoranthene, 4-azapyrene, benz[a]- and -[c]acridine, -10-azabenzo[a]pyrene, 7,9- and 7,10-dimethylbenz[c]acridine, dibenz[a,j]-, -[c,h] and [a,i]acridine) in airborne particulate matter is described. Each compound was detected and quantified operating in multiple reaction monitoring mode. Extraction of azaarenes was achieved using accelerated solvent extraction (ASE) with dichlormethane/methanol (50/50, v/v). After extraction, no additional clean-up procedure like solid phase or liquid/liquid extraction was necessary. Limits of quantification (S/N × 10) ranged from 0.2 pg/μl to 1.4 pg/μl, matrix dependent recoveries were between 57% and 94%, with relative standard deviations from 8% to 17%. Applicability of the method was demonstrated analyzing 10 samples of particulate matter (PM_2.5) collected in winter 2008. In all samples dimethylbenz[c]acridines as well as dibenzacridines were below the limit of quantification, concentration of the remaining analytes were in the range from 0.002 ng/m³ to 0.356 ng/m³.     

Speciation of antimony in airborne particulate matter using ultrasound probe fast extraction and analysis by HPLC-HG-AFS

A fast extraction procedure has been developed for Sb(III) and Sb(V) oxoanions speciation in airborne particulate matter samples. Different extraction media (diammonium tartrate, hidroxilammonium clorhidrate, citric acid + ascorbic acid, phosphoric acid and citrate solutions) were tried, with assistance of an ultrasonic probe. The operation power and time of extraction were also optimized. The higher extraction recoveries were obtained with a 100 mmol L⁻¹ hidroxilammonium clorhidrate aqueous solution assisted by the ultrasound probe operated at 50 W during 3 min. The extracts were analyzed by HPLC-HG-AFS. The chromatographic separation of Sb(III) and Sb(V) was also optimized using diammonium tartrate and phthalic acid as mobile phases. The separation of both Sb species was performed in less than 3 min under isocratic conditions, using a 200 mmol L⁻¹ diammonium tartrate solution. The proposed extraction procedure and the HPLC-HG-AFS instrumental coupling have been successfully applied to airborne particulate matter samples, with high Sb content, collected in heavy traffic streets from Buenos Aires (Argentina). The results showed the presence of both Sb species at similar concentrations in the ng m⁻³ level. The extraction yield was higher than 90% for all the analyzed samples.     

The effect of the wind velocity on the uptake rates of various diffusive samplers

This paper examines the results of experiments carried out in an exposure chamber to determine the wind effects on the performance of various diffusive sampler types commonly used for measuring gaseous pollutants in air. The resistance to wind of six diffusive samplers, two Palmes tubes, a badge with diffusion membrane, the EMD sampler and two radial diffusive samplers for different pollutants was compared in a range of velocities from 0 to 300?cm?s^?1. For all diffusive samplers tested, an increase in uptake rate was observed with increased air velocity usually following a logarithmic function. The consequences are an underestimation in the concentration measured by the diffusive samplers for low wind velocities below 30?cm?s^?1 and conversely an overestimation from 60?cm?s^?1. The magnitude of wind effects depends on diffusive sampler type and exceeds an uptake rate variation of ±20% for the axial diffusion tubes and the EMD sampler. With regard to the characteristics of each diffusive sampler, the dependence of uptake rate on wind velocity was analysed and discussed. The radial diffusive samplers for benzene and particularly the ones having a large and thick porous membrane appear to be the most effective design to minimise the influence of air velocity on passive sampling.