Thermal Carbon Analysis Research Articles

Unfolding of Lignin Structure Using Size-Exclusion Fractionation.

The heterogeneous and recalcitrant structure of lignin hinders its practical application. Here, we describe how new approaches to lignin characterization can reveal structural details that could ultimately lead to its more efficient utilization. A suite of methods, which enabled mass balance closure, the evaluation of structural features, and an accurate molecular weight (MW) determination, were employed and revealed unexpected structural features of the five alkali lignin fractions obtained with preparative size-exclusion chromatography (SEC). A thermal carbon analysis (TCA) provided quantitative temperature profiles based on sequential carbon evolution, including the final oxidation of char. The TCA results, supported with thermal desorption/pyrolysis gas chromatography-mass spectrometry (TD-Py-GC-MS) and 31P NMR spectroscopy, revealed the unfolding of the lignin structure as a result of the SEC fractionation, due to the disruption of the interactions between the high- and low-MW components. The "unraveled" lignin revealed poorly accessible hydroxyl groups and showed an altered thermal behavior. The fractionated lignin produced significantly less char upon pyrolysis, 2 vs. 47%. It also featured a higher occurrence of low-MW thermal evolution products, particularly guaiacol carbonyls, and more than double the number of OH groups accessible for phosphitylation. These observations indicate pronounced alterations in the lignin intermolecular association following size-exclusion fractionation, which may be used for more efficient lignin processing in biorefineries.

First insight into seasonal variability of urban air quality of northern Pakistan: An emerging issue associated with health risks in Karakoram-Hindukush-Himalaya region

There is a dire need of air quality monitoring in the high-mountain areas of Karakoram-Hindu Kush-Himalaya (HKH) region, particularly related to the recent activities undergoing the China-Pakistan Economic Corridor (CPEC). This study presents the first baseline monitoring and evaluation findings from Gilgit city, Gilgit-Baltistan. Hourly data collection for air quality parameters (PM2.5, NO, NO2, SO2, O3 and CO) were measured using air-pointer (recordum, Austria) from 1 Jan 2018 to 31 Mar 2018 (winter) and 1 Jun 2018 to 31 Aug 2018 (summer). Our findings depict PM2.5 health limits were crossed in the winter season, while NO, NO2 and SO2 remained below their health limits. O3 and CO showed a rising trend in summer months, crossing the 8-h health limits during the season. Seasonal correlation in meteorology found an inverse relationship between most parameters and temperatures; reverse was true for O3 and CO. In parallel, thermal optical carbon analysis filter-based sampling characterized air quality into mass concentrations of PM2.5, organic carbon (OC), elemental carbon (EC) and various heavy metals. Filter-based PM2.5 correlated well with analyzer-based PM2.5 for all months that were studied, except February and March 2018. PM2.5, OC and EC were higher in summer as compared to winter, whereas higher heavy metal contributions were measured predominantly during summer. Health impacts were found to be above health limits for Ni in children only. Furthermore, principal component analysis-multiple linear regression (PCA-MLR) technique was applied to determine source apportionment, confirming the role of biomass burning in winters, and vehicular emissions in summers, highlighting the need for flexible monitoring of technologies/approaches, and communications among the various public, private agencies, and all relevant stakeholders.

Quantitative insights on de/repolymerization and deoxygenation of lignin in subcritical water

The objective of the study was to investigate alkali lignin polymerization/depolymerization pathways in subcritical water (SW) without additives. Following a SW treatment at 200, 250, 275 and 300 °C, the products were subjected to a comprehensive suite of analyses addressing the product speciation and molecular weight (MW) distribution. The MW reduction (1.4 times) in the solid products following the SW treatment indicated a surprisingly reduced impact of cross-linking/repolymerization at 300 °C and lower temperatures. This was further confirmed by thermal carbon analysis (TCA) showing a reduction in pyrolytic charring after the SW treatment. The TD-Py gas chromatography analysis of the SW treated lignin indicated that the solid residue is less oxygenated than the initial lignin (23 vs. 29% as confirmed by elemental analysis). Thus, deoxygenation rather than re-polymerization appears to be the main process route in the absence of catalysts within the temperature range considered.

Quantitative evaluation of carbon nanomaterial releases during electric heating wire cutting and sawing machine cutting of expanded polystyrene-based composites using thermal carbon analysis

Field measurements were conducted at a facility where expanded polystyrene-based carbon nanomaterial composites, namely, carbon nanotube and carbon black composites, were cut with an electric heating wire cutter or a circular sawing machine. The aerosol particles released during the cutting of the composites were measured using real-time aerosol monitoring, gravimetric analysis, thermal carbon analysis, and scanning electron microscopic observations. This study had two major goals: (1) to quantitatively evaluate the concentrations of airborne carbon nanomaterials during the cutting of their composites; (2) to evaluate the capability of thermal carbon analysis to quantify airborne carbon nanomaterials in the presence of expanded polystyrene-derived particles. The results of thermal carbon analysis showed that the concentrations of elemental carbon (an indicator of carbon nanomaterials) for all the respirable dust samples in both cutting processes were less than the limit of detection (∼2 µg/m3), which is nearly equivalent to or lower than the occupational exposure limits for carbon nanotubes (1 to 50 µg/m3). For total dust, which includes particles larger than respirable size, although the elemental carbon concentrations during heating wire cutting were low (<3 µg/m3), those during sawing machine cutting were up to 58 µg/m3. In scanning electron microscopic observations, micron-sized particles composed of or including carbon nanotubes were detected only in aerosol particles collected during the sawing machine cutting. Therefore, heating wire cutting is considered preferable. This study demonstrated that thermal carbon analysis can quantify airborne carbon nanomaterials in the presence of expanded polystyrene-derived particles.

Production of lignin based insoluble polymers (anionic hydrogels) by C. versicolor

Unlike previous lignin biodegradation studies, white rot fungi were used to produce functional biopolymers from Kraft lignin. Lignin-based polymers (hydrogel precursors) partially soluble in both aqueous and organic solvents were produced employing a relatively fast (6 days) enzymation of Kraft lignin with basidiomycetes, primarily Coriolus versicolor, pre-grown on kenaf/lignin agar followed by either vacuum evaporation or acid precipitation. After drying followed by a treatment with alkaline water, this intermediate polymer became a pH-sensitive anionic hydrogel insoluble in either aqueous or organic solvents. The yield of this polymer increased from 20 to 72 wt% with the addition of 2% dimethylsulfoxide to distilled water used as a medium. The mechanical stability and buffering capacity of this hydrogel can be adjusted by washing the intermediate polymer/hydrogel precursor prior to drying with solvents of different polarity (water, methanol or ethanol). Any of these polymers featured a significant thermal resilience assessed as a high thermostable “coked” fraction in thermal carbon analysis, apparently resulting from significant covalent cross-linking that occurs during the treatment of their intermediate precursors.

Thermal Carbon Analysis Enabling Comprehensive Characterization of Lignin and Its Degradation Products

We have developed a novel thermal carbon analysis (TCA) method that provides both carbon mass balance and thermal fractionation profiles. Though not providing chemical structural information, this method enables a comprehensive characterization of both lignin and its degradation products, potential renewable and sustainable feedstocks. TCA is essential as a complement to a qualitative chemical speciation by thermal desorption–pyrolysis gas chromatography–mass spectrometry (TD–Py–GC–MS). Mono- and diaromatic oxygenated compounds were used as model compounds to optimize the method. The influence of various parameters such as solvents, amounts of sample loaded, and temperature ramp configuration, were investigated. A multistep temperature program with TD and pyrolytic temperatures with and without oxygen was employed for analysis of untreated lignin, where up to 55 wt % evolved in the presence of oxygen only, this fraction being unaccounted for by currently used methods. The TCA results were supported by the...

Quantitative measurement of carbon nanotubes released from their composites by thermal carbon analysis

The release of free carbon nanotubes (CNTs) and CNTs partly embedded in matrix debris into the air may occur during mechanical and abrasion processes involving CNT composites. Since the harmful effects of CNT-matrix mixtures have not yet been fully evaluated, it is considered that any exposure to CNTs, including CNT-matrix mixtures, should be measured and controlled. Thermal carbon analysis, such as Method 5040 of the National Institute for Occupational Safety and Health, is one of the most reliable quantitative methods for measuring CNTs in the air. However, when CNTs are released together with polymer matrices, this technique may be inapplicable. In this study, we evaluated the potential for using thermal carbon analysis to determine CNTs in the presence of polymer matrices. Our results showed that thermal carbon analysis was potentially capable of determining CNTs in distinction from polyamide 12, polybutylene terephthalate, polypropylene, and polyoxymethylene. However, it was difficult to determine CNTs in the presence of polyethylene terephthalate, polycarbonate, polyetheretherketone, or polyamide 6.

Biodegradation of lignin by fungi, bacteria and laccases

Indulin AT biodegradation by basidiomycetous fungi, actinobacteria and commercial laccases was evaluated using a suite of chemical analysis methods. The extent of microbial degradation was confirmed by novel thermal carbon analysis (TCA), as the treatments altered the carbon desorption and pyrolysis temperature profiles in supernatants. Laccase treatments caused only minor changes, though with increases occurring in the 850°C and char precursor fractions. After fungal treatments, lignin showed a similar change in the TCA profile, along with a gradual decrease of the total carbon, signifying lignin mineralization (combined with polymerization). By contrast, bacteria produced phenolic monomers without their further catabolism. After 54days of cultivation, a 20wt% weight loss was observed only for fungi, Coriolus versicolor, corroborating the near-80% carbon mass balance closure obtained by TCA. Compositional changes in lignin as a result of biodegradation were confirmed by thermal desorption (TD)-pyrolysis-GC–MS validating the carbon fractionation obtained by TCA.

Selective Synthesis of Phenolic Compounds from Alkali Lignin in a Mixture of Sub- and Supercritical Fluids: Catalysis by CO2

A successful selective liquefaction of lignin has been demonstrated in the presence of a H2O–CO2 mixture at 300 °C, yielding 40–50 wt % organic phenolic phase. The effect of the temperature at a constant pressure and short residence time on the selectivity and yield of phenolic products from the hydrothermal reforming of alkali lignin in a mixture of sub- and supercritical fluids (H2O mixed with CO2 or N2) has been investigated. Dependent upon the processing conditions, the lignin samples produced a homologous series of phenols, such as guaiacol, homovanillic acid, quaiacyl carbonyls, guaiacyl dimers, phenol, and cresol. Gas chromatography–mass spectrometry (GC–MS), total organic carbon (TOC), and pyrolysis–GC–MS (Py–GC–MS) were used for chemical analysis of the organic liquid and solid phases. The results from GC–MS analysis of the liquid organic phases demonstrated the trend of increasing the amounts of major guaiacol products with the temperature. The thermal carbon analysis (TCA) showed a significant ...

Quantitative measurement of carbon nanotubes released from their composites using thermal carbon analysis

The ability of thermal carbon analysis to determine CNTs was evaluated in the presence of a polymer (Polystyrene, PS). Samples placed in an Au (Pt) foil boat were measured using a thermal-carbon analyzer, and the results were compared with gravimetric measurements of sample masses obtained using an ultra-microbalance. First, debris from the polymer without CNTs (i.e., PS debris) was analyzed. The amount of PS debris detected in the organic carbon (OC) fraction was found to be in good agreement with the gravimetrically measured mass of the PS debris, while the amount of pyrolyticallygenerated carbon soot detected in the elemental carbon (EC) fraction was negligible. Next, single-wall CNT (AIST/TASC Super-Growth) powder was analyzed, and the amount of the CNT powder detected in the EC fraction was found to be 95-96% of the gravimetrically measured mass of the CNT powder. Subsequently, a mixture of the PS debris and the CNT powder was analyzed, and the amounts of detected OC and EC were found to be comparable to the gravimetrically measured masses of the PS debris and the CNT powder, respectively. Finally, debris from 5 wt% CNT-PS composites was analyzed, and amounts of OC and EC detected were found to be approximately comparable to the estimated masses of the PS and the CNTs in the debris of CNT-PS composite, respectively. The results therefore indicate thermal carbon analysis is capable of determining CNTs in the presence of PS.

The influence of temperature calibration on the OC–EC results from a dual-optics thermal carbon analyzer

Abstract. Thermal–optical analysis (TOA) is a widely used technique that fractionates carbonaceous aerosol particles into organic and elemental carbon (OC and EC), or carbonate. Thermal sub-fractions of evolved OC and EC are also used for source identification and apportionment; thus, oven temperature accuracy during TOA analysis is essential. Evidence now indicates that the "actual" sample (filter) temperature and the temperature measured by the built-in oven thermocouple (or set-point temperature) can differ by as much as 50 °C. This difference can affect the OC–EC split point selection and consequently the OC and EC fraction and sub-fraction concentrations being reported, depending on the sample composition and in-use TOA method and instrument. The present study systematically investigates the influence of an oven temperature calibration procedure for TOA. A dual-optical carbon analyzer that simultaneously measures transmission and reflectance (TOT and TOR) is used, functioning under the conditions of both the National Institute of Occupational Safety and Health Method 5040 (NIOSH) and Interagency Monitoring of Protected Visual Environment (IMPROVE) protocols. The application of the oven calibration procedure to our dual-optics instrument significantly changed NIOSH 5040 carbon fractions (OC and EC) and the IMPROVE OC fraction. In addition, the well-known OC–EC split difference between NIOSH and IMPROVE methods is even further perturbed following the instrument calibration. Further study is needed to determine if the widespread application of this oven temperature calibration procedure will indeed improve accuracy and our ability to compare among carbonaceous aerosol studies that use TOA.

Evaluating the capabilities of portable black carbon monitors and photometers for measuring airborne carbon nanotubes

For daily monitoring of occupational exposure to aerosolized carbon nanotubes (CNTs) where CNTs are manufactured and handled, inexpensive real-time measuring methods are preferable. In this study, we evaluated the capabilities of a portable black carbon monitor (BCM; also called an aethalometer) and a light-scattering aerosol photometer in detecting airborne CNTs. The responses of these instruments to airborne CNTs, aerosolized through vortex shaking, were evaluated by comparing the measurements of CNT mass concentrations made by these instruments to those determined through thermal carbon analysis. Results showed that their raw readings underestimated CNT mass concentrations in most cases. Their sensitivities depended on the type of CNTs and decreased with the particle sizes of aerosolized CNT clumps. We also found that the sensitivity of the BCM tended to substantially decrease with increasing filter load, even before the point at which the filter should be replaced as recommended by the manufacturer, which could be attributed to a clean environmental condition (i.e., the absence of ubiquitous light-scattering material). As an example of the use of these instruments for measuring airborne CNTs in the presence of background aerosols, a CNT-handling simulation was also conducted. Although both the BCM and the photometer could detect CNT emissions, the BCM was more sensitive to the detection of emitted CNTs in the presence of background aerosols. The correction factors obtained from the response evaluations could enhance the measurement accuracy of these instruments, which will be helpful for the daily monitoring of CNTs at workplaces.

Characterization of urban aerosol in Campinas, São Paulo, Brazil

A quantitative study was performed in Campinas, Brazil. Measurements were taken on an avenue with intense vehicle traffic in the city's downtown area from August 2003 to August 2004. A dichotomous sampler was employed for PM 2.5 and PM 10. Samples were collected for 24 h at 3-day intervals. In addition, seasonal variations were investigated, using a MOUDI cascade impactor and VOC adsorption tubes, during a specific 5-day period in the summer of 2003 (December) and the winter of 2004 (August). The polycarbonate filters were analyzed by gravimetry, Particle Induced X-ray Emission (PIXE), ion chromatography and reflectance, to identify the mass concentration, elemental composition, ions and elemental carbon mass, respectively. The quartz filters were analyzed by gravimetry and thermal combustion carbon analysis to identify the mass concentration and carbon mass. Results showed an annual mean of 20.85, 10.68 and 10.17 μg m − 3 for PM 10, PM 2.5 and PM 2.5–10, respectively. The cascade impactor provided mass distribution and revealed differences between the two seasons. The size distribution for chemical elements indicated soil-derived elements in the coarse fraction. PM winter concentrations were expected to be higher than those in summer, but that was not the case during the days of this study, when summer and winter concentrations were almost identical The PIXE analysis revealed metals and metal compounds, soil-derived elements, sulfates, carbonates, chlorides and other anthropogenic air-borne particles, supposing molecules in their usual composition. An analysis of the VOCs revealed benzene, toluene, m, p-xylene, n-hexane, 2-metilhexane and n-nonane. A mass balance analysis indicated different classes, among which elemental carbon was the most abundant, followed by organic carbon, soil elements and industrial sources.

An ion chromatographic analysis of water-soluble, short-chain organic acids in ambient particulate matter

Recent studies have shown that the inclusion of water-soluble short-chain (WSSC) organic acids in source apportionment using positive matrix factorization (PMF) resulted in an improvement in the model's ability to resolve sources, and in understanding secondary particle formation. In the United States, numerous network samplers are operational. Quartz-fibre filters for thermal optical carbon analysis have been collected over a period of years as a part of these sampling campaigns on a routine basis. However, only a small portion of these filters are used for the carbon analysis. Thus, there is the potential to utilize these samples to enhance organic speciation for subsequent use in source apportionment. In this work, an ion-chromatographic method was developed to identify and quantify the WSSC organic acids present in fine particulate matter (PM2.5). Samples collected to measure the concentrations of particles (PM2.5) in south-western (Stockton) and northern (Potsdam) New York, USA from November 2002 to June 2004 were used in this study. Acetic, formic, propionic, oxalic, and malonic acids were successfully identified. The identified species accounted for 5–15% of the organic matter mass and thus enhance the knowledge of atmospheric organic-matter constituents. Oxalic acid was the most abundant species at Potsdam and Stockton with median concentrations of 17.71 ng m−3 and 92 ng m−3, respectively. Acetic and formic acids were present in Potsdam at median concentrations of 12.54 ng m−3 and 14.48 ng m−3, while at Stockton they were present at 57.58 ng m−3 and 51.54 ng m−3, respectively. The median concentration values for all acids at Stockton were higher than Potsdam. These observations are consistent with a study conducted in a semi-urban location, Schenectady, New York. At both sites, propionic and malonic acids were found in much lower concentrations when compared with the other acids. The concentration time series of various acids and seasonal variations in individual acids are discussed. The co-variance of acetic and formic acids is also outlined.

Refining temperature measures in thermal/optical carbon analysis

Abstract. Thermal/optical methods have been widely used for quantifying total carbon (TC), organic carbon (OC), and elemental carbon (EC) in ambient and source particulate samples. Thermally defined carbon fractions have been used for source identification. Temperature precision in thermal carbon analysis is critical to the allocation of carbon fractions. The sample temperature is determined by a thermocouple, which is usually located in the oven near the sample. Sample and thermocouple temperature may differ owing to different thermal properties between the sample filter punch and the thermocouple, or inhomogeneities in the heating zone. Quick-drying temperature-indicating liquids (Tempil Inc., South Plainfield, NJ) of different liquefying points are used as temperature calibration standards. These consist of chemicals that change their appearance at specific temperatures and can be optically monitored to determine the sample temperature. Temperature measures were evaluated for three different models of carbon analyzers. Sample temperatures were found to differ from sensor temperatures by 10 to 50°C. Temperature biases of 14 to 22°C during thermal analysis were found to change carbon fraction measurements. The temperature indicators allow calibration curves to be constructed that relate the sample temperature to the temperature measured by a thermocouple.

Determination of Total Aerosol Nitrogen by Thermal Evolution

An aerosol nitrogen analyzer has been developed for determination of total nitrogen (TN) content in aerosols collected on a filter substrate. It uses rapid thermoevolution of nitrogenous species at 800°C in a 2.5% O2/97.5% He carrier gas. Evolved nitrogen is oxidized to nitrogen oxides on a manganese dioxide catalyst, converted to nitrogen monoxide on a molybdenum catalyst, and quantified with a chemiluminescence detector. The analyzer is built upon components of two commercially available instruments, a thermal aerosol carbon analyzer and a chemiluminescent NO x analyzer. This system is able to provide fast (3 min per sample) and highly sensitive (a detection limit of 26 ng N) TN measurements for aerosol samples of a small size (∼1× 1 cm2) without any pretreatment. When the aerosol nitrogen analyzer was properly calibrated by ammonium sulfate, excellent agreement was obtained between TN measurements of twelve aerosol samples by the aerosol nitrogen analyzer and those obtained from an elemental analyzer. ...

PM2.5 carbonate concentrations at regionally representative Interagency Monitoring of Protected Visual Environment sites

This experiment shows that carbonate concentrations are negligible at most Interagency Monitoring of Protected Visual Environments (IMPROVE) monitoring sites. Even when present, carbonate does not cause significant biases in total carbon (TC), organic carbon (OC), and elemental carbon (EC) concentrations in the IMPROVE protocol. The analysis also shows that acidification to remove interferences from carbonates is not necessary when using a thermal evolution method in which the highest temperature is less than 800°C. Seventy‐seven samples with the highest calcium concentrations from 58 sites in the IMPROVE network were analyzed for carbonate by acidification. Measured carbonate carbon concentrations at most sites were &lt;100 ng m−3, with many less than lower quantifiable limits; the highest carbonate carbon of 420 ng m−3 was measured at Guadalupe Mountains National Park in western Texas. Comparison of EC measured at 800°C with and without acidification showed no consistent biases for the nonacidified analysis, even when carbonate levels were high. Acidification may be advisable when sampling particle sizes larger than 2.5 μm, when samples are acquired at locations where carbonate carbon is expected to be high, or when &gt;800°C temperatures are applied during thermal evolution carbon analysis.

Comparison and evaluation of in situ and filter carbon measurements at the Fresno Supersite

The Fresno Supersite in Fresno, California, USA, acquires in situ 5‐ to 60‐min average PM2.5 organic carbon (OC), elemental carbon (EC), and total carbon (TC) measurements by the following methods: (1) thermal evolution carbon analyzer for organic, elemental, and total carbon; (2) single‐wavelength and seven‐color aethalometer for black carbon (BC); and (3) photoionization for particle‐bound polycyclic aromatic hydrocarbons. Twenty‐four‐hour average PM2.5 filter‐based measurements include (1) nondenuded quartz filters with no backup filter in a PM2.5 Federal Reference Method (FRM) sampler; (2) quartz filters behind an organic carbon denuder with a quartz backup filter in a Reference Ambient Aerosol Sampler (RAAS); (3) nondenuded quartz filters with backup filter in a RAAS; and (4) nondenuded quartz filters with no backup filter in a sequential filter sampler. Filter samples are analyzed after sampling by the Interagency Monitoring of Protected Visual Environments (IMPROVE) thermal/optical reflectance carbon analysis protocol. Collocated measurements are examined for year 2000. Measurement equivalence is found for PM2.5 mass, light transmission, and TC between the FRM and RAAS speciation samplers. The average ratios of front filter carbon between the denuded and nondenuded channels in the RAAS sampler are 0.83 ± 0.19 for TC, 0.81 ± 0.20 for OC, and 1.01 ± 0.33 for EC. The average differences for TC and OC are low (1.2 to 1.4 μg m‐3) and are comparable to the measurement uncertainties. Continuous thermal evolution carbon measurements are not comparable to filter measurements. Aethalometer BC and filter EC are highly correlated, but filter EC is consistently 20–25% higher than continuous aethalometer BC. Pairwise comparisons show filter EC measurements acquired in this study are predictable from aethalometer BC measurements.

Measuring the Size Distribution of Atmospheric Organic and Black Carbon Using Impactor Sampling Coupled with Thermal Carbon Analysis: Method Development and Uncertainties

A method for determining the mass size distribution of organic and black carbon (OC and BC) in atmospheric aerosols is introduced. The method relies on a particle sampling with 2 parallel size-segregating devices, a 12-stage Small Deposit area low pressure impactor (SDI) and a virtual impactor (VI), and the subsequent analysis of the samples with thermal and thermal-optical methods, respectively. The method development revealed that SDI is, like other sampling methods, susceptible to serious sampling artifacts and OC pyrolysis during thermal analysis. However, some of the SDI's limitations can be overcome by parallel VI measurements. The good correlation between the SDI and the VI data for most of the samples collected here indicates that under most conditions, the lack of the pyrolysis correction for the SDI samples does not cause significant errors in the OC/BC split. Valuable features of this method are that it offers a good size resolution in both sub- and supermicron size fractions, indicates if ther...

Comprehensive characterisation of atmospheric aerosols in Budapest, Hungary: physicochemical properties of inorganic species

As part of an air pollution project in Budapest, aerosol samples were collected by stacked filter units and cascade impactors at an urban background site, two downtown sites, and within a road tunnel in field campaigns conducted in 1996, 1998 and 1999. Some criteria pollutants were also measured at one of the downtown sites. The aerosol samples were analysed by one or more of the following methods: instrumental neutron activation analysis, particle-induced X-ray emission analysis, a light reflection technique, gravimetry, thermal profiling carbon analysis and capillary electrophoresis. The quantities measured or derived include atmospheric concentrations of elements (from Na to U), of particulate matter, of black and elemental carbon, and total carbonaceous fraction, of some ionic species (e.g., nitrate and sulphate) in the fine ( <2 μm equivalent aerodynamic diameter, EAD) or in both coarse (10– 2 μm EAD) and fine size fractions, atmospheric concentrations of NO, NO 2, SO 2, CO and total suspended particulate matter, and meteorological parameters. The analytical results were used for characterisation of the concentration levels, elemental composition, time trends, enrichment of and relationships among the aerosol species in coarse and fine size fractions, for studying their fine-to-coarse concentration ratios, spatial and temporal variability, for determining detailed elemental mass size distributions, and for examining the extent of chemical mass closure.