ACE-Asia intercomparison of a thermal-optical method for the determination of particle-phase organic and elemental carbon.

A laboratory intercomparison of organic carbon (OC) and elemental carbon (EC) measurements of atmospheric particulate matter samples collected on quartz filters was conducted among eight participants of the ACE-Asia field experiment The intercomparison took place in two stages: the first round of the intercomparison was conducted when filter samples collected during the ACE-Asia experiment were being analyzed for OC and EC, and the second round was conducted after the ACE-Asia experiment and included selected samples from the ACE-Asia experiment Each participant operated ECOC analyzers from the same manufacturer and utilized the same analysis protocol for their measurements. The precision of OC measurements of quartz fiber filters was a function of the filter's carbon loading but was found to be in the range of 4-13% for OC loadings of 1.0-25 microg of C cm(-2). For measurements of EC, the precision was found to be in the range of 6-21% for EC loadings in the range of 0.7-8.4 microg of C cm(-2). It was demonstrated for three ambient samples, four source samples, and three complex mixtures of organic compounds that the relative amount of total evolved carbon allocated as OC and EC (i.e., the ECOC split) is sensitive to the temperature program used for analysis, and the magnitude of the sensitivity is dependent on the types of aerosol particles collected. The fraction of elemental carbon measured in wood smoke and an extract of organic compounds from a wood smoke sample were sensitive to the temperature program used for the ECOC analysis. The ECOC split for the three ambient samples and a coal fly ash sample showed moderate sensitivity to temperature program, while a carbon black sample and a sample of secondary organic aerosol were measured to have the same split of OC and EC with all temperature programs that were examined.

Gas/solid partitioning of semivolatile organic compounds (SOCs) to air filters. 3. An analysis of gas adsorption artifacts in measurements of atmospheric SOCs and organic carbon (OC). WHen using teflon membrane filters and quartz fiber filters.

Adsorption of gaseous semivolatile organic compounds (SOCs) onto the filter(s) of a filter/sorbent sampler is a potential source of measurement error when determining specific SOCs as well as organic carbon (OC) levels in the atmosphere. This work examines partitioning to both Teflon membrane filters (TMFs) and quartz fiber filters (QFFs) for purposes of predicting the magnitude of the compound-dependent gas adsorption artifact as a function of various sampling parameters. The examination is based on values of Kp,face (m3 cm(-2)), the gas/filter partition coefficient expressed as [ng sorbed per cm2 of filter face]/[ng per m3 in the gas phase]. Values of Kp,face were calculated based on literature values of the gas/solid partition coefficient Kp,s [ng sorbed per m2 of filter]/[ng per m3 in gas phase] for the adsorption of various polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzodioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) to TMFs, and for the adsorption of PAHs to QFFs. At relative humidity (RH) values below approximately 50%, the Kp,face values for PAHs are lower on TMFs than on ambient-backup QFFs. The gas adsorption artifact will therefore be lower for PAHs with TMFs than with QFFs under these conditions. In the past, corrections for the gas/filter adsorption artifact have been made by using a backup filter, and subtracting the mass amount of each compound found on the backup filter from the total (particle phase + sorbed on filter) amount found on the front filter. This procedure assumes that the ng cm(-2) amounts of each SOC sorbed on the front and backup filters are equal. That assumption will only be valid after both filters have reached equilibrium with each of the gaseous SOCs in the incoming sample air. The front filter will reach equilibrium first. The minimum air sample volume Vmin,f+b required to reach gas/filter sorption equilibrium with a pair of filters is 2Kp,face Afilter where Afilter (cm2) is the per-filter face area. Kp,face values, and therefore Vmin,f+b values, depend on the compound, relative humidity (RH), temperature, and filter type. Compound-dependent Vmin,f+b values are presented for PAHs and PCDD/Fs on both TMFs and QFFs. Compound-dependent equations which give the magnitude of the filter adsorption artifact are presented for a range of different sampling arrangements and circumstances. The equations are not intended for use in actually correcting field data because of uncertainties in actual field values of relevant parameters such as the compound-dependent Kp,face and gas/particle Kp values, and because of the fact that the equations assume ideal step-function chromatographic movement of gas-phase compounds through the adsorbing filter. Rather, the main utility of the equations is as guidance tools in designing field sampling efforts that utilize filter/sorbent samplers and in evaluating prior work. The results indicate that some backup-filter-based corrections described in the literature were carried out using sample volumes that were too small to allow proper correction for the gas adsorption artifactfor some specific SOCs of interest. Similar conclusions are reached regarding artifacts associated with the measurement of gaseous and particulate OC.

Sampling atmospheric carbonaceous aerosols using a particle trap impactor/denuder sampler.

A particle trap impactor/denuder system has been developed and tested for the sampling of ambient carbonaceous aerosols. Use of a particle trap impactor allows for a reduction of particle bounce and re-entrainment at high particle loadings, and operation at high volumetric flow rates is achieved without the use of oiled impaction substrates, thus facilitating the chemical and physical analysis of the organic compounds comprising the collected gas (G) and particle (P) phases. Honeycomb denuders have a greater density of channels for a given denuder cross-sectional area than parallel plate or annular denuders; for a given sampling flow rate, honeycomb denuders can be fabricated in more compact shapes and will have a greater amount of surface area for the collection of gases. Field testing of the sampler was conducted primarily at night to minimize the evaporation of organic carbon (OC) from collected particles, which can result from the heating of collected particles as ambient temperatures rise during the day. In side-by-side testing with an open-face filter pack sampler, the denuder system was found to minimize positive gas adsorption artifacts caused by the adsorption of gaseous OC to quartz filter fiber (QFF) surfaces. In the denuder sampler, negligible amounts of OC were observed on a QFF placed downstream of a particle-loaded QFF, suggesting that OC detected on the backup QFF in the filter pack sampler resulted primarily from the adsorption of ambient G-phase OC rather than OC evaporated from particles collected on the front filter. Equations are presented for the evaluation of the magnitude of positive and negative sampling artifacts. Analysis of these equations indicates that the mass of OC evaporated from filter-bound particles present downstream of a denuder depends on (i) the volume of OC-free gas passed through the filter, (ii) the P-phase concentration and the P/G partition coefficients (Kp) of the compounds comprising the P-phase OC, (iii) the temperature (T) (values of Kp are inversely proportional to T), and (iv) the mass fraction of carbon in the compounds comprising P-phase OC. For these reasons, the magnitude of evaporative losses of OC in denuder samplers may vary among different sampling events. In addition, a method utilizing gas chromatography/mass spectrometry has been developed for determination of inertial impactor collection efficiency and denuder particle transmission efficiency. Using this method, only a single extraction of the sampler components is necessary, thereby reducing the number of extractions and analyses over conventional approaches by at least a factor of 2.