Trueness, precision, and detectability for sampling and analysis of organic species in airborne particulate matter.

Recovery, precision, limits of detection and quantitation, blank levels, calibration linearity, and agreement with certified reference materials were determined for two classes of organic components of airborne particulate matter, polycyclic aromatic hydrocarbons and hopanes, using typical sampling and gas chromatography/mass spectrometry analysis methods. These determinations were based on initial method proficiency tests and on-going internal quality control procedures. Recoveries generally ranged from 75% to 85% for all target analytes and collocated sample precision estimates were generally better than 20% for polycyclic aromatic hydrocarbons and better than 25% for hopanes. Results indicated substantial differences in data quality between the polycyclic aromatic hydrocarbons and hopanes. Polycyclic aromatic hydrocarbons demonstrated better collocated precision, lower method detection limits, lower blank levels, and better agreement with certified reference materials than the hopanes. The most serious area of concern was the disagreement between measured and expected values in the standard reference material for hopanes. With this exception, good data quality was demonstrated for all target analytes on all other data quality indicators.

Recovery of semivolatile organic compounds during sample preparation: implications for characterization of airborne particulate matter.

Semivolatile compounds present special analytical challenges not met by conventional methods for analysis of ambient particulate matter (PM). Accurate quantification of PM-associated organic compounds requires validation of the laboratory procedures for recovery over a wide volatility and polarity range. To meet these challenges, solutions of n-alkanes (nC12-nC40) and polycyclic aromatic hydrocarbons PAHs (naphthalene to benzo[ghi]perylene) were reduced in volume from a solvent mixture (equal volumes of hexane, dichloromethane and methanol), to examine recovery after reduction in volume. When the extract solution volume reached 0.5 mL the solvent was entirely methanol, and the recovery averaged 60% for n-alkanes nC12-nC25 and PAHs from naphthalene to chrysene. Recovery of higher MW compounds decreased with MW, because of their insolubility in methanol. When the walls of the flasks were washed with 1 mL of equal parts hexane and dichloromethane (to reconstruct the original solvent composition), the recovery of nC18 and higher MW compounds increased dramatically, up to 100% for nC22-nC32 and then slowly decreasing with MW due to insolubility. To examine recovery during extraction of the components of the High Capacity Integrated Gas and Particle Sampler, the same standards were used to spike its denuders and filters. For XAD-4 coated denuders and filters, normalized recovery was >95% after two extractions. Recovery from spiked quartz filters matched the recovery from the coated surfaces for alkanes nC18 and larger and for fluoranthene and larger PAHs. Lower MW compounds evaporated from the quartz filter with the spiking solvent. This careful approach allowed quantification of organics by correcting for volatility- and solubility-related sample preparation losses. This method is illustrated for an ambient sample collected with this sampler during the Texas Air Quality Study 2000.

Polycyclic aromatic hydrocarbons and other semivolatile organic compounds collected in New York City in response to the events of 9/11.

Concentrations of over 60 nonpolar semivolatile and nonvolatile organic compounds were measured in Lower Manhattan, NY, using a high-capacity integrated organic gas and particle sampler after the initial destruction of the World Trade Center (WTC). The results indicate that the remaining air plumes from the disaster site were comprised of many pollutants and classes and represent a complex mixture of biogenic (wood-smoke) and anthropogenic sources. This mixture includes compounds that are typically associated with fossil fuel emissions and their combustion products. The molecular markers for these emissions include the high molecular weight PAHs, the n-alkanes, a Carbon Preference Index approximately 1 (odd carbon:even carbon approximately 1), as well as pristane and phytane as specific markers for fuel oil degradation. These results are not unexpected considering the large number of diesel generators and outsized vehicles used in the removal phases. The resulting air plume would also include emissions of burning and remnant materials from the WTC site. Only a small number of molecular markers for these emissions have been identified such as retene and 1,4a-dimethyl-7-(methylethyl)-1,2,3,4,9,10,10a,4a-octahydrophenanthrene that are typically biogenic in origin. In addition, the compound 1,3-diphenylpropane[1',1'-(1,3-propanediyl)bis-benzene] was observed, and to our knowledge, this species has not previously been reported from ambient sampling. It has been associated with polystyrene and other plastics, which are in abundance at the WTC site. These emissions lasted for at least 3 weeks (September 26-October 21, 2001) after the initial destruction of the WTC.