Advances in offline approaches for trace measurements of complex organic compound mixtures via soft ionization and high-resolution tandem mass spectrometry.

Complex airborne mixtures of organic compounds can contain 10,000's of diverse compounds at trace concentrations. Here, we incorporate high-resolution mass spectrometry into our integrated offline sampling-to-analysis measurement system for routine molecular-level speciation of complex mixtures in gas- or particle-phase samples with detection limits of 2-20 pg L-1 (i.e. 0.2-1.9 ppt in 6 L samples). Analytes desorbed from custom adsorbent tubes (or filter extracts) were separated via gas chromatography (GC) and simultaneously analyzed by an electron ionization quadrupole mass spectrometer (EI-MS), and by atmospheric pressure chemical ionization (APCI) combined with a high-resolution quadrupole time-of-flight mass spectrometer (Q-TOF) with a resolution of 25,000-40,000 M/ΔM in HR-TOF and MS/MS modes. We demonstrated our system with simple standards, a Macondo crude oil standard as a reference for complex mixtures of common airborne compounds, and ambient samples using GC-TOF and GC-MS/MS. We speciated complex mixtures at mass accuracy error (i.e. mass tolerance) down to 8 ± 2 ppm (e.g. resolving analytes of mass 270.000 u with 0.003 u accuracy) using a targeted approach with 3000 molecular formulas, including hydrocarbons and functionalized analytes containing oxygen, sulfur, nitrogen, or phosphorous. This extended from compounds with 10 to 32 carbon atoms and up to 16 hydrocarbon formulas per carbon number, and a similar range for functionalized compound classes. We also demonstrated our MS/MS capabilities to differentiate structural isomers and determine the presence of specific functional groups; and our direct-TOF capability, which bypasses high-temperature chromatographic separation to preserve functionalized analytes.

Advances in offline approaches for chemically speciated measurements of trace gas-phase organic compounds via adsorbent tubes in an integrated sampling-to-analysis system.

Gas-phase organic compounds across a range of volatilities, including volatile organic compounds (VOCs), are key components of outdoor air, indoor spaces, and a variety of other anthropogenic and biogenic systems. The collection of offline samples on adsorbent-packed tubes for analysis on laboratory instrumentation has been in use for decades, but with limited sensitivities and compound coverage. We present and evaluate our integrated sampling-to-analysis system that enables offline detailed chemical characterization of multi-faceted organic mixtures at trace concentrations. Its capabilities extend across a diverse variety of VOCs with different molecular features, as well as intermediate and semivolatile organic compounds (I/SVOCs). Samples can be collected manually or via automated devices that have been applied in chamber, field, and aircraft platforms. The laboratory instrumentation can be coupled to both a high resolution mass spectrometer (MS) and a traditional quadrupole MS, though performance metrics presented in this study are determined via the traditional MS. We demonstrate capabilities for detailed chemical characterization and routine performance for a wide range of compound functionalities at sub-part per trillion (ppt) concentrations, and as low as <100 parts per quadrillion (ppq), yielding 3300 observed unique compound peaks in a single indoor air sample. These limits of detection and compound coverage were accomplished through a holistic optimization of the entire system and lifecycle of adsorbent tubes. We present our best practices for all aspects of tube production, handling, sampling, and analysis, and an examination of commercially-available materials and our custom adsorbent tubes using a diverse mix of VOC, IVOC, and SVOC standards, including difficult to measure analytes across a range of polarities and functionalities. In many aspects, the commercially-available materials and tube conditioners tested were insufficient for achieving low-ppt measurements.

The impact of particle size, relative humidity, and sulfur dioxide on iron solubility in simulated atmospheric marine aerosols.

Iron is a limiting nutrient in about half of the world's oceans, and its most significant source is atmospheric deposition. To understand the pathways of iron solubilization during atmospheric transport, we exposed size segregated simulated marine aerosols to 5 ppm sulfur dioxide at arid (23 ± 1% relative humidity, RH) and marine (98 ± 1% RH) conditions. Relative iron solubility increased as the particle size decreased for goethite and hematite, while for magnetite, the relative solubility was similar for all of the fine size fractions (2.5-0.25 µm) investigated but higher than the coarse size fraction (10-2.5 µm). Goethite and hematite showed increased solubility at arid RH, but no difference (p > 0.05) was observed between the two humidity levels for magnetite. There was no correlation between iron solubility and exposure to SO2 in any mineral for any size fraction. X-ray absorption near edge structure (XANES) measurements showed no change in iron speciation [Fe(II) and Fe(III)] in any minerals following SO2 exposure. SEM-EDS measurements of SO2-exposed goethite revealed small amounts of sulfur uptake on the samples; however, the incorporated sulfur did not affect iron solubility. Our results show that although sulfur is incorporated into particles via gas-phase processes, changes in iron solubility also depend on other species in the aerosol.

Respirable antimony and other trace-elements inside and outside an elementary school in Flagstaff, AZ, USA.

Because people spend almost 90% of their time indoors, ambient air monitors may severely underestimate actual exposure to atmospheric particulate matter (PM). Therefore, it becomes increasingly important to better understand the microenvironments where people are spending their time. For preadolescent children, the best estimates of exposure may be inside of their school. In this study, 11 size fractions of PM were collected inside and outside of an elementary school in Flagstaff, AZ, USA. In particles<1 µm (PM1), the total mass indoors was similar to the mass outdoors (indoor:outdoor, I:O, ratio=0.92 ± 0.16). In the PM1-10 fraction, however, the mass concentration inside the school was highly elevated relative to outside the school (I:O ratios=13 ± 3). Mass concentrations of 27 elements were analyzed by ICP-MS. For all metals except for antimony (Sb), the PM1 and PM1-10 I:O ratios are found to be similar to the overall PM mass (near 1 and 13, respectively). In addition, indoor and outdoor particle size distributions reveal a crustal character for every element except Cu, Zn, Pb, and Sb. Therefore, we hypothesize that most of the PM mass inside the school is a result of transport from outside the school followed by resuspension from floors and clothing. In the PM1 fraction, the indoor mass of Sb was 86 times greater than the outdoor mass and had an air concentration of 17 ngm(-3) - greater than many urban areas around the world. Cu:Sb ratios and size distribution functions suggest that the excess source of PM1 indoor Sb results from the suspension of embedded Sb (used as a flame retardant) in the carpeting. This is the first study to observe elevated submicron Sb in schools and further studies are required to determine if this is a widespread health risk.