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Abstract. Upper tropospheric and lower stratospheric acetone measurements have been performed in summer and winter 1994 through 1996 at latitudes between 30øN and 75øN using ionmolecule reaction mass spectrometry. We observed very high acetone volume mixing ratios of up to 3000 pptv (parts per trillion by volume) in extended air masses and in summer when acetone destruction by photodissociation is fast. This indicates efficient transport of acetone and photochemical acetone precursors to the upper troposphere and efficient upper tropospheric formation of acetone products, especially HO x radicals and PAN. Our data indicate large HOx production from acetone which has important implications for other trace gases and aerosols.

Intraoperative delineation of tumor margins is critical for effective pancreatic cancer surgery. Yet, intraoperative frozen section analysis of tumor margins is a time-consuming and often challenging procedure that can yield confounding results due to histologic heterogeneity and tissue-processing artifacts. We have previously described the development of the MasSpec Pen technology as a handheld mass spectrometry–based device for nondestructive tissue analysis. Here, we evaluated the usefulness of the MasSpec Pen for intraoperative diagnosis of pancreatic ductal adenocarcinoma based on alterations in the metabolite and lipid profiles in in vivo and ex vivo tissues. We used the MasSpec Pen to analyze 157 banked human tissues, including pancreatic ductal adenocarcinoma, pancreatic, and bile duct tissues. Classification models generated from the molecular data yielded an overall agreement with pathology of 91.5%, sensitivity of 95.5%, and specificity of 89.7% for discriminating normal pancreas from cancer. We built a second classifier to distinguish bile duct from pancreatic cancer, achieving an overall accuracy of 95%, sensitivity of 92%, and specificity of 100%. We then translated the MasSpec Pen to the operative room and predicted on in vivo and ex vivo data acquired during 18 pancreatic surgeries, achieving 93.8% overall agreement with final postoperative pathology reports. Notably, when integrating banked tissue data with intraoperative data, an improved agreement of 100% was achieved. The result obtained demonstrate that the MasSpec Pen provides high predictive performance for tissue diagnosis and compatibility for intraoperative use, suggesting that the technology may be useful to guide surgical decision-making during pancreatic cancer surgeries.

Mass spectrometry (MS) has emerged as a valuable technology for molecular and spatial evaluation of biological samples. Ambient ionization MS techniques, in particular, allow direct analysis of tissue samples with minimal pretreatment. Here, we describe the design and optimization of an alternative ambient liquid extraction MS approach for metabolite and lipid profiling and imaging from biological samples. The system combines a piezoelectric picoliter dispenser to form solvent nanodroplets onto the sample surface with controlled and tunable spatial resolution and a conductive capillary to directly aspirate/ionize the nanodroplets for efficient analyte transmission and detection. Using this approach, we performed spatial profiling of mouse brain tissue sections with different droplet sizes (390, 420, and 500 μm). MS analysis of normal and cancerous human brain and ovarian tissues yielded rich metabolic profiles that were characteristic of disease state and enabled visualization of tissue regions with different histologic composition. This method was also used to analyze the lipid profiles of human ovarian cell lines. Overall, our results demonstrate the capabilities of this system for spatially controlled MS analysis of biological samples.

Negative ion composition measurements and inferred gaseous sulfuric acid concentrations were for the first time obtained in the winter arctic vortex. The observations were made by a balloon‐borne quadrupole mass spectrometer, between 24 and 30 km altitude, on 18 January 1992. The H2SO4 data provide strong evidence for an additional OH source, other than photochemical OH‐production from O(¹D), operative in the winter arctic stratosphere. The additional OH source might be due to ion‐molecule reactions involving ambient ions, formed by galactic cosmic rays. This mechanism seems to explain the presence of gaseous sulfuric acid in the winter arctic vortex and may even influence H2SO4 abundances at midlatitudes during nighttime.