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Cavity ring-down spectrometers (CRDSs) have the capacity to make isotopic measurements of CO2 where concentrations range from atmospheric (~400 ppm) to 6000 ppm. Following field trials, it has come to light that the spectrographic lines used for CO2 have an interference with elevated (higher than ambient) amounts of hydrogen sulfide (H2S), which causes significant depletions in the δ13C measurement by the CRDSs. In order to deploy this instrument in environments with elevated H2S concentrations (i.e., active volcanoes), we require a robust method for eliminating this interference. Controlled experiments using a Picarro G1101-i optical spectrometer were done to characterize the H2S interference at varying CO2 and H2S concentrations. The addition of H2S to a CO2 standard gas reveals an increase in the 12CO2 concentration and a more significant decrease in the 13CO2 concentration, resulting in a depleted δ13C value. Reacting gas samples containing H2S with copper prior to analysis can eliminate this effect. Models post-dating the G1101-i carbon isotope analyzer have maintained the same spectral lines for CO2 and are likely to have a similar H2S response at elevated H2S concentrations. It is important for future work with CRDS, particularly in volcanic regions where H2S is abundant, to be aware of the H2S interference on the CO2 spectroscopic lines and to remove all H2S prior to analysis. We suggest employing a scrub composed of copper to remove H2S from all gas samples that have concentrations in excess of 1 ppb. [ABSTRACT FROM AUTHOR]

Ammonia (NH 3 ) is typically present at higher concentrations in indoor air (∼10-70 ppb) than in outdoor air (∼50 ppt to 5 ppb). It is the dominant neutralizer of acidic species in indoor environments, strongly influencing the partitioning of gaseous acidic and basic species to aerosols, surface films, and bulk water. We have measured NH 3 emissions from humans in an environmentally controlled chamber. A series of experiments, each with four volunteers, quantified NH 3 emissions as a function of temperature (25.1-32.6 °C), clothing (long-sleeved shirts/pants or T-shirts/shorts), age (teenagers, adults, and seniors), relative humidity (low or high), and ozone (<2 ppb or ∼35 ppb). Higher temperature and more skin exposure (T-shirts/shorts) significantly increased emission rates. For adults and seniors (long clothing), NH 3 emissions are estimated to be 0.4 mg h -1 person -1 at 25 °C, 0.8 mg h -1 person -1 at 27 °C, and 1.4 mg h -1 person -1 at 29 °C, based on the temperature relationship observed in this study. Human NH 3 emissions are sufficient to neutralize the acidifying impacts of human CO 2 emissions. Results from this study can be used to more accurately model indoor and inner-city outdoor NH 3 concentrations and associated chemistry.

Although ammonia (NH 3 ) is usually found at outdoor concentrations of 1-5 ppb, indoor ammonia concentrations can be much higher. Indoor ammonia is strongly emitted from cleaning products, tobacco smoke, building materials, and humans. Because of ammonia's high reactivity, solubility in water, and tendency to sorb to a variety of surfaces, it is difficult to measure, and thus a comprehensive evaluation of indoor ammonia concentrations remains an understudied topic. During HOMEChem, which was a comprehensive indoor chemistry study occurring in a test house during June 2018, the real-time concentration of ammonia indoors was measured using cavity ring-down spectroscopy. A mean unoccupied background concentration of 32 ppb was observed, with further enhancements of ammonia occurring during cooking, cleaning, and occupancy activities, reaching maximum concentrations during these activities of 130, 1592, and 99 ppb, respectively. Furthermore, ammonia concentrations were strongly influenced by indoor temperatures and heating, ventilation, and air conditioning (HVAC) operation. In the absence of activity-based sources, the HVAC operation was the main modulator of ammonia concentration indoors.