Abstract. We demonstrate a compact, open-path, quantum cascade-laser-based atmospheric ammonia sensor operating at 9.06 µm for high-sensitivity, high temporal resolution, ground-based measurements. Atmospheric ammonia (NH 3 ) is a gas-phase precursor to fine particulate matter, with implications for air quality and climate change. Currently, NH 3 sensing challenges have led to a lack of widespread in situ measurements. Our open-path sensor configuration minimizes sampling artifacts associated with NH 3 surface adsorption onto inlet tubing and reduced pressure sampling cells, as well as condensed-phase partitioning ambiguities. Multi-harmonic wavelength modulation spectroscopy allows for selective and sensitive detection of atmospheric pressurebroadened absorption features. An in-line ethylene reference cell provides real-time calibration (±20 % accuracy) and normalization for instrument drift under rapidly changing field conditions. The sensor has a sensitivity and noise-equivalent limit (1σ ) of 0.15 ppbv NH 3 at 10 Hz, a mass of ∼ 5 kg and consumes ∼ 50 W of electrical power. The total uncertainty in NH 3 measurements is 0.20 ppbv NH 3 ± 10 %, based on a spectroscopic calibration method. Field performance of this open-path NH 3 sensor is demonstrated, with 10 Hz time resolution and a large dynamic response for in situ NH 3 measurements. This sensor provides the capabilities for improved in situ gas-phase NH 3 sensing relevant for emission source characterization and flux measurements.

Ammonia (NH3) is a key precursor species to atmospheric fine particulate matter with strong implications for regional air quality and global climate change. NH3 from vehicles accounts for a significant fraction of total emissions of NH3 in urban areas. A mobile platform is developed to measure NH3, CO, and CO2 from the top of a passenger car. The mobile platform conducted 87 h of on-road measurements, covering 4500 km in New Jersey and California. The average on-road emission factor (EF) in CA is 0.49 ± 0.06 g NH3 per kg fuel and agrees with previous studies in CA (0.3-0.8 g/kg). The mean on-road NH3:CO emission ratio is 0.029 ± 0.005, and there is no systematic difference between NJ and CA. On-road NH3 EFs increase with road gradient by an enhancement of 53 mg/kg fuel per percentage of gradient. On-road NH3 EFs show higher values in both stop-and-go driving conditions and freeway speeds with a minimum near 70 km/h. Consistent with prior studies, the on-road emission ratios suggest a highly skewed distribution of NH3 emitters. Comparisons with existing NJ and CA on-road emission inventories indicate that there may be an underestimation of on-road NH3 emissions in both NJ and CA. We demonstrate that mobile, open-path measurements provide a unique tool to help quantitatively understand the on-road NH3 emissions in urban and suburban settings.

A compact and portable open-path sensor for simultaneous detection of atmospheric N(2)O and CO has been developed with a 4.5 μm quantum cascade laser (QCL). An in-line acetylene (C(2)H(2)) gas reference cell allows for continuous monitoring of the sensor drift and calibration in rapidly changing field environments and thereby allows for open-path detection at high precision and stability. Wavelength modulation spectroscopy (WMS) is used to detect simultaneously both the second and fourth harmonic absorption spectra with an optimized dual modulation amplitude scheme. Multi-harmonic spectra containing atmospheric N(2)O, CO, and the reference C(2)H(2) signals are fit in real-time (10 Hz) by combining a software-based lock-in amplifier with a computationally fast numerical model for WMS. The sensor consumes ~50 W of power and has a mass of ~15 kg. Precision of 0.15 ppbv N(2)O and 0.36 ppbv CO at 10 Hz under laboratory conditions was demonstrated. The sensor has been deployed for extended periods in the field. Simultaneous N(2)O and CO measurements distinguished between natural and fossil fuel combustion sources of N(2)O, an important greenhouse gas with poorly quantified emissions in space and time.

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