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Advances in natural gas extraction technology have led to increased activity in the production and transport sectors in the United States and, as a consequence, an increased need for reliable monitoring of methane leaks to the atmosphere. We present a statistical methodology in combination with an observing system for the detection and attribution of fugitive emissions of methane from distributed potential source location landscapes such as natural gas production sites. We measure long (> 500 m), integrated open-path concentrations of atmospheric methane using a dual frequency comb spectrometer and combine measurements with an atmospheric transport model to infer leak locations and strengths using a novel statistical method, the non-zero minimum bootstrap (NZMB). The new statistical method allows us to determine whether the empirical distribution of possible source strengths for a given location excludes zero. Using this information, we identify leaking source locations (i.e., natural gas wells) through rejection of the null hypothesis that the source is not leaking. The method is tested with a series of synthetic data inversions with varying measurement density and varying levels of model–data mismatch. It is also tested with field observations of (1) a non-leaking source location and (2) a source location where a controlled emission of 3.1 × 10−5 kg s−1 of methane gas is released over a period of several hours. This series of synthetic data tests and outdoor field observations using a controlled methane release demonstrates the viability of the approach for the detection and sizing of very small leaks of methane across large distances (4+ km2 in synthetic tests). The field tests demonstrate the ability to attribute small atmospheric enhancements of 17 ppb to the emitting source location against a background of combined atmospheric (e.g., background methane variability) and measurement uncertainty of 5 ppb (1σ), when measurements are averaged over 2 min. The results of the synthetic and field data testing show that the new observing system and statistical approach greatly decreases the incidence of false alarms (that is, wrongly identifying a well site to be leaking) compared with the same tests that do not use the NZMB approach and therefore offers increased leak detection and sizing capabilities.

Non-dispersive infrared (NDIR) sensors are a low-cost way to observe carbon dioxide concentrations in air, but their specified accuracy and precision are not sufficient for some scientific applications. An initial evaluation of six SenseAir K30 carbon dioxide NDIR sensors in a lab setting showed that without any calibration or correction, the sensors have an individual root mean square error (RMSE) between ∼ 5 and 21 parts per million (ppm) compared to a research-grade greenhouse gas analyzer using cavity enhanced laser absorption spectroscopy. Through further evaluation, after correcting for environmental variables with coefficients determined through a multivariate linear regression analysis, the calculated difference between the each of six individual K30 NDIR sensors and the higher-precision instrument had an RMSE of between 1.7 and 4.3 ppm for 1 min data. The median RMSE improved from 9.6 for off-the-shelf sensors to 1.9 ppm after correction and calibration, demonstrating the potential to provide useful information for ambient air monitoring.

Accurate measurements of carbon monoxide (CO) in humid air have been made using the cavity ring-down spectroscopy (CRDS) technique. The measurements of CO mole fractions are determined from the strength of its spectral absorption in the near-infrared region (~1.57 μm) after removing interferences from adjacent carbon dioxide (CO2) and water vapor (H2O) absorption lines. Water correction functions that account for the dilution and pressure-broadening effects as well as absorption line interferences from adjacent CO2 and H2O lines have been derived for CO2 mole fractions between 360–390 ppm and for reported H2O mole fractions between 0–4%. The line interference corrections are independent of CO mole fractions. The dependence of the line interference correction on CO2 abundance is estimated to be approximately −0.3 ppb/100 ppm CO2 for dry mole fractions of CO. Comparisons of water correction functions from different analyzers of the same type show significant differences, making it necessary to perform instrument-specific water tests for each individual analyzer. The CRDS analyzer was flown on an aircraft in Alaska from April to November in 2011, and the accuracy of the CO measurements by the CRDS analyzer has been validated against discrete NOAA/ESRL flask sample measurements made on board the same aircraft, with a mean difference between integrated in situ and flask measurements of −0.6 ppb and a standard deviation of 2.8 ppb. Preliminary testing of CRDS instrumentation that employs improved spectroscopic model functions for CO2, H2O, and CO to fit the raw spectral data (available since the beginning of 2012) indicates a smaller water vapor dependence than the models discussed here, but more work is necessary to fully validate the performance. The CRDS technique provides an accurate and low-maintenance method of monitoring the atmospheric dry mole fractions of CO in humid air streams.

Traditional techniques for measuring the mole fractions of greenhouse gases in the well-mixed atmosphere have required dry sample gas streams (dew point < −25 °C) to achieve the inter-laboratory compatibility goals set forth by the Global Atmosphere Watch programme of the World Meteorological Organisation (WMO/GAW) for carbon dioxide (±0.1 ppm in the Northern Hemisphere and ±0.05 ppm in the Southern Hemisphere) and methane (±2 ppb). Drying the sample gas to low levels of water vapour can be expensive, time-consuming, and/or problematic, especially at remote sites where access is difficult. Recent advances in optical measurement techniques, in particular cavity ring down spectroscopy, have led to the development of greenhouse gas analysers capable of simultaneous measurements of carbon dioxide, methane and water vapour. Unlike many older technologies, which can suffer from significant uncorrected interference from water vapour, these instruments permit accurate and precise greenhouse gas measurements that can meet the WMO/GAW inter-laboratory compatibility goals (WMO, 2011a) without drying the sample gas. In this paper, we present laboratory methodology for empirically deriving the water vapour correction factors, and we summarise a series of in-situ validation experiments comparing the measurements in humid gas streams to well-characterised dry-gas measurements. By using the manufacturer-supplied correction factors, the dry-mole fraction measurements have been demonstrated to be well within the GAW compatibility goals up to a water vapour concentration of at least 1%. By determining the correction factors for individual instruments once at the start of life, this water vapour concentration range can be extended to at least 2% over the life of the instrument, and if the correction factors are determined periodically over time, the evidence suggests that this range can be extended up to and even above 4% water vapour concentrations.

In March 2009 the NOAA/ESRL/GMD Carbon Cycle and Greenhouse Gases Group collaborated with the US Coast Guard (USCG) to establish the Alaska Coast Guard (ACG) sampling site, a unique addition to NOAA's atmospheric monitoring network. This collaboration takes advantage of USCG bi-weekly Arctic Domain Awareness (ADA) flights, conducted with Hercules C-130 aircraft from March to November each year. Flights typically last 8 h and cover a large area, traveling from Kodiak up to Barrow, Alaska, with altitude profiles near the coast and in the interior. NOAA instrumentation on each flight includes a flask sampling system, a continuous cavity ring-down spectroscopy (CRDS) carbon dioxide (CO2)/methane (CH4)/carbon monoxide (CO)/water vapor (H2O) analyzer, a continuous ozone analyzer, and an ambient temperature and humidity sensor. Air samples collected in flight are analyzed at NOAA/ESRL for the major greenhouse gases and a variety of halocarbons and hydrocarbons that influence climate, stratospheric ozone, and air quality. We describe the overall system for making accurate greenhouse gas measurements using a CRDS analyzer on an aircraft with minimal operator interaction and present an assessment of analyzer performance over a three-year period. Overall analytical uncertainty of CRDS measurements in 2011 is estimated to be 0.15 ppm, 1.4 ppb, and 5 ppb for CO2, CH4, and CO, respectively, considering short-term precision, calibration uncertainties, and water vapor correction uncertainty. The stability of the CRDS analyzer over a seven-month deployment period is better than 0.15 ppm, 2 ppb, and 4 ppb for CO2, CH4, and CO, respectively, based on differences of on-board reference tank measurements from a laboratory calibration performed prior to deployment. This stability is not affected by variation in pressure or temperature during flight. We conclude that the uncertainty reported for our measurements would not be significantly affected if the measurements were made without in-flight calibrations, provided ground calibrations and testing were performed regularly. Comparisons between in situ CRDS measurements and flask measurements are consistent with expected measurement uncertainties for CH4 and CO, but differences are larger than expected for CO2. Biases and standard deviations of comparisons with flask samples suggest that atmospheric variability, flask-to-flask variability, and possible flask sampling biases may be driving the observed flask versus in situ CO2 differences rather than the CRDS measurements.

A one hour integrated flask sampling system to collect air in automated NOAA/ESRL 12-flask packages is described. The integrating compressor system uses a mass flow controller to regulate the flow of air through a 15 l volume, thus providing a mixture of air collected over an hour-long period. By beginning with a high flow rate of 3.8 standard liters per minute and gradually decreasing the flow rate over time to 0.29 standard liters per minute it is possible to obtain a nearly uniformly time averaged sample of air and collect it into a pressurized 0.7 l flask. The weighting function determining the air mixture obtained is described in detail. Laboratory and field tests demonstrate that the integrated sample approximates a simple mean of air collected during the one-hour sampling time.

Non-dispersive infrared (NDIR) sensors are a low-cost way to observe carbon dioxide concentrations in air, but their specified accuracy and precision are not sufficient for some scientific applications. An initial evaluation of six SenseAir K30 carbon dioxide NDIR sensors in a lab setting showed that without any calibration or correction, the sensors have an individual root mean square error (RMSE) between ~5 and 21 parts per million (ppm) compared to a research-grade greenhouse gas analyzer using cavity enhanced laser absorption spectroscopy. Through further evaluation, after correcting for environmental variables with coefficients determined through a multivariate linear regression analysis, the calculated difference between the each of six individual K30 NDIR sensors and the higher-precision instrument had an RMSE of between 1.7 and 4.3 ppm for 1 min data. The median RMSE improved from 9.6 for off-the-shelf sensors to 1.9 ppm after correction and calibration, demonstrating the potential to provide useful information for ambient air monitoring., Competing Interests: Competing interests. The authors declare that they have no conflict of interest.