The presence of volatile organic compounds (VOCs) in unprocessed natural gas (NG) is well documented; however, the degree to which VOCs are present in NG at the point of end use is largely uncharacterized. We collected 234 whole NG samples across 69 unique residential locations across the Greater Boston metropolitan area, Massachusetts. NG samples were measured for methane (CH4), ethane (C2H6), and nonmethane VOC (NMVOC) content (including tentatively identified compounds) using commercially available USEPA analytical methods. Results revealed 296 unique NMVOC constituents in end use NG, of which 21 (or approximately 7%) were designated as hazardous air pollutants. Benzene (bootstrapped mean = 164 ppbv; SD = 16; 95% CI: 134-196) was detected in 95% of samples along with hexane (98% detection), toluene (94%), heptane (94%), and cyclohexane (89%), contributing to a mean total concentration of NMVOCs in distribution-grade NG of 6.0 ppmv (95% CI: 5.5-6.6). While total VOCs exhibited significant spatial variability, over twice as much temporal variability was observed, with a wintertime NG benzene concentration nearly eight-fold greater than summertime. By using previous NG leakage data, we estimated that 120-356 kg/yr of annual NG benzene emissions throughout Greater Boston are not currently accounted for in emissions inventories, along with an unaccounted-for indoor portion. NG-odorant content (tert-butyl mercaptan and isopropyl mercaptan) was used to estimate that a mean NG-CH4 concentration of 21.3 ppmv (95% CI: 16.7-25.9) could persist undetected in ambient air given known odor detection thresholds. This implies that indoor NG leakage may be an underappreciated source of both CH4 and associated VOCs.
Keywords: BTEX; cooking; fossil fuels; hazard identification; hazardous air pollutants; natural gas leak; odorants.