Atmospheric benzene observations from oil and gas production in the Denver-Julesburg Basin in July and August 2014

High time resolution measurements of volatile organic compounds (VOCs) were collected using a proton-transfer-reaction quadrupole mass spectrometry (PTR-QMS) instrument at the Platteville Atmospheric Observatory (PAO) in Colorado to investigate how oil and natural gas (O&NG) development impacts air quality within the Wattenburg Gas Field (WGF) in the Denver-Julesburg Basin. The measurements were carried out in July and August 2014 as part of NASA’s “Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality” (DISCOVER-AQ) field campaign. The PTR-QMS data were supported by pressurized whole air canister samples and airborne vertical and horizontal surveys of VOCs. Unexpectedly high benzene mixing ratios were observed at PAO at ground level (mean benzene = 0.53 ppbv, maximum benzene = 29.3 ppbv), primarily at night (mean nighttime benzene = 0.73 ppbv). These high benzene levels were associated with southwesterly winds. The airborne measurements indicate that benzene originated from within the WGF, and typical source signatures detected in the canister samples implicate emissions from O&NG activities rather than urban vehicular emissions as primary benzene source. This conclusion is backed by a regional toluene-to-benzene ratio analysis which associated southerly flow with vehicular emissions from the Denver area. Weak benzene-to-CO correlations confirmed that traffic emissions were not responsible for the observed high benzene levels. Previous measurements at the Boulder Atmospheric Observatory (BAO) and our data obtained at PAO allow us to locate the source of benzene enhancements between the two atmospheric observatories. Fugitive emissions of benzene from O&NG operations in the Platteville area are discussed as the most likely causes of enhanced benzene levels at PAO

Coastal New England pilot study to determine fossil and biogenic formaldehyde source contributions using radiocarbon

Author Posting. © American Geophysical Union, 2010. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 115 (2010): D10301, doi:10.1029/2009JD012810.Compound specific radiocarbon analyses of atmospheric formaldehyde are reported as fraction modern (Fm) for a limited number of winter and summer air samples collected in coastal southern New England in 2007. The 11 of 13 samples with Fm 0.2 (max ∼ 0.35) were collected on days with strong northwesterly flow and the least urban impact. The Fm data were combined with VOC observations from the Rhode Island Department of Environmental Management, estimates of oxygenated VOC (OVOC), and back trajectories to interpret the relative contributions of biogenic and fossil carbon sources. It is argued that CH2O sources were dominated by pollutant VOCs and OVOCs from upwind coastal cities as opposed to more local biogenic VOCs at the times of sample collection.This research was supported by a graduate student internship program at WHOI National Ocean Sciences Accelerator Mass Spectrometry Facility (NSF OCE‐9807266) and by NASA project NNG04GB38G

Houston’s rapid ozone increases: preconditions and geographic origins

Many of Houston’s highest 8-h ozone (O(3)) peaks are characterised by increases in concentrations of at least 40 ppb in 1 h, or 60 ppb in 2 h. These rapid increases are called non-typical O(3) changes (NTOCs). In 2004, the Texas Commission on Environmental Quality (TCEQ) developed a novel emissions control strategy aimed at eliminating NTOCs. The strategy limited routine and short-term emissions of ethene, propene, 1,3-butadiene and butene isomers, collectively called highly reactive volatile organic compounds (HRVOCs), which are released from petrochemical facilities. HRVOCs have been associated with NTOCs through field campaigns and modelling studies. This study analysed wind measurements and O(3), formaldehyde (HCHO) and sulfur dioxide (SO(2)) concentrations from 2000 to 2011 at 25 ground monitors in Houston. NTOCs almost always occurred when monitors were downwind of petrochemical facilities. Rapid O(3) increases were associated with low wind speeds; 75 % of NTOCs occurred when the 3-h average wind speed preceding the event was less than 6.5 km h(−1). Statistically significant differences in HCHO concentrations were seen between days with and without NTOCs. Early afternoon HCHO concentrations were greater on NTOC days. In the morning before an observed NTOC event, however, there were no significant differences in HCHO concentrations between days with and without NTOCs. Hourly SO(2) concentrations also increased rapidly, exhibiting behaviour similar to NTOCs. Oftentimes, the SO(2) increases preceded a NTOC. These findings show that, despite the apparent success of targeted HRVOC emission controls, further restrictions may be needed to eliminate the remaining O(3) events

Quantitative measurements and modeling of industrial formaldehyde emissions in the Greater Houston area during campaigns in 2009 and 2011

A sensitive Mobile differential optical absorption spectroscopy (DOAS) system with real-time evaluation capability and HCHO detection limit of 3 ppb over 100 m has been developed. The system was operated together with a Solar Occultation Flux system for large-scale vertical flux measurements of HCHO, NO2, SO2, and VOCs in the Houston-Galveston-Brazoria area during two studies, in 2009 (Study of Houston Atmospheric Radical Precursors campaign) and in 2011 (Air Quality Research Program study). Both in 2009 and 2011, HCHO plumes from five separate local sources in Texas City, Mont Belvieu, and Houston Ship Channel (HSC) were repeatedly detected using Mobile DOAS with emissions varying between 6 and 40 kg/h. In many cases significant alkene emissions were detected simultaneously with the HCHO plumes. Furthermore, in 2011 two additional sources were observed in Texas City and in HSC, with 10 kg/h and 31 kg/h HCHO, respectively. A plume chemistry model was applied to 13 cases to investigate whether the detected HCHO was emitted directly from the industries or was produced by photochemical degradation of VOCs. The model results showed that on average 90% of the detected HCHO was of primary origin and the photochemical production contributed more than 10% in only three cases. Based on the repeatability, it is likely that the most significant HCHO sources in the area are included in this study with an overall emission of 120 kg/h. On a regional scale, this emission is small compared to the secondary HCHO formed from oxidation of reactive VOCs emitted from the same industries, estimated to be an order of magnitude higher