Assessing Detection Efficiencies for Continuous Methane Emission Monitoring Systems at Oil and Gas Production Sites.

Continuous monitoring systems, consisting of multiple fixed sensors, are increasingly being deployed at oil and gas production sites to detect methane emissions. While these monitoring systems operate continuously, their efficiency in detecting emissions will depend on meteorological conditions, sensor detection limits, the number of sensors deployed, and sensor placement strategies. This work demonstrates an approach to assess the effectiveness of continuous sensor networks in detecting infinite-duration and fixed-duration emission events. The case studies examine a single idealized source and a group of nine different sources at varying heights and locations on a single pad. Using site-specific meteorological data and dispersion modeling, the emission detection performance is characterized. For these case studies, infinite-duration emission events are detected within 1 h to multiple days, depending on the number of sensors deployed. The percentage of fixed-duration emission events that are detected ranged from less than 10% to more than 90%, depending on the number of sources, emission release height, emission event duration, and the number of sensors deployed. While these results are specific to these case studies, the analysis framework described in this work can be broadly applied in the evaluation of continuous emission monitoring network designs.

Assessing the contribution of open crop straw burning to ground-level ozone and associated health impacts in China and the effectiveness of straw burning bans.

In recent years, ozone pollution in China has been shown to increase in frequency and persistence despite the concentrations of fine particulate matter (PM2.5) decreasing steadily. Open crop straw burning (OCSB) activities are extensive in China and emit large amounts of trace gases during a short period that could lead to elevated ozone concentrations. This study addresses the impacts of OCSB emissions on ground-level ozone concentration and the associated health impact in China. Total VOCs and NOx emissions from OCSB in 2018 were 798.8 Gg and 80.6 Gg, respectively, with high emissions in Northeast China (31.7%) and North China (23.7%). Based on simulations conducted for 2018, OCSB emissions are estimated to contribute up to 0.95 µg/m3 increase in annual averaged maximum daily 8-hour (MDA8) ozone and up to 1.35 µg/m3 for the ozone season average. The significant impact of OCSB emissions on ozone is mainly characterized by localized and episodic (e.g., daily) changes in ozone concentration, up to 20 µg/m3 in North China and Yangtze River Delta region and even more in Northeast China during the burning season. With the implementation of straw burning bans, VOCs and NOx emissions from OCSB dropped substantially by 46.9%, particularly over YRD (76%) and North China (60%). Consequently, reduced OCSB emissions result in an overall decrease in annual averaged MDA8 ozone, and reductions in monthly MDA8 ozone could be over 10 µg/m3 in North China. The number of avoided premature death due to reduced OCSB emissions (considering both PM2.5 and ozone) is estimated to be 6120 (95% Confidence Interval: 5320-6800), with most health benefits gained over east and central China. Our results illustrate the effectiveness of straw burning bans in reducing ozone concentrations at annual and national scales and the substantial ozone impacts from OCSB events at localized and episodic scales.

Reconciling Multiple Methane Detection and Quantification Systems at Oil and Gas Tank Battery Sites.

Emission rates were estimated for >100 oil and gas production sites with significant liquid-handling equipment (tank battery sites) in the Permian Basin of west Texas. Emission estimates based on equipment counts and emission factors, but not accounting for large uninventoried emission events, led to ensemble average emission rates of 1.8-3.6 kg/h per site. None of the site-specific emission estimates for individual sites, based on equipment counts, exceeded 10 kg/h. On-site drone-based emission measurements led to similar emission estimates for inventoried sources. Multiple aircraft measurement platforms were deployed and reported emissions exceeding 10 kg/h at 14-27% of the sites, and these high-emission rate sites accounted for 80-90% of total emissions for the ensemble of sites. The aircraft measurement systems were deployed asynchronously but within a 5 day period. At least half of the sites with emission rates above 10 kg/h detected by aircraft had emissions that did not persist at a level above 10 kg/h for repeat measurements, suggesting typical high-emission rate durations of a few days or less for many events. The two aircraft systems differed in their estimates of total emissions from the ensembles of sites sampled by more than a factor of 2; however, the normalized distributions of emissions for sites with emission rates of >10 kg/h were comparable for the two aircraft-based methods. The differences between the two aircraft-based platforms are attributed to a combination of factors; however, both aircraft-based emission measurement systems attribute a large fraction of emissions to sites with an emission rate of >10 kg/h.

Coupled Dynamic Material Flow, Multimedia Environmental Model, and Ecological Risk Analysis for Chemical Management: A Di(2-ethylhexhyl) Phthalate Case in China.

Di(2-ethylhexhyl) phthalate (DEHP) is a widely used plasticizer that has adverse effects on ecosystems and human health. However, data about its stocks, flows, emission rates, as well as ecological risks are generally unknown in China, one of the world's largest producers of chemicals including DEHP, limiting sound management of chemicals. Herein, dynamic material flow analysis, coupled with a multimedia environmental model and ecological risk analysis, was performed to fill the data gap about DEHP in China mainland from 1956 to 2020. Results indicate that the in-use stocks of DEHP increased from 6.54 × 106 kg in 1956 to 8.40 × 109 kg in 2020. With growth in the emission rates, DEHP concentrations in air, soil, water, and sediment kept increasing from 1956 to 2010, which declined after 2010 and regrew after 2015. Sediment was a main sink of DEHP with the highest ecological risk quotient of >10 after 1999, necessitating measures for controlling the risk, for example, technology innovation to reduce DEHP emission rates, and substitution of DEHP with low-toxic alternatives. The coupled models that connect socio-economic data with ecological risk output may provide a systematic methodology for verification of the data necessary for risk control of chemicals.

A Methane Emission Estimation Tool (MEET) for predictions of emissions from upstream oil and gas well sites with fine scale temporal and spatial resolution: Model structure and applications.

In comparing observation based methane emission estimates for oil and gas well sites to routine emissions reported in inventories, the time scale of the measurement should match the time scale over which the inventoried emissions are estimated. Since many measurements are of relatively short duration (seconds to hours), a tool is needed to estimate emissions over these time scales rather than the annual totals reported in most emission inventories. This work presents a tool for estimating routine emissions from oil and gas well sites at multiple time scales; emissions at well sites vary over time due to changes in oil and gas production rates, operating practices and operational modes at the sites. Distributions of routine emissions (expected and inventoried) from well sites are generally skewed, and the nature and degree to which the distributions are skewed depends on the time scales over which emissions are aggregated. Abnormal emissions can create additional skew in these distributions. At very short time scales (emissions aggregated over 1 min) case study distributions presented in this work are both skewed and bimodal, with the modes depending on whether liquid storage tanks are flashing at the time of the measurement and whether abnormal emissions are occurring. At longer time scales (emissions aggregated over 1 day) distributions of routine emissions simulated in this work can have multiple modes if short duration, high emission rate events, such as liquid unloadings or large abnormal emissions, occur at the site. Multiple applications of the methane emission estimation tool (MEET), developed in this work, are presented. These results emphasize the importance of developing detailed emission inventories, which incorporate operational data, when comparing measurements to routine emissions. The model described in this work supports such comparisons and is freely available.

Assessing the impact of episodic flare emissions on ozone formation in the Houston-Galveston-Brazoria area of Texas.

Ozone formation due to episodic industrial emissions was modeled for the Houston-Galveston-Brazoria (HGB) region in Texas. A total of more than 1000 synthetic emission scenarios were modeled, accounting for different sources, emission magnitudes, emission compositions, duration and timing of the emission events, meteorology at the time of the emissions, and location of the emission source. Episodic emissions consistent with the characteristics of flaring resulted in the greatest amount of ozone formation. An index, based on incremental reactivity, for characterizing the ozone formation potential of flaring emissions was developed using the synthetic scenarios and was applied to the ~4500 flares that report emissions in the state of Texas. The flares with the highest ranking index in the HGB were identified and additional modeling was performed on the ozone formation potential of these flares. If these flares are modeled with their annual average emission rates, the maximum increase in maximum daily 8-h average ozone (MDA8) formation associated with flaring emissions is <1 ppb. If, however, it is assumed that emissions from flaring are episodic, rather than continuous, and temporal patterns consistent with previous data collection on flare emission variability in the HGB are applied, MDA8 enhancements associated with flaring emissions are >10 ppb for multiple scenarios. This analysis suggests that, for flares emissions that have high ozone formation potential, the temporal patterns of flare emissions should be accounted for in developing ozone mitigation plans.

Modeling air emissions from complex facilities at detailed temporal and spatial resolution: The Methane Emission Estimation Tool (MEET).

Recent attention to methane emissions from oil and gas infrastructure has increased interest in comparing measurements with inventory emission estimates. While measurement methods typically estimate emissions over a few periods that are seconds to hours in length, current inventory methods typically produce long-term average emission estimates. This temporal mis-alignment complicates comparisons and leads to underestimates in the uncertainty of measurement methods. This study describes a new temporally and spatially resolved inventory emission model (MEET), and demonstrates the model by application to compressor station emissions - the key facility type in midstream natural gas operations The study looks at three common facility measurement methods: tracer flux methods for measuring station emissions, the use of ethane-methane ratios for source attribution of basin-scale estimates, and the behavior of continuous monitoring for leak detection at stations. Simulation results indicate that measurement methods likely underestimate uncertainties in emission estimates by failing to account for the variability in normal facility emissions and variations in ethane/methane ratios. A tracer-based measurement campaign could estimate emissions outside the 95% confidence interval of annual emissions 30% of the time, while ethane/methane ratios could be mis-estimated by as much as 50%. Use of MEET also highlights the need to improve data reporting from measurement campaigns to better capture the temporal and spatial variation in observed emissions.

Heterogeneous Formation of HONO Catalyzed by CO2.

Gas-phase nitrous acid (HONO) is a major precursor of hydroxyl radicals that dominate atmospheric oxidizing capacity. Nevertheless, pathways of HONO formation remain to be explored. This study unveiled an important CO2-catalysis mechanism of HONO formation, using Born-Oppenheimer molecular dynamics simulations and free-energy samplings. In the mechanism, HCO3- formed from CO2 hydrolysis reacts with NO2 dimers to produce HONO at water surfaces, and simultaneously, itself reconverts back to CO2 via intermediates OC(O)ONO- and HOC(O)ONO. A flow system experiment was performed to confirm the new mechanism, which indicated that HONO concentrations with CO2 injections were increased by 29.4-68.5%. The new mechanism can be extended to other humid surfaces. Therefore, this study unveiled a previously overlooked vital role of CO2 that catalyzes formation of HONO and affects atmospheric oxidizing capacity.

Organic acid-ammonia ion-induced nucleation pathways unveiled by quantum chemical calculation and kinetics modeling: A case study of 3-methyl-1,2,3-butanetricarboxylic acid.

Nucleation of organic acids (OAs) and H2SO4 is an important source for new particle formation in the atmosphere. However, it is still unclear whether organic acids can produce nanoparticles independent of H2SO4. In this study, 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA) was adopted as a model of OAs. Pathways of clustering from MBTCA, ammonia and ions (NH4+ and NO3-) to form a 1.9 nm nucleus were investigated by quantum chemical calculation and kinetic modeling. Results show recombination of charged clusters/ions plays an essential role in the nucleation processes. Cluster formation rates increase by a factor of 103 when NH3 increases from 2.6 × 108 molecules·cm-3 (under clean conditions) to 2.6 × 1011 molecules·cm-3 (under polluted conditions), as NH3 can stabilize MBTCA clusters and change ion compositions from H3O+ to NH4+. Although the proposed new mechanism cannot compete with H2SO4-NH3-H2O or H2SO4-OA nucleation currently, it may be important in the future with the decline of SO2 concentration.

Assessment of the effects of straw burning bans in China: Emissions, air quality, and health impacts.

Open biomass burning (OBB) plays an important role in air pollution and climate change by releasing short-term but intensive amounts of particulate matter and gaseous air pollutants. During past years, policies with respect to prohibition on open straw burning have been issued in China in order to mitigate the air pollution problems and the effectiveness of these straw burning bans in different regions remains to be evaluated. In this study, open crop straw burning (OCSB) emissions during 2010-2018 were analyzed based on a commonly used emission inventory with high spatial and temporal resolution. High emissions concentrated over Northeast China (31.8% of national total PM2.5 emissions in 2018), East China (24.0%), and North China (16.6%). Simulations based on an integrated meteorology-air quality modeling system and an exposure-response function show that OCSB emissions could increase monthly PM2.5 concentration by as much as 10 µg/m3 during burning seasons in Northeast China and were associated with 4741 premature deaths in 2018. Spatial heterogeneities were observed with respect to the trends of OCSB emissions during 2010-2018. In East China, North China, and Central China, OCSB emissions showed a general declining trend since 2013 while an opposing increasing trend was observed in Northeast China with peak emissions in 2017. Comparing 2013 (before intensive implementation of straw burning bans) and 2018 (after), national total PM2.5 emissions from OCSB activities decreased by 46.9%, ranging from -14.1% to +70% depending on the specific regions. Northeast China is the only region that showed higher OCSB emissions in 2018 compared to 2013, probably associated with the relatively delayed implementation of the straw burning bans. Avoided number of premature deaths due to reduced OCSB emissions was estimated to be 4256 on a national scale, with most health benefits gained in East and Central China. Results from this study demonstrate the importance of OCSB contribution to PM2.5 concentrations and spatial heterogeneities exist in terms of the effectiveness of the straw burning bans in reducing OCSB emissions and gained health benefits.

Anthropogenic emissions of atomic chlorine precursors in the Yangtze River Delta region, China.

Chlorine radical plays an important role in the formation of ozone and secondary aerosols in the troposphere. It is hence important to develop comprehensive emissions inventory of chlorine precursors in order to enhance our understanding of the role of chlorine chemistry in ozone and secondary pollution issues. Based on a bottom-up methodology, this study presents a comprehensive emission inventory for major atomic chlorine precursors in the Yangtze River Delta (YRD) region of China for the year 2017. Four primary chlorine precursors are considered in this study: hydrogen chloride (HCl), fine particulate chloride (Cl-) (Cl- in PM2.5), chlorine gas (Cl2), and hypochlorous acid (HClO) with emissions estimated for twelve source categories. The total emissions of these four species in the YRD region are estimated to be 20,424 t, 15,719 t, 1556 and 9331 t, respectively. The emissions of HCl are substantial, with major emissions from biomass burning and coal combustion, together accounting for 68% of the total HCl emissions. Fine particulate Cl- is mainly emitted from industrial processing, biomass burning and waste incineration. The emissions of Cl2 and HClO are mainly associated with usage of chlorine-containing disinfectants, for example, water treatment, wastewater treatment, and swimming pools. Emissions of each chlorine precursor are spatially allocated based on the characteristics of individual source category. This study provides important basic dataset for further studies with respect to the effects of chlorine chemistry on the formation of air pollution complex in the YRD region.

A Searchable Database for Prediction of Emission Compositions from Upstream Oil and Gas Sources.

Atmospheric emissions from oil and gas production operations are composed of multiple hydrocarbons and can have large variations in composition. Accurate estimates of emission compositions are needed to estimate the fate and impacts of emissions and to attribute emissions to sources. This work presents a database, constructed with empirical data and thermodynamic models, that can be queried to estimate hydrocarbon compositions from emission sources present at oil and gas production sites. The database can be searched for matches using between two and seven well parameters as query inputs (gas-to-oil ratio, API gravity, separator pressure, separator temperature, methane molar fraction in produced gas, ethane molar fraction of produced gas, and propane molar fraction in produced gas). Database query performance was characterized by comparing returns from database queries to a test data set. Application of the database to well parameters for tens of thousands of wells in the Barnett, Eagle Ford, and Fayetteville production regions demonstrates variations in emission compositions. Ethane to methane ratio varies by more than an order of magnitude from well to well and source to source. VOC to methane ratios are comparable in variability to ethane to methane ratios for most emission sources, but have a higher variability for emissions from flashing of liquid hydrocarbon tanks.

Projecting the Temporal Evolution of Methane Emissions from Oil and Gas Production Basins.

The methane emission intensity (methane emitted/gas produced or methane emitted/methane produced) of individual unconventional oil and gas production sites in the United States has a characteristic temporal behavior, exhibiting a brief period of decrease followed by a steady increase, with intensities after 10 years of production reaching levels that are 2-10 times the 10 year production-weighted average. Temporal patterns for methane emission intensity for entire production regions are more complex. Historical production data and facility data were used with a detailed basin-wide methane emission model to simulate the collective behavior of tens of thousands of wells and associated midstream facilities. For production regions with few to no new wells being brought to production, and existing wells having reached a mature stage, as in the Barnett Shale production region in north central Texas, the methane emission intensity gradually increases, as natural gas production decreases faster than emissions decrease, following the general pattern exhibited by individual wells. In production regions that are rapidly evolving, either with large numbers of new wells being put into production or with the introduction of source-specific regulations, the behavior is more complex. In the Eagle Ford Shale, which has had both a large number of new wells and the introduction of source-specific regulations, the methane emission intensity stays within relatively narrow bounds but the distribution of sources varies. As source distributions vary, basin-wide propane-to-methane and ethane-to-methane emission ratios vary, impacting methods used in source attribution.

Projecting the Temporal Evolution of Methane Emissions from Oil and Gas Production Sites.

Many recent studies have reported methane emissions from oil and gas production regions, often reporting results as a methane emission intensity (methane emitted as a percentage of natural gas produced or methane produced). Almost all of these studies have been instantaneous snapshots of methane emissions; however, total methane emissions from a production site and the methane emission intensity would be expected to evolve over time. A detailed site-level methane emission estimation model is used to estimate the temporal evolution of methane emissions and the methane emission intensity for a variety of well configurations with and without emission mitigation measures in place. The general pattern predicted is that total emissions decrease over time as production declines. Methane emission intensity shows complex behavior because production-dependent emissions decline at different rates and some emissions do not decline over time. Prototypical uncontrolled wet gas wells can have approximately half of their emissions over a 10 year period occur in the first year; instantaneous wellsite methane emission intensities range over a factor of 3 (0.62-2.00%) in the same period, with a 10 year production weighted-average lifecycle methane emission intensity of 0.79%. Including emission control in the form of a flare can decrease the average lifecycle methane emission intensity to 0.23%. Emissions from liquid unloadings, which are observed in subsets of wells, can increase the lifecycle methane emission intensity by up to a factor of 2-3, between 1.2 and 2.3%, depending on the characteristics of the unloadings. Emissions from well completion flowbacks raise the average lifecycle methane emission intensity from 0.79 to 0.81% for flowbacks with emission controls; for flowbacks with uncontrolled emissions, lifecycle methane emissions increase to 1.26%. Dry gas and oil wells show qualitatively similar temporal behavior but different absolute emission rates.