Quantifying methane emissions from United States landfills.

Methane emissions from solid waste may represent a substantial fraction of the global anthropogenic budget, but few comprehensive studies exist to assess inventory assumptions. We quantified emissions at hundreds of large landfills across 18 states in the United States between 2016 and 2022 using airborne imaging spectrometers. Spanning 20% of open United States landfills, this represents the most systematic measurement-based study of methane point sources of the waste sector. We detected significant point source emissions at a majority (52%) of these sites, many with emissions persisting over multiple revisits (weeks to years). We compared these against independent contemporaneous in situ airborne observations at 15 landfills and established good agreement. Our findings indicate a need for long-term, synoptic-scale monitoring of landfill emissions in the context of climate change mitigation policy.

Quantification of natural gas and other hydrocarbons from production sites in northern West Virginia using tracer flux ratio methodology.

Tracer flux ratio (TFR) methodology performed downwind of 15 active oil and natural gas production sites in Ohio County, West Virginia sought to quantify air pollutant emissions over two weeks in April 2018. In coordination with a production company, sites were randomly selected depending on wind forecasts and nearby road access. Methane (CH4), ethane (C2H6), and tracer gas compounds (acetylene and nitrous oxide) were measured via tunable infrared direct absorption spectroscopy. Ion signals attributed to benzene (C6H6) and other volatile gases (e.g., C7 - C9 aromatics) were measured via proton-transfer reaction time-of-flight mass spectrometry. Short-term whole facility emission rates for 12 sites are reported. Results from TFR were systematically higher than the sum of concurrent on-site full flow sampler measurements, though not all sources were assessed on-site in most cases. In downwind plumes, the mode of the C2H6:CH4 molar ratio distribution for all sites was 0.2, which agreed with spot sample analysis from the site operator. Distribution of C6H6:CH4 ratios was skew but values between 1 and 5 pptv ppbv-1 were common. Additionally, the aromatic profile has been attributed to condensate storage tank emissions. Average ratios of C7 - C9 to C6H6 were similar to other literature values reported for natural gas wells.

Assessment of Chemical Facility Ethylene Oxide Emissions Using Mobile and Multipoint Monitoring.

Ethylene oxide (EtO) is a hazardous air pollutant that can be emitted from a variety of difficult to measure industrial sources, such as fugitive leaks, wastewater handling, and episodic releases. Emerging next generation emission measurement (NGEM) approaches capable of time-resolved, low parts per billion by volume (ppbv) method detection limits (MDLs) can help facilities understand and reduce EtO and other air pollutant emissions from these sources yielding a range of environmental and public health benefits. In October 2021, a first of its kind 4-day observational study was conducted at an EtO chemical facility in the midwestern United States. The study had dual objectives to both improve understanding of EtO emission sources within the facility and advance NGEM methods. Using cavity ring-down spectroscopy (CRDS) instruments, a combination of mobile surveys and stationary multipoint process unit monitoring assessed EtO concentrations in and near facility operations, while testing and comparing measurement methods. The study concluded that four main areas of EtO source emissions existed within the facility, each possessing unique emission characteristics. Episodic EtO emissions from supply railcar switchovers and batch reactor washouts, lasting seconds to minutes in duration, produced EtO concentrations exceeding 500 ppbv inside the process unit in some cases. In one instance, EtO at ~30 ppbv was briefly observed hundreds of meters from the process unit. Lower level but more sustained EtO concentrations were observed near an EtO transfer pump and wastewater tank outfall and drain system. Overall, 4.6% of mobile survey data were above the 1.2 ppbv mobile test MDL while the nine stationary sampling locations ranged from 17.7% to 82.8% of data above the 1.0 ppbv multipoint test MDL. This paper describes the EtO emissions observed in and near the four defined source areas within the facility and provides details of the NGEM method development advances accomplished as part of the study.

Evaluating Natural Gas Emissions from Pneumatic Controllers from Upstream Oil and Gas Facilities in West Virginia.

In April of 2018, an optical gas imaging (OGI) and full flow sampler (FFS) emissions measurement study of pneumatic controllers (PCs) was conducted at 15 oil and natural gas production sites in West Virginia. The objective of the study was to identify and characterize PC systems with excessive emissions caused by maintenance issues or nonoptimized process conditions. A total of 391 PC systems were found on the sites and all were classified by the operator as snap-acting (on/off) intermittent venting PCs (IPCs) that should exhibit little gas release while the PC is closed between actuation events. The population was comprised of two groups, 259 infrequently actuating, lower emitting (LE) IPCs and 132 gas processing unit (GPU) liquid level IPCs and associated dump valve actuators that vent more frequently and have larger emission volumes. Using a PC-specific OGI inspection protocol with an assumed whole gas OGI detection threshold of 2.0 scfh, only 2 out of 259 LE-IPCs exhibited OGI detectable emissions indicating good inspection and maintenance practices for this category. Due to combined (ganged) GPU exhaust vents, the OGI inspection of the GPU liquid level IPCs was comparatively less informative and determination of single component IPC emissions by the FFS was more difficult. The time resolved FFS measurements of GPU IPCs defined three categories of operation: one that indicated proper function and two associated with higher emissions that may result from an IPC maintenance or process issues. The overall GPU IPC emission distribution was heavy tailed, with a median value of 12.8 scfh, similar to the 13.5 scfh whole gas IPC emission factor (EF). Total emissions were dominated by non-optimal temporal profile high-emitter IPC cases with the top 20% of IPC systems accounting for between 51.3% and 70.7% of GPU liquid level IPC emissions by volume. The uncertainty in the estimate was due to the ganged nature of the GPU exhaust vents. The highest GPU IPC emission came from a single malfunctioning unit with a measured whole gas value of 157 scfh. Up to six IPCs exceeded 100 scfh. An analysis of FFS emission measurements compared to liquids production per IPC unit employed indicated that production sites operating at a high level of liquids production test the limits of the site engineering, likely resulting in higher IPC emissions. Overall, this study found that the LE-IPCs with OGI-verified low closed bleed rates may emit well below the IPC EF while GPU liquid level IPC systems are likely well represented by the current IPC EF. IPCs that are experiencing a maintenance or process issue or that are operating at sites with a very high product throughput per IPC employed can emit at rates exceeding ten times IPC EF.

Demonstration of VOC Fenceline Sensors and Canister Grab Sampling near Chemical Facilities in Louisville, Kentucky.

Experimental fenceline sensor pods (SPods) fitted with 30 s duration canister grab sampling (CGS) systems were deployed at a site near chemical facilities in Louisville, KY, from 4 June 2018 to 5 January 2020. The objective of the study was to better understand lower cost 10.6 eV photoionization detector (PID)-based volatile organic compound (VOC) sensors and investigate their utility for near-source emissions detection applications. Prototype SPods containing PID sensor elements from two different manufacturers yielded between 78% and 86% valid data over the study, producing a dataset of over 120,000 collocated pair fenceline measurements averaged into 5-min datapoints. Ten-second time-resolved SPod data from an elevated fenceline sensor signal day are presented, illustrating source emission detections from the direction of a facility 500 m west of the monitoring site. An SPod-triggered CGS acquired in the emission plume on this day contained elevated concentrations of 1,3-butadiene and cyclohexane (36 parts per billion by volume (ppbv) and 637 ppbv, respectively), compounds known to be emitted by this facility. Elevated concentrations of these compounds were observed in a subset of the 61 manual and triggered CGS grab samples acquired during the study, with winds from the west. Using novel wind-resolved visualization and normalization approaches described herein, the collocated pair SPod datasets exhibited similarity in emission source signature. With winds from the west, approximately 50% of SPod readings were above our defined theoretical detection limit indicating persistent measurable VOC signal at this site. Overall, this 19-month study demonstrated reasonable prototype SPod operational performance indicating that improved commercial forms of lower cost PID sensors could be useful for select VOC fenceline monitoring applications.

Methane emissions from oil and gas production sites and their storage tanks in West Virginia.

A measurement campaign characterized methane and other emissions from 15 natural gas production sites. Sites were surveyed using optical gas imaging (OGI) cameras to identify fugitive and vented emissions, with the methane mass emission rate quantified using a full flow sampler. We present storage tank emissions in context of all site emissions, followed by a detailed account of the former. In total, 224 well pad emission sources at 15 sites were quantified yielding a total emission rate of 57.5 ± 2.89 kg/hr for all sites. Site specific emissions ranged from 0.4 to 10.5 kg/hr with arithmetic and geometric means of 3.8 and 2.2 kg/hr, respectively. The two largest categories of emissions by mass were pneumatic devices (35 kg/hr or ~61% of total) and tanks (14.3 kg/hr or ~25% of total). Produced water and condensate tanks at all sites employed emissions control devices. Nevertheless, tanks may still lose gas via component leaks as observed in this study. The total number of tanks at all sites was 153. One site experienced a major malfunction and direct tank measurements were not conducted due to safety concerns and may have represented a super-emitter as found in other studies. The remaining sites had 143 tanks, which accounted for 42 emissions sources. Leaks on controlled tanks were associated with ERVs, PRVs, and thief hatches. Since measurements represented snapshots-in-time and could only be compared with modeled tank emission data, it was difficult to assess real capture efficiencies accurately. Our estimates suggest that capture efficiency ranged from 63 to 92% for controlled tanks.

Pyrolysis processing of PFAS-impacted biosolids, a pilot study.

Concentrations of per- and poly-fluoroalkyl substances (PFAS) present in wastewater treatment biosolids are a growing concern. Pyrolysis is a thermal treatment technology for biosolids that can produce a useful biochar product with reduced levels of PFAS and other contaminants. In August 2020, a limited-scope study investigated target PFAS removal of a commercial pyrolysis system processing biosolid with the analysis of 41 target PFAS compounds in biosolids and biochar performed by two independent laboratories. The concentrations of 21 detected target compounds in the input biosolids ranged between approximately 2 µg/kg and 85 µg/kg. No PFAS compounds were detected in the biochar. The PFAS concentrations in the biochar were assumed to equal the compounds' minimum detection limits (MDLs). The pyrolysis system's target PFAS removal efficiencies (REs) were estimated to range between >81.3% and >99.9% (mean >97.4%) with the lowest REs being associated with the lowest detected PFAS concentrations and the highest MDLs. No information on non-target PFAS compounds in influent or effluent media or products of incomplete combustion was considered. Selected gaseous emissions were measured by Fourier transform infrared spectroscopy and gas chromatography time-of-flight mass spectrometry to provide additional information on air emissions after process controls. This limited-scope study indicated that additional research to further understand this process is warranted.Implications: Development of alternative approaches to manage PFAS-impacted biosolids is of emerging international importance. A commercially operating biosolid pyrolysis process was shown to lower target PFAS levels in produced biochar. Additional research is warranted to understand all potential PFAS transformation emission routes and optimal air pollution emissions control strategies for this technology class.

Developing innovative treatment technologies for PFAS-containing wastes.

The release of persistent per- and polyfluoroalkyl substances (PFAS) into the environment is a major concern for the United States Environmental Protection Agency (U.S. EPA). To complement its ongoing research efforts addressing PFAS contamination, the U.S. EPA's Office of Research and Development (ORD) commissioned the PFAS Innovative Treatment Team (PITT) to provide new perspectives on treatment and disposal of high priority PFAS-containing wastes. During its six-month tenure, the team was charged with identifying and developing promising solutions to destroy PFAS. The PITT examined emerging technologies for PFAS waste treatment and selected four technologies for further investigation. These technologies included mechanochemical treatment, electrochemical oxidation, gasification and pyrolysis, and supercritical water oxidation. This paper highlights these four technologies and discusses their prospects and the development needed before potentially becoming available solutions to address PFAS-contaminated waste.Implications: This paper examines four novel, non-combustion technologies or applications for the treatment of persistent per- and polyfluoroalkyl substances (PFAS) wastes. These technologies are introduced to the reader along with their current state of development and areas for further development. This information will be useful for developers, policy makers, and facility managers that are facing increasing issues with disposal of PFAS wastes.

Supercritical Water Oxidation as an Innovative Technology for PFAS Destruction.

Water above 374 °C and 22.1 MPa, becomes supercritical, a special state where organic solubility increases and oxidation processes are accelerated. Supercritical water oxidation (SCWO) has been previously shown to destroy hazardous substances such as halogenated compounds. Three separate providers of SCWO technology were contracted to test the efficacy of SCWO systems to reduce per- and poly-fluoroalkyl substances (PFAS) concentrations from solutions of dilute aqueous film-forming foam (AFFF). The findings of all three demonstration studies, showed greater than 99% reduction of the total PFAS identified in a targeted-compound analysis, including perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). PFOS was reduced from 26.2 mg/L to 240 µg/L, 30.4 mg/L to 0.310 µg/L, and 190 mg/L to 8.57 µg/L, from the Aquarden, Battelle, and 374Water demonstrations, respectively. Similarly, PFOA was reduced from 930 to 0.14 µg/L, 883 to 0.102 µg/L, and 3,100 µg/L to non-detect in the three evaluations. Additionally, chemical oxygen demand of the dilute AFFF was shown to reduce from 4,750 to 5.17 mg/L after treatment, indicating significant organic compound destruction. In one demonstration, a mass balance of the influent and effluent found that the targeted compounds accounted for only 27% of the generated fluoride, suggesting that more PFAS were destroyed than measured and emphasizing the limitations of targeted analysis alone. As a destructive technology, SCWO may be an alternative to incineration and could be a permanent solution for PFAS-laden wastewaters rather than disposal by injection into a deep-well or landfilling. Additional investigation of reaction by-products remains to be conducted for a complete assessment of SCWO's potential as a safe and effective PFAS treatment technology.

SMOOTH DENSITY SPATIAL QUANTILE REGRESSION.

We derive the properties and demonstrate the desirability of a model-based method for estimating the spatially-varying effects of covariates on the quantile function. By modeling the quantile function as a combination of I-spline basis functions and Pareto tail distributions, we allow for flexible parametric modeling of the extremes while preserving non-parametric flexibility in the center of the distribution. We further establish that the model guarantees the desired degree of differentiability in the density function and enables the estimation of non-stationary covariance functions dependent on the predictors. We demonstrate through a simulation study that the proposed method produces more efficient estimates of the effects of predictors than other methods, particularly in distributions with heavy tails. To illustrate the utility of the model we apply it to measurements of benzene collected around an oil refinery to determine the effect of an emission source within the refinery on the distribution of the fence line measurements.

Detection Limits of Optical Gas Imaging for Natural Gas Leak Detection in Realistic Controlled Conditions.

Optical gas imaging (OGI) is a commonly utilized leak detection method in the upstream and midstream sectors of the U.S. natural gas industry. This study characterized the detection efficacy of OGI surveyors, using their own cameras and protocols, with controlled releases in an 8-acre outdoor facility that closely resembles upstream natural gas field operations. Professional surveyors from 16 oil and gas companies and 8 regulatory agencies participated, completing 488 tests over a 10 month period. Detection rates were significantly lower than prior studies focused on camera performance. The leak size required to achieve a 90% probability-of-detection in this study is an order-of-magnitude larger than prior studies. Study results indicate that OGI survey experience significantly impacts leak detection rate: Surveyors from operators/contractors who had surveyed more than 551 sites prior to testing detected 1.7 (1.5-1.8) times more leaks than surveyors who had completed fewer surveys. Highly experienced surveyors adjust their survey speed, examine components from multiple viewpoints, and make other adjustments that improve their leak detection rate, indicating that modifications of survey protocols and targeted training could improve leak detection rates overall.

Spatial analysis of volatile organic compounds using passive samplers in the Rubbertown industrial area of Louisville, Kentucky, USA.

Select volatile organic compounds (VOCs) were measured in the vicinity of chemical facilities and other operations in the Rubbertown industrial area of Louisville, Kentucky (USA) using modified EPA Methods 325A/B passive sampler tubes. Two-week, time-integrated passive samplers were deployed at ten sites which were aggregated into three site groups of varying distances from the Rubbertown area facilities. In comparison to canister data from 2001 to 2005, two of the sites suggested generally lower current VOC levels. Good precision was obtained from the duplicate tubes (≤ 12%) for benzene, toluene, ethylbenzene, and xylene isomers (BTEX), styrene, 1,3-butadiene, perchloroethylene, and other trace VOCs. BTEX, styrene, and 1,3-butadiene concentrations were statistically significantly higher at two site groups near Rubbertown sources than the site group farther away. As found in a similar study in South Philadelphia, BTEX concentrations were also lower for sites farther from a source, though the decline was less pronounced on a percentage basis in Rubbertown. These results suggest that EPA Methods 325A/B can be useful to assess VOC gradients for emissions from chemical facilities besides fenceline benzene levels from refineries.

Understanding oil and gas pneumatic controllers in the Denver-Julesburg basin using optical gas imaging.

In the spring of 2018, a 10-day field study was conducted in Colorado's Denver-Julesburg oil and natural gas production basin to improve information on well pad pneumatic controller (PC) populations and identify PCs with potential maintenance issues (MIs) causing excess emissions through a novel optical gas imaging (OGI) survey approach. A total of 500 natural gas-emitting PCs servicing 102 wells (4.9 PCs/well) were surveyed at 31 facilities operated by seven different companies. The PCs were characterized by their designed operational function and applications, with 83% of the PC population identified as intermittent PCs (IPCs). An OGI inspection protocol was used to investigate emissions on 447 working PCs from this set. OGI detected continuous emissions from 11.3% of observed IPCs and these were classified as experiencing some level of MIs. OGI imaging modes were observed to have a significant effect on emission detectability with high sensitivity mode detection rates being approximately 2 times higher compared to auto mode. Fourteen snapshot emission measurements (not including actuations) were conducted on IPCs in this category using a high-volume sampling device with augmented quality assurance procedures with observed emissions rates ranging from 0.1 up to 31.3 scf/hr (mean = 2.8 scf/hr). For PCs with continuous depressurization type (CPC), 36.8% had continuous emissions observed by OGI. Four supporting emission measurements were conducted on CPCs with one unit exceeding the low bleed regulatory emission threshold with an emission rate of 9.9 scf/hr (mean = 4.2 scf/hr). Additional information was collected on PC actuation events, as observed with OGI, which showed a strong correlation between observed actuation events and facility production compared to observed continuous emissions caused by MIs which did not correlate with facility production.Implications: A novel survey approach of pneumatic controllers at oil and natural gas production facilities in the Denver-Julesburg basin, using optical gas imaging and supporting emission measurements, was demonstrated as an effective method to identify controllers with potential maintenance issues causing excess emissions. The results of the pneumatic controller and optical gas imaging surveys improved information on pneumatic controller populations within the basin and also demonstrated the significant effect optical gas imaging modes have on emission detections.

Rubbertown Next Generation Emissions Measurement Demonstration Project.

Industrial facilities and other sources can emit air pollutants from fugitive leaks, process malfunctions and area sources that can be difficult to understand and to manage. Next generation emissions measurement (NGEM) approaches executed near facilities are enabling new ways to assess these sources and their impacts to nearby populations. This paper describes complementary uses of emerging NGEM systems in a Louisville, KY industrial district (Rubbertown), focusing on an important area air toxic, 1,3-butadiene. Over a one-year deployment starting in September 2017, two-week average passive samplers (PSs) at 11 sites showed both geospatial and temporal trends. At 0.24 ppbv annual average 1,3-butadiene concentration, a group of PSs located near facility fence lines was elevated compared to a PS group located in the community and upwind from facilities (0.07 ppbv average). Two elevated PS periods capturing emission events were examined using time-resolved NGEM approaches as case studies. In one event a 1.18 ppbv PS reading was found to be relatively localized and was caused by a multiday emission from a yet to be identified, non-facility source. In the other event, the airshed was more broadly impacted with PS concentrations ranging from 0.71 ppbv for the near-facility group to 0.46 ppbv for the community group. This case was likely influenced by a known emission event at an industrial facility. For both case studies, air pollutant and wind data from prototype NGEM systems were combined with source location models to inform the emission events. This research illustrates the power of applying NGEM approaches to improve both the understanding of emissions near sources and knowledge of impacts to near-source communities.

Sample integrity evaluation and EPA method 325B interlaboratory comparison for select volatile organic compounds collected diffusively on Carbopack X sorbent tubes.

A sample integrity evaluation and an interlaboratory comparison were conducted in application of U.S. Environmental Protection Agency (EPA) Methods 325A and 325B for diffusively monitoring benzene and other selected volatile organic compounds (VOCs) using Carbopack X sorbent tubes. To evaluate sample integrity, VOC samples were refrigerated for up to 240 days and analyzed using thermal desorption/gas chromatography-mass spectrometry at the EPA Office of Research and Development laboratory in Research Triangle Park, NC, USA. For the interlaboratory comparison, three commercial analytical laboratories were asked to follow Method 325B when analyzing samples of VOCs that were collected in field and laboratory settings for EPA studies. Overall results indicate that the selected VOCs collected diffusively on sorbent tubes generally were stable for 6 months or longer when samples were refrigerated. This suggests the specified maximum 30-day storage time of VOCs collected diffusively on Carbopack X passive samplers and analyzed using Method 325B might be able to be relaxed. Interlaboratory comparison results were in agreement for the challenge samples collected diffusively in an exposure chamber in the laboratory, with most measurements within ±25% of the theoretical concentration. Statistically significant differences among laboratories for ambient challenge samples were small, less than 1 part per billion by volume (ppbv). Results from all laboratories exhibited good precision and generally agreed well with each other.

Assessment of Uinta Basin Oil and Natural Gas Well Pad Pneumatic Controller Emissions.

In the fall of 2016, a field study was conducted in the Uinta Basin Utah to improve information on oil and natural gas well pad pneumatic controllers (PCs). A total of 80 PC systems at five oil sites (supporting six wells) and three gas sites (supporting 12 wells) were surveyed, and emissions data were produced using a combination of measurements and engineering emission estimates. Ninety-six percent of the PCs surveyed were low actuation frequency intermittent vent type. The overall whole gas emission rate for the study was estimated at 0.36 scf/h with the majority of emissions occurring from three continuous vent PCs (1.0 scf/h average) and eleven (14%) malfunctioning intermittent vent PC systems (1.6 scf/h average). Oil sites employed, on average 10.3 PC systems per well compared to 1.5 for gas sites. Oil and gas sites had group average PC emission rates of 0.28 scf/h and 0.67 scf/h, respectively, with this difference due in part to site selection procedures. The PC system types encountered, the engineering emissions estimate approach, and comparisons to measurements are described. Survey methods included identification of malfunctioning PC systems and emission measurements with augmented high volume sampling and installed mass flow meters, each providing a somewhat different picture of emissions that are elucidated through example cases.

Comparison of Field Measurements to Methane Emissions Models at a New Landfill.

Estimates of methane emissions from landfills rely primarily on models due to both technical and economic limitations. While models are easy to implement, there is uncertainty due to the use of parameters that are difficult to validate. The objective of this research was to compare modeled emissions using several greenhouse gas (GHG) emissions reporting protocols including: (1) Intergovernmental Panel on Climate Change (IPCC); (2) U.S. Environmental Protection Agency Greenhouse Gas Reporting Program (EPA GHGRP); (3) California Air Resources Board (CARB); and (4) Solid Waste Industry for Climate Solutions (SWICS), with measured emissions data collected over three calendar years from a young landfill with no gas collection system. By working with whole landfill measurements of fugitive methane emissions and methane oxidation, the collection efficiency could be set to zero, thus eliminating one source of parameter uncertainty. The models consistently overestimated annual methane emissions by a factor ranging from 4-31. Varying input parameters over reasonable ranges reduced this range to 1.3-8. Waste age at the studied landfill was less than four years and the results suggest the need for measurements at additional landfills to evaluate the accuracy of the tested models to young landfills.

South Philadelphia passive sampler and sensor study.

UNLABELLED: From June 2013 to March 2015, in total 41 passive sampler deployments of 2 wk duration each were conducted at 17 sites in South Philadelphia, PA, with results for benzene discussed here. Complementary time-resolved measurements with lower cost prototype fenceline sensors and an open-path ultraviolet differential optical absorption spectrometer were also conducted. Minimum passive sampler benzene concentrations for each sampling period ranged from 0.08 ppbv to 0.65 ppbv, with a mean of 0.25 ppbv, and were negatively correlated with ambient temperature (-0.01 ppbv/°C, R(2) = 0.68). Co-deployed duplicate passive sampler pairs (N = 609) demonstrated good precision with an average and maximum percent difference of 1.5% and 34%, respectively. A group of passive samplers located within 50 m of a refinery fenceline had a study mean benzene concentration of 1.22 ppbv, whereas a group of samplers located in communities >1 km distant from facilities had a mean of 0.29 ppbv. The difference in the means of these groups was statistically significant at the 95% confidence level (p < 0.001). A decreasing gradient in benzene concentrations moving away from the facilities was observed, as was a significant period-to-period variation. The highest recorded 2-wk average benzene concentration for the fenceline group was 3.11 ppbv. During this period, time-resolved data from the prototype sensors and the open-path spectrometer detected a benzene signal from the west on one day in particular, with the highest 5-min path-averaged benzene concentration measured at 24 ppbv. IMPLICATIONS: Using a variation of EPA's passive sampler refinery fenceline monitoring method, coupled with time-resolved measurements, a multiyear study in South Philadelphia informed benzene concentrations near facilities and in communities. The combination of measurement strategies can assist facilities in identification and mitigation of emissions from fugitive sources and improve information on air quality complex air sheds.

Spatial analysis of volatile organic compounds in South Philadelphia using passive samplers.

UNLABELLED: Select volatile organic compounds (VOCs) were measured in the vicinity of a petroleum refinery and related operations in South Philadelphia, Pennsylvania, USA, using passive air sampling and laboratory analysis methods. Two-week, time-integrated samplers were deployed at 17 sites, which were aggregated into five site groups of varying distances from the refinery. Benzene, toluene, ethylbenzene, and xylene isomers (BTEX) and styrene concentrations were higher near the refinery's fenceline than for groups at the refinery's south edge, mid-distance, and farther removed locations. The near fenceline group was significantly higher than the refinery's north edge group for benzene and toluene but not for ethylbenzene or xylene isomers; styrene was lower at the near fenceline group versus the north edge group. For BTEX and styrene, the magnitude of estimated differences generally increased when proceeding through groups ever farther away from the petroleum refining. Perchloroethylene results were not suggestive of an influence from refining. These results suggest that emissions from the refinery complex contribute to higher concentrations of BTEX species and styrene in the vicinity of the plant, with this influence declining as distance from the petroleum refining increases. IMPLICATIONS: Passive sampling methodology for VOCs as discussed here is employed in recently enacted U.S. Environmental Protection Agency Methods 325A/B for determination of benzene concentrations at refinery fenceline locations. Spatial gradients of VOC concentration near the refinery fenceline were discerned in an area containing traffic and other VOC-related sources. Though limited, these findings can be useful in application of the method at such facilities to ascertain source influence.