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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.

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.

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.

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.

Unlabelled: A pilot study was conducted in application of the U.S. Environmental Protection Agency (EPA) Methods 325A/B variant for monitoring volatile organic compounds (VOCs) near two oil and natural gas (ONG) production well pads in the Texas Barnett Shale formation and Colorado Denver-Julesburg Basin (DJB), along with a traffic-dominated site in downtown Denver, CO. As indicated in the EPA method, VOC concentrations were measured for 14-day sampling periods using passive-diffusive tube samplers with Carbopack X sorbent at fenceline perimeter and other locations. VOCs were significantly higher at the DJB well pad versus the Barnett well pad and were likely due to higher production levels at the DJB well pad during the study. Benzene and toluene were significantly higher at the DJB well pad versus downtown Denver. Except for perchloroethylene, VOCs measured at passive sampler locations (PSs) along the perimeter of the Barnett well pad were significantly higher than PSs farther away. At the DJB well pad, most VOC concentrations, except perchloroethylene, were significantly higher prior to operational changes than after these changes were made. Though limited, the results suggest passive samplers are precise (duplicate precision usually ≤10%) and that they can be useful to assess spatial gradients and operational conditions at well pad locations over time-integrated periods., Implications: Recently enacted EPA Methods 325A/B use passive-diffusive tube samplers to measure benzene at multiple fenceline locations at petrochemical refineries. This pilot study presents initial data demonstrating the utility of Methods 325A/B for monitoring at ONG facilities. Measurements revealed elevated concentrations reflective of production levels and spatial gradients of VOCs relative to source proximity at the Barnett well pad, as well as operational changes at the DJB well pad. Though limited, these findings indicate that Methods 325A/B can be useful in application to characterize VOCs at well pad boundaries.

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.

Unlabelled: Emissions of volatile organic compounds (VOCs) and hazardous air pollutants (HAPs) from oil and natural gas production were investigated using direct measurements of component-level emissions on pads in the Denver-Julesburg (DJ) Basin and remote measurements of production pad-level emissions in the Barnett, DJ, and Pinedale basins. Results from the 2011 DJ on-site study indicate that emissions from condensate storage tanks are highly variable and can be an important source of VOCs and HAPs, even when control measures are present. Comparison of the measured condensate tank emissions with potentially emitted concentrations modeled using E&P TANKS (American Petroleum Institute [API] Publication 4697) suggested that some of the tanks were likely effectively controlled (emissions less than 95% of potential), whereas others were not. Results also indicate that the use of a commercial high-volume sampler (HVS) without corresponding canister measurements may result in severe underestimates of emissions from condensate tanks. Instantaneous VOC and HAP emissions measured on-site on controlled systems in the DJ Basin were significantly higher than VOC and HAP emission results from the study conducted by Eastern Research Group (ERG) for the City of Fort Worth (2011) using the same method in the Barnett on pads with low or no condensate production. The measured VOC emissions were either lower or not significantly different from the results of studies of uncontrolled emissions from condensate tanks measured by routing all emissions through a single port monitored by a flow measurement device for 24 hr. VOC and HAP concentrations measured remotely using the U.S. Environmental Protection Agency (EPA) Other Test Method (OTM) 33A in the DJ Basin were not significantly different from the on-site measurements, although significant differences between basins were observed., Implications: VOC and HAP emissions from upstream production operations are important due to their potential impact on regional ozone levels and proximate populations. This study provides information on the sources and variability of VOC and HAP emissions from production pads as well as a comparison between different measurement techniques and laboratory analysis protocols. On-site and remote measurements of VOC and HAP emissions from oil and gas production pads indicate that measurable emissions can occur despite the presence of control measures, often as a result of leaking thief hatch seals on condensate tanks. Furthermore, results from the remote measurement method OTM 33A indicate that it can be used effectively as an inspection technique for identifying oil and gas well pads with large fugitive emissions.

This research characterizes associations between multiple pollutants in the near-road environment attributed to a roadway line source. It also examines the use of a tracer gas as a surrogate of mobile source pollutants. Air samples were collected in summa canisters along a 300 m transect normal to a highway in Raleigh, North Carolina for five sampling periods spanning four days. Samples were subsequently measured for volatile organic compounds (VOCs) using an electron capture gas chromatograph. Sulfur hexafluoride (SF6) was released from a finite line source adjacent to the roadway for two of the sampling periods, collected in the canisters and measured with the VOCs. Associations between each VOC, and between VOCs and the tracer, were quantified with Pearson correlation coefficients to assess the consistency of the multi-pollutant dispersion profiles, and assess the tracer as a potential surrogate for mobile source pollutants. As expected, benzene, toluene, ethylbenzene, and m,p- and o-xylenes (collectively, BTEX) show strong correlations between each other; further BTEX shows a strong correlation to SF6. Between 26 VOCs, correlation coefficients were greater than 0.8, and 14 VOCs had coefficients greater than 0.6 with the tracer gas. Even under non-downwind conditions, chemical concentrations had significant correlations with distance. Results indicate that certain VOCs are representative of a larger multi-pollutant mixture, and many VOCs are well-correlated with the tracer gas.

In 2009, the U.S. Environmental Protection Agency (EPA) executed a year-long field study at a refinery in Corpus Christi, TX, to evaluate the use of passive diffusive sampling technology for assessing time-averaged benzene concentrations at the facility fence line. The purpose of the study was to investigate the implementation viability and performance of this type of monitoring in a real-world setting as part of EPA's fence-line measurement research program. The study utilized 14-day, time-integrated Carbopack X samplers deployed at 18 locations on the fence line and at two nearby air monitoring sites equipped with automated gas chromatographs. The average fence-line benzene concentration during the study was 1075 parts per trillion by volume (pptv) with a standard deviation of 1935 pptv. For a 6-month period during which wind direction was uniform, the mean concentration value for a group of downwind sites exceeded the mean value of a similar upwind group by 1710 pptv. Mean value differences for these groups were not statistically significant for the remaining 6-month time period when wind directions were mixed. The passive sampling approach exhibited acceptable performance with a data completeness value of 97.1% (n = 579). Benzene concentration comparisons with automated gas chromatographs yielded an r2 value of 0.86 and a slope of 0.90 (n = 50). A linear regression of duplicate pairs yielded an r2 of 0.97, unity slope, and zero intercept (n = 56). In addition to descriptions of technique performance and general results, time-series analyses are described, providing insight into the utility of 2-week sampling for source apportionment under differing meteorological conditions. The limitations of the approach and recommendations for future measurement method development work are also discussed.

There is a need for robust and accurate techniques for the measurement of ammonia (NH3) and other atmospheric pollutant emissions from poultry production facilities. Reasonable estimates of NH3 emission rate (ER) from poultry facilities are needed to guide discussions about the industry's impact on local and regional air quality. The design of these facilities features numerous emission points and results in emission characteristics of relatively low concentrations and exhaust flow rates that vary diurnally, seasonally, and with bird age over a considerable range. These factors combine to render conventional emissions monitoring approaches difficult to apply. Access to these facilities is also often restricted for biosecurity reasons. The three objectives of this study were (1) to compare three methods for measuring exhaust NH3 concentrations and thus ERs, (2) to compare ventilation rates using in situ measured fan characteristics versus using manufacturer sourced fan curves, and (3) to examine limitations of the alternative measurement technologies. In this study, two open-path monitoring systems operating outside of the buildings were compared with a portable monitoring system sampling upstream of a primary exhaust fan. The position of the open-path systems relative to the exhaust fans, measurement strategy adopted, and weather conditions significantly influenced the quality of data collected when compared with the internally located, portable monitoring system. Calculation of exhaust airflow from the facility had a large effect on calculated emissions and assuming that the installed fans performed as per published performance characteristics potentially overestimated emissions by 13.6-26.8%. The open-path measurement systems showed promise for being able to obtain ER measurements with minimal access to the house, although the availability of individual fan characteristics markedly improved the calculated ER accuracy. However, substantial operator skill and experience and favorable weather conditions were required to obtain good quality results.

Assessment of near-road air quality is challenging in urban environments that have roadside structures, elevated road sections, or depressed roads that may impact the dispersion of traffic emissions. Vehicles traveling on arterial roadways may also contribute to air pollution spatial variability in urban areas. To characterize the nature of near-road air quality in a complex urban environment, an instrumented all-electric vehicle was deployed to perform high spatial- and temporal-resolution mapping of ultrafine particles (UFPs, particle diameter <100 nm) and carbon monoxide (CO). Sampling was conducted in areas surrounding a highway in Durham, NC, with multiple repeats of the driving route accomplished within a morning or evening commute time frame. Six different near-road transects were driven, which included features such as noise barriers, vegetation, frontage roads, and densely built houses. Under downwind conditions, median UFP and CO levels in near-road areas located 20-150 m from the highway were a factor of 1.8 and 1.2 higher, respectively, than in areas characterized as urban background. Sampling in multiple near-road neighborhoods during downwind conditions revealed significant variability in absolute UFP and CO concentrations as well as in the rate of concentration attenuation with increasing distance from the highway. During low-speed meandering winds, regional UFP and CO concentrations nearly doubled relative to crosswind conditions; however, near-road UFP levels were still higher than urban background levels by a factor of 1.2, whereas near-road CO concentrations were not significantly different than the urban background.

Understanding motor vehicle emissions, near-roadway pollutant dispersion, and their potential impact to near-roadway populations is an area of growing environmental interest. As part of ongoing U.S. Environmental Protection Agency research in this area, a field study was conducted near Interstate 440 (I-440) in Raleigh, NC, in July and August of 2006. This paper presents a subset of measurements from the study focusing on nitric oxide (NO) concentrations near the roadway. Measurements of NO in this study were facilitated by the use of a novel path-integrated optical remote sensing technique called deep ultraviolet differential optical absorption spectroscopy (DUV-DOAS). This paper reviews the development and application of this measurement system. Time-resolved near-road NO concentrations are analyzed in conjunction with wind and traffic data to provide a picture of emissions and near-road dispersion for the study. Results show peak NO concentrations in the 150 ppb range during weekday morning rush hours with winds from the road accompanied by significantly lower afternoon and weekend concentrations. Traffic volume and wind direction are shown to be primary determinants of NO concentrations with turbulent diffusion and meandering accounting for significant near-road concentrations in off-wind conditions. The enhanced source capture performance of the open-path configuration allowed for robust comparisons of measured concentrations with a composite variable of traffic intensity coupled with wind transport (R2 = 0.84) as well as investigations on the influence of wind direction on NO dilution near the roadway. The benefits of path-integrated measurements for assessing line source impacts and evaluating models is presented. The advantages of NO as a tracer compound, compared with nitrogen dioxide, for investigations of mobile source emissions and initial dispersion under crosswind conditions are also discussed.

Air pollutant emission from unconfined sources is an increasingly important environmental issue. The U.S. Environmental Protection Agency (EPA) has developed a ground-based optical remote-sensing method that enables direct measurement of fugitive emission flux from large area sources. Open-path Fourier transform infrared spectroscopy (OP-FTIR) has been the primary technique for acquisition of pollutant concentration data used in this emission measurement method. For a number of environmentally important compounds, such as ammonia and methane, open-path tunable diode laser absorption spectroscopy (OP-TDLAS) is shown to be a viable alternative to Fourier transform spectroscopy for pollutant concentration measurements. Near-IR diode laser spectroscopy systems offer significant operational and cost advantages over Fourier transform instruments enabling more efficient implementation of the measurement strategy. This article reviews the EPA's fugitive emission measurement method and describes its multipath tunable diode laser instrument. Validation testing of the system is discussed. OP-TDLAS versus OP-FTIR correlation testing results for ammonia (R2 = 0.980) and methane (R2 = 0.991) are reported. Two example applications of tunable diode laser-based fugitive emission measurements are presented.