Benzene Mixing Ratios Research Articles

Spatially Resolved Source Apportionment of Industrial VOCs Using a Mobile Monitoring Platform

Industrial emissions of volatile organic compounds (VOCs) directly impact air quality downwind of facilities and contribute to regional ozone and secondary organic aerosol production. Positive matrix factorization (PMF) is often used to apportion VOCs to their respective sources using measurement data collected at fixed sites, for example air quality monitoring stations. Here, we apply PMF analysis to high time-resolution VOC measurement data collected both while stationary and while moving using a mobile monitoring platform. The stationary monitoring periods facilitated the extraction of representative industrial VOC source profiles while the mobile monitoring periods were critical for the spatial identification of VOC hotspots. Data were collected over five days in a heavily industrialized region of southwestern Ontario containing several refineries, petrochemical production facilities and a chemical waste disposal facility. Factors associated with petroleum, chemical waste and rubber production were identified and ambient mixing ratios of selected aromatic, unsaturated and oxygenated VOCs were apportioned to local and background sources. Fugitive emissions of benzene, highly localized and predominantly associated with storage, were found to be the dominant local contributor to ambient benzene mixing ratios measured while mobile. Toluene and substituted aromatics were predominantly associated with refining and traffic, while methyl ethyl ketone was linked to chemical waste handling. The approach described here facilitates the apportionment of VOCs to their respective local industrial sources at high spatial and temporal resolution. This information can be used to identify problematic source locations and to inform VOC emission abatement strategies.

Environmental and health risks of VOCs in the longest inner–city tunnel in Xi’an, Northwest China: Implication of impact from new energy vehicles

Traffic source–dominated volatile organic compound (VOC) samples were collected during four time-intervals in a day (Ⅰ: 7:30–10:30, Ⅱ: 11:00–14:00, Ⅲ: 16:30–19:30, and Ⅳ: 20:00–23:00) in a tunnel in summer, 2019, in Xi’an, China. The total measured VOC (TVOC) in periods Ⅰ and Ⅲ (rush hours, 107.2 ± 8.2 parts per billion by volume [ppbv]) was 1.8 times that in periods Ⅱ and Ⅳ (non-rush hours, 58.6 ± 13.8 ppbv), consistent with the variation in vehicle numbers in the tunnel. The considerably elevated ethane and ethylbenzene levels could have been attributed to emissions from compressed natural gas vehicles and the rapid development of methanol-fueled taxis in Xi’an in 2019. The mixing ratios of benzene, toluene, ethylbenzene, and xylenes (BTEX) contributed 9.4%–12.7% to TVOCs, and the contributions were nearly 40% higher in periods Ⅰ and Ⅲ than in Ⅱ and Ⅳ, indicating that BTEX levels were strongly affected by vehicle emissions. The indicators of motor vehicle emission, namely ethylene, propylene, toluene, m/p-xylenes, o-xylene, and propane, contributed to more than half of the ozone formation potential in this study. The noncarcinogenic risks of VOCs in this study were within the international safety standard, whereas the carcinogenic risks exceeded the standard by 2.3–4.6 times, suggesting that carcinogenic risks were more serious than noncarcinogenic risks. VOCs presented 2.2 and 1.4 times noncarcinogenic and carcinogenic risks during rush hours than during non-rush hours, respectively. Notably, the carcinogenic risk in period Ⅳ was comparable with that in period Ⅲ; however, the vehicle numbers and VOC mixing ratios were the lowest at night, which may have attributed to the increasing number and proportion of methanol M100-fueled vehicles in the tunnel. Therefore, VOCs emitted by new energy vehicles should also be seriously considered while evaluating fossil fuel vehicle emissions.

Aromatic compounds in a semi-urban site of western India: Seasonal variability and emission ratios

Ambient concentrations of benzene, toluene, and carbon-monoxide (CO) were measured at a semi-urban site in western India during the year 2015. Monthly mixing ratios of benzene, toluene, and CO were in the ranges of 0.58–1.18, 0.62–1.48, and 218–548 ppbv, respectively. In wintertime, the higher concentrations of aromatic volatile organic compounds (VOCs) and CO were due to shallower boundary layer depths and transport from polluted Indo-Gangetic Plain. The ∆toluene/∆benzene slope of 1.18 ± 0.41 ppb ppb−1 characterizes vehicle exhaust emissions. The higher values of ∆toluene/∆benzene in May coincided with the higher ambient temperatures (average ~ 35 °C) indicating emissions from evaporative sources. The emission ratios of ∆benzene/∆CO (1.82 ± 0.47 ppb ppm−1) and ∆toluene/∆CO (2.2 ± 0.72 ppb ppm−1) in the winter season are comparable to those for several urban regions of the world. The ozone formation potential and propylene-equivalent concentration of aromatics were lower than those of alkanes and alkenes measured during the same study period. Ethane (4.4 ± 3 ppbv), propane (3.4 ± 2 ppbv), and n-Butane (3.9 ± 2 ppbv), ethene (5.8 ± 3 ppbv), and propene (1.6 ± 1 ppbv) were the dominant alkane and alkene compounds measured during the study period. The composition of non-methane volatile organic compounds shows small change with the photochemical age suggesting the contributions of several other sources in addition to vehicular exhaust. The positive matrix factorization analysis suggests relatively high loadings of benzene (~30%), toluene (45%), and CO (32%), respectively from vehicle exhaust. The study highlights major contributions of vehicle exhaust, but emissions from other sources such as biomass burning, industries, evaporative loss, and biogenic are also significant.

Characteristics and source implications of aromatic hydrocarbons at urban and background areas in Beijing, China

The characteristics of benzene, toluene, ethylbenzene, and xylene (BTEX) concentrations, their temporal and spatial variations, and their source origins from September–December 2017 at an urban and a background site in Beijing, China were investigated. The averaged (±σ) total mixing ratios of benzene, toluene, ethylbenzene, m, p-xylenes, and o-xylene were 0.40 ± 0.39 ppbv, 0.31 ± 0.34 ppbv, 0.08 ± 0.07 ppbv, 0.08 ± 0.08 ppbv, and 0.05 ± 0.05 ppbv at the SDZ site, which were 63%, 79%, 83%, 85%, and 89% lower than those at the Chinese Academy of Meteorological Sciences site (CMA). It is worth noting that the average mixing ratios of BTEX at SDZ and CMA were 0.86 ± 1.03 ppbv and 3.38 ± 2.80 ppbv during the heating period (HP), which were 2.3% and 21.9% lower than those before the HP, a decrease that was mainly related to the frequent occurrence of strong northerly and northwesterly winds and low relative humidity (RH) during the HP. Obvious differences were also observed between the BTEX composition proportions at the SDZ and CMA sites. On average, benzene comprised 44% of the total BTEX at SDZ, whereas toluene was the largest contributor to the total BTEX at CMA, accounting for 37%. In addition, the contributions of C8 aromatics (the sum of ethylbenzene, m, p-xylenes, and o-xylene) at CMA (36%) were also higher than those at SDZ (21%), reflecting the different emission sources of the two sites. In addition, the BTEX species showed similar and pronounced diurnal profiles at SDZ and CMA, all characterized by much higher values at night than during the day. Diagnostic ratios and source implications suggested that SDZ was affected mainly by biomass/biofuel/coal burning, with substantially elevated benzene levels during the winter HP, whereas CMA was affected both by traffic-related emissions and biomass/biofuel/coal burning emissions. These findings suggest the necessity of regionally-tailored control strategies both to reduce BTEX levels and to mitigate their environmental impact. Further analysis of the backward trajectories revealed that the BTEX compounds varied greatly in terms of air mass origins, but generally exhibited high values for slow air masses passing over areas south of Beijing, with dominant contributions from benzene, toluene, and m, p-xylenes.

Non-methane hydrocarbons in a controlled ecological life support system

Non-methane hydrocarbons (NMHCs) are vital to people's health and plants' growth, especially inside a controlled ecological life support system (CELSS) built for long-term space explorations. In this study, we measured 54 kinds of NMHCs to study their changing trends in concentration levels during a 4-person-180-day integrated experiment inside a CELSS with four cabins for plants growing and other two cabins for human daily activities and resources management. During the experiment, the total mixing ratio of measured NMHCs was 423 ± 283 ppbv at the first day and it approached 2961 ± 323 ppbv ultimately. Ethane and propane were the most abundant alkanes and their mixing ratios kept growing from 27.5 ± 19.4 and 31.0 ± 33.6 ppbv to 2423 ± 449 ppbv and 290 ± 10 ppbv in the end. For alkenes, ethylene and isoprene presented continuously fluctuating states during the experimental period with average mixing ratios of 30.4 ± 19.3 ppbv, 7.4 ± 5.8 ppbv. For aromatic hydrocarbons, the total mixing ratios of benzene, toluene, ethylbenzene and xylenes declined from 48.0 ± 44 ppbv initially to 3.8 ± 1.1 ppbv ultimately. Biomass burning, sewage treatment, construction materials and plants all contributed to NMHCs inside CELSS. In conclusion, the results demonstrate the changing trends of NMHCs in a long-term closed ecological environment's atmosphere which provides valuable information for both the atmosphere management of CELSS and the exploration of interactions between humans and the total environment.

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

AbstractHigh 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.

Tunable diode laser spectroscopy of benzene near 1684 nm with a low-temperature VCSEL

We describe the application of a long-wavelength vertical-cavity surface-emitting laser (VCSEL) with extended tuning range to the detection of benzene vapor at atmospheric pressure. A benzene absorption feature centered at 1684.24 nm was accessed by reducing the heat sink temperature of a VCSEL designed for room-temperature operation to −55°C. This allowed us to increase the injection current and thus to extend a single-scan tuning interval up to 46.4 cm−1 or 13.2 nm around a central wavelength of 1687.4 nm. Five absorption lines of methane in the 5903–5950 cm−1 range could be acquired within single laser scans at a repetition rate of 500 Hz. A benzene absorption feature between 5926 and 5948 cm−1 was recorded for concentration measurements at atmospheric pressure using a single-pass 1.2 m absorption cell. A 50 ppmv mixture of CH4 in N2 was introduced into the cell along with benzene vapor to calibrate benzene concentration measurements. Benzene mixing ratios down to ∼90 ppmv were measured using a direct absorption technique. The minimum detectable absorbance and detection limit of benzene were estimated to be ∼10−4 and 30 ppmv, respectively. Using the wavelength modulation technique, we measured a second harmonic sensor response to benzene vapor absorption in air at atmospheric pressure as a function of modulation index. We conclude that a low-temperature monolithic VCSEL operating near 1684 nm can be employed in compact benzene sensors with a detection limit in the sub-ppm range.

Ground-Based and Airborne Measurements of Nonmethane Hydrocarbons in BERLIOZ: Analysis and Selected Results

During the Berlin Ozone Experiment BERLIOZ in July–August 1998 quasi-continuous measurements ofC2–C12 nonmethane hydrocarbons (NMHCs) were carried out at 10 sites in and around the city of Berlin using on-line gas-chromatographic systems (GCs) with a temporal resolution of 20–120 minutes. Additional airborne NMHCmeasurements were made using canister sampling on three aircraft and an on-line GC system on a fourth aircraft. The ground based data are analyzed to characterize the different sites and to identify the influence of emissions from Berlin on its surroundings. Benzene mixing ratios at the 4 rural sites were rather low (<0.5 ppbv). Berlin (and the surrounding highway ring) was identified as the main source of anthropogenic NMHCs at Eichstadt and Blossin, whilst other sources were important at the furthermost site Menz. The median toluene/benzene concentration ratio in Berlin was 2.3 ppbv/ppbv, agreeing well with measurements in other German cities. As expected, the ratios at the background sites decreased with increasing distance to Berlin and were usually around one or below. On 20 and 21 July, the three northwesterly sites were situated downwind of Berlin and thus were influenced by its emissions. Considering the distance between the sites and the windspeed, the city plume was observed at reasonable time scales, showing decreasing toluene/benzene ratios of 2.3, 1.6 and 1.3 with increasing distance from Berlin. Isoprene was the only biogenic NMHC measured at BERLIOZ. It was themost abundant compound at the background sites on the hotter days, dominating the local NMHC reactivity with averaged contributions to the total OH loss rate of 51% and 70% at Pabstthum and Blossin, respectively. Emissionratios (relative to CO and to the sum of analysed NMHCs) were derived from airborne measurements. The comparison with an emission inventory suggests traffic-related emissions to be the predominating source of the considered hydrocarbon species. Problems were identified with the emission inventory for propane, ethene and pentanes.

Winter indoor air pollution in Alaska: identifying a myth

The benzene and toluene levels inside three homes with attached garages were measured for 12 consecutive weeks during the winter months in Fairbanks, Alaska (Latitude 64.5°N). Results for air samples collected over 12 h for the homes showed indoor benzene mixing ratios ranging from 1.6 to 20.4 parts per billion of mixing ratio volume (ppbv), and toluene air mixing ratios ranging from 7.3 to 41.6 ppbv. A correlation between benzene and toluene levels in each home and similar regression lines suggested the same major emission source, car and small equipment gasoline, present in attached garages. In one home, there was a correlation between indoor benzene mixing ratios and the urinary biomarker, trans,trans-muconic acid. Inside, air mixing ratios of benzene and toluene decreased with decreasing outside temperature in all homes studied, even though homes were relatively tight to prevent heat loss during this period of low winter outdoor temperatures. It is suggested that buildup of these pollutants indoors is prevented by the influence of an increased indoor/outdoor temperature differential and an ensuing increase in home ventilation.