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1.
In recent years, ambient measurements of hourly ozone precursor concentrations, namely speciated and total nonmethane organic compounds (NMOCs), have become available through the Photochemical Assessment Monitoring Stations (PAMS) program. Prior to this, NMOCs were measured in the central business district using a canister to obtain the 3-hr integrated sample for the 6:00 a.m.-9:00 a.m. period. Such sampling had been carried out annually for nearly a decade at three locations in the New York City metropolitan area. The intent of these measurements, along with measurements of the other ozone precursor, NO(x), was to provide an understanding of ozone formation and the emissions loading and mix in the urban area. The analysis of NMOC and NO(x) measurements shows a downward trend in the case of NMOC. In addition, we compared the canister-based NMOC concentrations with data obtained from the PAMS program for the 6:00 a.m.-9:00 a.m. period. Analysis of the NMOC concentrations reveals poor spatial correlation between the various monitors, reflecting the effect of localized emissions. This suggests that NMOC measurements made at a single location cannot be viewed as representative of the entire region. On the other hand, correlations were found to be higher among the NO(x) monitors, indicating the commonality of emission  相似文献   

2.
Volatile organic compounds (VOCs) are emitted from anthropogenic and natural (biogenic) sources into the atmosphere. Characterizing their ambient mixing ratios or concentrations is a challenge because VOCs comprise hundreds of species, and accurate measurements are difficult. Long-term hourly and daily-resolution data have been collected in the metropolitan area of Atlanta, Georgia, a major city dominated by motor vehicle emissions. A series of observations of daily, speciated C2–C10 non-methane organic compounds (NMOC) and oxygenated hydrocarbons (OVOC) in mid-town Atlanta (Jefferson Street, JST) are compared with data from three urban-suburban sites and a nearby non-urban site. Annual-average mixing ratios of NMOC and OVOC at JST declined from 1999 through 2007. Downward trends in NMOC, CO, and NOy corroborate expected emission changes as reflected in emission inventories for Atlanta’s Fulton County. Comparison of the JST NMOC composition with data from roadside and tunnel sampling reveals similarities to motor vehicle dominated samples. The JST annual average VOC-OH reactivities from 1999 to 2007 were relatively constant compared with the decline in annual-average NMOC mixing ratios. Mean reactivity at JST, in terms of concentration*kOH, was approximately 40% alkenes, 22% aromatics, 16% isoprene and 6% other biogenics, 13% C7–C10 alkanes and 3% C2-C6 alkanes, indicating that biogenic NMOCs are important but not dominant contributors to the urban reactive NMOC mix. In contrast, isoprene constituted ~50% of the VOC-OH reactivities at two non-urban sites. Ratios of 24-hour average CO/benzene, CO/isopentane, and CO/acetylene concentrations indicate that such species are relatively conserved, consistent with their low reactivity. Ratios of more-reactive to less-reactive species show diurnal variability largely consistent with expected emission patterns, transport and mixing of air, and chemical processing.  相似文献   

3.
This paper describes some characteristics of speciated nonmethane organic compound (NMOC) data collected in 1994 at five Photochemical Assessment Monitoring Stations (PAMS) and archived in the U.S. Environmental Protection Agency's Aerometric Information Retrieval System (AIRS). Topics include data completeness, distribution of individual NMOCs in concentration categories relative to minimum detectable levels, percentage of total NMOC associated with the sum of the 55 PAMS target compounds, and use of scatterplots to diagnose chromatographic misidentification of compounds. This is an early examination of a database that is expanding rapidly, and the insights presented here may be useful to both the producers and future users of the data for establishing consistency and quality control.  相似文献   

4.
Carbon bond (CB-III) fractions for non-methane organic carbon compounds (NMOC) measured in the background alrmass adverted into several urban areas in the eastern and southern United States are reported. These, together with ozone measured aloft, were used In an Empirical Kinetic Modeling Approach (EKMA) to model urban ozone production and urban ozone control strategies.

Over a range of zero to double the mean of the measured NMOC concentrations aloft (0 to 70 ppbC) and zero to the highest ozone levels recorded aloft (0 to 65 ppb), it was found that urban ozone production and control strategies were relatively insensitive to NMOC from aloft. However, urban ozone production was sensitive to ozone from aloft, while ozone control strategies were insensitive to ozone from aloft.  相似文献   

5.
ABSTRACT

This paper describes some characteristics of speciated nonmethane organic compound (NMOC) data collected in 1994 at five Photochemical Assessment Monitoring Stations (PAMS) and archived in the U.S. Environmental Protection Agency’s Aerometric Information Retrieval System (AIRS). Topics include data completeness, distribution of individual NMOCs in concentration categories relative to minimum detectable levels, percentage of total NMOC associated with the sum of the 55 PAMS target compounds, and use of scatterplots to diagnose chromatographic misidentification of compounds. This is an early examination of a database that is expanding rapidly, and the insights presented here may be useful to both the producers and future users of the data for establishing consistency and quality control.  相似文献   

6.
This study compares speciated model-predicted concentrations (i.e., mixing ratios) of volatile organic compounds (VOCs) with measurements from the Photochemical Assessment Monitoring Stations (PAMS) network at sites within the northeastern US during June–August of 2006. Measurements of total non-methane organic compounds (NMOC), ozone (O3), oxides of nitrogen (NOx) and reactive nitrogen species (NOy) are used for supporting analysis. The measured VOC species were grouped into the surrogate classes used by the Carbon Bond IV (CB4) chemical mechanism. It was found that the model typically over-predicted all the CB4 VOC species, except isoprene, which might be linked to overestimated emissions. Even with over-predictions in the CB4 VOC species, model performance for daily maximum O3 was typically within ±15%. Analysis at an urban site in NY, where both NMOC and NOx data were available, suggested that the reasonable ozone performance may be possibly due to compensating overestimated NOx concentrations, thus modulating the NMOC/NOx ratio to be in similar ranges as that of observations.  相似文献   

7.
This analysis represents the first characterization of the photochemistry and transport of ozone in the Detroit metropolitan area and provides a basis for comparing data for Detroit to that for other cities. The characterization is based on a comprehensive set of meteorological and chemical measurements obtained at a site in the urban core of Detroit during the summer of 1981, together with measurements of O3, nitrogen oxides (NO X ), and nonmethane organic compounds (NMOC) from rural, suburban, and urban areas in southeastern Michigan and adjacent areas of Ontario.

For the quartile (23 days) with highest ozone maxima (97-180 ppb), the maxima occurred 10-70 km north-northeast of the city on days that were warm and hazy with light southsouthwest winds. On such days there was a marked accumulation of ozone precursors (NMOC and NOX) in the early morning, as well as a rapid chemical removal of NO X (NO X half-life of ~5 h) from morning to midday. The timing of the daily ozone increase across the study region suggests that local photochemical generation in a moving plume was responsible for more than half of the ozone measured downwind. However, there was also evidence that ozone transported into Detroit as part of the regional background was a significant part of the O3 maxima on high ozone days. The average contributions of photochemistry and transport for the 23 days with the highest ozone maxima were estimated to be 57 ppb and 47 ppb, respectively.  相似文献   

8.
ABSTRACT

Profiles of the sources of nonmethane organic compounds (NMOCs) were developed for emissions from vehicles, petroleum fuels (gasoline, liquefied petroleum gas [LPG], and natural gas), a petroleum refinery, a smelter, and a cast iron factory in Cairo, Egypt. More than 100 hydrocarbons and oxygenated hydrocarbons were tentatively identified and quantified. Gasoline-vapor and whole-gasoline profiles could be distinguished from the other profiles by high concentrations of the C5 and C6 saturated hydrocarbons. The vehicle emission profile was similar to the whole-gasoline profile, with the exception of the unsaturated and aromatic hydrocarbons, which were present at higher concentrations in the vehicle emission profile. High levels of the C2-C4 saturated hydrocarbons, particularly n-butane, were characteristic features of the petroleum refinery emissions. The smelter and cast iron factory emissions were similar to the refinery emissions; however, the levels of benzene and toluene were greater in the former two sources. The LPG and natural gas emissions contained high concentrations of n-butane and ethane, respectively. The NMOC source profiles for Cairo were distinctly different from profiles for U.S. sources, indicating that NMOC source profiles are sensitive to the particular composition of petroleum fuels that are used in a location.  相似文献   

9.
Non-methane organic carbon (NMOC) measurements made in Atlanta, Georgia from 1999–2007 are used with nitrogen oxide (NOx or NOy) and ozone (O3) data to investigate relationships between O3 precursors and peak 8-hour O3 concentrations in the city. Data from a WNW-to-ENE transect of sites illustrate that the mean urban peak 8-hour O3 excess constitutes about 20% of the peak 8-hour O3 measured at the area-wide maximum O3 site when air-mass movement is from the northwest quadrant; local influence is potentially greater on days with more stagnation or recirculation. The peak 8-hour O3 concentrations in Atlanta increase as (1) surface temperature (T), ambient NMOC and NOy concentrations, and previous-day peak O3 concentrations increase, and as (2) relative humidity, surface wind speeds, and ratios of NMOC-to-NOy decrease. An observation-based statistical model is introduced to relate area-wide peak 8-hour O3 concentrations to ambient NMOC and NOy concentrations, while accounting for the non-linear dependences of peak 8-hour O3 concentrations on meteorological factors. On the majority of days when the area-wide peak 8-hour O3 exceeds 75 ppbv, meteorologically-adjusted peak 8-hour O3 concentrations increase as ambient NMOC concentrations increase (NMOC sensitive) and ambient NOy concentrations decrease. This result contrasts with regional conditions in which O3 formation appears to be NOx-sensitive in character. The results offer observationally-based information of relevance to O3 management strategies in the Atlanta area, potentially contributing to “weight-of-evidence” assessments.  相似文献   

10.
Nonmethane organic carbon (NMOC) is a measure of total organic carbon except for that from CH4. We recently reported the development of online instrumentation for continuous NMOC monitoring. This instrument, referred to as C-NMOC, uses a microsorbent trap in combination with a gas-sampling valve as the sampling interface. A conventional oxidation/reduction NMOC detector is used for quantitation. In addition to being an online concentrator and an injector, the microtrap serves as a separator that isolates NMOC from H2O, CO, CO2, CH4, and other background gases. Therefore, the C-NMOC is able to handle high concentrations of background gases commonly found in stack emissions and has detection limits in the ppb levels. This paper reports the results of field validation and testing of a C-NMOC analyzer at a coatings facility in the eastern United States. The instrument was able to monitor the process transients in real time, based on which corrective actions could be taken. It demonstrated good accuracy, high precision, and long-term stability.  相似文献   

11.
Numerous papers analyze ground-level ozone (O3) trends since the 1980s, but few have linked O3 trends with observed changes in nitrogen oxide (NOx) and volatile organic compound (VOC) emissions and ambient concentrations. This analysis of emissions and ambient measurements examines this linkage across the United States on multiple spatial scales from continental to urban. O3 concentrations follow the general decreases in both NOx and VOC emissions and ambient concentrations of precursors (nitrogen dioxide, NO2; nonmethane organic compounds, NMOCs). Annual fourth-highest daily peak 8-hr average ozone and annual average or 98th percentile daily maximum hourly NO2 concentrations show a statistically significant (p < 0.05) linear fit whose slope is less than 1:1 and intercept is in the 30 to >50 ppbv range. This empirical relationship is consistent with current understanding of O3 photochemistry. The linear O3–NO2 relationships found from our multispatial scale analysis can be used to extrapolate the rate of change of O3 with projected NOx emission reductions, which suggests that future declines in annual fourth-highest daily average 8-hr maximum O3 concentrations are unlikely to reach 65 ppbv or lower everywhere in the next decade. Measurements do not indicate increased annual reduction rates in (high) O3 concentrations beyond the multidecadal precursor proportionality, since aggressive measures for NOx and VOC reduction are in place and have not produced an accelerated O3 reduction rate beyond that prior to the mid-2000s. Empirically estimated changes in O3 with emissions suggest that O3 is less sensitive to precursor reductions than is found by the CAMx (v. 6.1) photochemical model. Options for increasing the rate of O3 change are limited by photochemical factors, including the increase in NOx sensitivity with time (NMOC/NOx ratio increase), increase in O3 production efficiency at lower NOx concentrations (higher O3/NOy ratio), and the presence of natural NOx and NMOC precursors and background O3.

Implications:?This analysis demonstrates empirical relations between O3 and precursors based on long term trends in U.S. locations. The results indicate that ground-level O3 concentrations have responded predictably to reductions in VOC and NOx since the 1980s. The analysis reveals linear relations between the highest O3 and NO2 concentrations. Extrapolation of the historic trends to the future with expected continued precursor reductions suggest that achieving the 2014 proposed reduction in the U.S. National Ambient Air Quality Standard to a level between 65 and 70 ppbv is unlikely within the next decade. Comparison of measurements with national results from a regulatory photochemical model, CAMx, v. 6.1, suggests that model predictions are more sensitive to emissions changes than the observations would support.  相似文献   

12.
Abstract

This paper describes a statistic to quantify spatial representativeness for the air measurements of an urban fixed-site ambient air monitoring station. The application of such a statistic of representativeness has also been successfully demonstrated by two data sets collected at the Gu-Ting monitoring station in Taipei. By measuring NO2 at 22 sites simultaneously around the Gu-Ting station, the statistic has characterized different degrees of spatial representativeness for nitrogen dioxide (NO2) at various areas and microenvironments surrounding this fixed-site monitoring station. By measuring ambient air concentrations at six sites sequentially around the Gu-Ting station, the statistic has also characterized different degrees of representativeness for particulates less than 10 urn in size—(PM10), carbon monoxide (CO), sulfur dioxide (SO2), ozone (O3), NO2, nitrogen oxides (NOX), nitrogen monoxide (NO), total hydrocarbons (THC), and nonmethane hydrocarbons (NMHQ—at an open area surrounding this fixed-site monitoring station. This statistical method identifies the Gu-Ting station is well representative of outdoor concentrations of all nine air pollutants for a period of three weeks at the areas within a 700 m radius around this station. The indoor NO2 concentrations, however, are not represented by the measurements at the fixed-site monitoring station.  相似文献   

13.
ABSTRACT

Non-methane organic carbon (NMOC) is a measure of total organic carbon in an air emission, excluding that from methane. Thus, it measures the total amount of carbon, irrespective of the structure and functional groups in the molecule. The U.S. Environmental Protection Agency (EPA) Method 25 is used for quantification of NMOC in emission sources and in ambient air. This method involves laboratory analysis of collected air samples and cannot be used for real-time measurements. It is prone to interferences from CO2, CH4, and CO, as well as moisture. In this paper, a novel method for continuous, on-line monitoring of NMOC in air emissions and ambient air is presented. Detection limits are at ppb levels, and interference of permanent gases have been eliminated.  相似文献   

14.
On-road vehicle emissions of carbon monoxide (CO), nitrogen oxides (NOx), and volatile organic compounds (VOCs) during 1995–2009 in the Atlanta Metropolitan Statistical Area were estimated using the Motor Vehicle Emission Simulator (MOVES) model and data from the National Emissions Inventories and the State of Georgia. Statistically significant downward trends (computed using the nonparametric Theil-Sen method) in annual on-road CO, NOx, and VOC emissions of 6.1%, 3.3%, and 6.0% per year, respectively, are noted during the 1995–2009 period despite an increase in total vehicle distance traveled. The CO and NOx emission trends are correlated with statistically significant downward trends in ambient air concentrations of CO and NOx in Atlanta ranging from 8.0% to 11.8% per year and from 5.8% to 8.7% per year, respectively, during similar time periods. Weather-adjusted summertime ozone concentrations in Atlanta exhibited a statistically significant declining trend of 2.3% per year during 2001–2009. Although this trend coexists with the declining trends in on-road NOx, VOC, and CO emissions, identifying the cause of the downward trend in ozone is complicated by reductions in multiple precursors from different source sectors.
Implications:Large reductions in on-road vehicle emissions of CO and NOx in Atlanta from the late 1990s to 2009, despite an increase in total vehicle distance traveled, contributed to a significant improvement in air quality through decreases in ambient air concentrations of CO and NOx during this time period. Emissions reductions in motor vehicles and other source sectors resulted in these improvements and the observed declining trend in ozone concentrations over the past decade. Although these historical trends cannot be extrapolated to the future because pollutant concentration contributions due to on-road vehicle emissions will likely become an increasingly smaller fraction of the atmospheric total, they provide an indication of the benefits of past control measures.  相似文献   

15.
Woody biomass waste is generated throughout California from forest management, hazardous fuel reduction, and agricultural operations. Open pile burning in the vicinity of generation is frequently the only economic disposal option. A framework is developed to quantify air emissions reductions for projects that alternatively utilize biomass waste as fuel for energy production. A demonstration project was conducted involving the grinding and 97-km one-way transport of 6096 bone-dry metric tons (BDT) of mixed conifer forest slash in the Sierra Nevada foothills for use as fuel in a biomass power cogeneration facility. Compared with the traditional open pile burning method of disposal for the forest harvest slash, utilization of the slash for fuel reduced particulate matter (PM) emissions by 98% (6 kg PM/BDT biomass), nitrogen oxides (NOx) by 54% (1.6 kg NOx/BDT), nonmethane volatile organics (NMOCs) by 99% (4.7 kg NMOCs/BDT), carbon monoxide (CO) by 97% (58 kg CO/BDT), and carbon dioxide equivalents (CO2e) by 17% (0.38 t CO2e/BDT). Emission contributions from biomass processing and transport operations are negligible. CO2e benefits are dependent on the emission characteristics of the displaced marginal electricity supply. Monetization of emissions reductions will assist with fuel sourcing activities and the conduct of biomass energy projects.  相似文献   

16.
The observed ranges in nonmethane organic compound (NMOC) concentrations, NMOC composition and nitrogen oxides (NOX) concentrations have been evaluated for urban and nonurban areas at ground level and aloft of the contiguous United States. The ranges in NMOC to NOX ratios also are considered. The NMOC composition consistently shifts towards less reactive compounds, especially the alkanes, in air parcels over nonurban areas compared to the NMOC composition near ground level within urban areas. The values for the NMOC to NOX ratios, 1.2 to 4.2, in air aloft over nonurban areas are lower than in air at ground level urban sites, ≥8, and much lower than in air at ground level nonurban sites, ≥20.

The layers of air aloft over a number of nonurban areas of the United States tend to accumulate NOX emissions from the tall stacks of large fossil fuel power plants located at nonurban sites. During the night into the morning hours, the air aloft is isolated from any fresh NMOC emissions predominately coming from near surface sources. Conversely, during this extended period of restricted vertical mixing, air near the surface accumulates NMOC emissions while this air is isolated from the major NOX sources emitting aloft. These differences in the distribution of NMOC and NOX sources appear to account for the much larger NMOC to NOX ratios reported near ground level compared to aloft over nonurban areas.

Two types of experimental results are consistent with these conclusions: (1) observed increases in surface rural NOX concentrations during the morning hours during which the mixing depth increases to reach the altitude at which NOX from the stacks of fossil fuel power plants is being transported downwind; (2) high correlations of total nitrate at rural locations with Se, which is a tracer for coal-fired power plant NOX emissions.

The implications of these conclusions from the standpoint of air quality strategies are suggested by use of appropriate scenarios applied to both urban and regional scale photochemical air quality models. The predictions from urban model scenarios with NMOC to NOX ratios up to 20 are that NOX control will result in the need for the control of more NMOC emissions than necessary in the absence of NOX control, in order to meet the O3 standard. On a regional scale, control of NOX emissions from fossil fuel power plants has little overall effect regionally but does result on a more local scale in both small decreases and increases in O3 concentrations compared to the baseline scenario without NOX control. The regional modeling results obtained to date suggest that NOX control may be effective in reducing O3 concentrations only for a very limited set of conditions in rural areas.  相似文献   

17.
The mesoscale meteorological model TVM, coupled to a photochemical/transport module in which different chemical mechanisms (RACM, EMEP) are implemented, has been evaluated. Field measurements and numerical results are used to determine the impact of the mesoscale flows on the photochemical smog episodes observed in the Greater Madrid Area for two selected days, characterised by the presence of a thermal low-pressure system over the Iberian Peninsula. During the 14 July 1992, the synoptic flow from the southeast favoured the transport of the precursors to the Guadarrama mountain range, where high concentrations of ozone were registered, exceeding the population information threshold. On the 15 July 1995, the synoptic wind from the northwest interacted with the local thermally driven flows, pushing the pollutants far away from the metropolitan area with the result that high ozone concentrations were measured to the east-southeast of the city.  相似文献   

18.
To investigate the effects of low (0.05 micromol/mol) and relatively low (0.10 micromol/mol) concentrations of ozone on photoassimilate partitioning, rice plants grown in a water culture were fed with (13)C-labelled carbon dioxide at the reproductive stage in an assimilation chamber with constant concentration of (12)CO(2) and (13)CO(2). Rice plants were exposed to ozone 4 weeks before and 3 weeks after (13)CO(2) feeding. The dry weight of whole plants decreased with increasing ozone concentration, whereas net photosynthetic rate (apparent CO(2) uptake per unit leaf area) was unaffected, compared with the control, at the time of (13)CO(2) feeding. Dry matter distribution into leaf sheaths and culms was reduced more than that into leaf blades by ozone exposure. Although panicle dry weight per plant was reduced by ozone, the percentage of panicle dry weight to the whole plant tended to increase considerably. Exposure to ozone accelerated translocation of (13)C from source leaves to other plant parts. Partitioning of (13)C to panicles and roots was higher under ozone treatment than in the control. Respiratory losses of fixed (13)C from plants tended to decrease under treatment with ozone. The increase in photoassimilate partitioning in panicles can be considered to be an acclimation response of rice plants to complete reproductive stage under the restricted biomass production caused by ozone.  相似文献   

19.
Strategies for control of ozone aim at regulation of its chemical precursors, non-methane organic compounds (NMOC) and nitrogen oxides (NOx). It is therefore important to analyze how these precursors vary temporally and geographically. This study finds significant and important differences among four Texas ozone nonattainment sites, Dallas, Ft. Worth, El Paso, and Houston, for 1984, 1985, and 1986 for NMOC, NOx, and their ratio NNR. These differences were detected through nonparametric analysis of variance and Student-New-man-Keuls’s test for multiple comparisons on rank-transformed data. A noteworthy feature of the data analysis is its attention to the assumptions underlying the statistical methods. Classical models based on normal or lognormal theory had to be abandoned for lack of realism. It is demonstrated how alternative models may be applied to yield appropriate, rather than inappropriate, conclusions.  相似文献   

20.
Reformulated gasoline (RFG) contains oxygen additives such as methyl tertiary butyl ether or ethanol. The additives enable vehicles to burn fuel with a higher air/fuel ratio, thereby lowering the emission of carbon monoxide (CO) and volatile organic compounds (VOCs). Because VOCs react with sunlight to form ozone (O3), the Clean Air Act requires severe O3 nonattainment areas such as southeastern Wisconsin to use RFG. On July 17, 2001, the U.S. Environmental Protection Agency (EPA) granted Milwaukee, WI, and Chicago, IL, a waiver from the VOC reduction requirement of Phase II RFG. The VOC reduction requirement was lowered from 27.4% of the 1990 baseline fuel to 25.4%. The assumption was that ethanol-blended RFG would lower summertime CO concentrations sufficiently to offset the increased VOC emissions. The waiver is estimated to increase VOC emissions by approximately 0.8%, or 0.4 t of VOC on a hot summer weekday. This study evaluates whether RFG has been effective in lowering southeastern Wisconsin ambient CO concentrations. Three years of ambient CO data before RFG was introduced were compared with the first three years of ambient CO data after RFG was introduced. This paper also evaluates how the meteorology, vehicle inspection/maintenance program, vehicle miles traveled, and stationary source emissions influence CO concentrations. The winter decrease in ambient CO concentrations was found to be statistically significant, while the summer data showed no statistically significant change, indicating that RFG is most effective lowering ambient CO concentrations in cold weather.  相似文献   

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