NMOC,ozone, and organic aerosol in the southeastern United States, 1999–2007: 2. Ozone trends and sensitivity to NMOC emissions in Atlanta,Georgia

Non-methane organic carbon (NMOC) measurements made in Atlanta, Georgia from 1999–2007 are used with nitrogen oxide (NO_x or NO_y) 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 NO_y concentrations, and previous-day peak O₃ concentrations increase, and as (2) relative humidity, surface wind speeds, and ratios of NMOC-to-NO_y decrease. An observation-based statistical model is introduced to relate area-wide peak 8-hour O₃ concentrations to ambient NMOC and NO_y 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 NO_y concentrations decrease. This result contrasts with regional conditions in which O₃ formation appears to be NO_x-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.     

Atmospheric aerosol over two urban–rural pairs in the southeastern United States: Chemical composition and possible sources

Positive matrix factorization (PMF) was used to infer the sources of PM_2.5 observed at four sites in Georgia and Alabama. One pair of urban and rural sites in each state is used to examine the regional and urban influence on PM_2.5 concentrations in the Southeast. Eight factors were resolved for the two urban sites and seven factors were resolved for the two rural sites. Spatial correlations of factors were investigated using the square of correlation coefficient (R²) calculated from the resolved G factors. Fourier transform was used to define the temporal characteristics of PM_2.5 factors at these sites. Factors were normalized by using aerosol fine mass concentration data through multiple linear regression to obtain the quantitative factor contributions for each resolved factor. Common factors include: (1) secondary sulfate dominated by high concentrations of sulfate and ammonium with a strong seasonal variation peaking in summer; (2) nitrate and the associated ammonium with a seasonal maximum in winter; (3) “coal combustion/other” factor with presence of sulfate, EC, OC, and Se; (4) soil represented by Al, Ca, Fe, K, Si and Ti; and (5) wood smoke with the high concentrations of EC, OC and K. The motor vehicle factor with high concentrations of EC and OC and the presence of some soil dust components is found at the urban sites, but cannot be resolved for the two rural sites. Among the other factors, two similar industry factors are found at the two sites in each state. For the wood smoke factor, different seasonal trends are found between urban and rural sites, suggesting different wood burning patterns between urban and rural regions. For the industry factors, different seasonal variations are also found between urban and rural sites, suggesting that this factor may come from different sources or a common source may impact the two sites differently. Generally, sulfate, soil, and nitrate factors at the four sites showed similar chemical composition profiles and seasonal variation patterns reflecting the regional characteristics of these factors. These regional factors have predominantly low frequency variations while local factors such as coal combustion, motor vehicle, wood smoke, and industry factors have high frequency variations in addition to low frequency variations.     

Trends in exceedances of the ozone air quality standard in the continental United States, 1980–1998

In 1997, the United States National Ambient Air Quality Standard (NAAQS) for ozone was revised from a 1-h average of 0.12 parts per million (ppm) to an 8-h average of 0.08 ppm. Analysis of ozone data for the ensemble of the contiguous United States and for the period 1980–1998 shows that the average number of summer days per year in exceedance of the new standard is in the range 8–24 in the Northeast and in Texas, and 12–73 in southern California. The probability of exceedance increases with temperature and exceeds 20% in the Northeast for daily maximum temperatures above 305 K. We present the results of several different approaches to analyzing the long-term trends in the old and new standards over the continental United States from 1980 to 1998. Daily temperature data are used to resolve meteorological variability and isolate the effects of changes in anthropogenic emissions. Significant negative trends are found in the Northeast urban corridor, in the Los Angeles Basin and on the western bank of Lake Michigan. Temperature segregation enhances the detection of negative trends. Positive trends occur at isolated sites, mostly in the Southeast; a strong positive trend is found in Nashville (Tennessee). There is some evidence that, except in the Southwest, air quality improvements from the 1980s to the 1990s have leveled off in the past decade.     

Spatial and Temporal Variability of Ozone Exposure in Forested Areas of the United States and Canada: 1978—1988

Ambient O₃ exposures have reduced growth rates of tree genotypes in some areas of the United States. For characterizing O₃ exposures in forested areas, data from primarily population-oriented sites have been used. It has been speculated that exposures calculated from population-oriented sites provide estimates greater than those that would actually be experienced in the majority of forested areas. Accordingly, we compared 1988 O₃ data from three remote forested sites with data from several population-oriented monitoring sites in and around the mid? and southern Appalachian Mountains. The number of hours ≥0.08 ppm was lower at the remote forested sites than at the nearby population-oriented locations. In addition, we characterized the temporal variability of O₃ exposures in forested regions of the United States and Canada for the period 1978-1988. We found that the years of highest O₃ exposure in the eastern United States during 1978-1988 were 1978, 1980, 1983, and 1988, with 1988 being the worst year in four of seven eastern forest regions. In 1988, the Whiteface Mountain summit site (1483 m) experienced approximately 10 percent more hourly average concentrations ≥0.08 ppm than in the second highest O₃ exposure year (i.e., 1979). Consistently throughout the 11-year period, the highest O₃ exposures at the Whiteface Mountain site occurred during the late evening and early morning hours, with the result that the longterm 7-h (0900-1559h) exposure index could not distinguish those years in which the highest exposures occurred from those in which the lowest occurred. Similar to the Whiteface Mountain site, two high-elevation Shenandoah National Park sites experienced their highest O₃ exposures in 1988. With the exception of 1986, the lower elevation site (Dickey Ridge) consistently experienced more frequent occurrences of hourly average concentrations ≥0.08 ppm than the higher elevation site (Big Meadows).     

Characterizing changes in surface ozone levels in metropolitan and rural areas in the United States for 1980–2008 and 1994–2008

In this analysis, we characterize urban and rural ozone (O₃) trends across the US for the periods 1980–2008 (29 years) and 1994–2008 (15 years) using three exposure metrics, which summarize daily O₃ concentrations to reflect different ways O₃ may affect human health and vegetation. We observe that a statistically significant trend at a specific monitoring site, using one exposure metric, does not necessarily result in a similar trend using the other two metrics. The two most common trends among the monitoring sites are either a continuation of negative trending over the 29-year period or a shift from negative to no trend status, indicating a leveling off of the trending. Very few sites exhibit statistically significant increases in the exposure indices. In characterizing the statistically significant changes in the distribution of hourly average O₃, we observe subtle statistically significant changes in the lower part of the distribution (i.e., below 50 ppb) that are not necessarily captured by the trending patterns associated with the three exposure metrics. Using multisite data from 12 metropolitan cities, we find that as the frequency of higher hourly average concentrations is reduced, the lower hourly average concentrations also move upward toward the mid-level values. The change in the number of the hourly average concentrations in the lower range is consistent with decreased NO scavenging. We recommend assessing possible subtle shifts in O₃ concentrations by characterizing changes in the distribution of hourly average concentrations by month. Identifying statistically significant monthly changes in the mid- and low-level hourly average concentrations may provide important information for assessing changes in physical processes associated with global climate change, long-range transport, and the efficacy of models used for emission and risk reductions. Our results indicate that it is important to investigate the change in the trending pattern with time (e.g., moving 15-year trending) in order to assess how year-to-year variability may influence the trend calculation.     

A long-term study of background ozone concentrations in the central Mediterranean—diurnal and seasonal variations on the island of Gozo

A four and a half year study of ozone concentrations in the Central Mediterranean was carried out between January 1997 and August 2001 on a background monitoring station located on the island of Gozo midway between Southern Europe and North Africa.Seasonal and diurnal variations of background ozone are documented. They show the existence of seasonal cycles with a primary maximum in spring followed by a secondary, more variable maximum in summer which indicates that photochemically produced ozone is being transported over the Mediterranean to the rural island of Gozo. Although peak ozone concentrations seldom exceeded 100 ppbv during summer, the background ozone-mixing ratios (as monthly averages) are some of the highest values which can be found at low latitude sites throughout the world. An increasing trend in the annual background ozone concentration from 48.2 ppbv in 1997 to 52.2 ppbv in 2000 is observed. During wintertime the average ozone mixing-ratio (as monthly averages) of 44 ppbv in December is approximately twice as high as on the European continent. This may imply that on Malta, due to higher average ozone concentrations between autumn and spring (the main growing season), crop damage of high economic value may occur.     

The effect of water on gas–particle partitioning of secondary organic aerosol. Part I: α-pinene/ozone system

The effect of relative humidity (RH) on aerosol formation by the semi-volatile oxidation products of the α-pinene/O₃ system has been comprehensively studied. Experiments were performed in the presence of ammonium sulfate (aqueous, dry), ammonium bisulfate seed (aqueous, dry), and aqueous calcium chloride seed aerosols to ascertain their effect on the partitioning of the oxidation products. The yield of organic aerosol varies little with RH, and is not affected by the presence of dry inorganic salt aerosols. Aqueous salt aerosols reduce the yield of organic aerosol compared to that under seed-free or dry seed conditions. The degree of reduction is electrolyte dependent, with aqueous ammonium sulfate leading to the largest reduction and aqueous calcium chloride the smallest. Hygroscopic growth of the organic aerosol from <2% to 85% RH was also monitored, and could be satisfactorily represented as the sum of the individual contributions of the organic and inorganic fractions. The implications of the growth factor measurements for concentration/activity relationships of the condensed phase organic material (assuming a liquid solution) was explored. The formation of the organic aerosol was investigated using a simple two component model, and also one including the 12 product compounds identified in a previous study. The experimental results for <2% and 50% RH (without salt seed aerosols) could be satisfactorily predicted. However, the aqueous salt seed aerosols are predicted to increase the overall yield due to the dissolution of the organic compounds into the water associated with the seed aerosol—the opposite effect to that observed. The implications of two distinct phases existing the aerosol phase were investigated.     

An assessment of source contributions to the ozone concentrations in southern Ontario, 1979–1985

Source contributions to the surface O₃ concentrations in southern Ontario were assessed for the 1979–1985 period. Ozone episode analyses indicate a frequency of about nine episodes per year (15 episode-days). These occur primarily in the summer months and are generally manifestations of the northern extent of the O₃ problem in eastern North America. Widespread elevated O₃ levels tend to occur under weather classes indicative of back or centre of the high pressure situations and associated flow/trajectory from areas south/southwest of the lower Great Lakes. These episodes vary considerably from year-to-year. Local impacts on O₃ levels are generally small.A study of O₃ levels during cloud-free summer days for the period 1981–1985 gave local ‘background’ O₃ levels of about 20–30 ppb daily and 30–50 ppb hourly maxima. The O₃ contributions from the U.S. to southern Canada (assuming local ‘background’ O₃ levels to be independent of wind direction) were estimated to be 30–35 ppb daily and 30–50 ppb hourly maxima. These results indicate an overall O₃ contribution of about 50–60% from the U.S. to southern Ontario. For episode-days, the U.S. contribution is even more significant.     

Sources,distribution, and acidity of sulfate–ammonium aerosol in the Arctic in winter–spring

We use GEOS-Chem chemical transport model simulations of sulfate–ammonium aerosol data from the NASA ARCTAS and NOAA ARCPAC aircraft campaigns in the North American Arctic in April 2008, together with longer-term data from surface sites, to better understand aerosol sources in the Arctic in winter–spring and the implications for aerosol acidity. Arctic pollution is dominated by transport from mid-latitudes, and we test the relevant ammonia and sulfur dioxide emission inventories in the model by comparison with wet deposition flux data over the source continents. We find that a complicated mix of natural and anthropogenic sources with different vertical signatures is responsible for sulfate concentrations in the Arctic. East Asian pollution influence is weak in winter but becomes important in spring through transport in the free troposphere. European influence is important at all altitudes but never dominant. West Asia (non-Arctic Russia and Kazakhstan) is the largest contributor to Arctic sulfate in surface air in winter, reflecting a southward extension of the Arctic front over that region. Ammonium in Arctic spring mostly originates from anthropogenic sources in East Asia and Europe, with added contribution from boreal fires, resulting in a more neutralized aerosol in the free troposphere than at the surface. The ARCTAS and ARCPAC data indicate a median aerosol neutralization fraction [NH₄⁺]/(2[SO₄^2?] + [NO₃^?]) of 0.5 mol mol^?1 below 2 km and 0.7 mol mol^?1 above. We find that East Asian and European aerosol transported to the Arctic is mostly neutralized, whereas West Asian and North American aerosol is highly acidic. Growth of sulfur emissions in West Asia may be responsible for the observed increase in aerosol acidity at Barrow over the past decade. As global sulfur emissions decline over the next decades, increasing aerosol neutralization in the Arctic is expected, potentially accelerating Arctic warming through indirect radiative forcing and feedbacks.     

Trend analysis of monthly sulfur dioxide emissions in the conterminous United States, 1975–1984

Trends in monthly sulfur dioxide emissions for the 48 conterminous United States during the decade 1975–1984 are identified using a robust nonparametric procedure. Statistically significant downward trends are indicated in 32 States, upward trends appear in 10 States, and no significant trend is apparent in six States. Geographically, a distinct regional pattern of emission increases and decreases is evident with declines dominating the Eastern and Western States; increases aligning longitudinally from border to border in most of the Great Plains States, in several New England States, and in Georgia; and no trends frequently occurring in proximity to the upward trending emissions in the Plains States. A time-series decomposition of the monthly values indicates that one distinct emissions pattern commonly occurred through the period of record. This pattern is characterized by an initial emissions increase that peaks between 1977 and 1978, followed by a shallow and undulating decrease through the end of 1984. It is suggested that this signature represents the ‘national’ trend for the period. In addition, five regions of coherent sulfur dioxide emissions behavior are defined on the basis of seasonal occurrence of maximum and minimum emission loadings. A winter-summer, latitudinal opposition is apparent in the timing of emissions maxima, whereas an equinox-summer, longitudinal opposition is apparent in the timing of emissions minima.     

Rural Ozone Across the Eastern United States: Analysis of CASTNet Data, 1988–1995

ABSTRACT

A predominantly rural ozone monitoring network was operated under the auspices of the Clean Air Status and Trends Network (CASTNet) from 1988 until 1995. Ozone data from sites in the eastern United States are presented and several indices are used to describe the spatial and temporal distribution of ozone concentration and exposure. These indices are SUM06, W126, the 8-hour rolling average (MAX_8hr>80), and the current National Ambient Air Quality Standards (NAAQS) for ozone. Ozone indices were selected to illustrate the spatial and temporal distribution of ozone, and the sensitivity of this distribution to different representations of concentration or exposure.

CASTNet is unique in that a uniform set of site selection criteria and uniform procedures, including traceability to a single primary standard, provide a high degree of comparability across sites. Sites were selected to avoid undue influence from point sources, area sources, or local activities. The sites reflect a wide range of land use and terrain types including agricultural and forested, in flat, rolling, and complex terrain from the eastern seaboard across the Appalachian Mountains to the Midwest.

Results indicate that ozone concentrations varied greatly in time and space across the eastern United States. Sites in the upper northeast, upper midwest, and southern periphery subregions experienced relatively low ozone during the years of record compared to sites in the northeast, midwest, and south central subregions. Ozone exposures at an individual rural site are dependent on many factors, including terrain, meteorology, and distance from sources of precursors. Relative to the current (as of 1996) NAAQS, only a handful of CASTNet sites near major urban areas report exceedances. In contrast, the majority of CASTNet sites might exceed the proposed new primary standard for ozone.

Sites at high elevation (>900m) in the east exhibit relatively high exposure statistics (e.g., SUM06 and W126), but no exceedance of the current ozone standard from 1988 through 1995. Terrain effects explain some of the variability within subregions and are an important consideration in the design of monitoring networks for ozone and possibly other pollutants.     

Seasonal variations of hydrophobic organic contaminant concentrations in the water-column of the Seine Estuary and their transfer to a planktonic species Eurytemora affinis (Calanoïda, copepoda). Part 1: PCBs and PAHs

Hydrophobic organic contaminants (HOC) (i.e. PAHs and PCBs) were measured in the water column and in Eurytemora affinis samples from the Seine Estuary collected from November 2002 to February 2005. Results showed seasonal variations of both total PCB and PAH levels in the suspended particulate matter (SPM) and in the copepods with maximum levels during winter times. PAH and PCB concentrations in the SPM ranged from 499 to 5819ngg(-1) and from 58 to 463ngg(-1), respectively. Phenanthrene, pyrene and benzo[b+j+k]fluoranthene (B[b+j+k]F) were the predominant PAH compounds in the water column, while CB 101, 118, 153 and 138 were the most abundant PCB congeners. PCBs and PAHs bioaccumulated by E. affinis (EA) varied between 383 and 1785ngg(-1) and 165-3866ngg(-1). CB101, 153, 138 and B[b+j+k] were, respectively, the major compounds of PCB and PAH fingerprints in EA. Thereby, the copepods could reach high accumulation factor (ACF) (91000 for PCBs and 17000 for PAHs). The principal component analyses of contaminant concentrations and environmental parameter datasets distinguished two groups of copepods. The winter time cluster, with high percentage of adult copepods, which bioaccumulated the highest PCB and PAH body-burdens, and the second cluster with juveniles showing the lowest HOC concentrations. Thus, PAH and PCB concentrations in EA exhibited significant correlations with the percentage of adults making up the samples.     

Spatial variations in the aeolian deposition of dust – the effect of a city: a case study in Be'er-Sheva,Israel

The effect of buildings on the dry deposition of dust particles was investigated in Be'er-Sheva, a desert city with about 140,000 inhabitants in southern Israel, and at two reference points in the surrounding rural area. The mineral and chemical composition of dust sampled at all sites was similar, reflecting the composition of the local loess soil, its likely origin. However, dust deposited in the traps set up in the vicinity of buildings in the city was significantly coarser than the dust which accumulated in similar traps at exposed sites in the countryside. The amount of dust (by weight) in the urban dust traps was on an average more than twice the amount deposited in the rural area. The differences in grain-size distribution and quantity of dust are attributed to the properties of the urban wind field and to various effects of human activity in the city.     

A History of the Production and Use of Carbon Tetrachloride,Tetrachloroethylene, Trichloroethylene and 1,1,1-Trichloroethane in the United States: Part 1—Historical Background; Carbon Tetrachloride and Tetrachloroethylene

Carbon tetrachloride (CTC), tetrachloroethylene (PCE), trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) were four of the most widely used cleaning and degreasing solvents in the United States. These compounds were also used in a wide variety of other applications. The history of the production and use of these four compounds is linked to the development and growth of the United States' synthetic organic chemical industry, and historical events that affected the development and use of chlorinated solvents in general. Part 1 of this article includes a discussion of the historical background common to each of the four solvents, followed by discussion on the history of CTC and PCE. In the early years of the 20th century, CTC became the first of the four solvents to come into widespread use. CTC was used as a replacement for petroleum distillates in the dry-cleaning industry, but was later replaced by PCE. In the 1990s, CTC was phased out under the Montreal Protocol due to its role in stratospheric ozone depletion.     

Photochemical air pollutant levels and ozone phytotoxicity in the region of Mesogia–Attica, Greece

The levels of photochemical air pollutants: O₃, NO and NO₂, were monitored in Athens and in the neighbouring region of the Mesogia plain (Spata, Artemis and Markopoulo) from 1 May–31 August 2000. Phytodetection of ozone was also conducted using bioindicator plants of Bel-W3 and Zichnomirodata (KK6/5) tobacco varieties. The average maximum daily O3 concentration was 60–75 ppb, while the 24 hour average ranged from 40–65 ppb. The AOT40 (ppb hours) index was very high in Athens (16 679 over 121 days), Spata (16 325 over 110 days), Artemis (8093 over 22 days) and Markopoulo (18 646 over 113 days), suggesting potentially phytotoxic ozone levels. The ozone bioindicator plants of Bel-W3 and KK6/5 tobacco varieties were highly injured in all regions confirming the phytotoxicity of those ozone levels. The levels of NO and NO₂ recorded at the three stations, in the Mesogia plain, were considerably lower than those occurring in Athens. The data presented here provide important background information concerning pollution levels in the Mesogia plain shortly before the operation of the new international airport 'Eleftherios Venizelos' in this region (March 2001).     

A History of the Production and Use of Carbon Tetrachloride,Tetrachloroethylene, Trichloroethylene and 1,1,1-Trichloroethane in the United States: Part 2—Trichloroethylene and 1,1,1-Trichloroethane

Carbon tetrachloride (CTC), tetrachloroethylene (PCE), trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) were four of the most widely used cleaning and degreasing solvents in the United States. Part 2 of this article describes the history of TCE and TCA. TCE production in the United States began in the early 1920s. TCE was used as a replacement for petroleum distillates in the dry-cleaning industry, and became the solvent of choice for vapor degreasing in the 1930s. TCE’s use as a degreaser decreased in the 1960s due to toxicity concerns and the increasing popularity of TCA. Significant TCA use began in the 1950s with the development of suitable stabilizer formulations. In the 1990s, TCA was phased out under the Montreal Protocol due to its role in stratospheric ozone depletion.     

The effect of water on gas–particle partitioning of secondary organic aerosol: II. m-xylene and 1,3,5-trimethylbenzene photooxidation systems

An investigation of the effect of relative humidity on aerosol formation from m-xylene and 1,3,5-trimethylbenzene photooxidation is reported. Experiments were performed in the presence and absence of ammonium sulfate seed particles (both aqueous and dry) to ascertain the effect of partitioning of oxidation products into a strong electrolytic solution or onto dry crystalline seed particles. In marked contrast to the α-pinene/ozone system, the final measured secondary organic aerosol yield was unaffected by the presence of gas-phase or liquid-phase water at relative humidities (RH) up to 50%. The hygroscopic nature of the aerosol generated upon photooxidation of m-xylene and 1,3,5-trimethylbenzene was examined; the hygroscopicity of the aerosol at 85% RH for both parent organics increased with the extent of the reaction, indicating that the first-generation oxidation products undergo further oxidation. Limited identification of the gas- and aerosol-phase products of m-xylene and 1,3,5-trimethylbenzene photooxidation is reported. It is evident that a more complete molecular identification of aromatic photooxidation aerosol awaits analytical techniques not yet brought to bear on this problem.     

Towards the analysis of urban livability in China: spatial–temporal changes,regional types,and influencing factors

Environmental Science and Pollution Research - The increasing drift of urbanization and its impact on urban human settlements are of major concern for China cities. Therefore, demystifying the...     

Spatial–temporal evolution of the relationship between agricultural material inputs and agricultural greenhouse gas emissions: experience from China 2003–2018

Environmental Science and Pollution Research - Agricultural materials input (fertilizer and pesticide, etc.), together with straw burning, rice planting, and livestock breeding, constitute the...