An Analysis of the Yearly Changes in Sulfur Concentrations at Various National Parks in the United States, 1980-1996

ABSTRACT

An apparent increasing trend in the summer concentrations of particulate sulfur at Shenandoah (for the time period 1982-1995) and at Great Smoky Mountains (for the time period 1984-1995) has been pointed out by some researchers. Others have suggested that these increasing trends may be an analytical artifact resulting from the switch from the Stacked Filter Units (SFU) measurement system to the IMPROVE (Interagency Monitoring of Protected Visual Environments) measurement system that occurred during the winter of 1987. To obtain a better understanding of the effect of the protocol change, we investigate the changes in the seasonal averages of sulfur concentrations for successive pairs of years for the period 1980-1996 for about 20 national park sites in the United States. For the period 1980-1987, we use sulfur data from the old (SFU) database and for the period 1988-1996, we use the IMPROVE database. Changes from one year to the next similar to that between 1987 and 1988 occurred during other years and seasons suggesting that chance causes alone could perhaps explain it, the degree to which chance could have caused the changes was measured using the permutation test for matched. At the very least, additional information such as side by side readings using SFU and IMPROVE measurement methods, may be needed to better understand any systematic effect in the sulfur measurements that may be ascribable to the protocol change.     

The IMPROVE_A temperature protocol for thermal/optical carbon analysis: maintaining consistency with a long-term database

Thermally derived carbon fractions including organic carbon (OC) and elemental carbon (EC) have been reported for the U.S. Interagency Monitoring of PROtected Visual Environments (IMPROVE) network since 1987 and have been found useful in source apportionment studies and to evaluate quartz-fiber filter adsorption of organic vapors. The IMPROVE_A temperature protocol defines temperature plateaus for thermally derived carbon fractions of 140 degrees C for OC1, 280 degrees C for OC2, 480 degrees C for OC3, and 580 degrees C for OC4 in a helium (He) carrier gas and 580 degrees C for EC1, 740 degrees C for EC2, and 840 degrees C for EC3 in a 98% He/2% oxygen (O2) carrier gas. These temperatures differ from those used previously because new hardware used for the IMPROVE thermal/optical reflectance (IMPROVE_TOR) protocol better represents the sample temperature than did the old hardware. A newly developed temperature calibration method demonstrates that these temperatures better represent sample temperatures in the older units used to quantify IMPROVE carbon fractions from 1987 through 2004. Only the thermal fractions are affected by changes in temperature. The OC and EC by TOR are insensitive to the change in temperature protocol, and therefore the long-term consistency of the IMPROVE database is conserved. A method to detect small quantities of O2 in the pure He carrier gas shows that O2 levels above 100 ppmv also affect the comparability of thermal carbon fractions but have little effect on the IMPROVE_TOR split between OC and EC.     

The IMPROVE_A Temperature Protocol for Thermal/Optical Carbon Analysis: Maintaining Consistency with a Long-Term Database

Abstract

Thermally derived carbon fractions including organic carbon (OC) and elemental carbon (EC) have been reported for the U.S. Interagency Monitoring of PROtected Visual Environments (IMPROVE) network since 1987 and have been found useful in source apportionment studies and to evaluate quartz-fiber filter adsorption of organic vapors. The IMPROVE_A temperature protocol defines temperature plateaus for thermally derived carbon fractions of 140 °C for OC1, 280 °C for OC2, 480 °C for OC3, and 580 °C for OC4 in a helium (He) carrier gas and 580 °C for EC1, 740 °C for EC2, and 840 °C for EC3 in a 98% He/2% oxygen (O₂) carrier gas. These temperatures differ from those used previously because new hardware used for the IMPROVE thermal/optical reflectance (IMPROVE_TOR) protocol better represents the sample temperature than did the old hardware. A newly developed temperature calibration method demonstrates that these temperatures better represent sample temperatures in the older units used to quantify IMPROVE carbon fractions from 1987 through 2004. Only the thermal fractions are affected by changes in temperature. The OC and EC by TOR are insensitive to the change in temperature protocol, and therefore the long-term consistency of the IMPROVE database is conserved. A method to detect small quantities of O₂ in the pure He carrier gas shows that O₂ levels above 100 ppmv also affect the comparability of thermal carbon fractions but have little effect on the IMPROVE_TOR split between OC and EC.     

PM2.5 mass and light extinction reconstruction in IMPROVE

Compliance under the Regional Haze Rule of 1999 is based on Interagency Monitoring of Protected Visual Environments (IMPROVE) protocols for reconstructing aerosol mass and light extinction from aerosol chemical concentrations measured in the IMPROVE network. The accuracy, consistency, and potential biases in these formulations were examined using IMPROVE aerosol chemistry and light extinction data from 1988-1999. Underestimation of particulate matter with an aerodynamic diameter < 2.5 microm (PM2.5) by the IMPROVE mass reconstruction formula by 12%, on average, appears to be related to the exclusion of sodium, chlorine, and other elements and to artifacts associated with the measurement of organic carbon, but not to absorption of water by sulfates and nitrates on IMPROVE Teflon filters during weighing. Light scattering measured by transmissometry is not consistent with nephelometer scattering or single-scatter albedos expected for remote locations. Light scattering was systematically overestimated by 34%, on average, with the IMPROVE particle scattering (Bsp) reconstruction formula. The use of climatologically based hygroscopic growth factors f(RH) suggested for compliance with the Haze Rule contributes significantly to this overestimation and increases the amount of light extinction attributable to sulfates for IMPROVE samples between 1993 and 1999 by 5 percentage points.     

Interpretation of trends of PM2.5 and reconstructed visibility from the IMPROVE network

Under the IMPROVE visibility monitoring network, federal land managers have monitored visibility and fine particle concentrations at 29 Class I area sites (mostly national parks and wilderness areas) and Washington, DC since 1988. This paper evaluates trends in reconstructed visibility and fine particles for the 10th (best visibility days), 50th (average visibility days), and 90th (worst visibility days) percentiles over the nine-year period from 1988-96. Data from these sites provides an indication of regional trends in air quality and visibility resulting from implementation of various emission reduction strategies.     

Interpretation of Trends of PM25 and Reconstructed Visibility from the IMPROVE Network

ABSTRACT

Under the IMPROVE visibility monitoring network, federal land managers have monitored visibility and fine particle concentrations at 29 Class I area sites (mostly national parks and wilderness areas) and Washington, DC since 1988. This paper evaluates trends in reconstructed visibility and fine particles for the 10th (best visibility days), 50th (average visibility days), and 90th (worst visibility days) percentiles over the nine-year period from 1988-96. Data from these sites provides an indication of regional trends in air quality and visibility resulting from implementation of various emission reduction strategies.     

An examination of the physical and optical properties of aerosols collected in the IMPROVE program

The Interagency Monitoring of Protected Visual Environments (IMPROVE) protocols for reconstructing the ambient light extinction coefficient (b_ext) from measured aerosol species are the basis for evaluating compliance under the Regional Haze Rule. Aerosol mass composition and optical properties have been measured as part of the IMPROVE program since 1988, providing a long-term data set of aerosol properties at 38 sites around the US. This data set is used to evaluate assumptions made in calculating reconstructed mass and b_ext by applying statistical analysis techniques. In particular, the molecular weight to carbon weight ratio used to compute particulate organic matter is investigated. An annual average value of 1.7±0.2 for the IMPROVE sites, compared to the value of 1.4 currently assumed in the IMPROVE algorithm, is derived. Regression analysis also indicates that fine soil mass concentrations are underestimated by roughly 20% on average. Finally, aerosol mass scattering and extinction efficiencies assumed in the IMPROVE reconstructed b_ext protocol are examined. Fine mode (D_p<2.5 μm) mass scattering efficiencies have a functional dependence on mass concentrations at many sites, and use of a mass-concentration-dependent adjustment factor to refine the assumed efficiencies provides for closer agreement between measured and reconstructed b_ext.     

Determination of the organic aerosol mass to organic carbon ratio in IMPROVE samples

The ratio of organic mass (OM) to organic carbon (OC) in PM(2.5) aerosols at US national parks in the IMPROVE network was estimated experimentally from solvent extraction of sample filters and from the difference between PM(2.5) mass and chemical constituents other than OC (mass balance) in IMPROVE samples from 1988 to 2003. Archived IMPROVE filters from five IMPROVE sites were extracted with dichloromethane (DCM), acetone and water. The extract residues were weighed to determine OM and analyzed for OC by thermal optical reflectance (TOR). On average, successive extracts of DCM, acetone, and water contained 64%, 21%, and 15%, respectively, of the extractable OC, respectively. On average, the non-blank-corrected recovery of the OC initially measured in these samples by TOR was 115+/-42%. OM/OC ratios from the combined DCM and acetone extracts averaged 1.92 and ranged from 1.58 at Indian Gardens, AZ in the Grand Canyon to 2.58 at Mount Rainier, WA. The average OM/OC ratio determined by mass balance was 2.07 across the IMPROVE network. The sensitivity of this ratio to assumptions concerning sulfate neutralization, water uptake by hygroscopic species, soil mass, and nitrate volatilization were evaluated. These results suggest that the value of 1.4 for the OM/OC ratio commonly used for mass and light extinction reconstruction in IMPROVE is too low.     

Evaluation of multisectional and two-section particulate matter photochemical grid models in the Western United States

Version 4.10s of the comprehensive air-quality model with extensions (CAMx) photochemical grid model has been developed, which includes two options for representing particulate matter (PM) size distribution: (1) a two-section representation that consists of fine (PM2.5) and coarse (PM2.5-10) modes that has no interactions between the sections and assumes all of the secondary PM is fine; and (2) a multisectional representation that divides the PM size distribution into N sections (e.g., N = 10) and simulates the mass transfer between sections because of coagulation, accumulation, evaporation, and other processes. The model was applied to Southern California using the two-section and multisection representation of PM size distribution, and we found that allowing secondary PM to grow into the coarse mode had a substantial effect on PM concentration estimates. CAMx was then applied to the Western United States for the 1996 annual period with a 36-km grid resolution using both the two-section and multisection PM representation. The Community Multiscale Air Quality (CMAQ) and Regional Modeling for Aerosol and Deposition (REMSAD) models were also applied to the 1996 annual period. Similar model performance was exhibited by the four models across the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Clean Air Status and Trends Network monitoring networks. All four of the models exhibited fairly low annual bias for secondary PM sulfate and nitrate but with a winter overestimation and summer underestimation bias. The CAMx multisectional model estimated that coarse mode secondary sulfate and nitrate typically contribute <10% of the total sulfate and nitrate when averaged across the more rural IMPROVE monitoring network.     

An assessment of spatial and temporal variation of sulfur dioxide levels over Istanbul, Turkey

Sulfur dioxide concentration levels are investigated in Istanbul to assess air pollution during the heating seasons in which the concentration of air pollutants reach high levels due to the consumption of low-quality fossil fuels. Results reveal that in the 1985-91 period there is an increasing trend in the concentrations of air pollutants. One reason for this increase is found to be the switching to use of low-quality fossil fuels instead of cleaner ones; the consumption ratio of coal/fuel-oil increased drastically in the 1980s from the ratio of 0.62 during 1980 to 3.09 by 1990. Linear regression analysis also indicated the similar variability of sulfur dioxide and particulate matter curves with a correlation coefficient R2=0.87. An optimum interpolation technique, kriging, is used to obtain the spatial distribution of sulfur dioxide over the area. Results indicated that the maximum concentration regions over the European side, exceeding 300 microg/m(3) monthly averages, are found to be the Fatih-Gaziosmanpa?a-Bayrampa?a, Beyo?lu-Si?li, and Emin?nü areas. On the Asian side, the G?ztepe-Kadik?y area received a major threat from sulfur dioxide pollution. Results also indicated that there was a considerable decrease in air pollution levels over Istanbul in the 1995-96 season compared with the previous two seasons. This can be explained by (1) the increase in ventilation, (2) switching to natural gas as a home and business heating fuel, and (3) treatment of coal before its entrance to the city. The variability in weather conditions is explained by the adoption of a ventilation index, which is the product of wind speed and inversion height.     

Spatial and temporal characterization of PM2.5 mass concentrations in California, 1980-2007

Systematic measurement of fine particulate matter (aerodynamic diameter less than 2.5 microm [PM2.5]) mass concentrations began nationally with implementation of the Federal Reference Method (FRM) network in 1998 and 1999. In California, additional monitoring of fine particulate matter (PM) occurred via a dichotomous sampler network and several special studies carried out between 1982 and 2002. The authors evaluate the comparability of FRM and non-FRM measurements of PM2.5 mass concentrations and establish conversion factors to standardize fine mass measurements from different methods to FRM-equivalent concentrations. The authors also identify measurements of PM2.5 mass concentrations that do not agree with FRM or other independent PM2.5 mass measurements. The authors show that PM2.5 mass can be reconstructed to a high degree of accuracy (r2 > 0.9; mean absolute error approximately 2 microg m(-3)) from PM with an aerodynamic diameter < or =10 microm (PM10) mass and species concentrations when site-specific and season-specific conversion factors are used and a statewide record of fine PM mass concentrations by combining the FRM PM2.5 measurements, non-FRM PM2.5 measurements, and reconstructions of PM2.5 mass concentrations. Trends and spatial variations are evaluated using the integrated data. The rates of change of annual fine PM mass were negative (downward trends) at all 22 urban and 6 nonurban (Interagency Monitoring of Protected Visual Environments [IMPROVE]) monitoring locations having at least 15 yr of data during the period 1980-2007. The trends at the IMPROVE sites ranged from -0.05 to -0.25 microg m(-3) yr(-1) (median -0.11 microg m(-3) yr(-1)), whereas urban-site trends ranged from -0.13 to -1.29 microg m(-3) yr(-1) (median -0.59 microg m(-3) yr(-1)). The urban concentrations declined by a factor of 2 over the period of record, and these decreases were qualitatively consistent with changes in emissions of primary PM2.5 and gas-phase precursors of secondary PM. Mean PM2.5 mass concentrations ranged from 3.3 to 7.4 microg m(-3) at IMPROVE sites and from 9.3 to 37.1 microg m(-3) at urban sites.     

Global sulfur emissions from 1850 to 2000

The ASL database provides continuous time-series of sulfur emissions for most countries in the World from 1850 to 1990, but academic and official estimates for the 1990s either do not cover all years or countries. This paper develops continuous time series of sulfur emissions by country for the period 1850-2000 with a particular focus on developments in the 1990s. Global estimates for 1996-2000 are the first that are based on actual observed data. Raw estimates are obtained in two ways. For countries and years with existing published data I compile and integrate that data. Previously published data covers the majority of emissions and almost all countries have published emissions for at least 1995. For the remaining countries and for missing years for countries with some published data, I interpolate or extrapolate estimates using either an econometric emissions frontier model, an environmental Kuznets curve model, or a simple extrapolation, depending on the availability of data. Finally, I discuss the main movements in global and regional emissions in the 1990s and earlier decades and compare the results to other studies. Global emissions peaked in 1989 and declined rapidly thereafter. The locus of emissions shifted towards East and South Asia, but even this region peaked in 1996. My estimates for the 1990s show a much more rapid decline than other global studies, reflecting the view that technological progress in reducing sulfur based pollution has been rapid and is beginning to diffuse worldwide.     

Improved light extinction reconstruction in interagency monitoring of protected visual environments

The U.S. Environmental Protection Agency (EPA) published the Regional Haze Rule (RHR) in 1999. The RHR default goal is to reduce haze linearly from the baseline period of 2000 through 2004 to natural background in 2064. EPA-recommended method for estimating baseline and natural haze uses the Interagency Monitoring of Protected Visual Environments (IMPROVE) light extinction formula. The IMPROVE formula predicts light extinction from measured aerosol chemical concentrations and estimates of the relative humidity multiplier. On average, the IMPROVE formula overpredicts 6156 nephelometer days (24-hr average measured particle light scattering, bsp) of data by 25%. A new IMPROVED method that reconstructs light extinction using a concentration power law model overpredicts these nephelometer days of data by just 2%. Ignoring the 20% lowest light scattering days, this new IMPROVED formula has a 3% underprediction bias over the 4925 highest nephelometer days with light scattering > or =8 inverse megameters. For comparison, the IMPROVE formula has a 12% overprediction bias for the same days. The IMPROVE formula overprediction averages 77%, 27%, 17%, 9%, and -5% broken down by quintile from lowest to highest nephelometer measured light scattering days. The new IMPROVED formula average overprediction is 21%, -5%, -5%, -2%, and 0%. So, agreement between measured and predicted light scattering improves by modifying the current IMPROVE light extinction formula.     

Selections from the history of environmental pollution, with special attention to air pollution. Part 2: From medieval times to the 19th century

Several comprehensive publications have been issued recently on the environmental pollution of past times, especially from medieval times (e.g. Brimblecombe, 1987a; oldstein, 1988; Brimblecombe and Pfister, 1990; Hughes, 1993; Markham, 1994; Brimblecombe, 1995). The aim of this paper is to give an overview of information on the subject – mainly related to the period between medieval times and the 19th century.     

Temporal trends in polychlorinated dibenzo-p-dioxins and dibenzofurans, dioxin-like PCBs, and polybrominated diphenyl ethers in Niagara river suspended sediments

Archived suspended sediment samples collected over the period 1980-2002 at Niagara-on-the-Lake in the Niagara river were analyzed to assess temporal trends in contaminants associated with historical industrial activities in the watershed (PCDDs/PCDFs, DLPCBs), compared to more modern industrial chemicals (PBDEs). The temporal trends for PCDDs/PCDFs and DLPCBs were generally similar, and showed a general trend toward decreasing concentrations, which was presumably due to implementation of control measures in the Niagara river watershed, including the remediation of hazardous waste facilities. The temporal trend in PBDEs contrasted with those of PCDDs/PCDFs and DLPCBs. Prior to 1988, PBDEs (sum of 16 congeners including deca-BDE) were generally detected at low-ppb concentrations, but showed a trend toward increasing concentrations over the period 1980-1988. After 1988, PBDE concentrations in the Niagara river showed a more rapidly increasing trend to a maximum of approximately 35 ng/g in 1995, with deca-BDE as the predominant congener detected. Samples collected over the period February 2003 to March 2004 at the head and mouth of the Niagara river were also analyzed for PBDEs; in all cases PBDE concentrations were higher at the mouth of the river at the outflow to Lake Ontario, indicating the Niagara river watershed is a source of PBDE contamination to Lake Ontario. However, PBDE concentrations in suspended sediments of the Niagara river were comparable to, or lower than, concentrations in bottom sediments in other industrialized/urbanized areas of the world. Based on these comparisons of global PBDE bottom sediment concentrations, the Niagara river watershed does not appear to be a significant local source of PBDEs to Lake Ontario, and concentrations in suspended sediments appear to be indicative of general PBDE contamination from a contamination of local, regional, and continental sources.     

Precipitation in light extinction reconstruction

The U.S. Environmental Protection Agency (EPA) published the Regional Haze Rule (RHR) in 1999. The RHR default goal is to reduce haze linearly to natural background in 2064 from the baseline period of 2000-2004. The EPA default method for estimating natural and baseline visibility uses the Interagency Monitoring of Protected Visual Environments (IMPROVE) formula. The IMPROVE formula predicts the light extinction coefficient from aerosol chemical concentrations measured by the IMPROVE network. The IMPROVE light scattering coefficient formula using data from 1994-2002 underestimated the measured light scattering coefficient by 700 Mm(-1), on average, on days with precipitation. Also, precipitation occurred as often on the clearest as haziest days. This led to estimating the light extinction coefficient of precipitation, averaged over all days, as the light scattering coefficient on days with precipitation (700 Mm(-1)) multiplied by the percent of precipitation days in a year. This estimate added to the IMPROVE formula light extinction estimate gives a real world estimate of visibility for the 20% clearest, 20% haziest, and all days. For example, in 1993, the EPAs Report to Congress projected visibility in Class I areas would improve by 3 deciviews by 2010 across the haziest portions of the eastern United States because of the 1990 Clean Air Act Amendments. Omitted was the light extinction coefficient of precipitation. Adding in the estimated light extinction coefficient of precipitation, the estimated visibility improvement declines to <1 deciview.     

Ozone in the urban southeastern United States

Ozone measurements (daily maximum values) from the Aerometric Information Retrieval System database are analyzed for selected sites, during 1980 to 1988, in southeastern USA. Frequency distributions, for most sites during most years, show a typical bell-shaped curve with the higher frequency around the yearly daily maximum ozone mean of about 100 to about 110 microg m(-3) (50-55 ppbv). Abnormal years in ozone concentration may skew the distribution as the mean shifts. A correlation of daily maximum ozone concentrations above 140 microg m(-3) (70 ppbv) between sites shows a division between the sites in the northern protion of the region and those in the southern portion of the region. Variations in ozone levels are well correlated over distances of several hundred kilometers, suggesting that high values are associated with synoptic scale episodes. An ozone exposure analysis also shows higher ozone exposures (250-300 ppm days) in the northerly sites as compared to the southerly sites (150-170 ppm days).     

Haze trends over the United States, 1980–1995

The patterns and trends of haze over the United States for the period of 1980–1995 are presented. Haze measurements are based on human visual range observations at 298 synoptic meteorological stations operated by the United States Weather Service. There was a significant (∼10%) decline in haziness over the 15-yr period. The reductions were evident throughout the eastern United States as well as over the hazy air basins of California. During the same period, in the eastern United States sulfur emissions also declined by about 10%. However, a causality for the reductions has not been established. This report is an update of an earlier survey of haze patterns and trends from 1950 to 1980.     

Seasonal aerosol sulfate trends for selected regions of the United States

Site and regional trends in seasonally averaged particle SO4(2-) concentrations were examined for a large portion of the United States using data collected by the CASTNet air monitoring network. Trends were analyzed for overlapping periods of 1988-1999 and 1992-1999. The largest absolute SO4(2-) decreases--approximately -0.4 microg/m3/yr--between 1988 and 1999 occurred in summer for sites in the Ohio River Valley and areas to the east. Generally, the largest SO4(2-) reductions were found for summer, but larger relative reductions often occurred for spring and autumn. Sulfate changes during 1992-1999 were quite different from those found for 1988-1999 and were not entirely consistent with changes in SO2 emissions. In some locations, the 1992-1999 period saw smaller declines in SO4(2-), while in other places seasonal SO4(2-) actually increased. Increases were mostly confined to summer and autumn across the southern and southwestern states. Multivariate analysis of ambient sulfur levels, by region, versus SO2 emissions reveals that annual emissions are associated with more than 80% of the variance in seasonal sulfur (SO2 and SO4(2-)) in more than three-quarters of the cases examined. The weakest associations were found for the southeastern United States.     

Regional patterns in foliar (15)N across a gradient of nitrogen deposition in the northeastern US

Recent studies have demonstrated that natural abundance (15)N can be a useful tool for assessing nitrogen saturation, because as nitrification and nitrate loss increase, delta(15)N of foliage and soil also increases. We measured foliar delta(15)N at 11 high-elevation spruce-fir stands along an N deposition gradient in 1987-1988 and at seven paired northern hardwood and spruce-fir stands in 1999. In 1999, foliar delta(15)N increased from -5.2 to -0.7 per thousand with increasing N deposition from Maine to NY. Foliar delta(15)N decreased between 1987-1988 and 1999, while foliar %N increased and foliar C:N decreased at most sites. Foliar delta(15)N was strongly correlated with N deposition, and was also positively correlated with net nitrification potential and negatively correlated with soil C:N ratio. Although the increase in foliar %N is consistent with a progression towards N saturation, other results of this study suggest that, in 1999, these stands were further from N saturation than in 1987-1988.