Field validation of a semi-continuous method for aerosol black carbon (aethalometer) and temporal patterns of summertime hourly black carbon measurements in southwestern PA

Two methods for measuring aerosol elemental carbon (EC) are compared. Three-hour integrated carbon samples were collected on quartz filters during the summer of 1990 in Uniontown, PA, primarily during episodes of elevated particulate pollution levels. These samples were analyzed for EC and organic carbon (OC) using a thermo/optical reflectance (TOR) method. Aerosol black carbon (BC) was measured using an Aethalometer, a semi-continuous optical absorption method. The optical attenuation factor for ambient BC was supplied by the instrument manufacturer. Three-hour average concentrations were calculated from the semi-continuous BC measurements to temporally match the EC/OC integrated quartz filter samples. BC and EC concentrations are highly correlated over the study period (R²=0.925). The regression equation is BC (μg m^-3)=0.95 (±0.04) EC−0.2 (±0.4). The means of 3 h average measurements for EC and BC are 2.3 and 2.0 μg m^-3, respectively, average concentrations of EC and BC ranged from 0.6 to 9.4 and 0.5 to 9.0 μg m^-3 respectively. TOR OC and EC concentrations were not highly correlated (R²=0.22). The mean OC/EC ratio was 1.85.The 10-week Aethalometer hourly dataset was analyzed for daily and weekly temporal patterns. A strong diurnal BC pattern was observed, with peaks occurring between 7 a.m. and 9 a.m. local time. This is consistent with the increase in emissions from ground level combustion sources in the morning, coupled with poor dispersion before daytime vertical mixing is established. There was also some indication of a day-of-week effect on BC concentrations, attributed to activity of local ground level anthropogenic sources. Comparison of BC concentrations with co-located measurements of coefficient of haze in a separate field study in Philadelphia, PA, during the summer of 1992 showed good correlation between the two measurements (R²=0.82).     

Assessing the importance of ab- and adsorption to the gas-particle partitioning of PCDD/Fs

The gas-particle partitioning of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) was examined (i) by re-interpreting results from controlled field experiments and (ii) in diurnal samples taken in the New Jersey (NJ), New York (NY) City region. In the controlled field experiments, aerosol-laden filters were exposed to elevated concentrations of PCDD/Fs. Gas-particle partitioning coefficients, K_p's, were significantly correlated with octanol–air partitioning coefficients, K_oa's. The regression of all individual datapoints resulted in the following best fit (r²=0.74, n=87): log K_p,meas=1.00(±0.13) log(10⁻¹²f_omK_oa/ρ_oct)−0.15(±0.48). We interpret this as showing that the ability of organic matter (OM) to absorb PCDD/Fs is generally well described by the octanol–air partitioning model (f_omK_oa). At the NJ land-based sites, samples were taken and analyzed for organic carbon (OC) and elemental carbon (EC), gaseous and particulate PCDD/Fs. K_p's were significantly correlated with the f_omK_oa approach. Adsorption to the filter and possibly to black carbon (BC), which was estimated based on EC measurements, could have contributed to the observed K_p values. Gas-particle predictions based on BC adsorption and OM absorption, with K_p=f_omK_oa/(10¹²ρ_oct)+f_BCK_BC–air/(10¹²ρ_BC) resulted in K_p predictions that were close to measured values. Adsorption to the filter might have been the major reason for elevated K_p's: The one NJ site with highest K_p's was most prone to the filter adsorption sampling artefact because of relatively low sampling volumes and concentrations of total suspended particulates. In addition, while adsorption to BC would result in better prediction of K_p values, no influence of f_BC or f_BC/f_om ratios was seen, suggesting that it was of lesser importance in our sample set.     

Cloud chemistry in the eastern United States, as sampled from three high-elevation sites along the Appalachian Mountains

Atmospheric deposition of acidic cloud water is thought to be one of the causes for the recent forest decline in industrialized areas of the world. The present paper presents results from the Mountain Acid Deposition Program (MADPro), a part of EPA's Clean Air Status and Trends Network, (CASTnet). We used automated cloud water collectors at three selected mountain sites (Whiteface Mt., NY; Whitetop Mt., VA; and Clingman's Dome, TN) to take hourly samples from non-precipitating clouds during temperate (non- freezing) seasons of each year from 1994 to 1997. Samples were promptly analyzed for pH, conductivity, and concentration of dissolved ions. Cloud liquid water content (LWC) and meteorological parameters were measured at each site. Mean cloud frequencies and LWC of clouds were higher at Whiteface Mt., NY, than in the Southern Appalachians. The four most prevalent ions found in cloud water samples were usually, in order of decreasing concentration: sulfate (SO²⁻₄) hydrogen (H⁺), ammonium (NH₄⁺), and nitrate (NO₃⁻). Within cloud events the concentration of these major ions tended to co-vary. Typically there was an inverse relationship between LWC of the cloud and ionic concentration of the cloud water. During the sampling season, the highest ionic concentrations were seen during mid-summer. Ionic concentrations of samples from the southern sites were significantly higher than samples from Whiteface Mt., but further analysis indicates that this is at least partially due to the north–south difference in the LWC of clouds. MADPro results are shown to be comparable with previous studies of cloud chemistry in North America.     

Development of an improved optical transmission technique for black carbon (BC) analysis

A new optical transmission technique for black carbon (BC) analysis was developed to minimize interferences due to scattering effects in filter samples. A standard thermal analysis method (VDI, 1999) is used to link light attenuation by the filter samples to elemental carbon (EC) concentration. Scattering effects are minimized by immersion of the filters in oil of a similar refractive index, as is often done for microscopy purposes. Light attenuation was measured using both a white light source and a red LED of 650 nm. The usual increase in overestimation of BC concentrations with decreasing BC amount in filter samples was found considerably reduced. Some effects of BC properties (e.g. fractal dimension, microstructure and size distribution) on the specific attenuation coefficient B_ATN, however, are still present for the treated samples. B_ATN was found close to 1 m² g⁻¹ for dry-dispersed industrial BC and 7 m² g⁻¹ for nebulized BC. Good agreement was found between the oil immersion, integrating sphere and a polar photometer technique and Mie calculations. The average specific attenuation coefficient of ambient samples in oil varied between 7 and 11 m² g⁻¹ for white light and 6 and 9 m² g⁻¹ for red light (LED). B_ATN was found to have much less site variation for the treated than for the untreated samples. The oil immersion technique improved also the correlation with thermally analyzed EC. This new immersion technique therefore presents a considerable improvement over conventional optical transmission techniques and may therefore serve as a simple, fast and cost-effective alternative to thermal methods.     

Characterisation of fresh particulate vehicular exhausts near a Paris high flow road

Simultaneous continuous measurements of PM_2.5, PM₁₀, black carbon mass (BCae), Black smoke (BS) and particle number density (N) were conducted in the close vicinity of a high traffic road around Paris during a three-month period beginning in August 1997. In parallel some aerosol collection was performed on filters in order to assess the black carbon (BC), organic carbon (OC) and water soluble organic fractions (WSOC) of the freshly emitted traffic aerosols. The high hourly concentrations of PM_2.5 (39±20 μg m⁻³), BCae (14±7 μg m⁻³), and N (220,000±115,000 cm⁻³), were found to be well correlated with each other. On average PM_2.5 represented 66±13% of PM₁₀ and appears to be composed primarily of BC (43±20%). On the contrary no correlation was found between PM_2.5 and the coarse (PM₁₀–PM_2.5) mass fractions which was attributed to resuspension processes by vehicles. Black carbon mass concentrations obtained from both filter analyses (BC) and Aethalometre data (BCae) show a good agreement suggesting that the Aethalometre calibration based on a black carbon specific attenuation coefficient (σ) of 19 m² g⁻¹ is well adapted to nearby roadside measurements. Daily BC (used as a surrogate for fine particles) concentrations and wind speed were found to be anti-correlated. Average daily variations of BC could be related to traffic intensity and regime as well as to the boundary layer height. As expected for freshly emitted traffic aerosols, filter analyses indicated a high BC/TC ratio (29±5%) and a low mean WSOC/OC ratio (12.5±5%) for the bulk aerosol. For these two ratios no day/night differences were observed, the sampling station being probably too close to traffic to evidence photochemical modification of the aerosol phase. Finally, a linear relationship was found between BC and BS hourly concentrations (BC=0.10×BS+1.18; r²=0.93) which offers interesting perspectives to retrieve BC concentrations from existing BS archives.     

Atmospheric polychlorinated biphenyl concentrations and apparent degradation in coastal New Jersey

To characterize the atmospheric dynamics and behavior of organic compounds in the NY–NJ Harbor Estuary, atmospheric concentrations of polychlorinated biphenyls (PCBs) were measured at coastal, suburban and urban sites in New Jersey in 1997–1999. ∑PCB concentrations at the suburban site varied from 86 to 2300 pg m⁻³ and from 84 to 1100 pg m⁻³ at the coastal site. Although the temporal trends of total concentrations were significantly different at the three sites (p<0.01), PCB congener profiles revealed similar patterns (r²>0.90, p<0.001) implicating a dominant emission type and/or process. Temperature explained >50% of the total variability in ln[PCB] at both sites. Atmospheric concentrations at the suburban site increased when winds blew from an eastnortheast vector, while increased wind speeds led to a slight dilution. Wind speed and direction were not significantly correlated with the concentrations measured at the coastal site. Temporal changes in congener distribution at the suburban site are consistent with the preferential atmospheric removal of 3–5 Cl-biphenyls by hydroxyl radical attack with estimated half-lives of 0.7–1.8 years.     

Polychlorinated biphenyls (PCB) and dichlorodiphenyltrichloroethane (DDE) air concentrations in the Lake Ontario region: Trends and potential sources

Airborne particle and gas samples were collected approx every 12 days from April 2002 to June 2006 at the Sterling Nature Center located near the southeast corner of Lake Ontario. These samples were analyzed for polychlorinated biphenyls (PCBs) and dichlorodiphenyltrichloroethane (DDE). Clausius-Clapeyron (C–C) regression analyses of PCBs and DDE yielded moderate correlations (r² = 0.54, p < 0.001; r² = 0.74, p < 0.001, respectively) indicating that much of the variations in concentrations can be explained by temperature. Back trajectory analysis indicated that the most important factors driving unusually high PCB partial pressures relative to those predicted by the C–C regression were slow wind speeds and winds generally from the southwest. This combination, which occurred frequently in 2004, increased contact of the air with contaminated upwind surfaces with minimum dilution. Hybrid receptor modeling (Potential Source Contribution Function (PSCF)) results for the total PCBs identified the midwestern US region that contains the urban areas of southern Indiana (IN), southwestern Ohio (OH), and northern Kentucky (KY) having the highest PSCF values. In general urban areas like Chicago (IL), Detroit (MI), Cleveland (OH), St. Louis (MO), and Nashville (TN) also had significant possibilities. In contrast, the PSCF modeling for DDE identified northern Alabama as the area with the highest probability where DDT was applied to cotton fields.     

Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta

Twenty-four hour PM_2.5 samples from a rural site, an urban site, and a suburban site (next to a major highway) in the metropolitan Atlanta area in December 2003 and June 2004 were analyzed for 19 polycyclic aromatic hydrocarbons (PAH). Extraction of the air samples was conducted using an accelerated solvent extraction method followed by isotope dilution gas chromatography/mass spectrometry determination. Distinct seasonal variations were observed in total PAH concentration (i.e. significantly higher concentrations in December than in June). Mean concentrations for total particulate PAHs in December were 3.16, 4.13, and 3.40 ng m^?3 for the urban, suburban and rural sites, respectively, compared with 0.60, 0.74, and 0.24 ng m^?3 in June. Overall, the suburban site, which is impacted by a nearby major highway, had higher PAH concentration than did the urban site. Total PAH concentrations were found to be well correlated with PM_2.5, organic carbon (OC), and elemental carbon (EC) in both months (r² = 0.36–0.78, p < 0.05), although the slopes from the two months were different. PAHs represented on average 0.006% of total PM_2.5 mass and 0.017% of OC in June, compared with 0.033% of total PM_2.5 and 0.14% of OC in December. Total PAH concentrations were also correlated with potassium ion (r² = 0.39, p = 0.014) in December, but not in June, suggesting that in winter biomass burning can potentially be an important source for particulate PAH. Retene was found at a higher median air concentration at the rural site than at the urban and suburban sites—unlike the rest of the PAHs, which were found at lower levels at the rural site. Retene also had a larger seasonal difference and had the weakest correlation with the rest of the PAHs measured, suggesting that retene, in particular, might be associated with biomass burning.     

A passive sampler for ambient gaseous oxidized mercury concentrations

This paper reports on the development of a passive sampler for estimating gaseous oxidized mercury concentrations. Atmospheric gaseous oxidized mercury concentrations calculated from passive sampler data were correlated with those obtained using an automated analyzer (r² = 0.71, p < 0.01, n = 110 for one-week deployments; r² = 0.89, p < 0.01, n = 22 for two-week deployments). Sampler uptake was not significantly affected by changes in temperature, humidity, or ozone concentration, but it was slightly dependent on wind speed. As such, an equation for correcting data due to this factor was developed based on wind tunnel and field data. The detection limit for a two-week sampler deployment was ～5 pg m^?3. Field data collected in Nevada and the southeastern United States showed these samplers are useful for investigating spatial and temporal variability in gaseous oxidized mercury concentrations.     

Effects of meteorology on diurnal and nocturnal levels of priority polycyclic aromatic hydrocarbons and elemental and organic carbon in PM10 at a source and a receptor area in Mexico City

PM₁₀ levels of the 16 US-EPA Priority Pollutant polycyclic aromatic hydrocarbons (PAHs) were measured from March 17 to 31, 2003, in 8-h time bins (morning, afternoon and nighttime) at Merced, a source site dominated by vehicular traffic emissions near the center of Mexico City, and at Pedregal, a receptor area located downwind in a residential area of low traffic. Along with PAH, elemental (EC) and organic carbon (OC), mass, and prevailing meteorological parameters were measured. At the source location, measured concentrations of benzo[a]pyrene (BAP), an agent suspected of being carcinogenic to humans and of causing oxidative DNA damage, reached concentrations as high as 2.04 and 2.11 ng m^?3 during the morning of a weekday and the night period of a holiday. Compared with source dominated areas in Central Los Angeles, the BAP levels found in Central Mexico City are approximately 6 times higher. Benzo[ghi]perylene (BGP) levels were, in general, the highest among the target PAH, both at the source (7.2 ng m^?3) and the receptor site (2.8 ng m^?3), suggesting that, at both locations, exhaust emission by light-duty (LD) vehicles is an important contributor to the atmospheric PAH burden. Higher PAH concentrations were observed during the morning period (5:00–13:00 h) at the source and the receptor site. The concentrations of PAHs found predominantly in the particle-phase (MW > 202) correlated well (r = 0.57–0.71) with the occurrence of surface thermal inversions and with mixing heights (r = ?0.57 to ?0.72). Organic and elemental carbon ratios also indicated that Pedregal is impacted by secondary aerosols during the afternoon hours.     

Elemental carbon (EC) and black carbon (BC) measurements with a thermal method and an aethalometer at the high-alpine research station Jungfraujoch

A thermal method for the determination of ambient organic carbon (OC) and elemental carbon (EC) concentrations in carbonaceous samples was further developed. Possible artifacts were investigated and were shown to be low. Good agreement of EC data with the German VDI reference method was found and detection limits were 1.3 μg for EC and 1.8 μg for OC. The method was applied to samples obtained with an aethalometer from an ongoing campaign at the high-alpine research station Jungfraujoch from July 1995 to June 1997. Measurements of EC concentration were used to derive a new site-specific calibration factor (instrumental absorption efficiency α_API) for the determination of the black carbon (BC) concentration. Despite a distinct seasonal cycle in BC, of around one order in magnitude with a maximum in summer and minimum in winter, α_API exhibited no significant seasonality. The derived calibration factor for the Jungfraujoch, α_API=9.3±0.4 m² g^-1, is lower than the manufacturer calibration by a factor ∼2. The results confirm the observation that the aethalometer determined BC concentration, underestimates the true value at remote sites, when the manufacturer calibration is used.     

Surface ozone-temperature relationships in the eastern US: A monthly climatology for evaluating chemistry-climate models

We use long-term, coincident O₃ and temperature measurements at the regionally representative US Environmental Protection Agency Clean Air Status and Trends Network (CASTNet) over the eastern US from 1988 through 2009 to characterize the surface O₃ response to year-to-year fluctuations in weather, for the purpose of evaluating global chemistry-climate models. We first produce a monthly climatology for each site over all available years, defined as the slope of the best-fit line (m_O3-T) between monthly average values of maximum daily 8-hour average (MDA8) O₃ and monthly average values of daily maximum surface temperature (T_max). Applying two distinct statistical approaches to aggregate the site-specific measurements to the regional scale, we find that summer time m_O3-T is 3–6 ppb K^?1 (r = 0.5–0.8) over the Northeast, 3–4 ppb K^?1 (r = 0.5–0.9) over the Great Lakes, and 3–6 ppb K^?1 (r = 0.2–0.8) over the Mid-Atlantic. The Geophysical Fluid Dynamics Laboratory (GFDL) Atmospheric Model version 3 (AM3) global chemistry-climate model generally captures the seasonal variations in correlation coefficients and m_O3-T despite biases in both monthly mean summertime MDA8 O₃ (up to +10 to +30 ppb) and daily T_max (up to +5 K) over the eastern US. During summer, GFDL AM3 reproduces m_O3-T over the Northeast (m_O3-T = 2–6 ppb K^?1; r = 0.6–0.9), but underestimates m_O3-T by 4 ppb K^?1 over the Mid-Atlantic, in part due to excessively warm temperatures above which O₃ production saturates in the model. Combining T_max biases in GFDL AM3 with an observation-based m_O3-T estimate of 3 ppb K^?1implies that temperature biases could explain up to 5–15 ppb of the MDA8 O₃ bias in August and September though correcting for excessively cool temperatures would worsen the O₃ bias in June. We underscore the need for long-term, coincident measurements of air pollution and meteorological variables to develop process-level constraints for evaluating chemistry-climate models used to project air quality responses to climate change.     

Intercomparison of the measurements of oxalic acid in aerosols by gas chromatography and ion chromatography

Oxalate, the anion of oxalic acid, is one of the most abundant measurable organic species in atmospheric aerosols. Traditionally, this bifunctional species has been measured by gas chromatography (GC) after derivatization to butyl ester and by ion chromatography (IC) without derivatization. However, there are few published comparisons of the two techniques. Here, we report the results of an intercomparison study for the measurement of oxalic acid in Arctic aerosols (<2.5 μm, n = 82) collected in 1992 using GC and IC. The concentrations of oxalic acid by GC ranged from 6.5–59.1 ng m^?3 (av. 26.0 ng m^?3, median 26.2 ng m^?3) whereas those by IC ranged from 6.6–52.1 ng m^?3 (av. 26.6 ng m^?3, median 25.4 ng m^?3). They showed a good correlation (r = 0.84) with a slope of 0.96. Thus, observations of oxalate obtained by GC employing dibutyl esters are almost equal to those by IC. Because the accuracy of oxalic acid by GC method largely depends on the method used, it is important to strictly examine the recovery in each study.     

Drop size-dependent chemical composition in clouds and fogs. Part I. Observations

The first observations of size-dependent cloud and fog drop inorganic ion and trace metal concentrations obtained using the Colorado State University 5-Stage cloud water collector (CSU 5-Stage) during field studies of orographic clouds (Whiteface Mountain, NY, July 1998) and radiation fogs (Davis, CA, January 1999) are reported. Although some mixing between drop sizes occurs, the CSU 5-Stage effectively separates the largest drops (>≈30 μm in diameter) from the smallest ones (<≈10 μm in diameter) permitting the discernment of size-dependent drop composition not possible with previous two- or three-stage collectors. At Whiteface, pH and the concentrations of the “major” ions −NH₄⁺, NO₃⁻, and SO₄²⁻—appeared largely independent of drop size as measured by a two-stage collector. The same major ion concentrations differed in Davis fogs by up to a factor of approximately 10 in the two-stage collector with consistently higher small drop concentrations. In both locations, CSU 5-Stage data generally indicate a greater range of concentrations is present across the drop size spectrum. CSU 5-Stage data show “U”- shaped profiles of major ion concentration vs. drop size at Whiteface and “L”- shaped profiles at Davis and the maximum/minimum concentration differences between fractions increased up to a factor of 2 (Whiteface) and 30 (Davis). Lower concentration species at both locations showed multiple concentration vs. drop size profiles with CSU 5-Stage data again exhibiting more variability than observed with the two-stage collector. While rarely reported, significant nitrite concentrations—relatively higher in the larger drops—were observed, and copper concentrations merit further investigation in the Davis fogs. The findings presented here are consistent with other studies. The implications and benefits of the increased resolution of size-dependent drop composition provided by the CSU 5-Stage are explored for the Davis fogs in a companion paper (Moore et al., Atmos. Environ. (2004), this issue).     

Measurements of primary trace gases and NOY composition in Houston,Texas

Concentrations of CO, SO₂, NO, NO₂, and NO_Y were measured atop the University of Houston's Moody Tower supersite during the 2006 TexAQS-II Radical and Aerosol Measurement Project (TRAMP). The lowest concentrations of all primary and secondary species were observed in clean marine air in southerly flow. SO₂ concentrations were usually low, but increased dramatically in sporadic midday plumes advected from sources in the Houston Ship Channel (HSC), located NE of the site. Concentrations of CO and NO_x displayed large diurnal variations in keeping with their co-emission by mobile sources in the Houston Metropolitan Area (HMA). CO/NO_x emission ratios of 5.81 ± 0.94 were observed in the morning rush hour. Nighttime concentrations of NO_x (NO_x = NO + NO₂) and NO_Y (NO_Y = NO + NO₂ + NO₃ + HNO₃ + HONO + 21N₂O₅ + HO₂NO₂ + PANs + RONO₂ + p-NO₃^? + …) were highest in winds from the NNW-NE due to emission from mobile sources. Median ratios of NO_x/NO_Y were approximately 0.9 overnight, reflecting the persistence and/or generation of NO_Z (NO_Z = NO_Y ? NO_x) species in the nighttime Houston boundary layer, and approached unity in the morning rush hour. Daytime concentrations of NO_x and NO_Y were highest in winds from the HSC. NO_x/NO_Y ratios reached their minimum values (median ca 0.63) from 1300 to 1500 CST, near local solar noon, and air masses often retained enough NO_x to sustain additional O₃ formation farther downwind. HNO₃ and PANs comprised the dominant NO_Z species in the HMA, and on a median basis represented 17–20% and 12–15% of NO_Y, respectively, at midday. Concentrations of HNO₃, PANs, and NO_Z, and fractional contributions of these species to NO_Y, were at a maximum in NE flow, reflecting the source strength and reactivity of precursor emissions in the HSC. As a result, daytime O₃ concentrations were highest in air masses with HSC influence. Overall, our findings confirm the impact of the HSC as a dominant source region within the HMA. A comparison of total NO_Y measurements with the sum of measured NO_Y species (NO_Yi = NO_x + HNO₃ + PANs + HONO + p-NO₃^?) yielded excellent overall agreement during both day ([NO_Y](ppb) = ([NO_Yi](ppb)11.03 ± 0.16) ? 0.42; r² = 0.9933) and night ([NO_Y](ppb) = ([NO_Yi](ppb)11.01 ± 0.16) + 0.18; r² = 0.9975). A similar comparison between NO_Y–NO_x concentrations and the sum of NO_Zi (NO_Zi = HNO₃ + PANs + HONO + p-NO₃^?) yielded good overall agreement during the day ([NO_Z](ppb) = ([NO_Zi](ppb)11.01 ± 0.30) + 0.044 ppb; r² = 0.8527) and at night ([NO_Z](ppb) = ([NO_Zi](ppb)11.12 ± 0.69) + 0.16 ppb; r² = 0.6899). Median ratios of NO_Z/NO_Zi were near unity during daylight hours but increased to approximately 1.2 overnight, a difference of 0.15–0.50 ppb. Differences between NO_Z and NO_Zi rarely exceeded combined measurement uncertainties, and variations in NO_Z/NO_Zi ratios may have resulted solely from errors in conversion efficiencies of NO_Y species and changes in NO_Y composition. However, nighttime NO_Z/NO_Zi ratios and the magnitude of NO_Z ? NO_Zi differences were generally consistent with recent observations of ClNO₂ in the nocturnal Houston boundary layer.     

Measurements of atmospheric nitrous acid and nitric acid

A highly sensitive technique for the measurement of atmospheric HONO and HNO₃ is reported. The technique is based on aqueous scrubbing using two coil samplers, followed by conversion of HNO₃ to nitrite, derivatization of nitrite to a highly light-absorbing azo dye with sulfanilamide (SA) and N-(1-naphthyl) ethylenediamine (NED), and high performance liquid chromatography (HPLC) analysis. HNO₃ concentration was obtained by the difference of the two channels. Two scrubbing solutions were used for sampling the two species: a 1-mM phosphate buffer solution (pH 7) for the measurement of HONO and a 180 mM NH₄Cl/NH₃ buffer solution (pH 8.5) for the measurement of HONO+HNO₃. The scrubbing solution flow rate was 0.24 ml min⁻¹ and the gas sampling flow rate was 2 l min⁻¹. HNO₃ in the NH₄Cl/NH₃ buffer solution was quantitatively reduced to nitrite along an on-line 0.8-cm Cd reductor column. Nitrite in both channels was derivatized with 2 mM SA and 0.2 mM NED in 25 mM HCl. Quantitative derivatization was achieved within 5 min at 55°C. The azo dye derivative was then separated from the SA/NED reagent by reversed-phase HPLC and detected with a UV-vis detector at 540 nm. With an on-line SEP-PAK C-18 cartridge for the reagent purification, the method detection limit is estimated to be better than 1 pptv for HONO and about 20 pptv for HNO₃. The sample integration time was about 2 min and the sampling frequency is every 10 min. Data collected in downtown Albany and Whiteface Mountain, NY, are shown as examples of applications of this technique in both urban and remote clean environments.     

Measurement of black carbon aerosols near two Chinese megacities and the implications for improving emission inventories

Knowledge of the distribution and sources of black carbon (BC) is essential to understanding its impact on radiative forcing and the establishment of a control strategy. In this study, we analyze atmospheric BC and its relationships with fine particles (PM_2.5) and trace gases (CO, NO_y and SO₂) measured in the summer of 2005 in two areas frequently influenced by plumes from Beijing and Shanghai, the two largest cities in China. The results revealed different BC source characteristics for the two megacities. The average concentration of BC was 2.37 (±1.79) and 5.47 (±4.00) μg m^?3, accounting for 3.1% and 7.8% of the PM_2.5 mass, in Beijing and Shanghai, respectively. The good correlation between BC, CO and NO_y (R² = 0.54–0.77) and the poor correlation between BC and SO₂ suggest that diesel vehicles and marine vessels are the dominant sources of BC in the two urban areas during summer. The BC/CO mass ratio in the air mass from Shanghai was found to be much higher than that in the air mass from Beijing (0.0101 versus 0.0037 ΔgBC/ΔgCO), which is attributable to a larger contribution from diesel burning (diesel-powered vehicles and marine vessels) in Shanghai. Based on the measured ratios of BC/CO and annual emissions of CO, we estimate that the annual emissions of BC in Beijing and Shanghai are 9.51 Gg and 18.72 Gg, respectively. The improved emission rates of BC will help reduce the uncertainty in the assessment of the impact of megacities on regional climate.     

State of mixture of atmospheric submicrometer black carbon particles and its effect on particulate light absorption

The state of mixture of light-absorbing carbonaceous particles was investigated in relation to light absorption properties using electron microscopic examinations, black carbon (BC) analyses of quartz filter by thermal/optical reflectance (TOR) method, measurements with two continuous light-absorbing photometers at a suburban site of Tsukuba, about 60 km northeast of Tokyo. The volume fraction of water-soluble material (?) in individual particles is important for assessing particulate light-absorbing and/or scattering of atmospheric aerosols. The values of ? in BC particles were evaluated by electron micrographs before and after dialysis (extraction) of water-soluble material. The mass absorption coefficient (MAC in units of m² g^?1) tended to increase with increasing the average ? in BC particles with the radius range of 0.05–0.5 μm. Thus, our results indicate that coatings of water-soluble material around BC particles can enhance the absorption of solar radiation. Moreover, the single scattering albedo (SSA) will increase because a large amount of coating material will scatter more light.     

Characterization of odor released during handling of swine slurry: Part II. Effect of production type,storage and physicochemical characteristics of the slurry

The quality of rural life can be affected by offensive odors released from animal buildings and storage units. The objectives of this study were to compare the concentrations of odor and odorants above different types of stirred swine slurry to analyze the relationships between concentrations of odor (and odorants) and physicochemical characteristics of the slurry (i.e. pH, temperature, dry matter, volatile solids, and concentration of 22 chemical compounds); and to propose predictive models for the odor concentration (OC) based on these physicochemical characteristics (solely and in combination with concentrations of specific odorants in the air above the slurries). The study comprised data on concentrations of odor and odorants in the air above slurry samples (fresh and/or stored) collected from production units with farrowing sows, finishing swines, or weaning pigs at eight swine operations (N = 48). OC measured in the air above stirred swine slurry samples were not significantly different among production types or storage times. The physicochemical characteristics of the slurries were not useful for predicting OC or concentrations of hydrogen sulfide (or organic sulfides) above the slurry, but were related to concentrations of other emitted gases such as phenols and indoles (r² = 0.65–0.79, p <0.05), ammonia (r² = 0.86, p < 0.05) and carboxylic acids (r² = 0.23–0.59, p <0.05). There was good precision of predictive models of OC based on selected slurry characteristics (i.e. pH, dry matter, nitrogen content, sulfur content or concentrations of individual aromatic compounds and carboxylic acids) together with concentrations of specific odorants in the air (e.g. hydrogen sulfide) (r² between 0.70 and 0.92). This study suggests that predictive models could be useful for evaluating odor nuisance potentials of swine slurry during handling.     

Carbonaceous aerosol in jet engine exhaust: emission characteristics and implications for heterogeneous chemical reactions

Characteristic parameters of black carbon aerosol (BC) emitted from jet engine were measured during ground tests and in-flight behind the same aircraft. Size distribution features were a primary BC mode at a modal diameter D≈0.045 μm, and a BC agglomeration mode at D<0.2 μm. The total BC number concentration at the engine exit was 2.9×10⁷ cm^-3 with good agreement between model results and in-flight measured number concentrations of non-volatile particles with D⩾0.014 μm. A comparison between total number concentration of BC particles and the non-volatile fraction of the total aerosol at the exit plane suggests that the non-volatile fraction of jet engine exhaust aerosol consists almost completely of BC. In-flight BC mass emission indices ranged from 0.11 to 0.15 g BC (kg fuel)^-1. The measured in-flight particle emission value was 1.75±0.15×10¹⁵ kg^-1 with corresponding ground test values of 1.0–8.7×10¹⁴ kg^-1. Both size distribution properties and mass emission indices can be scaled from ground test to in-flight conditions. Implications for atmospheric BC loading, BC and cirrus interaction and the potential of BC for perturbation of atmospheric chemistry are briefly outlined.