Ammonia flux from open-lot dairies: development of measurement methodology and emission factors

Ammonia emissions contribute to the formation of secondary particulate matter (PM) and violations of the National Ambient Air Quality Standard. Ammonia mass concentration measurements were made in February 1999 upwind and downwind of an open-lot dairy in California, using a combination of active bubbler and passive filter samplers. Ammonia fluxes were calculated from concentrations measured at 2, 4, and 10 m above ground at three locations on the downwind edge of the dairy, using micrometeorological techniques. A new method was developed to interpolate fluxes at six additional locations from ammonia concentrations measured at a single height, providing measurements at sufficient spatial resolution along the downwind border of the dairy to account for the heterogeneity of the source. PM measured up- and downwind of the dairy demonstrated insignificant ammonium particle formation in the immediate vicinity of the dairy and negligible contribution of dissociated ammonium nitrate to measured ammonia concentrations. Ammonium nitrate concentrations measured downwind of the dairy ranged from 26 to 0.26 microg m(-3) and from 2 to 43% of total PM2.5 mass concentrations. Measured ammonia fluxes showed that liquid manure retention ponds represented relatively minor sources of ammonia in winter on the dairy studied. Ammonia emission factors derived from the measurements ranged from 19 to 143 g head(-1) day(-1), showing an increase with warmer, drier weather and a decrease with increased relative humidity and lower temperatures.     

Photochemical model performance for PM2.5 sulfate,nitrate, ammonium,and precursor species SO2, HNO3, and NH3 at background monitor locations in the central and eastern United States

Health studies have shown premature death is statistically associated with exposure to particulate matter <2.5 μm in diameter (PM2.5). The United States Environmental Protection Agency requires all States with PM2.5 non-attainment counties or with sources contributing to visibility impairment at Class I areas to submit an emissions control plan. These emission control plans will likely focus on reducing emissions of sulfur oxides and nitrogen oxides, which form two of the largest chemical components of PM2.5 in the eastern United States: ammonium sulfate and ammonium nitrate. Emission control strategies are simulated using three-dimensional Eulerian photochemical transport models.A monitor study was established using one urban (Detroit) and nine rural locations in the central and eastern United States to simultaneously measure PM2.5 sulfate ion (SO₄²⁻), nitrate ion (NO₃⁻), ammonium ion (NH₄⁺), and precursor species sulfur dioxide (SO₂), nitric acid (HNO₃), and ammonia (NH₃). This monitor study provides a unique opportunity to assess how well the modeling system predicts the spatial and temporal variability of important precursor species and co-located PM2.5 ions, which is not well characterized in the central and eastern United States.The modeling system performs well at estimating the PM2.5 species, but does not perform quite as well for the precursor species. Ammonia is under-predicted in the coldest months, nitric acid tends to be over-predicted in the summer months, and sulfur dioxide appears to be systematically over-predicted. Several indicators of PM2.5 ammonium sulfate and ammonium nitrate formation and chemical composition are estimated with the ambient data and photochemical model output. PM2.5 sulfate ion is usually not fully neutralized to ammonium sulfate in ambient measurements and is usually fully neutralized in model estimates. The model and ambient estimates agree that the ammonia study monitors tend to be nitric acid limited for PM2.5 nitrate formation. Regulatory strategies in this part of the country should focus on reductions in NO_X rather than ammonia to control PM2.5 ammonium nitrate.     

Modeling wintertime particulate matter formation in central California

A wintertime episode during the 2000 California Regional PM Air Quality Study (CRPAQS) was simulated with the air quality model CMAQ–MADRID. Model performance was evaluated with 24-h average measurements available from CRPAQS. Modeled organic matter (OM) was dominated by emissions, which were probably significantly under-represented, especially in urban areas. In one urban area, modeled daytime nitrate concentrations were low and evening concentrations were high. This diurnal profile was not explained by the partition of nitrate between the gas and particle phases, because gaseous nitric acid concentrations were low compared to PM nitrate. Both measured and simulated nitrate concentrations aloft were lower than at the surface at two tower locations during this episode. Heterogeneous reactions involving NO₃ and N₂O₅ accounted for significant nitrate production in the model, resulting in a nighttime peak. The sensitivity of PM nitrate to precursor emissions varied with time and space. Nitrate formation was on average sensitive to NO_x emissions. However, for some periods at urban locations, reductions in NO_x caused the contrary response of nitrate increases. Nitrate was only weakly sensitive to reductions in anthropogenic VOC emissions. Nitrate formation tended to be insensitive to the availability of ammonia at locations with high nitrate, although the spatial extent of the nitrate plume was reduced when ammonia was reduced. Reductions in PM emissions caused OM to decrease, but had no effect on nitrate despite the role of heterogeneous reactions. A control strategy that focuses on NO_x and PM emissions would be effective on average, but reductions in VOC and NH₃ emissions would also be beneficial for certain times and locations.     

Modelling the formation and atmospheric transport of secondary inorganic aerosols with special attention to regions with high ammonia emissions

Regional simulations of sulfate, nitrate and ammonium aerosols were performed by a nested application of the online-coupled three-dimensional Eulerian model system COSMO-MUSCAT. This was done in a domain covering the northern part of Germany and surrounding regions for the full month of May and a 6-week period in August/September 2006 with the primary focus on secondary inorganic aerosol levels caused by ammonia emissions from domesticated animals and agricultural operations.The results show that in situations with westerly winds ammonium nitrate dominates with concentrations of about 5–10 μg m^?3 whereas the ammonium sulfate concentrations are about 5 μg m^?3. In situations with winds mainly from the East characterized by warmer and dryer air the ammonium sulfate concentrations have their maximum at about 10 μg m^?3 whereas at the same time no ammonium nitrate is present.A reduction of agricultural NH₃ emissions by 50% in a regional scale reduces the ammonium nitrate concentrations to a maximum of 30%, while the ammonium sulfate concentrations are unchanged. The reduction of NH₃ emissions in a more limited area (here in the Federal state of Germany Niedersachsen) does have no noticeable effect neither on ammonium sulfate nor on ammonium nitrate.     

Radon emissions from natural gas power plants at The Pennsylvania State University

Burning natural gas in power plants may emit radon (²²²Rn) into the atmosphere. On the University Park campus of The Pennsylvania State University, atmospheric radon enhancements were measured and modeled in the vicinity of their two power plants. The three-part study first involved measuring ambient outdoor radon concentrations from August 2014 through January 2015 at four sites upwind and downwind of the power plants at distances ranging from 80 m to 310 m. For each plant, one site served as a background site, while three other sites measured radon concentration enhancements downwind. Second, the radon content of natural gas flowing into the power plant was measured, and third, a plume dispersion model was used to predict the radon concentrations downwind of the power plants. These predictions are compared to the measured downwind enhancements in radon to determine whether the observed radon concentration enhancements could be attributed to the power plants’ emissions. Atmospheric radon concentrations were consistently low as compared to the EPA action level of 148 Bq m^?3, averaging 34.5 ± 2.7 Bq m^?3 around the East Campus Steam Plant (ECSP) and 31.6 ± 2.7 Bq m^?3 around the West Campus Steam Plant (WCSP). Significant concentrations of radon, ranging from 516 to 1,240 Bq m^?3, were detected in the natural gas. The measured enhancements downwind of the ECSP averaged 6.2 Bq m^?3 compared to modeled enhancements of 0.08 Bq m^?3. Measured enhancements around the WCSP averaged ?0.2 Bq m^?3 compared to the modeled enhancements of 0.05 Bq m^?3, which were not significant compared to observational error. The comparison of the measured to modeled downwind radon enhancements shows no correlation over time. The measurements of radon levels in the vicinity of the power plants appear to be unaffected by the emissions from the power plants.

Implications: Radon measurements at sites surrounding power plants that utilize natural gas did not indicate that the radon concentrations originated from the plants’ emissions. There were elevated radon concentrations in the natural gas supply flowing into the power plants, but combustion dilution puts the concentration below EPA action levels coming out of the stack, so no hazardous levels were expected downwind. Power plant combustion of natural gas is not likely to pose a radiation health hazard unless very different gas radon concentrations or combustion dilution ratios are encountered.     

Ammonia concentrations and modeling of inorganic particulate matter in the vicinity of an egg production facility in Southeastern USA

Ammonia (NH₃) is an important base gas and can react with acidic species to form atmospheric aerosols. Due to the rapid growth of poultry and swine production in the North Carolina Coastal Plain, atmospheric NH₃ concentrations across the region have subsequently increased. Ammonia concentrations and inorganic particulate matter (PM) at four ambient stations in the vicinity of an egg production facility were measured for 1 year using PM_2.5 speciation samplers with honeycomb denuders and ion chromatography (IC). Meanwhile, concentrations of NH₃ and inorganic PM in one of the egg production houses were also simultaneously measured using a gas analyzer for NH₃ and the filter pack plus IC method for inorganic PM. An equilibrium model-ISORROPIA II was applied to predict the behavior of inorganic aerosols in response to precursor gas concentrations and environmental parameters. Average ambient NH₃ concentrations varied from 10.0 to 27.0 μg/m³, and they were negatively correlated with the distances from the ambient location to the nearest egg production house exhausts. Ambient NH₃ concentrations were higher in warm seasons than in cold seasons. Measured NH₃ concentrations agreed well with ISORROPIA II model predictions at all sampling stations. For the ambient stations, there was a good agreement in particle phase NH₄ ⁺ between the model simulation and observations. For the in-house station, the model simulation was applied to correct the overestimation of particle phase NH₄ ⁺ due to gas phase NH₃ breaking through the denuders. Changes in SO₄ ^2?, NO₃ ^?, and Cl^? yield proportional changes in inorganic PM mass. Due to the abundance of NH₃ gas in the vicinity area of the monitored farm, changes in NH₃ concentrations had a small effect on inorganic PM mass. Aerosol equilibrium modeling may be used to assess the influence of precursor gas concentrations on inorganic PM formation when the measurements for some species are unavailable.     

Evaluation of a diode laser based photoacoustic instrument combined with preconcentration sampling for measuring surface–atmosphere exchange of ammonia with the aerodynamic gradient method

We present here a novel instrument for measuring surface–atmosphere exchange fluxes of ammonia. The instrument is the upgraded version of a recently developed near-infrared diode laser based photoacoustic ammonia concentration monitoring instrument, i.e. the original instrument is supplemented with two additional sampling lines, an appropriate gas handling system and an advanced software controlling gradient measurements. As a result of these developments, ammonia concentration can be measured simultaneously at three different heights above the ground and ammonia fluxes can be calculated from these data using the aerodynamic gradient method. The instrument operates fully automatically, requires minimal maintenance and has a temperature controlled, waterproof housing which makes it suitable for measurements even under harsh field conditions. Preliminary tests on stability and accuracy were carried out during two two-week field measurement campaigns, with the three sampling inlets being placed at the same height together with the inlet of a reference instrument. The readings of the three channels agreed well (with correlation coefficients above 0.96). Comparison to reference instruments showed good stability of the photoacoustic instrument, there was no measurable zero-drift or change in sensitivity during the tests. Flux measurements were carried out during a three-week field campaign in southern Scotland over fertilized grassland with reference to a wet-chemical AMANDA instrument in gradient configuration. Ammonia fluxes calculated from the data of the two instruments agreed well. Fluxes up to 2500 ng m^?2 s^?1 were observed after fertilization. The minimum detectable ammonia flux was calculated on the basis of “virtual ammonia fluxes”, from measurements carried out with all inlets at the same height and was found to be ±60 ng m^?2 s^?1 which ensures reliable measurements above intensively managed grasslands or agricultural fields.     

Loss of PM2.5 nitrate from filter samples in central California

Evaporative loss of particulate matter (with aerodynamic diameter < 2.5 microm, [PM2.5]) ammonium nitrate from quartz-fiber filters during aerosol sampling was evaluated from December 3, 1999, through February 3, 2001, at two urban (Fresno and Bakersfield) and three nonurban (Bethel Island, Sierra Nevada Foothills, and Angiola) sites in central California. Compared with total particulate nitrate, evaporative nitrate losses ranged from < 10% during cold months to > 80% during warm months. In agreement with theory, evaporative loss from quartz-fiber filters in nitric acid denuded samplers is controlled by the ambient nitric acid-to-particulate nitrate ratio, which is determined mainly by ambient temperature. Accurate estimation of nitrate volatilization requires a detailed thermodynamic model and comprehensive chemical measurements. For the 14-month average of PM2.5 acquired on Teflon-membrane filters, measured PM2.5 mass was 8-16% lower than actual PM2.5 mass owing to nitrate volatilization. For 24-hr samples, measured PM2.5 was as much as 32-44% lower than actual PM2.5 at three California Central Valley locations.     

Processes influencing secondary aerosol formation in the San Joaquin Valley during winter

Air quality data collected in the California Regional PM10/ PM(2.5) Air Quality Study (CRPAQS) are analyzed to qualitatively assess the processes affecting secondary aerosol formation in the San Joaquin Valley (SJV). This region experiences some of the highest fine particulate matter (PM(2.5)) mass concentrations in California (< or = 188 microg/m3 24-hr average), and secondary aerosol components (as a group) frequently constitute over half of the fine aerosol mass in winter. The analyses are based on 15 days of high-frequency filter and canister measurements and several months of wintertime continuous gas and aerosol measurements. The phase-partitioning of nitrogen oxide (NO(x))-related nitrogen species and carbonaceous species shows that concentrations of gaseous precursor species are far more abundant than measured secondary aerosol nitrate or estimated secondary organic aerosols. Comparisons of ammonia and nitric acid concentrations indicate that ammonium nitrate formation is limited by the availability of nitric acid rather than ammonia. Time-resolved aerosol nitrate data collected at the surface and on a 90-m tower suggest that both the daytime and nighttime nitric acid formation pathways are active, and entrainment of aerosol nitrate formed aloft at night may explain the spatial homogeneity of nitrate in the SJV. NO(x) and volatile organic compound (VOC) emissions plus background O3 levels are expected to determine NO(x) oxidation and nitric acid production rates, which currently control the ammonium nitrate levels in the SJV. Secondary organic aerosol formation is significant in winter, especially in the Fresno urban area. Formation of secondary organic aerosol is more likely limited by the rate of VOC oxidation than the availability of VOC precursors in winter.     

Sources and concentrations of gaseous and particulate reduced nitrogen in the city of Münster (Germany)

Atmospheric ammonia mixing ratios and the main inorganic ions NH₄⁺, NO₃⁻ and SO₄²⁻ of size-resolved particles in the range from 0.05 to 10 μm were measured at an urban site in Münster, Germany. High mixing ratios of ammonia with a median of 5.2 ppb and a maximum of 50 ppb were detected. The mass fraction of submicron particles was much higher during the day than at night. At night, a greater particle mass and an increased presence of particulate nitrate was measured. Recurring patterns of particle distribution were distinguished and their characteristics analysed. In half of the measurements, the accumulation mode was clearly dominating, which is an indication of aged aerosol. In some measurements, higher concentrations of fine particles were found indicating particle formation. In these cases, a smaller particle mass and about four times greater ratios of ammonia versus ammonium concentrations were observed. These data show that ammonia contributes considerably to the formation of secondary particulate material.     

Size and composition distribution of airborne particulate matter in northern California: I--particulate mass, carbon, and water-soluble ions

The San Joaquin Valley (SJV) in California has one of the most severe particulate air quality problems in the United States during the winter season. In the current study, measurements of particulate matter (PM) smaller than 10 microm in aerodynamic diameter (PM10), fine particles (PM18), and ultrafine particles (PM0.1) made during the period December 16, 2000-February 3, 2001, at six locations near or within the SJV are discussed: Bodega Bay, Davis, Sacramento, Modesto, Bakersfield, and Sequoia National Park. Airborne PM1.8 concentrations at the most heavily polluted site (Bakersfield) increased from 20 to 172 microg/m3 during the period December 16, 2000-January 7, 2001. The majority of the fine particle mass was ammonium nitrate driven by an excess of gas-phase ammonia. Peak PM0.1 concentrations (8-12 hr average) were approximately 2.4 microg/m3 measured at night in Sacramento and Bakersfield. Ultrafine particle concentrations were distinctly diurnal, with daytime concentrations approximately 50% lower than nighttime concentrations. PMO.1 concentrations did not accumulate during the multiweek stagnation period; rather, PMO.1 mass decreased at Bakersfield as PM1.8 mass was increasing. The majority of the ultrafine particle mass was associated with carbonaceous material. The high concentrations of ultrafine particles in the SJV pose a potential serious public health threat that should be addressed.     

Sensitivity analyses of factors influencing CMAQ performance for fine particulate nitrate

Improvement of air quality models is required so that they can be utilized to design effective control strategies for fine particulate matter (PM_2.5). The Community Multiscale Air Quality modeling system was applied to the Greater Tokyo Area of Japan in winter 2010 and summer 2011. The model results were compared with observed concentrations of PM_2.5 sulfate (SO₄^2-), nitrate (NO₃^?) and ammonium, and gaseous nitric acid (HNO₃) and ammonia (NH₃). The model approximately reproduced PM_2.5 SO₄^2? concentration, but clearly overestimated PM_2.5 NO₃^? concentration, which was attributed to overestimation of production of ammonium nitrate (NH₄NO₃). This study conducted sensitivity analyses of factors associated with the model performance for PM_2.5 NO₃^? concentration, including temperature and relative humidity, emission of nitrogen oxides, seasonal variation of NH₃ emission, HNO₃ and NH₃ dry deposition velocities, and heterogeneous reaction probability of dinitrogen pentoxide. Change in NH₃ emission directly affected NH₃ concentration, and substantially affected NH₄NO₃ concentration. Higher dry deposition velocities of HNO₃ and NH₃ led to substantial reductions of concentrations of the gaseous species and NH₄NO₃. Because uncertainties in NH₃ emission and dry deposition processes are probably large, these processes may be key factors for improvement of the model performance for PM_2.5 NO₃^?.

Implications: The Community Multiscale Air Quality modeling system clearly overestimated the concentration of fine particulate nitrate in the Greater Tokyo Area of Japan, which was attributed to overestimation of production of ammonium nitrate. Sensitivity analyses were conducted for factors associated with the model performance for nitrate. Ammonia emission and dry deposition of nitric acid and ammonia may be key factors for improvement of the model performance.     

Comparison of the Annular Denuder System and the Transition Flow Reactor for Measurements of Selected Dry Deposition Species

An intensive field study was conducted in Research Triangle Park, North Carolina in the fall of 1986. Ambient concentrations of the following constituents were obtained: nitric acid, nitrous acid, nitrogen dioxide, sulfur dioxide, ammonia, hydrogen ion, and particulate nitrate, sulfate, and ammonium. Results collected using the annular denuder system (ADS) and the transition flow reactor (TFR) are presented and compared.

Both types of samplers had operational detection limits on daily (22-hour) samples that were generally below 1 μg m_-3 suggesting that both samplers can provide sensitive measurements for most of the constituents of interest. Both the ADS and TFR show reasonable (>25 percent) within-sampler precision for most of the measured species concentrations, except TFR fine particulate nitrate measurements where results were frequently negative (The TFR fine particulate nitrate measurement is calculated using subtraction of positive numbers).

Comparison of ADS and TFR daily results showed good agreement for total particulate sulfate, the sum of total (coarse plus fine) particulate and gaseous nitrate, and ammonia. As a result of different inlet particle collection efficiencies, the ADS fine particulate sulfate exceeded the TFR (5 percent). In the absence of a filter to collect volatilized particulate ammonium in the ADS, the sum of total particulate and gaseous ammonium in the TFR exceeded that in the ADS. Of potentially more importance, ADS measurements of SO₂ and H⁺ exceeded those of the TFR, while TFR measurements of HNO₃ exceeded those of the ADS. Results of this study suggest that the TFR may provide biased measurements of SO₂, H⁺, HNO₃, and Fine NO₃ ^- that cannot be corrected without modifications to the fundamental design of the sampling system.     

Processes Influencing Secondary Aerosol Formation in the San Joaquin Valley during Winter

Abstract

Air quality data collected in the California Regional PM₁₀/PM_2.5 Air Quality Study (CRPAQS) are analyzed to qualitatively assess the processes affecting secondary aerosol formation in the San Joaquin Valley (SJV). This region experiences some of the highest fine particulate matter (PM_2.5) mass concentrations in California (≤188 μg/m³ 24-hr average), and secondary aerosol components (as a group) frequently constitute over half of the fine aerosol mass in winter. The analyses are based on 15 days of high-frequency filter and canister measurements and several months of wintertime continuous gas and aerosol measurements. The phase-partitioning of nitrogen oxide (NO_x)-related nitrogen species and carbonaceous species shows that concentrations of gaseous precursor species are far more abundant than measured secondary aerosol nitrate or estimated secondary organic aerosols. Comparisons of ammonia and nitric acid concentrations indicate that ammonium nitrate formation is limited by the availability of nitric acid rather than ammonia. Time-resolved aerosol nitrate data collected at the surface and on a 90-m tower suggest that both the daytime and nighttime nitric acid formation pathways are active, and entrainment of aerosol nitrate formed aloft at night may explain the spatial homogeneity of nitrate in the SJV. NO_x and volatile organic compound (VOC) emissions plus background O₃ levels are expected to determine NO_x oxidation and nitric acid production rates, which currently control the ammonium nitrate levels in the SJV. Secondary organic aerosol formation is significant in winter, especially in the Fresno urban area. Formation of secondary organic aerosol is more likely limited by the rate of VOC oxidation than the availability of VOC precursors in winter.     

Nitrate Artifacts during PM25 Sampling in the South Coast Air Basin of California

ABSTRACT

In February 1993, the South Coast Air Basin (SCAB) was redesignated as a “serious” nonattainment area for PM10. To improve the understanding and characterization of fine particulate matter in the SCAB, the South Coast Air Quality Management District (SCAQMD) initiated a comprehensive PM₁₀ Technical Enhancement Program (PTEP). Using enhanced PTEP monitors (specially designed multichannel/multifilter samplers), a one-year fine particulate matter (PM) monitoring program was initiated in January 1995. As part of the special monitoring program, nitric acid, ammonia, and speciated PM₁₀ and PM_2.5 concentrations were measured at five locations in the SCAB (downtown Los Angeles, Anaheim, Diamond Bar, Fontana, and Rubidoux) and at one background station (San Nicolas Island). The PM2.5 data are the first spatially resolved speciated data collected in the SCAB on an annual basis. Within the SCAB, where nitrate is a major component of PM_2.5, nitrate losses have been documented. The spatial and temporal variations of the nitrate losses during PM_2.5 sampling and the uncertainties of the nitrate losses are discussed. Significant losses occur at a low mass range, between 10 and 50 ìg/m³. Significant gains occur at an even lower mass range of less than 30 ìg/m³. On an annual average basis, nitrate losses vary between 1.25 and 2.32 ìg/m³ and the SCAB-wide average value of nitrate loss is 1.8 ìg/m³ based on five PTEP stations in the SCAB. The maximum nitrate losses for each station vary from 6.4 ìg/m³ to 22.5 ìg/m ³. Theoretical prediction of the sampling efficiency of the nitrate during PM_2.5 sam - pling was compared with the PTEP data. In general, theoretical prediction was in good agreement with measured values.     

Altitude-dependent wet,dry and occult nitrogen deposition in an Alpine Region

From November 1995 to October 1996 and from October 1997 to September 1998, samples of wet precipitation, cloud water, as well as of reactive gases and particulate matter, were collected at three elevational levels (920 m, 1280 m and 1758 m a.s.l.) in Achenkirch, Austria. The samples were analysed for ammonium and nitrate in wet precipitation and in cloud water, for ammonia, nitric acid and nitrogen dioxide in the gas phase and for particulate ammonium and particulate nitrate in aerosol. Total nitrogen deposition was calculated combining measured concentrations in wet, dry and occult depositions with the corresponding deposition fluxes. Two multilayer deposition models were used for the calculation of dry and occult deposition. The total nitrogen input in 1995/96 was estimated to be 29 kg N ha⁻¹a⁻¹ at the Christlumkopf station (1758 m), 20 kg N ha⁻¹a⁻¹ at the Christlumalm station (1280 m) and 28 kg N ha⁻¹a⁻¹ at the Talboden station (930 m). Respective data for the 1997/98 observation period were 31 kg N ha⁻¹a⁻¹ at the Christlumkopf station (1758 m) and 18 kg N ha⁻¹a⁻¹ at the Mühleggerköpfl station (920 m). Critical Loads of nitrogen for coniferous forests were exceeded significantly near-source regions represented by areas of intense agricultural use and at high elevation sites.

     

Demonstration of a global modeling methodology to determine the relative importance of local and long-distance sources

A global three-dimensional (3D) transport–dispersion model was used to simulate Krypton-85 (⁸⁵Kr) background concentrations at five sampling locations along the US east coast during 1982–1983. The samplers were established to monitor the ⁸⁵Kr plume downwind of the Savannah river plant (SRP), a nuclear fuel reprocessing facility. The samplers were located 300–1000 km downwind of the SRP. In the original analyses of the measurements, a constant background concentration, representing an upper-limit and different for each sampling station, was subtracted from the measurements to obtain the part of the measurement representing the SRP plume. The use of a 3D global model, which includes all major ⁸⁵Kr sources worldwide, was able to reproduce the day-to-day concentration background variations at the sampling locations with correlation coefficients of 0.36–0.46. These 3D model background predictions, without including the nearby SRP source, were then subtracted from the measured concentrations at each sampler, the result representing the portion of the measurement that can be attributed to emissions from the SRP. The revised plume estimates were a factor of 1.3–2.4 times higher than from the old method using a constant background subtraction. The greatest differences in the SRP plume estimates occurred at the most distant sampling stations.     

Air-water PCB fluxes from southwestern Lake Michigan revisited

From simultaneous air and water polychlorinated biphenyl (PCB) measurements collected in September 2010, we re-evaluated the direction and magnitude of net air-water exchange of PCBs in southwest Lake Michigan and compared them with estimations made using similar approaches 15 years prior. Air and water samples were collected during a research expedition on Lake Michigan at 5 km off the coast of Chicago, with prevailing winds from the southwest of our location. Gas-phase ΣPCB concentrations ranged from 190 to 1100 pg m^?3 with a median of 770 pg m^?3, which is similar to the concentrations measured in the City of Chicago at the same time and similar to concentrations measured in this part of the lake over the last 20 years. Water dissolved-phase ΣPCB concentrations ranged from 150 to 170 pg L^?1 with a median of 160 pg L^?1, which is one-tenth of that measured in the 1990s. ?PCB net fluxes showed a slightly absorptive behavior, with a median of (?) 21 ng m^?2 day^?1 and an interquartile range of (?) 47 to (+) 5 ng m^?2 day^?1, where (?) and (+) fluxes indicate absorption and volatilization, respectively. Airborne PCB concentrations were higher when the winds were coming from Chicago and drive the deposition. Our fluxes are not significantly different from estimations from 1994 and 1995 and suggest that absorption of PCBs into the waters is slightly more prevalent than 15 years ago. It was confirmed that Chicago remains an important atmospheric source of PCBs to Lake Michigan.