J. David Felix

Nitrogen Isotopic Composition of Coal-Fired Power Plant NOx: Influence of Emission Controls and Implications for Global Emission Inventories

Despite the potential use of δ(15)N as a tracer of NO(x) source contributions, prior documentation of δ(15)N of various NO(x) emission sources is exceedingly limited. This manuscript presents the first measurements of the nitrogen isotopic composition of NO(x) (δ(15)N-NO(x)) emitted from coal-fired power plants in the U.S. at typical operating conditions with and without the presence of selective catalytic reduction (SCR) and selective noncatalytic reduction (SNCR) technology. To accomplish this, a novel method for collection and isotopic analysis of coal-fired stack NO(x) emission samples was developed based on modifications of a historic U.S. EPA stack sampling method. At the power plants included in this study, large differences exist in the isotopic composition of NO(x) emitted with and without SCRs and SNCRs; further the isotopic composition of power plant NO(x) is higher than that of other measured NO(x) emission sources confirming its use as an environmental tracer. These findings indicate that gradual implementation of SCRs at power plants will result in an industry-wide increase in δ(15)N values of NO(x) and NO(y) oxidation products from this emission source.

Characterizing the isotopic composition of atmospheric ammonia emission sources using passive samplers and a combined oxidation‐bacterial denitrifier approach

RATIONALE Ammonia (NH3) emissions are a substantial source of nitrogen pollution to sensitive terrestrial, aquatic, and marine ecosystems and dependable quantification of NH3 sources is of growing importance due to recently observed increases in ammonium (NH4(+)) deposition rates. While determination of the nitrogen isotopic composition of NH3 (δ(15)N-NH3) can aid in the quantification of NH3 emission sources, existing methods have precluded a comprehensive assessment of δ(15)N-NH3 values from major emission sources. METHODS We report an approach for the δ(15)N-NH4(+) analysis of low concentration NH4(+) samples that couples the bromate oxidation of NH4(+) to NO2(-) and the microbial denitrifier method for δ(15)N-NO2(-) analysis. This approach reduces the required sample mass by 50-fold relative to standard elemental analysis (EA) procedures, is capable of high throughput, and eliminates toxic chemicals used in a prior method for the analysis of low concentration samples. Using this approach, we report a comprehensive inventory of δ(15)N-NH3 values from major emission sources (including livestock operations, marine sources, vehicles, fertilized cornfields) collected using passive sampling devices. RESULTS The δ(15)N-NH4(+) analysis approach developed has a standard deviation of ±0.7‰ and was used to analyze passively collected NH3 emissions with a wide range of ambient NH3 concentrations (0.2 to 165.6 µg/m(3)). The δ(15)N-NH3 values reveal that the NH3 emitted from volatilized livestock waste and fertilizer has relatively low δ(15)N values (-56 to -23‰), allowing it to be differentiated from NH3 emitted from fossil fuel sources that are characterized by relatively high δ(15)N values (-15 to +2‰). CONCLUSIONS The isotopic source signatures presented in this emission inventory can be used as an additional tool in identifying NH3 emission sources and tracing their transport across localized landscapes and regions. The insight into the transport of NH3 emissions provided by isotopic investigation is an important step in devising strategies to reduce future NH3 emissions, a mounting concern for air quality scientists, epidemiologists, and policy-makers.

Temporal and spatial variability of trace volatile organic compounds in rainwater.

This study presents the first detailed concentration profile of trace VOCs in atmospheric waters. Analytes were detected and quantified in 111 unique rain events in Wilmington, NC, USA over a one-year period. Headspace solid phase microextraction was optimized for detection of these compounds at sub-nanomolar levels. Distinct seasonality in both the occurrence and concentration of compounds was observed with the lowest abundance occurring during low irradiance winter months. In contrast to other rainwater components studied at this location, VOCs did not show any correlation between rainfall amount and concentrations. There was significant spatial variation with regards to air-mass back-trajectory for methyfuran with higher concentrations observed in terrestrial events during the growing season. Air mass back trajectory also impacted CCl4 concentrations in rainwater with evidence of a possible oceanic input. However there was no significant impact of air-mass back-trajectory on the concentration of BTEX observed in rain indicating that storm origin is not the controlling factor driving concentrations of these analytes in precipitation. Members of the BTEX family did, however, have significant correlations with each other occurring in ratios aligned closely with ratios reported in the literature for gas-phase BTEX. Using available gas-phase data from locations with similar anthropogenic sources and Henrys Law constants, calculated concentrations agreed with VOC levels found in Wilmington rain. Results of this study indicate local gas-phase scavenging is the major source of VOCs in rain and wet deposition is not an efficient removal mechanism (<0.1%) of VOCs from the atmosphere.

Surface waters as a sink and source of atmospheric gas phase ethanol.

This study reports the first ethanol concentrations in fresh and estuarine waters and greatly expands the current data set for coastal ocean waters. Concentrations for 153 individual measurements of 11 freshwater sites ranged from 5 to 598 nM. Concentrations obtained for one estuarine transect ranged from 56 to 77 nM and levels in five coastal ocean depth profiles ranged from 81 to 334 nM. Variability in ethanol concentrations was high and appears to be driven primarily by photochemical and biological processes. 47 gas phase concentrations of ethanol were also obtained during this study to determine the surface water degree of saturation with respect to the atmosphere. Generally fresh and estuarine waters were undersaturated indicating they are not a source and may be a net sink for atmospheric ethanol in this region. Aqueous phase ethanol is likely converted rapidly to acetaldehyde in these aquatic ecosystems creating the undersaturated conditions resulting in this previously unrecognized sink for atmospheric ethanol. Coastal ocean waters may act as either a sink or source of atmospheric ethanol depending on the partial pressure of ethanol in the overlying air mass. Results from this study are significant because they suggest that surface waters may act as an important vector for the uptake of ethanol emitted into the atmosphere including ethanol from biofuel production and usage.

Removal of atmospheric ethanol by wet deposition

The global wet deposition flux of ethanol is estimated to be 2.4 ± 1.6 Tg/yr with a conservative range of 0.2–4.6 Tg/yr based upon analyses of 219 wet deposition samples collected at 12 locations globally. This estimate calculated by using observed wet deposition ethanol concentrations is in agreement with previous models (1.4–5 Tg/yr) predicting the wet deposition sink using Henrys law coefficients and atmospheric ethanol concentrations. Wet deposition is estimated to remove between 6 and 17% of the total ethanol emitted to the atmosphere on an annual basis. The concentration of ethanol in marine rain (25 ± 6 nM) is an order of magnitude less than in the majority of terrestrial rains (345 ± 280 nM). Terrestrial rain samples collected in locations impacted by high local sources of biofuel usage and locations downwind from ethanol distilleries were an order of magnitude higher in ethanol concentration (3090 ± 448 nM) compared to rain collected in terrestrial locations not impacted by these sources. These results indicate that wet deposition of ethanol is heavily influenced by local sources. Results of this study are important because they suggest that as biofuel production and usage increase, the concentration of ethanol in the atmosphere will increase as well the wet deposition flux. Additional research constraining the sources, sinks, and atmospheric impacts of ethanol is necessary to better assist in the debate as whether or not to increase consumption of the alcohol as a biofuel.

Variability of ethanol concentration in rainwater driven by origin versus season in coastal and inland North Carolina, USA

Rainwater ethanol concentrations were measured for one year (June 2013-May 2014) in central (Elon, NC) and coastal (Wilmington, NC) North Carolina, allowing for a comparison of the effects of coastal and marine rain on ethanol concentration and deposition both at the coast and 250 km inland. Rain samples were collected on an event basis and analyzed using enzyme oxidation and headspace solid-phase microextraction (HS-SPME). The volume-weighted average ethanol concentration at Elon (609 ± 116 nM) was higher than at Wilmington (208 ± 21 nM). Rainfall influenced by air masses originating over the Atlantic Ocean has previously been observed to be lower in ethanol concentration than terrestrial rain at the Wilmington location, and this was true during this study as well. Lower-ethanol marine and coastal air masses did not affect the concentration of ethanol in Elon rain, 250 km from the coast. This is likely due to the rapid supply of locally emitted ethanol to air masses moving over the land. No difference in rainwater ethanol concentrations was observed for Elon rain based on air mass back trajectories, most likely because all the rain was impacted by both anthropogenic and biogenic terrestrial sources typical of most inland areas. Seasonal variation in ethanol concentrations was significant in the inland location with elevated ethanol concentrations observed in fall; no seasonal variation was observed in coastal location rain. This study presents for the first time the different drivers for ethanol concentrations in rainwater from a coastal and a proximal inland location.