Isotopic compositions of organic and inorganic nitrogen reveal processing and source dynamics at septic influenced and undeveloped estuary sites.

Historically, dissolved organic nitrogen (DON) has not been characterized in the nitrogen profiles of most estuaries despite its significant contribution to total nitrogen and projected increase in loading. The characterization of dissolved inorganic nitrogen (DIN) and DON processing from groundwater to surface water also remains unconstrained. This study attempts to fill in these knowledge gaps by quantifying the DON pool and potential sources in a semiarid, low inflow estuary (Baffin Bay, Texas) using stable isotope techniques. High NO3- and DON concentrations, and high δ15N-NH4+ (+55.0 ± 56.7 ‰), δ15N-NO3- (+23.9 ± 8.6 ‰) and δ15N-DON (+22.3 ± 6.5 ‰) were observed in groundwaters of a septic-influenced estuarine area, indicating coupled septic contamination and nitrification/denitrification. In contrast, groundwater of an undeveloped area provided evidence of inundation by bay water through high NH4+ concentrations and δ15N-NH4+ (+8.4 ± 3.0 ‰) resembling estuary porewater. NH4+ was the dominant nitrogen species in porewater of both areas and δ15N-NH4+ indicated production via organic nitrogen mineralization and dissimilatory nitrate reduction to ammonium. Surface water had similar nitrogen profiles (DON constituted ∼98 % of dissolved nitrogen pool) and potential source contributions, despite distinct nitrogen processing and profiles found in each water table. This was attributed to low nitrogen removal rates and prolonged mixing associated with long residence time. This study emphasizes the importance of DON in a low-inflow estuary and the isotopic approach to comprehensively examine both inorganic and organic N processing and sources serving as a guide to investigate N cycling in high DON estuaries globally.

Modern analogs for ammonia flux from terrestrial hydrothermal features to the Archean atmosphere.

The isotopic composition of nitrogen in the rock record provides valuable evidence of reactive nitrogen sources and processing on early Earth, but the wide range of δ15N values (- 10.2 to + 50.4‰) leads to ambiguity in defining the early Precambrian nitrogen cycle. The high δ15N values have been explained by large fractionation associated with the onset of nitrification and/or fractionation produced by ammonia-ammonium equilibrium and water-air flux in alkaline paleolakes. Previous flux sensitivity studies in modern water bodies report alkaline pH is not a prerequisite and temperature can be the dominate parameter driving water-air flux. Here, I use the chemical and physical components of 1022 modern hydrothermal features to provide evidence that water-air NH3 flux produced a significant source of fixed nitrogen to early Earth's atmosphere and biosphere. With regard to the modeled average NH3 flux (2.1 kg N m-2 year-1) and outlier removed average flux (1.2 kg N m-2 year-1), the Archean Earth's surface would need to be 0.0092, and 0.017% terrestrial hydrothermal features, respectively, for the flux to match the annual amount of N produced by biogenic fixation on modern Earth. Water-air NH3 flux from terrestrial hydrothermal features may have played a significant role in supplying bioavailable nitrogen to early life.

Determining organic nitrogen emission sources and secondary formations in an urban coastal airshed via stable isotope techniques.

Organic nitrogen (ON) has been excluded in the majority of atmospheric N studies. However, dissolved organic nitrogen (DON) deposition influences coastal water quality and primary production creating an urgent need for comprehensive atmospheric ON characterization, especially in coastal airsheds. This study measured the concentration and isotopic composition of rainwater DON (δ15N-DON) and applied stable isotope mixing models to determine the ON emission source apportionments in a small-sized coastal city. The DON concentration averaged 10.6 ± 7.6 µM (n = 42), which was 29% of the total dissolved nitrogen in rainwater and produced a deposition flux of 1.5 kg N·ha-1·yr-1. The average rainwater δ15N-DON value was 8.3 ± 5.3‰ and isotope mixing model results suggested vehicles as a dominant source, overall contributing 35 ± 15% of ON emissions, followed by marine emissions (24 ± 16%), organic amines (18 ± 11%), organic nitrates (17 ± 11%), and biomass burning (8 ± 3%). Although secondary ON formations (i.e., organic amines and nitrates) had less contributions than primary emission sources (i.e., vehicles, marine, and biomass burning), it can be significant and rival primary emissions when the fertilizer application started. Our results fill knowledge gaps of ON wet deposition and emission sources in small-sized coastal cities and inform future atmospheric N mitigation strategies and coastal watershed restoration plans in similar regions. We call for further research determining the isotopic composition of ON emission sources and fractionation associated with primary emission and secondary formation in anticipation of creating a similar isotope-based foundation that has been used for decades to investigate inorganic nitrogen emissions.

Nitrogen isotopes indicate vehicle emissions and biomass burning dominate ambient ammonia across Colorado's Front Range urban corridor.

Urban ammonia (NH3) emissions contribute to poor local air quality and can be transported to rural landscapes, impacting sensitive ecosystems. The Colorado Front Range urban corridor encompasses the Denver Metropolitan Area, rural farmland/rangeland and montane forest between the city and the Rocky Mountains. Reactive nitrogen emissions from the corridor are partly responsible for increased N deposition to the wildland-urban interface (WUI) in this region. To determine the significance of individual NH3 sources to WUI ecosystems, we measured the concentration and isotopic composition (δ15N-NH3) of ambient NH3(g) from April to October 2018 across a five-site urban to rural gradient in the corridor. The urban sites had higher NH3 concentrations and δ15N-NH3 values than the rural/suburban sites. Based on isotope mixing models, NH3 emission source contributions for all sites were fertilizer (12 ± 5.7%), livestock waste (18 ± 12%), vehicles (37 ± 23%), and biomass burning (34 ± 20%). Vehicle contributions were consistent across all months with an average of 35% and summer months showed a peak in biomass burning contributions (40%). As wildfires are projected to increase due to climate change, we stress a need for constraints on the isotopic signature of NH3 emitted from wildfires. Vehicle emissions contributed the greatest amount of NH3 (40%) at the urban sites while rural/suburban sites had higher agricultural contributions (41%). Had 2018 not had an anomalously high wildfire season, 46% and 60% of the NH3 would have been attributed to vehicle emissions at the WUI site and urban sites, respectively. NH3 emissions have historically been ascribed to agricultural activities but these findings illustrate the universal significance of vehicle emissions and the potential for sustained wildfire activity to be a primary contributor to NH3. Air quality (e.g., particulate matter) and nitrogen deposition reduction plans may benefit by including management practices that address vehicle NH3 emissions.

Seasonal pattern of ammonium 15N natural abundance in precipitation at a rural forested site and implications for NH3 source partitioning.

Excess ammonia (NH3) emissions and deposition can have negative effects on air quality and terrestrial ecosystems. Identifying NH3 sources is a critical step for effectively reducing NH3 emissions, which are generally unregulated around the world. Stable nitrogen isotopes (δ15N) of ammonium (NH4+) in precipitation have been directly used to partition NH3 sources. However, nitrogen isotope fractionation during atmospheric processes from NH3 sources to sinks has been previously overlooked. Here we measured δ15NNH4+ in precipitation on a daily basis at a rural forested site in Northeast China over three years to examine its seasonal pattern and attempt to constrain the NH3 sources. We found that the NH4+ concentrations in precipitation ranged from 5 to 1265 µM, and NH4+ accounted for 65% of the inorganic nitrogen deposition (20.0 kg N ha-1 yr-1) over the study period. The δ15N values of NH4+ fluctuated from -24.6 to +16.2‰ (average -6.5‰) and showed a repeatable seasonal pattern with higher values in summer (average -2.3‰) than in winter (average -16.4‰), which could not be explained by only the seasonal changes in the NH3 sources. Our results suggest that in addition to the NH3 sources, isotope equilibrium fractionation contributed to the seasonal pattern of δ15NNH4+ in precipitation, and thus, nitrogen isotope fractionation should be considered when partitioning NH3 sources based on δ15NNH4+ in precipitation.

Compound-Specific Carbon Isotopic Composition of Ethanol in Brazil and US Vehicle Emissions and Wet Deposition.

Global atmospheric ethanol budget models include large uncertainties in the magnitude of ethanol emission sources and sinks. To apply stable isotope techniques to constrain ethanol emission sources, a headspace solid phase microextraction gas chromatograph-combustion-isotope ratio mass spectrometry method (HS-SPME-GC-C-IRMS) was developed to measure the carbon isotopic composition of aqueous phase ethanol at natural abundance levels (1-30 µM) with a precision of 0.4‰. The method was applied to determine the carbon isotope signatures (δ13C) of vehicle ethanol emission sources in Brazil (-12.8 ± 2.4‰) and the US (-9.8 ± 2.5‰), and to measure the carbon isotope composition of ethanol in wet deposition (-22.6 to -12.7‰). A two end-member isotope mixing model was developed using anthropogenic and biogenic end members and fractionation scenarios to estimate ethanol source contributions to wet deposition collected in Brazil and US. Mixing model results indicate anthropogenic sources contribute two and a half to four times more ethanol to the atmosphere than previously predicted in modeled global ethanol inventories. As established and developing countries continue to rapidly increase ethanol fuel consumption and subsequent emissions, understanding the magnitude of all ethanol sources and sinks will be essential for modeling future atmospheric chemistry and air quality impacts.

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 ±â€¯116 nM) was higher than at Wilmington (208 ±â€¯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.

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.

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 Henry's 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.

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.

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.