Nitrogen Isotopes Reveal High NOx Emissions from Arid Agricultural Soils in the Salton Sea Air Basin.

Air quality management commonly aims to mitigate emissions of oxides of nitrogen (NOx) from combustion, reducing ozone and particulate matter pollution. Despite such efforts, regulations have recently proven ineffective in rural areas like the Salton Sea Air Basin of Southern California, which routinely violates air quality standards. With $2 billion in annual agricultural sales and low population density, air quality in the region is likely influenced by year-round farming. We conducted NOx source apportionment using nitrogen stable isotopes of ambient NO2, which indicate a substantial contribution of soil-emitted NOx. The soil source strength was estimated based on the mean δ15N-NOx from each emission category in the California Air Resources Board's NOx inventory. Our annual average soil emission estimate for the air basin was 11.4 ± 4 tons/d, representing ~30% of the extant NOx inventory, 10× larger than the state's inventory. Therefore, the impact of soil NOx in agricultural regions must be re-evaluated.

Nitrogen isotopic characteristics of aerosol ammonium in a Chinese megacity indicate the reduction from vehicle emissions during the lockdown period.

The role of agricultural versus vehicle emissions in urban atmospheric ammonia (NH3) remains unclear. The lockdown due to the outbreak of COVID-19 provided an opportunity to assess the role of source emissions on urban NH3. Concentrations and δ15N of aerosol ammonium (NH4+) were measured before (autumn in 2017) and during the lockdown (summer, autumn, and winter in 2020), and source contributions were quantified using SIAR. Despite the insignificant decrease in NH4+ concentrations, significantly lower δ15N-NH4+ was found in 2020 (0.6 ± 1.0‰ in PM2.5 and 1.4 ± 2.1‰ in PM10) than in 2017 (15.2 ± 6.7‰ in PM2.5), which indicates the NH3 from vehicle emissions has decreased by∼50% during the lockdown while other source emissions are less affected. Moreover, a reversed seasonal pattern of δ15N-NH4+ during the lockdown in Changsha has been revealed compared to previous urban studies, which can be explained by the dominant effect of non-fossil fuel emissions due to the reductions of vehicle emissions during the lockdown period. Our results highlight the effects of lockdown on aerosol δ15N-NH4+ and the importance of vehicle emissions to urban atmospheric NH3, providing conclusive evidence that reducing vehicle NH3 emissions could be an effective strategy to reduce PM2.5 in Chinese megacities.

Large Seasonal Variation in Nitrogen Isotopic Abundances of Ammonia Volatilized from a Cropland Ecosystem and Implications for Regional NH3 Source Partitioning.

Ammonia (NH3) volatilization from agricultural lands is a main source of atmospheric reduced nitrogen species (NHx). Accurately quantifying its contribution to regional atmospheric NHx deposition is critical for controlling regional air nitrogen pollution. The stable nitrogen isotope composition (expressed by δ15N) is a promising indicator to trace atmospheric NHx sources, presupposing a reliable nitrogen isotopic signature of NH3 emission sources. To obtain more specific seasonal δ15N values of soil NH3 volatilization for reliable regional seasonal NH3 source partitioning, we utilized an active dynamic sampling technique to measure the δ15N-NH3 values volatilized from maize cropping land in northeast China. These values varied from -38.0 to -0.2‰, with a significantly lower rate-weighted value observed in the early period (May-June, -30.5 ± 6.7‰) as compared with the late period (July-October, -8.5 ± 4.3‰). Seasonal δ15N-NH3 variations were related to the main NH3 production pathway, degree of soil ammonium consumption, and soil environment. Bayesian isotope mixing model analysis revealed that without considering the seasonal δ15N variation in soil-volatilized NH3 could result in an overestimate by up to absolute 38% for agricultural volatile NH3 to regional atmospheric bulk ammonium deposition during July-October, further demonstrating that it is essential to distinguish seasonal δ15N profile of agricultural volatile NH3 in regional source apportionment.

Triple oxygen stable isotope analysis of nitrite measured using continuous flow isotope ratio mass spectrometry.

Oxygen stable isotopes (i.e., 16O, 17O, 18O) of nitrite (NO2-) are useful for investigating chemical processes and sources contributing to this important environmental contaminant and nutrient. However, it remains difficult to quantify the oxygen isotope compositions of NO2- due to the lack of internationally recognized NO2- reference materials with a well-known Δ(17O) value. Here we have adopted a combination of methodologies to develop a technique for measuring Δ(17O) of NO2- by reducing nitrate (NO3-) materials with internationally recognized Δ(17O) values to NO2- using activated cadmium catalyzed by chloride in a basic solution while conserving Δ(17O). The NO3- reference materials reduced to NO2- and sample NO2- unknowns are converted to N2O using sodium azide/acetic acid reagent and decomposed to O2 by passing through a heated gold tube and introduced into a continuous flow isotope ratio mass spectrometer for analysis at m/z 32, 33, and 34 for Δ(17O) quantification. The adapted method involves the following main points:•NO3- reference materials with internationally recognized oxygen isotope composition are reduced to NO2- under high pH conditions that conserve Δ(17O) values.•The NO3- reference materials reduced to NO2- and sample NO2- with unknown Δ(17O) values are reduced to N2O using chemical methods involving sodium azide/acetic acid.•The product N2O is extracted, purified, decomposed to O2, and analyzed for its isotope composition using a continuous flow isotope ratio mass spectrometer for Δ(17O) quantification. The Δ(17O) of NO2- samples are calibrated with respect to the NO3- reference materials with known Δ(17O) values.

Long-term trends in inorganic aerosol chemical composition and chemistry at an urban and rural site in the northeastern US.

Atmospheric nitrate and sulfate are major inorganic particulate matter components that impact human and ecosystem health and air quality. Over the last several decades, emissions of the precursor gases, nitrogen oxides (NOx = NO + NO2) and sulfur dioxide (SO2), have dramatically decreased in the US in response to federal regulations. However, the response in concentrations of particulate nitrate (pNO3) and sulfate (pSO4) have not followed predictions due to complex non-linear chemistry feedbacks that may differ amongst environments (i.e., urban vs. rural). In this study, we explored the long-term response of particle chemistry for urban and rural environments in southern New England, a region historically impacted by NOx and SO2 emissions. Particulate matter (PM10) samples collected via the same method from 2005 to 2015 at urban and rural locations in Rhode Island were analyzed for their major inorganic components, and air mass trajectories and statistical analysis were used to identify source regions over time. Our results indicated a significant urban-rural aerosol chemical composition gradient for sampling locations within 40 km. Over time, as anthropogenic influences have decreased, the relative contribution of marine and crustal sources has increased greatly, impacting fine and coarse particle chemistry in recent years. Total mass concentrations of chemical species, particularly anthropogenic pSO4 and particulate ammonium (pNH4), have shown dramatic decreases over the ten years at both the urban and rural sites; however, pNO3 concentration increased by 95 % and 57 % in the urban and rural sites, respectively, despite significant NOx emission reductions. Our results demonstrate that changes in chemical mechanisms due to the decrease in SO2 emissions contributed to decreases in pNH4, along with enhanced pNO3 concentration. Furthermore, the change in SO2 emissions has significantly impacted the atmospheric lifetime and transport distance of pNH4, favoring more localized contributions in recent years.

Revisiting the dynamics of gaseous ammonia and ammonium aerosols during the COVID-19 lockdown in urban Beijing using machine learning models.

The concentration of atmospheric ammonia (NH3) in urban Beijing substantially decreased during the COVID-19 lockdown (24 January to 3 March 2020), likely due to the reduced human activities. However, quantifying the impact of anthropogenic interventions on NH3 dynamics is challenging, as both meteorology and chemistry mask the real changes in observed NH3 concentrations. Here, we applied machine learning techniques based on random forest models to decouple the impacts of meteorology and emission changes on the gaseous NH3 and ammonium aerosol (NH4+) concentrations in Beijing during the lockdown. Our results showed that the meteorological conditions were unfavorable during the lockdown and tended to cause an increase of 8.4 % in the NH3 concentration. In addition, significant reductions in NOx and SO2 emissions could also elevate NH3 concentrations by favoring NH3 gas-phase partitioning. However, the observed NH3 concentration significantly decreased by 35.9 % during the lockdown, indicating a significant reduction in emissions or enhanced chemical sinks. Rapid gas-to-particle conversion was indeed found during the lockdown. Thus, the observed reduced NH3 concentrations could be partially explained by the enhanced transformation into NH4+. Therefore, the sum of NH3 and NH4+ (collectively, NHx) is a more reliable tracer than NH3 or NH4+ alone to estimate the changes in NH3 emissions. Compared to that under the scenario without lockdowns, the NHx concentration decreased by 26.4 %. We considered that this decrease represents the real decrease in NH3 emissions in Beijing due to the lockdown measures, which was less of a decrease than that based on NH3 only (35.9 %). This study highlights the importance of considering chemical sinks in the atmosphere when applying machine learning techniques to link the concentrations of reactive species with their emissions.

Nitrate isotopes (δ15N, δ18O) in precipitation: best practices from an international coordinated research project.

Stable isotope ratios of nitrogen and oxygen (15N/14N and 18O/16O) of nitrate (NO3-) are excellent tracers for developing systematic understanding of sources, conversions, and deposition of reactive atmospheric nitrogen (Nr) in the environment. Despite recent analytical advances, standardized sampling of NO3-) isotopes in precipitation is still lacking. To advance atmospheric studies on Nr species, we propose best-practice guidelines for accurate and precise sampling and analysis of NO3- isotopes in precipitation based on the experience obtained from an international research project coordinated by the International Atomic Energy Agency (IAEA). The precipitation sampling and preservation strategies yielded a good agreement between the NO3- concentrations measured at the laboratories of 16 countries and at the IAEA. Compared to conventional methods (e.g., bacterial denitrification), we confirmed the accurate performance of the lower cost Ti(III) reduction method for isotope analyses (15N and 18O) of NO3- in precipitation samples. These isotopic data depict different origins and oxidation pathways of inorganic nitrogen. This work emphasized the capability of NO3- isotopes to assess the origin and atmospheric oxidation of Nr and outlined a pathway to improve laboratory capability and expertise at a global scale. The incorporation of other isotopes like 17O in Nr is recommended in future studies.

Collection of Nitrogen Dioxide for Nitrogen and Oxygen Isotope Determination─Laboratory and Environmental Chamber Evaluation.

The family of atmospheric oxides of nitrogen, NOy (e.g., nitrogen oxides (NOx) + nitric acid (HNO3) + nitrous acid (HONO) + peroxyacetyl nitrate (PAN) + particulate nitrate (pNO3-) + other), have an influential role in atmospheric chemistry, climate, and the environment. The nitrogen (δ15N) and oxygen (δ18O and Δ17O) stable isotopes of NOy are novel tools for potentially tracking emission sources and quantifying oxidation chemistry. However, there is a lack of well-established methods, particularly for speciated gas-phase components of NOy, to accurately quantify δ15N, δ18O, and Δ17O. This work presents controlled laboratory experiments and complex chamber α-pinene/NOx oxidation experiments of a sampling apparatus constructed for the simultaneous capture of multiple NOy species for isotope analysis using a series of coated denuders, with a focus on nitrogen dioxide (NO2•). The laboratory tests indicate complete NO2• capture for the targeted concentration of 15 ppbv for at least 24 h collections at 10 liters per minute, with δ15N and δ18O precisions of ±1.3‰ and 1.0‰, respectively, and minimal (2.2% ± 0.1%) NO2• collection on upstream denuders utilized for the capture of HNO3 and other acidic gases. The multispecies NOy collection system showed excellent concentration correlations with online instrumentation for both HNO3 and NO2• and isotope reproducibility of ±1.7‰, ±1.8‰, and ±0.7‰ for δ15N, δ18O, and Δ17O, respectively, for replicate experiments and highly time-resolved collections. This work demonstrates a new method that can enable the simultaneous collection of HNO3 and NO2• for accurate quantification of concentration and isotopic composition.

Significant contributions of combustion-related sources to ammonia emissions.

Atmospheric ammonia (NH3) and ammonium (NH4+) can substantially influence air quality, ecosystems, and climate. NH3 volatilization from fertilizers and wastes (v-NH3) has long been assumed to be the primary NH3 source, but the contribution of combustion-related NH3 (c-NH3, mainly fossil fuels and biomass burning) remains unconstrained. Here, we collated nitrogen isotopes of atmospheric NH3 and NH4+ and established a robust method to differentiate v-NH3 and c-NH3. We found that the relative contribution of the c-NH3 in the total NH3 emissions reached up to 40 ± 21% (6.6 ± 3.4 Tg N yr-1), 49 ± 16% (2.8 ± 0.9 Tg N yr-1), and 44 ± 19% (2.8 ± 1.3 Tg N yr-1) in East Asia, North America, and Europe, respectively, though its fractions and amounts in these regions generally decreased over the past decades. Given its importance, c-NH3 emission should be considered in making emission inventories, dispersion modeling, mitigation strategies, budgeting deposition fluxes, and evaluating the ecological effects of atmospheric NH3 loading.

Is fertilization the dominant source of ammonia in the urban atmosphere?

It was previously believed that ammonia (NH3) has a short residence time in the atmosphere and cannot be transported far from its sources. In late March, however, this study observed a severe NH3 episode in urban Beijing when fertilizer was intensively applied on the North China Plain, with the highest hourly concentrations of 66.9 µg m-3 throughout the year. The stable nitrogen isotopic composition of NH3 (δ15N-NH3) during this episode (-37.0 to -20.0‰) fell in the range of endmembers of fertilizer and livestock, suggesting the long-range transport of NH3 from agricultural to urban regions. Based on a Bayesian isotope mixing model, the contribution of agriculture (fertilization) to urban NH3 concentrations was apportioned as 43.5% (26.0%) on polluted days. However, these contributions were reduced to 29.1% (12.8%) when nitrogen isotope fractionation between NH3 and ammonium was considered. In contrast to the limited contribution of agricultural sources, we found that nonagricultural emissions, particularly vehicles, dominate the source of NH3 in urban Beijing, even during the fertilization period. This finding indicated that nonagricultural sources should be considered when designing a control strategy for NH3 to reduce haze pollution in the urban atmosphere.

Vehicular Emissions Enhanced Ammonia Concentrations in Winter Mornings: Insights from Diurnal Nitrogen Isotopic Signatures.

A general feature in the diurnal cycle of atmospheric ammonia (NH3) concentrations is a morning spike that typically occurs around 07:00 to 10:00 (LST). Current hypotheses to explain this morning's NH3 increase remain elusive, and there is still no consensus whether traffic emissions are among the major sources of urban NH3. Here, we confirmed that the NH3 morning pulse in urban Beijing is a universal feature, with an annual occurrence frequency of 73.0% and a rapid growth rate (>20%) in winter. The stable nitrogen isotopic composition of NH3 (δ15N-NH3) in winter also exhibited a significant diurnal variation with an obvious morning peak at 07:00 to 10:00 (-18.6‰, mass-weighted mean), higher than other times of the day (-26.3‰). This diurnal pattern suggests that a large fraction of NH3 in the morning originated from nonagricultural sources, for example, power plants, vehicles, and coal combustion that tend to have higher δ15N-NH3 emission signatures relative to agricultural emissions. In particular, the contribution from vehicular emissions increased from 18% (00:00 to 07:00) to 40% (07:00 to 10:00), while the contribution of fertilizer sources to NH3 was reduced from 15.8% at 00:00 to 07:00 to 5.2% at 07:00 to 10:00. We concluded that NH3 concentrations in winter mornings in urban Beijing were indeed enhanced by vehicle emissions, which should be considered in air pollution regulations.

Atmospheric nitrate formation pathways in urban and rural atmosphere of Northeast China: Implications for complicated anthropogenic effects.

Effects of human activities on atmospheric nitrate (NO3-) formation remain unclear, though the knowledge is critical for improving atmospheric chemistry models and nitrogen deposition reduction strategies. A potentially useful way to explore this is to compare NO3- oxidation processes in urban and rural atmospheres based upon the oxygen stable isotope composition of NO3- (Δ17O-NO3-). Here we compared the Δ17O-NO3- from three-years of daily-based bulk deposition in urban (Shenyang) and forested rural sites (Qingyuan) in northeast China and quantified the relative contributions of different formation pathways based on the SIAR model. Our results showed that the Δ17O in Qiangyuan (26.2 ± 3.3‰) is significantly higher (p < 0.001) than in Shenyang (24.0 ± 4.0‰), and significantly higher in winter (Shenyang: 26.1 ± 6.7‰, Qingyuan: 29.6 ± 2.5‰) than in summer (Shenyang: 22.7 ± 2.9‰, Qingyuan: 23.8 ± 2.4‰) in both sites. The lower values in the urban site are linked with conditions that favored a higher relative contribution of nitrogen dioxide reaction with OH pathway (0.76-0.91) than in rural site (0.47-0.62), which should be induced by different levels of human activities in the two sites. The seasonal variations of Δ17O-NO3- in both sites are explained by a higher relative contribution of ozone-mediated oxidation chemistry and unfavorable conditions for the OH pathway during winter relative to summer, which is affected by human activities and seasonal meteorological condition change. Based on Δ17O, wintertime conditions led to a contribution of O3 related pathways (NO3 + DMS/HC and N2O5 hydrolysis) of 0.63 in Qingyuan and 0.42 in Shenyang, while summertime conditions led to 0.15 in Qingyuan and 0.05 in Shenyang. Our comparative study on Δ17O-NO3- between urban and rural sites reveals different anthropogenic effects on nitrate formation processes on spatial and temporal scales, illustrating different responses of reactive nitrogen chemistry to changes in human activities.

Important contributions of non-fossil fuel nitrogen oxides emissions.

Since the industrial revolution, it has been assumed that fossil-fuel combustions dominate increasing nitrogen oxide (NOx) emissions. However, it remains uncertain to the actual contribution of the non-fossil fuel NOx to total NOx emissions. Natural N isotopes of NO3- in precipitation (δ15Nw-NO3-) have been widely employed for tracing atmospheric NOx sources. Here, we compiled global δ15Nw-NO3- observations to evaluate the relative importance of fossil and non-fossil fuel NOx emissions. We found that regional differences in human activities directly influenced spatial-temporal patterns of δ15Nw-NO3- variations. Further, isotope mass-balance and bottom-up calculations suggest that the non-fossil fuel NOx accounts for 55 ± 7% of total NOx emissions, reaching up to 21.6 ± 16.6Mt yr-1 in East Asia, 7.4 ± 5.5Mt yr-1 in Europe, and 21.8 ± 18.5Mt yr-1 in North America, respectively. These results reveal the importance of non-fossil fuel NOx emissions and provide direct evidence for making strategies on mitigating atmospheric NOx pollution.

Substantial nitrogen oxides emission reduction from China due to COVID-19 and its impact on surface ozone and aerosol pollution.

A top-down approach was employed to estimate the influence of lockdown measures implemented during the COVID-19 pandemic on NOx emissions and subsequent influence on surface PM2.5 and ozone in China. The nation-wide NOx emission reduction of 53.4% due to the lockdown in 2020 quarter one in China may represent the current upper limit of China's NOx emission control. During the Chinese New Year Holiday (P2), NOx emission intensity in China declined by 44.7% compared to the preceding 3 weeks (P1). NOx emission intensity increased by 20.3% during the 4 weeks after P2 (P3), despite the unchanged NO2 column. It recovered to 2019 level at the end of March (P4). The East China (22°N - 42°N, 102°E - 122°E) received greater influence from COVID-19. Overall NOx emission from East China for 2020 first quarter is 40.5% lower than 2019, and in P4 it is still 22.9% below the same period in 2019. The 40.5% decrease of NOx emission in 2020 first quarter in East China lead to 36.5% increase of surface O3 and 12.5% decrease of surface PM2.5. The elevated O3 promotes the secondary aerosol formation through heterogeneous pathways. We recommend that the complicated interaction between PM2.5 and O3 should be considered in the emission control strategy making process in the future.

Speciated Collection of Nitric Acid and Fine Particulate Nitrate for Nitrogen and Oxygen Stable Isotope Determination.

Stable isotopic composition of atmospheric nitrate (nitric acid (HNO3) + particulate nitrate (pNO3-)) provides a higher-order dimensional analysis of critical atmospheric components, enabling a process-level understanding of precursor emissions, oxidation chemistry, aerosol acidity, and depositional patterns. Current methods have not been evaluated for their ability to accurately speciate and determine nitrogen (δ15N) and oxygen (δ18O and Δ17O) isotope compositions for gaseous and particle phases. Suitability of a denuder-filter sampling system for the collection of speciated HNO3(g) and pNO3- for off-line concentration and isotopic determination was tested using both laboratory and field collections. Honeycomb denuders coated with either NaCl or Na2CO3 solutions were used to collect HNO3(g). Laboratory experiments found that both coating solutions quantitatively collected HNO3(g), with the Na2CO3 solution demonstrating a higher operative capacity (>1470 µg of HNO3; n = 25) compared to the NaCl solution (∼750 µg of HNO3; n = 25). The precision values for laboratory-tested HNO3(g) collections are ±0.6‰ and ±1.2‰ for δ15N and δ18O for the NaCl solution and ± 0.8‰ and ±1.2‰ for the Na2CO3 solution. Replicate (urban) samples indicate that the Na2CO3 solution is significantly less selective for HNO3(g) collection than the NaCl solution. Nylon filters were found to collect efficiently and retain laboratory-generated NaNO3 and NH4NO3 particles, with maximum standard deviations for δ15N and δ18O of ±0.3‰ and ±0.3‰, respectively. Field replicates, while predictably more variable, also show consistency for δ15N and δ18O of ±0.6‰ and ±1.3‰ for particulate species, respectively. Recommended methods for field collections of speciated HNO3(g) and pNO3- for isotopic measurements would best utilize the NaCl solution and Nylon filters.

Isotopic evidence that recent agriculture overprints climate variability in nitrogen deposition to the Tibetan Plateau.

The stable isotopes of nitrogen in nitrate archived in polar ice have been interpreted as reflecting a shift in reactive nitrogen sources or changes in atmospheric chemical reactivity. Here, we present a novel concentration and isotopic record of nitrate (δ15N-NO3-) from a central Tibetan Plateau ice core over the last ~200 years. We find that nitrate concentration increased from 6.0 ± 2.3 µeq/L (mean ± 1σ) in the preindustrial period (prior to 1900s) to 7.3 ± 2.7 µeq/L in post-1950. Over the same time period, the δ15N-NO3- decreased from 8.7 ± 3.7‰ to 4.2 ± 3.1‰, with much larger interannual variation in δ15N-NO3- during the preindustrial period. We present a useful framework for quantifying the sensitivity of the isotopic composition of atmospheric nitrate to changes in both sources and chemistry (gas and aerosol phase). After 1950, nitrogen deposition is primarily driven by fertilizer use, leading to significant increases in concentration and decreases in δ15N-NO3-. The large interannual variability of ice core δ15N-NO3- in the preindustrial reflects natural processes, namely the El Niño Southern Oscillation (ENSO) and dust events. Our results highlight a new connection between the nitrogen cycle and ENSO, and the overprinting of natural climate signals by recent anthropogenic increases in reactive nitrogen release.

Selective Collection of Particulate Ammonium for Nitrogen Isotopic Characterization Using a Denuder-Filter Pack Sampling Device.

Nitrogen stable isotope analysis (δ15N) of particulate ammonium (NH4+) may provide additional constraints on this critical component of fine particulate matter; however, no previous collection method has been verified for its ability to accurately and precisely characterize δ15N(NH4+). This is a critical point due to the difficulty of quantitative NH4+ collection and possible sampling artifacts. Here, we report on δ15N(NH4+) precision using an established denuder-filter pack combination with two filter configurations including (1) a nylon filter plus an acid-impregnated cellulose filter and (2) an acid-impregnated glass fiber filter for NH4+ collection in both laboratory-controlled environments and ambient air samples. Laboratory NH4+ were generated from the nebulization of ammonium salt solutions and collected using a filter pack sampling train for off-line concentration and isotopic measurement. Quantitative collection of NH4+ was achieved using both filter configurations in both laboratory and field collections. Laboratory experiments indicate a δ15N(NH4+) precision of ±0.9‰ (1σ; n = 24) and ±0.6‰ ( n = 9) for the nylon plus citric acid impregnated cellulose filter and for the citric acid impregnated glass fiber filter, respectively. Field sample reproducibility was assessed from 24 h collected side-by-side samples and indicated δ15N(NH4+) to be reproducible within 1.1‰, consistent with the laboratory findings. This work represents the first established method for speciated NH4+ collection for isotopic analysis with important implications for furthering our understanding of its atmospheric dynamics.

Analysis of biogeographic ancestry reveals complex genetic histories for indigenous communities of St. Vincent and Trinidad.

OBJECTIVES: From a genetic perspective, relatively little is known about how mass emigrations of African, European, and Asian peoples beginning in the 16th century affected Indigenous Caribbean populations. Therefore, we explored the impact of serial colonization on the genetic variation of the first Caribbean islanders. MATERIALS AND METHODS: Sixty-four members of St. Vincent's Garifuna Community and 36 members of Trinidad's Santa Rosa First People's Community (FPC) of Arima were characterized for mitochondrial DNA and Y-chromosome diversity via direct sequencing and targeted SNP and STR genotyping. A subset of 32 Garifuna and 18 FPC participants were genotyped using the GenoChip 2.0 microarray. The resulting data were used to examine genetic diversity, admixture, and sex biased gene flow in the study communities. RESULTS: The Garifuna were most genetically comparable to African descendant populations, whereas the FPC were more similar to admixed American groups. Both communities also exhibited moderate frequencies of Indigenous American matrilines and patrilines. Autosomal SNP analysis indicated modest Indigenous American ancestry in these populations, while both showed varying degrees of African, European, South Asian, and East Asian ancestry, with patterns of sex-biased gene flow differing between the island communities. DISCUSSION: These patterns of genetic variation are consistent with historical records of migration, forced, or voluntary, and suggest that different migration events shaped the genetic make-up of each island community. This genomic study is the highest resolution analysis yet conducted with these communities, and provides a fuller understanding of the complex bio-histories of Indigenous Caribbean peoples in the Lesser Antilles.

Collection of Ammonia for High Time-Resolved Nitrogen Isotopic Characterization Utilizing an Acid-Coated Honeycomb Denuder.

Nitrogen stable isotope analysis (δ15N) of ammonia (NH3) has shown potential to be a useful tool for characterizing emission sources and sink processes. However, to properly evaluate NH3 emission sources and sink processes under ambient conditions, it is necessary to collect and characterize the chemical speciation between NH3 and particulate ammonium (p-NH4+), together referred to as NH x. Current NH3 collection methods have not been verified for their ability to accurately characterize δ15N-NH3 and/or provide necessary chemical speciation (i.e., δ15N-NH3 and δ15N-NH4+). Here, we report on the suitability of an established collection device that can provide NH x speciation, an acid-coated (2% citric acid (w/v) + 1% glycerol (w/v) in 80:20 methanol to water solution) honeycomb denuder (HCD) with a downstream filter pack housed in the ChemComb Speciation Cartridge (CCSC), for characterizing δ15N-NH3 under a variety of laboratory-controlled conditions and field collections. The collection method was tested under varying NH3 concentration, relative humidity, temperature, and collection time at a flow rate of 10 L per minute (LPM). The acid-coated HCD collection device and subsequent chemical processing for δ15N-NH3 analysis is found to have excellent accuracy and precision of ±1.6‰ (2σ), with an operative capacity of ∼400 µg of collected NH3 for concentrations ≤207 ppbv. This work presents the first laboratory verified method for δ15N-NH3 analysis and will be useful in future air quality studies.

Ab initio study of nitrogen and position-specific oxygen kinetic isotope effects in the NO + O3 reaction.

Ab initio calculations have been carried out to investigate nitrogen (k15/k14) and position-specific oxygen (k17/k16O & k18/k16) kinetic isotope effects (KIEs) for the reaction between NO and O3 using CCSD(T)/6-31G(d) and CCSD(T)/6-311G(d) derived frequencies in the complete Bigeleisen equations. Isotopic enrichment factors are calculated to be -6.7‰, -1.3‰, -44.7‰, -14.1‰, and -0.3‰ at 298 K for the reactions involving the 15N16O, 14N18O, 18O16O16O, 16O18O16O, and 16O16O18O isotopologues relative to the 14N16O and 16O3 isotopologues, respectively (CCSD(T)/6-311G(d)). Using our oxygen position-specific KIEs, a kinetic model was constructed using Kintecus, which estimates the overall isotopic enrichment factors associated with unreacted O3 and the oxygen transferred to NO2 to be -19.6‰ and -22.8‰, respectively, (CCSD(T)/6-311G(d)) which tends to be in agreement with previously reported experimental data. While this result may be fortuitous, this agreement suggests that our model is capturing the most important features of the underlying physics of the KIE associated with this reaction (i.e., shifts in zero-point energies). The calculated KIEs will useful in future NOx isotopic modeling studies aimed at understanding the processes responsible for the observed tropospheric isotopic variations of NOx as well as for tropospheric nitrate.