Methyl and ethyl nitrate saturation anomalies in the Southern Ocean (36 - 65°S, 30 - 70°W)

2008 ◽  
Vol 5 (1) ◽  
pp. 11 ◽  
Author(s):  
Claire Hughes ◽  
Adele L. Chuck ◽  
Suzanne M. Turner ◽  
Peter S. Liss

Environmental Context. The alkyl nitrates are a group of organic compounds that are known to be produced naturally in seawater. The sea-to-air flux of alkyl nitrates is believed to contribute significantly to the ‘odd nitrogen’ reservoir of the atmosphere and to play an important role in regulating tropospheric ozone levels in remote marine regions. Here we expand our knowledge of alkyl nitrate concentration distributions and saturation anomalies to Southern Ocean waters. Abstract. We report the first coupled atmosphere and seawater alkyl nitrate measurements for the Southern Ocean in the area bounded by 36–65°S, 30–70°W (November/December, 2004). Methyl and ethyl nitrate concentrations in seawater were 3.1–194.9 and 0.3–71.8 pmol L–1, respectively. Atmospheric mixing ratios ranged from 1.0 to 71.5 ppt for methyl nitrate and 0.6 to 16.6 ppt for ethyl nitrate. No correlations between alkyl nitrate distributions, and sea surface temperature, windspeed or chlorophyll a were observed. However, methyl and ethyl nitrate were well correlated in both the air and seawater, which suggests a common source. Calculations based on these observations estimate median saturation anomalies of –40% (–95 to 220%) for methyl nitrate and –11% (–98 to 174%) for ethyl nitrate. Positive saturation anomalies were spatially patchy, which suggests that some methyl and ethyl nitrate production was taking place in isolated areas of the study region. Overall our negative median saturation anomaly values suggest that during late austral spring (2004) the region of the Southern Ocean in which our measurements were made was not a net source of methyl or ethyl nitrate to the atmosphere. These results reinforce previous findings which suggest that whilst the equatorial ocean is a major source of methyl and ethyl nitrates to the atmosphere, higher latitude waters are generally at equilibrium or under-saturated. More measurements are required to assess how representative our results are of other areas of the Southern Ocean.

2009 ◽  
Vol 9 (6) ◽  
pp. 23371-23418 ◽  
Author(s):  
R. S. Russo ◽  
Y. Zhou ◽  
K. B. Haase ◽  
O. W. Wingenter ◽  
E. K. Frinak ◽  
...  

Abstract. Seven C1-C5 alkyl nitrates were measured both on the mainland and off the coast of New Hampshire using gas chromatographic techniques. Five separate data sets will be presented to characterize the seasonal and diurnal trends and the major sources and loss processes of these compounds. In situ measurements were conducted at the University of New Hampshire (UNH) Atmospheric Observing Station at Thompson Farm (TF) located in southeast NH during winter (January–February) and summer (June–August) 2002 and summer (July–August) 2004. The median (±standard deviation) total alkyl nitrate mixing ratio (ΣRONO2) was 25 (±7) in winter and 16 (±14) pptv in summer. Furthermore, daily canister samples collected at midday and later analyzed in the laboratory from January 2004–February 2008 gave median ΣRONO2 of 23 (±8) in winter and 14 (±10) pptv in summer. Alkyl nitrate mixing ratios increased throughout the morning and were highest in the afternoon reflecting mixing of remnant boundary layer air toward the surface and photochemical production during the day. During summers 2002 and 2004, MeONO2 decreased overnight and reached minimum hourly average mixing ratios in the early morning (05:00–07:00 LT). Comparison with wind speed and trace gas (i.e., hydrocarbons, ozone, carbon monoxide, total reactive nitrogen) trends suggested that dry deposition contributed to the early morning MeONO2 minimum which is a previously unaccounted for removal mechanism. The mean dry deposition rate and velocity of MeONO2 was estimated to be −0.5 nmol m−2 hr−1 and 0.13 cm s−1, respectively. Results from ambient air and surface seawater measurements made onboard the NOAA R/V Ronald H. Brown in the Gulf of Maine during the 2002 New England Air Quality Study and from ambient canister samples collected throughout the Great Bay estuary in August 2003 are also presented. Comparisons between the alkyl nitrate trends with anthropogenic and marine source fingerprints and tracers suggest that a marine source of alkyl nitrates is not significant in coastal New England. Given the apparent prominence of a secondary source, comparisons between observed and predicted alkyl nitrate/parent hydrocarbon ratios were made which demonstrated that background mixing ratios have a continuous and prevalent influence on the alkyl nitrate distribution.


2010 ◽  
Vol 10 (4) ◽  
pp. 1865-1883 ◽  
Author(s):  
R. S. Russo ◽  
Y. Zhou ◽  
K. B. Haase ◽  
O. W. Wingenter ◽  
E. K. Frinak ◽  
...  

Abstract. Seven C1-C5 alkyl nitrates were measured both on the mainland and off the coast of New Hampshire using gas chromatographic techniques. Five separate data sets are presented to characterize the seasonal and diurnal trends and the major sources and loss processes of these compounds. Based on in situ measurements conducted at the University of New Hampshire (UNH) Atmospheric Observing Station at Thompson Farm (TF) located in southeast NH during winter (January–February) 2002, summer (June–August) 2002, summer (July–August) 2004, and on daily canister samples collected at midday from January 2004–February 2008, the median total alkyl nitrate mixing ratio (ΣRONO2) was 23–25 pptv in winter and 14–16 pptv in summer. During summers 2002 and 2004, MeONO2 decreased overnight and reached minimum hourly average mixing ratios in the early morning. Comparison with wind speed and trace gas trends suggested that dry deposition contributed to the early morning MeONO2 minimum which is a previously unaccounted for removal mechanism. The mean dry deposition rate and velocity of MeONO2 was estimated to be −0.5 nmol m−2 hr−1 and 0.13 cm s−1, respectively. Results from ambient air and surface seawater measurements made onboard the NOAA R/V Ronald H. Brown in the Gulf of Maine during the 2002 New England Air Quality Study and from ambient canister samples collected throughout the Great Bay estuary in August 2003 are also presented. Comparisons between the alkyl nitrate trends with anthropogenic and marine tracers suggest that a marine source of alkyl nitrates is not significant in coastal New England. Given the apparent prominence of a secondary source, comparisons between observed and predicted alkyl nitrate/parent hydrocarbon ratios were made which demonstrated that background mixing ratios have a continuous and prevalent influence on the alkyl nitrate distribution.


2021 ◽  
Author(s):  
Jessica Mary Burger ◽  
Julie Granger ◽  
Emily Joyce ◽  
Meredith Galanter Hastings ◽  
Kurt Angus McDonald Spence ◽  
...  

Abstract. Atmospheric nitrate originates from the oxidation of nitrogen oxides (NOx = NO + NO2) and impacts both tropospheric chemistry and climate. NOx sources, cycling, and NOx to nitrate formation pathways are poorly constrained in remote marine regions, especially the Southern Ocean where pristine conditions serve as a useful proxy for the preindustrial atmosphere. Here, we measured the isotopic composition (δ15N and δ18O) of atmospheric nitrate in coarse-mode (> 1 μm) aerosols collected in the summertime marine boundary layer of the Atlantic Southern Ocean from 34.5° S to 70° S, and across the northern edge of the Weddell Sea. The δ15N-NO3− decreased with latitude from −2.7 ‰ to −43.1 ‰. The decline in δ15N with latitude is attributed to changes in the dominant NOx sources: lightning at the low latitudes, oceanic alkyl nitrates at the mid latitudes, and photolysis of nitrate in snow at the high latitudes. There is no evidence of any influence from anthropogenic NOx sources or equilibrium isotopic fractionation. Using air mass back trajectories and an isotope mixing model, we calculate that oceanic alkyl nitrate emissions have a δ15N signature of −22.0 ‰ ± 7.5 ‰. Given that measurements of alkyl nitrate contributions to remote nitrogen budgets are scarce, this may be a useful tracer for detecting their contribution in other oceanic regions. The δ18O-NO3− was always less than 70 ‰, indicating that daytime processes involving OH are the dominant NOx oxidation pathway during summer. Unusually low δ18O-NO3− values (less than 31 ‰) were observed at the western edge of the Weddell Sea. The air mass history of these samples indicates extensive interaction with sea ice covered ocean, which is known to enhance peroxy radical production. The observed low δ18O-NO3− is therefore attributed to increased exchange of NO with peroxy radicals, which have a low δ18O, relative to ozone, which has a high δ18O. This study reveals that the mid- and high-latitude surface ocean may serve as a more important NOx source than previously thought, and that the ice-covered surface ocean impacts the reactive nitrogen budget as well as the oxidative capacity of the marine boundary layer.


2013 ◽  
Vol 13 (8) ◽  
pp. 20111-20163
Author(s):  
J. E. Williams ◽  
G. Le Bras ◽  
A. Kukui ◽  
H. Ziereis ◽  
C. A. M. Brenninkmeijer

Abstract. The formation, abundance and distribution of organic nitrates are relevant for determining the production efficiency and resident mixing ratios of tropospheric ozone (O3) at both regional and global scales. Here we investigate the effect of applying the recently measured direct chemical production of methyl nitrate (CH3ONO2) during NOx recycling involving the methyl-peroxy radical on the global tropospheric distribution of CH3ONO2 and the perturbations introduced towards tropospheric NOx and O3 using the TM5 global chemistry transport model. By comparing against numerous observations we show that the global surface distribution of CH3ONO2 can be largely explained by introducing the chemical production mechanism using a branching ratio of 0.3%, when assuming a direct oceanic emission source of ~0.29 Tg N yr−1. The resident mixing ratios are found to be highly sensitive towards the dry deposition velocity of CH3ONO2 that is prescribed, where more than 50% of the direct oceanic emission of CH3ONO2 is lost near the source regions thereby mitigating subsequent effects on tropospheric composition due to long range and convective transport. For the higher alkyl nitrates (C2 and above) we find improvements in their simulated distribution in the tropics in TM5 improves when introducing direct oceanic emissions of ~0.17 Tg N yr−1. For the tropical upper troposphere (UT) a significant low model bias for all alkly nitrates occurs due to either missing transport pathways or chemical precursors, although measurements show significant variability in resident mixing ratios at high altitudes with respect to both latitude and longitude. For total reactive nitrogen (NOy) ~20% originates from alkyl nitrates in the tropical and extra-tropical UT, where the introduction of both direct oceanic emission sources and the chemical production of CH3ONO2 only increases NOy by ~5% when compared with aircraft observations. We find that the increases in tropospheric O3 due to direct oceanic emissions are mitigated by introducing the direct chemical production of CH3ONO2 resulting in rather moderate effects on nitrogen oxides and tropospheric O3.


2014 ◽  
Vol 14 (5) ◽  
pp. 2363-2382 ◽  
Author(s):  
J. E. Williams ◽  
G. Le Bras ◽  
A. Kukui ◽  
H. Ziereis ◽  
C. A. M. Brenninkmeijer

Abstract. The formation, abundance and distribution of organic nitrates are relevant for determining the production efficiency and resident mixing ratios of tropospheric ozone (O3) on both regional and global scales. Here we investigate the effect of applying the recently measured direct chemical production of methyl nitrate (CH3ONO2) during NOx recycling involving the methyl-peroxy radical on the global tropospheric distribution of CH3ONO2 and the perturbations introduced towards tropospheric NOx and O3 using the TM5 global chemistry transport model. By comparisons against numerous observations, we show that the global surface distribution of CH3ONO2 can be largely explained by introducing the chemical production mechanism using a branching ratio of 0.3%, when assuming a direct oceanic emission source of ~0.15 Tg N yr−1. On a global scale, the chemical production of CH3ONO2 converts 1 Tg N yr−1 from nitrogen oxide for this branching ratio. The resident mixing ratios of CH3ONO2 are found to be highly sensitive to the dry deposition velocity that is prescribed, where more than 50% of the direct oceanic emission is lost near the source regions, thereby mitigating the subsequent effects due to long-range and convective transport out of the source region. For the higher alkyl nitrates (RONO2) we find improvements in the simulated distribution near the surface in the tropics (10° S–10° N) when introducing direct oceanic emissions equal to ~0.17 Tg N yr−1 . In terms of the vertical profile of CH3ONO2, there are persistent overestimations in the free troposphere and underestimations in the upper troposphere across a wide range of latitudes and longitudes when compared against data from measurement campaigns. This suggests either a missing transport pathway or source/sink term, although measurements show significant variability in resident mixing ratios at high altitudes at global scale. For the vertical profile of RONO2, TM5 performs better at tropical latitudes than at mid-latitudes, with similar features in the comparisons to those for CH3ONO2. Comparisons of CH3ONO2 with a wide range of surface measurements shows that further constraints are necessary regarding the variability in the deposition terms for different land surfaces in order to improve on the comparisons presented here. For total reactive nitrogen (NOy) ~20% originates from alkyl nitrates in the tropics and subtropics, where the introduction of both direct oceanic emissions and the chemical formation mechanism of CH3ONO2 only makes a ~5% contribution to the total alkyl nitrate content in the upper troposphere when compared with aircraft observations. We find that the increases in tropospheric O3 that occur due oxidation of CH3ONO2 originating from direct oceanic emission is negated when accounting for the chemical formation of CH3ONO2, meaning that the impact of such oceanic emissions on atmospheric lifetimes becomes marginal when a branching ratio of 0.3% is adopted.


Author(s):  
Chibuike Chiedozie Ibebuchi

AbstractAtmospheric circulation is a vital process in the transport of heat, moisture, and pollutants around the globe. The variability of rainfall depends to some extent on the atmospheric circulation. This paper investigates synoptic situations in southern Africa that can be associated with wet days and dry days in Free State, South Africa, in addition to the underlying dynamics. Principal component analysis was applied to the T-mode matrix (variable is time series and observation is grid points at which the field was observed) of daily mean sea level pressure field from 1979 to 2018 in classifying the circulation patterns in southern Africa. 18 circulation types (CTs) were classified in the study region. From the linkage of the CTs to the observed rainfall data, from 11 stations in Free State, it was found that dominant austral winter and late austral autumn CTs have a higher probability of being associated with dry days in Free State. Dominant austral summer and late austral spring CTs were found to have a higher probability of being associated with wet days in Free State. Cyclonic/anti-cyclonic activity over the southwest Indian Ocean, explained to a good extent, the inter-seasonal variability of rainfall in Free State. The synoptic state associated with a stronger anti-cyclonic circulation at the western branch of the South Indian Ocean high-pressure, during austral summer, leading to enhanced low-level moisture transport by southeast winds was found to have the highest probability of being associated with above-average rainfall in most regions in Free State. On the other hand, the synoptic state associated with enhanced transport of cold dry air, by the extratropical westerlies, was found to have the highest probability of being associated with (winter) dryness in Free State.


2016 ◽  
Author(s):  
Mike J. Newland ◽  
Patricia Martinerie ◽  
Emmanuel Witrant ◽  
Detlev Helmig ◽  
David R. Worton ◽  
...  

Abstract. The NOX (NO and NO2) and HOX (OH and HO2) budgets of the atmosphere exert a major influence on atmospheric composition, controlling removal of primary pollutants and formation of a wide range of secondary products, including ozone, that can influence human health and climate. However, there remain large uncertainties in the changes to these budgets over recent decades. Due to their short atmospheric lifetimes, NOX and HOX are highly variable in space and time, and so the measurements of these species are of very limited value for examining long term, large scale changes to their budgets. Here, we take an alternative approach by examining long-term atmospheric trends of alkyl nitrates, the formation of which is dependent on the atmospheric NO / HO2 ratio. We derive long term trends in the alkyl nitrates from measurements in firn air from the NEEM site, Greenland. Their mixing ratios increased by a factor of 4–5 between the 1970s and 1990s. This was followed by a steep decline to the sampling date of 2008. Moreover, we examine how the trends in the alkyl nitrates compare to similarly derived trends in their parent alkanes (i.e. the alkanes which, when oxidised in the presence of NOX, lead to the formation of the alkyl nitrates). The ratios of the alkyl nitrates to their parent alkanes increase from around 1970 to the late 1990's consistent with large changes to the [NO] / [HO2] ratio in the northern hemisphere atmosphere during this period. These could represent historic changes to NOX sources and sinks. Alternatively, they could represent changes to concentrations of the hydroxyl radical, OH, or to the transport time of the air masses from source regions to the Arctic.


Elem Sci Anth ◽  
2021 ◽  
Vol 9 (1) ◽  
Author(s):  
María Cazorla ◽  
René Parra ◽  
Edgar Herrera ◽  
Francisco Raimundo da Silva

In this study, we characterize atmospheric ozone over the tropical Andes in the boundary layer, the free troposphere, and the stratosphere; we quantify each contribution to total column ozone, and we evaluate the performance of the multi-sensor reanalysis (MSR2) in the region. Thus, we present data taken in Ecuador and Peru (2014–2019). The contribution from the surface was determined by integrating ozone concentrations measured in Quito and Cuenca (Ecuador) up to boundary layer height. In addition, tropospheric and stratospheric column ozone were quantified from ozone soundings (38) launched from Quito during the study time period. Profiles were compared against soundings at Natal (SHADOZ network) for being the closest observational reference with sufficient data in 2014–2019. Data were also compared against stratospheric mixing ratios from the Aura Microwave Limb Sounder (Aura MLS). Findings demonstrate that the stratospheric component of total column ozone over the Andes (225.2 ± 8.9 Dobson Units [DU]) is at similar levels as those observed at Natal (223.3 ± 8.6 DU), and observations are comparable to Aura MLS data. In contrast, the tropospheric contribution is lower over the Andes (20.2 ± 4.3 DU) when compared to Natal (35.4 ± 6.4 DU) due to a less deep and cleaner troposphere. From sounding extrapolation of Quito profiles down to sea level, we determined that altitude deducts about 5–7 DU from the total column, which coincides with a 3%–4% overestimation of the MSR2 over Quito and Marcapomacocha (Peru). In addition, when MSR2 data are compared along a transect that crosses from the Amazon over Quito, the Ecuadorian coast side, and into the Pacific, observations are not significantly different among the three first locations. Results point to coarse reanalysis resolution not being suitable to resolve the formidable altitude transition imposed by the Andes mountain chain. This work advances our knowledge of atmospheric ozone over the study region and provides a robust time series of upper air measurements for future evaluations of satellite and reanalysis products.


2009 ◽  
Vol 9 (2) ◽  
pp. 8857-8902 ◽  
Author(s):  
A. W. Rollins ◽  
A. Kiendler-Scharr ◽  
J. Fry ◽  
T. Brauers ◽  
S. S. Brown ◽  
...  

Abstract. Alkyl nitrates and secondary organic aerosol (SOA) produced during the oxidation of isoprene by nitrate radicals has been observed in the SAPHIR chamber. We find the yield of nitrates is 70±8% from the isoprene+NO3 reaction, and the yield for secondary dinitrates produced in the reaction of primary isoprene nitrates with NO3 is 40±20%. We find an effective rate constant for reaction of NO3 with the group of first generation oxidation products to be 7×10−14 cm3 s−1. At the low total organic aerosol concentration in the chamber (max ≈0.6 μg m−3) we observed a mass yield (ΔSOA mass/Δisoprene mass) of 2% for the entire 16 h experiment. However a comparison of the timing of the observed SOA production to a box model simulation of first and second generation oxidation products shows that the yield from the first generation products was <0.2% while the further oxidation of the initial products leads to a yield of 10% (defined as ΔSOA/Δisoprene2x where Δisoprene2x is the mass of isoprene which reacted twice with NO3). The SOA yield of 10% is consistent with equilibrium partitioning of highly functionalized C5 products of isoprene oxidation.


2020 ◽  
Vol 13 (3) ◽  
pp. 1055-1073 ◽  
Author(s):  
Kyunghwa Lee ◽  
Jinhyeok Yu ◽  
Sojin Lee ◽  
Mieun Park ◽  
Hun Hong ◽  
...  

Abstract. For the purpose of providing reliable and robust air quality predictions, an air quality prediction system was developed for the main air quality criteria species in South Korea (PM10, PM2.5, CO, O3 and SO2). The main caveat of the system is to prepare the initial conditions (ICs) of the Community Multiscale Air Quality (CMAQ) model simulations using observations from the Geostationary Ocean Color Imager (GOCI) and ground-based monitoring networks in northeast Asia. The performance of the air quality prediction system was evaluated during the Korea-United States Air Quality Study (KORUS-AQ) campaign period (1 May–12 June 2016). Data assimilation (DA) of optimal interpolation (OI) with Kalman filter was used in this study. One major advantage of the system is that it can predict not only particulate matter (PM) concentrations but also PM chemical composition including five main constituents: sulfate (SO42-), nitrate (NO3-), ammonium (NH4+), organic aerosols (OAs) and elemental carbon (EC). In addition, it is also capable of predicting the concentrations of gaseous pollutants (CO, O3 and SO2). In this sense, this new air quality prediction system is comprehensive. The results with the ICs (DA RUN) were compared with those of the CMAQ simulations without ICs (BASE RUN). For almost all of the species, the application of ICs led to improved performance in terms of correlation, errors and biases over the entire campaign period. The DA RUN agreed reasonably well with the observations for PM10 (index of agreement IOA =0.60; mean bias MB =-13.54) and PM2.5 (IOA =0.71; MB =-2.43) as compared to the BASE RUN for PM10 (IOA =0.51; MB =-27.18) and PM2.5 (IOA =0.67; MB =-9.9). A significant improvement was also found with the DA RUN in terms of bias. For example, for CO, the MB of −0.27 (BASE RUN) was greatly enhanced to −0.036 (DA RUN). In the cases of O3 and SO2, the DA RUN also showed better performance than the BASE RUN. Further, several more practical issues frequently encountered in the air quality prediction system were also discussed. In order to attain more accurate ozone predictions, the DA of NO2 mixing ratios should be implemented with careful consideration of the measurement artifacts (i.e., inclusion of alkyl nitrates, HNO3 and peroxyacetyl nitrates – PANs – in the ground-observed NO2 mixing ratios). It was also discussed that, in order to ensure accurate nocturnal predictions of the concentrations of the ambient species, accurate predictions of the mixing layer heights (MLHs) should be achieved from the meteorological modeling. Several advantages of the current air quality prediction system, such as its non-static free-parameter scheme, dust episode prediction and possible multiple implementations of DA prior to actual predictions, were also discussed. These configurations are all possible because the current DA system is not computationally expensive. In the ongoing and future works, more advanced DA techniques such as the 3D variational (3DVAR) method and ensemble Kalman filter (EnK) are being tested and will be introduced to the Korean air quality prediction system (KAQPS).


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