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<journal-meta>
<journal-id journal-id-type="publisher-id">Front. Astron. Space Sci.</journal-id>
<journal-title>Frontiers in Astronomy and Space Sciences</journal-title>
<abbrev-journal-title abbrev-type="pubmed">Front. Astron. Space Sci.</abbrev-journal-title>
<issn pub-type="epub">2296-987X</issn>
<publisher>
<publisher-name>Frontiers Media S.A.</publisher-name>
</publisher>
</journal-meta>
<article-meta>
<article-id pub-id-type="publisher-id">1224659</article-id>
<article-id pub-id-type="doi">10.3389/fspas.2023.1224659</article-id>
<article-categories>
<subj-group subj-group-type="heading">
<subject>Astronomy and Space Sciences</subject>
<subj-group>
<subject>Review</subject>
</subj-group>
</subj-group>
</article-categories>
<title-group>
<article-title>A review of N<sup>&#x2b;</sup> observations in the ionosphere-magnetosphere system</article-title>
<alt-title alt-title-type="left-running-head">Ilie et al.</alt-title>
<alt-title alt-title-type="right-running-head">
<ext-link ext-link-type="uri" xlink:href="https://doi.org/10.3389/fspas.2023.1224659">10.3389/fspas.2023.1224659</ext-link>
</alt-title>
</title-group>
<contrib-group>
<contrib contrib-type="author" corresp="yes">
<name>
<surname>Ilie</surname>
<given-names>Raluca</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="corresp" rid="c001">&#x2a;</xref>
<uri xlink:href="https://loop.frontiersin.org/people/983320/overview"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Lin</surname>
<given-names>Mei-Yun</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1200097/overview"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Bashir</surname>
<given-names>Muhammad Fraz</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/80774/overview"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Majumder</surname>
<given-names>Abhiraj</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<uri xlink:href="https://loop.frontiersin.org/people/2380448/overview"/>
</contrib>
</contrib-group>
<aff id="aff1">
<sup>1</sup>
<institution>Electrical and Computer Engineering Department</institution>, <institution>University of Illinois at Urbana Champaign</institution>, <addr-line>Urbana</addr-line>, <addr-line>IL</addr-line>, <country>United States</country>
</aff>
<aff id="aff2">
<sup>2</sup>
<institution>Department of Earth, Planetary, and Space Sciences</institution>, <institution>University of California, Los Angeles</institution>, <addr-line>Los Angeles</addr-line>, <addr-line>CA</addr-line>, <country>United States</country>
</aff>
<author-notes>
<fn fn-type="edited-by">
<p>
<bold>Edited by:</bold> <ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/1361047/overview">Thomas Earle Moore</ext-link>, Third Rock Research, United States</p>
</fn>
<fn fn-type="edited-by">
<p>
<bold>Reviewed by:</bold> <ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/108556/overview">Octav Marghitu</ext-link>, Space Science Institute, Romania</p>
<p>
<ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/2182007/overview">Naritoshi Kitamura</ext-link>, Nagoya University, Japan</p>
</fn>
<corresp id="c001">&#x2a;Correspondence: Raluca Ilie, <email>rilie@illinois.edu</email>
</corresp>
</author-notes>
<pub-date pub-type="epub">
<day>04</day>
<month>10</month>
<year>2023</year>
</pub-date>
<pub-date pub-type="collection">
<year>2023</year>
</pub-date>
<volume>10</volume>
<elocation-id>1224659</elocation-id>
<history>
<date date-type="received">
<day>18</day>
<month>05</month>
<year>2023</year>
</date>
<date date-type="accepted">
<day>20</day>
<month>09</month>
<year>2023</year>
</date>
</history>
<permissions>
<copyright-statement>Copyright &#xa9; 2023 Ilie, Lin, Bashir and Majumder.</copyright-statement>
<copyright-year>2023</copyright-year>
<copyright-holder>Ilie, Lin, Bashir and Majumder</copyright-holder>
<license xlink:href="http://creativecommons.org/licenses/by/4.0/">
<p>This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.</p>
</license>
</permissions>
<abstract>
<p>Most studies have yet to consider and assess the transport and energization of N<sup>&#x2b;</sup> ions throughout the ionosphere-magnetosphere system, in addition to that of O<sup>&#x2b;</sup> and other heavy ion species. The limited observational record of N<sup>&#x2b;</sup> presence in near-Earth plasma, partly due to instrument limitations to distinguish ion species of similar masses, has obscured its significant contribution to the near-Earth plasma. This letter reviews the most notable observations of N<sup>&#x2b;</sup> ions, starting from the early low altitude measurements from Sputnik III in the ionosphere to the measurements reported by the Enhanced Polar Outflow Probe (e-POP) mission. The available observational data set suggests that nitrogen ions are constant companions of outflowing oxygen ions, and their abundances vary with season, solar cycle, time of day, and geomagnetic activity. This strong record of nitrogen presence in the ionosphere-magnetosphere system raises the question of ionic composition and the need for caution when interpreting O<sup>&#x2b;</sup> measurements from current missions.</p>
</abstract>
<kwd-group>
<kwd>ionospheric composition</kwd>
<kwd>magnetospheric composition</kwd>
<kwd>nitrogen ions</kwd>
<kwd>observations</kwd>
<kwd>heavy ions</kwd>
</kwd-group>
<custom-meta-wrap>
<custom-meta>
<meta-name>section-at-acceptance</meta-name>
<meta-value>Space Physics</meta-value>
</custom-meta>
</custom-meta-wrap>
</article-meta>
</front>
<body>
<sec sec-type="intro" id="s1">
<title>1 Introduction</title>
<p>The energization and subsequent vertical transport of H<sup>&#x2b;</sup>, He<sup>&#x2b;</sup>, and O<sup>&#x2b;</sup> ions from the high latitude ionosphere to the terrestrial magnetosphere has been an active area of research in the last several decades (<xref ref-type="bibr" rid="B52">Schunk and Raitt, 1980</xref>; <xref ref-type="bibr" rid="B43">Mukai et al., 1994</xref>; <xref ref-type="bibr" rid="B53">Schunk and Sojka, 1997</xref>; <xref ref-type="bibr" rid="B19">Daglis et al., 1999</xref>; <xref ref-type="bibr" rid="B64">Winglee et al., 2002</xref>; <xref ref-type="bibr" rid="B45">Nos&#xe9; et al., 2005</xref>; <xref ref-type="bibr" rid="B1">Barakat and Schunk, 2006</xref>; <xref ref-type="bibr" rid="B21">Glocer et al., 2009</xref>; <xref ref-type="bibr" rid="B20">Garcia et al., 2010</xref>; <xref ref-type="bibr" rid="B34">Ilie et al., 2013</xref>; <xref ref-type="bibr" rid="B33">Ilie et al., 2015</xref>). However, the energization, circulation, and redistribution of N<sup>&#x2b;</sup>, in addition to that of O<sup>&#x2b;</sup>, has received less attention, even though several direct and indirect measurements (<xref ref-type="bibr" rid="B2">Bashir and Ilie, 2018</xref>; <xref ref-type="bibr" rid="B3">Bashir and Ilie, 2021</xref>) have confirmed that N<sup>&#x2b;</sup> plays a crucial role in the near-Earth plasma dynamics.</p>
<p>The first ionospheric measurements of upflowing nitrogen ions were reported as early as 1961 by the Sputnik III mission. The existing observational record spans six solar cycles and consists of measurements spanning a wide range of altitudes, from <inline-formula id="inf1">
<mml:math id="m1">
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<mml:mn>200</mml:mn>
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</inline-formula> km from the Sputnik III to millions of km from the WIND mission. <xref ref-type="fig" rid="F1">Figure 1</xref> compiles the temporal and spatial coverage of these measurements, along with the reported N<sup>&#x2b;</sup> to O<sup>&#x2b;</sup> ratio. These observations indicate vast variations in the N<sup>&#x2b;</sup> to O<sup>&#x2b;</sup> ratio, ranging from less than 0.1 to supra-unitary. Albeit limited (and likely inconclusive), observational studies based on high-altitude measurements report on larger N<sup>&#x2b;</sup> to O<sup>&#x2b;</sup> ratio, as seen in <xref ref-type="fig" rid="F1">Figure 1</xref>.</p>
<fig id="F1" position="float">
<label>FIGURE 1</label>
<caption>
<p>Top panel: Spacecraft trajectories for missions that reported a N<sup>&#x2b;</sup> to O<sup>&#x2b;</sup> ratio (see <xref ref-type="table" rid="T1">Table 1</xref>) differentiated by altitude: low-altitude (left), mid-altitude (center), and high-altitude (right). Middle panel: Sunspot number from 1958 to 2022 (green line) indicative of solar cycles 19 through 24. The &#x201c;nitrogen measuring&#x201d; missions and the corresponding operation time are represented by horizontal bars. Note that the actual data availability for N<sup>&#x2b;</sup> covers a time window less than the mission lifetime (as seen in the top panel). Bottom panel: The N<sup>&#x2b;</sup> to O<sup>&#x2b;</sup> density ratio reported based on mission-specific measurements. The color bar represents the reported range of the N<sup>&#x2b;</sup> to O<sup>&#x2b;</sup> ratio.</p>
</caption>
<graphic xlink:href="fspas-10-1224659-g001.tif"/>
</fig>
<p>However, the N<sup>&#x2b;</sup> to O<sup>&#x2b;</sup> density ratio has been reported to vary not only with the solar cycle but also with the season, geomagnetic activity, latitude, magnetic local time (MLT), and time of day. These variations imply that N <sup>&#x2b;</sup> and O <sup>&#x2b;</sup> obey different chemical and energization processes as they are lofted from the ionosphere and possibly follow different paths of energization as they convect and drift throughout the magnetosphere. Therefore, their differential transport and circulation depend not only on the external drivers but also on the local atmospheric conditions.</p>
<p>Instruments onboard most space missions could not reliably separate the N<sup>&#x2b;</sup> from O<sup>&#x2b;</sup>, and relatively few currently active ion spectrometers in space have the appropriate mass resolution to distinguish between these two ion species. Therefore, the separate observational record of N<sup>&#x2b;</sup> has been overlooked. These satellite-borne ion composition observations reveal several essential features attributable to &#x201c;non-classical&#x201d; acceleration mechanisms, i.e., centrifugal acceleration due to field line convection and curvature changes, transverse heating of ions as a result of wave-particle interactions, ponderomotive forces of Alfv&#xe9;n waves or Field Aligned Currents (FACs) driving the parallel electric field, and low altitude frictional heating <xref ref-type="bibr" rid="B47">Peterson et al. (1994)</xref>; <xref ref-type="bibr" rid="B66">Yau et al. (2007)</xref>. Therefore, questions regarding the relative contribution of the different sources of the high-altitude ionospheric outflow remain unanswered. In this letter, we review the most notable observations of nitrogen ions in the ionosphere-magnetosphere system to provide the reader with the context of these observations while emphasizing the need to develop instrumentation capable of distinguishing between O<sup>&#x2b;</sup> and N<sup>&#x2b;</sup> ions.</p>
</sec>
<sec id="s2">
<title>2 Production and loss of nitrogen ions in the ionosphere</title>
<p>There are several possible mechanisms responsible for producing N<sup>&#x2b;</sup> in the sunlit ionosphere: dissociative ionization of N<sub>2</sub> by photons or photo-electrons, charge transfer reactions between <inline-formula id="inf2">
<mml:math id="m2">
<mml:msubsup>
<mml:mrow>
<mml:mi mathvariant="normal">N</mml:mi>
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</inline-formula> and N, and dissociative charge transfer reactions between He<sup>&#x2b;</sup> and N<sub>2</sub>. On the other hand, nitrogen ions are lost through interactions with atomic and molecular oxygen (<xref ref-type="bibr" rid="B38">Lin et al., 2020</xref>). It is important to note that the dissociation energy of N<sub>2</sub> is different from that of O<sub>2</sub> (9.8 eV vs. 5.2 eV binding energy). Also, the ionization energies of nitrogen and oxygen (15.581 eV vs. 12.069 eV) are different. These differences dictate independent photo-chemical processes responsible for producing and losing N<sup>&#x2b;</sup> and O<sup>&#x2b;</sup>, but also distinct escape scenarios.</p>
<p>This section presents the altitude profiles of production and loss processes for N<sup>&#x2b;</sup> ions from 200 to 2,500 km altitude in the polar ionosphere. These are derived from hybrid simulations using the Seven Ion Polar Wind Outflow Model (7iPWOM) (<xref ref-type="bibr" rid="B38">Lin et al., 2020</xref>), and the solution is based on the combined hydrodynamic approximation below 1,000 km altitude and particle-in-cell approach above 1,000 km altitude. Since solar activity is known to alter the density profiles of atmospheric neutrals, as well as the photo- and secondary electron spectra (<xref ref-type="bibr" rid="B56">Solomon et al., 1988</xref>), we present here the steady-state simulation results for summer solstice, both for Solar Maximum conditions (F10.7 &#x3d; 180 &#xd7; 10<sup>&#x2212;22</sup> WHz/m<sup>2</sup>), as well as for Solar Minimum (F10.7 &#x3d; 80 &#xd7; 10<sup>&#x2212;22</sup> WHz/m<sup>2</sup>), as shown in <xref ref-type="fig" rid="F2">Figure 2</xref>. For both cases, the solution is based on a steady-state numerical simulation for which the magnetic field lines originated at 80&#xb0; latitude and 12 MLT in the northern hemisphere. The neutral densities are obtained from NRLMSISE-00 empirical model (<xref ref-type="bibr" rid="B49">Picone et al., 2002</xref>), while neutral NO, NO(<sup>2</sup>D), N(<sup>2</sup>D), and N(<sup>4</sup>S) densities are retrieved from the Global Ionosphere Thermosphere Model (GITM) (<xref ref-type="bibr" rid="B51">Ridley et al., 2006</xref>). It is important to note that the neutral densities, in particular the density of neutral hydrogen, are of great importance for determining the global fluence of ionospheric outflow as the ionosphere and thermosphere are strongly coupled through the resonant charge exchange reactions between ionospheric ions and the colocated neutral hydrogen population. For instance, the supply of H<sup>&#x2b;</sup> to the ionosphere is limited by the local distribution of hydrogen density. However, there is controversy regarding the available supply of neutral hydrogen; studies report that the predicted neutral H density by the NRLMSISE-00 model is either overestimated by as much as &#x223c;36%&#x2013;67% (<xref ref-type="bibr" rid="B59">Waldrop and Paxton, 2013</xref>) or underestimated by as much as a factor of two (<xref ref-type="bibr" rid="B46">Nossal et al., 2012</xref>; <xref ref-type="bibr" rid="B37">Kotov et al., 2018</xref>). Furthermore, the density of hydrogen in the upper thermosphere is reported to vary with the solar cycle and is reported to be larger during solar minimum conditions as compared to solar maximum (<xref ref-type="bibr" rid="B50">Qian et al., 2018</xref>). Therefore, the production and loss rates presented in <xref ref-type="fig" rid="F2">Figure 2</xref> are only intended to provide context for the chemistry involving N<sup>&#x2b;</sup> ions in the high-latitude terrestrial ionosphere and are not representative of all conditions.</p>
<fig id="F2" position="float">
<label>FIGURE 2</label>
<caption>
<p>Chemical reactions leading to the N<sup>&#x2b;</sup> production (colored lines) and loss (grey lines) between 200 and 2,500 km altitude range, based on the 7iPWOM simulation results for Solar Maximum (middle row) and Minimum (bottom row) summer noon conditions. The top diagram shows the chemical reactions responsible for the production and loss of N<sup>&#x2b;</sup> ions, where the thickness of the arrows represents the magnitude of reaction rates (cm<sup>&#x2212;3</sup>s<sup>&#x2212;1</sup>).</p>
</caption>
<graphic xlink:href="fspas-10-1224659-g002.tif"/>
</fig>
<p>The top panel in <xref ref-type="fig" rid="F2">Figure 2</xref> lists the chemical reactions contributing to the production and loss of N<sup>&#x2b;</sup> ions, based on the reaction rates published in <xref ref-type="bibr" rid="B38">Lin et al. (2020)</xref>. Each of the ion species involved in the ion-neutral-electron collisions is shown in colored text: O<sup>&#x2b;</sup> (blue), N<sup>&#x2b;</sup> (orange), He<sup>&#x2b;</sup> (dark green), H<sup>&#x2b;</sup> (light green), <inline-formula id="inf3">
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</inline-formula> (dark red), NO<sup>&#x2b;</sup> (purple), and <inline-formula id="inf4">
<mml:math id="m4">
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</inline-formula> (brown). e&#x2a; and h<italic>&#x3bd;</italic> denote the suprathermal electrons (SE) and photons that produce N<sup>&#x2b;</sup> ions. The orange arrows represent the production of N<sup>&#x2b;</sup> ions through chemical reactions, while the grey arrows denote reactions through which N<sup>&#x2b;</sup> is being lost. The thickness of these arrows indicates the efficiency of the reaction to produce or lose N<sup>&#x2b;</sup> ions, i.e., thicker arrows indicate chemical reactions that are most efficient to produce or lose this species, as derived from the specific reaction rate. The middle and bottom panels of <xref ref-type="fig" rid="F2">Figure 2</xref> show the production (orange lines) and loss profiles (grey lines) of N<sup>&#x2b;</sup> ions during Solar Maximum (center panel) and Solar Minimum (bottom panel) conditions.</p>
<p>The Suprathermal Electron(SE) production (solid orange line) and the charge exchange between neutral N(<sup>2</sup>D) species (orange &#x2b; symbol line) dominate the production of N<sup>&#x2b;</sup> ions at altitudes between 200 and 2,500 km. In contrast, N<sup>&#x2b;</sup> ions are lost via charge exchange reactions with neutral NO (grey <italic>Y</italic> symbol line) and neutral O (grey &#x2b; symbol line) in the low-altitude F2 region, while the dissociative recombination with electrons (solid grey line) and charge exchange with neutral H species (grey triangle line) take over the loss of N<sup>&#x2b;</sup> ions in the high-altitude region. In addition, the production and loss profiles indicate that the interplay between O<sup>&#x2b;</sup>, N<sup>&#x2b;</sup>, and molecular ions via ionospheric chemistry is critical to determining the budget of heavy ions in the low-altitude region. The production rates of molecular <inline-formula id="inf5">
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</inline-formula> and NO<sup>&#x2b;</sup> ions via charge exchange between N<sup>&#x2b;</sup> and neutral NO (grey <italic>Y</italic> symbol line) are comparable with that of N<sup>&#x2b;</sup> production via SE (solid orange line) below 1,000 km altitude. This implies that the abundances of N<sup>&#x2b;</sup> ions in the ionosphere are regulated by those of <inline-formula id="inf6">
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</inline-formula> and NO<sup>&#x2b;</sup> in the low-altitude region.</p>
<p>Although the primary reactions to produce and lose N<sup>&#x2b;</sup> ions are similar between Solar Maximum and Minimum conditions, the relative contributions of these reactions change under different solar activities, especially the SE production rate. For example, the loss rate of N<sup>&#x2b;</sup> ions via charge exchange with neutral H is larger than the production rates of N<sup>&#x2b;</sup> via SE production above 1,500 km altitude during Solar Maximum. However, this transition occurs at around 1,000 km altitude during Solar Minimum conditions. These variations in the production and loss altitude profiles hint at a dynamic interplay between all ionospheric species at lower altitudes, significantly altering the peak production rates for N<sup>&#x2b;</sup> for various conditions. In addition, the abundances of N<sup>&#x2b;</sup> ions in the polar ionosphere are mainly controlled by the SE production rate, therefore hinting at a possible connection between N<sup>&#x2b;</sup> density and solar driving via the F10.7 index. Furthermore, the N<sup>&#x2b;</sup> production rates during Solar Minimum conditions dominate up to 1,000 km altitude. In contrast, during Solar Maximum conditions, the SE production and the charge exchange between neutral N(<sup>2</sup>D) species are most effective below 500 km altitude. This suggests that N<sup>&#x2b;</sup> ions might have extended lifetimes during Solar Minimum compared to Solar Maximum conditions.</p>
</sec>
<sec id="s3">
<title>3 Observations of nitrogen ions in the ionosphere</title>
<p>The first direct measurements of ionic composition in the topside ionosphere came from the Bennett type Radio Frequency (RF) quadrupole mass spectrometer onboard the Soviet Sputnik III satellite (<xref ref-type="bibr" rid="B35">Istomin, 1961</xref>). Sputnik III was launched on 15 May 1958, to study the upper atmosphere and the near-Earth space, on an orbit with 65.18&#xb0; inclination, spanning space from 217 km to 1,864 km altitude, and re-entered the atmosphere in 1960. The mass spectrometer it carried provided measurements of ions with masses between 6 and 48 atomic mass units. <xref ref-type="fig" rid="F3">Figure 3</xref> shows the first measurements of N<sup>&#x2b;</sup> and <inline-formula id="inf7">
<mml:math id="m7">
<mml:msubsup>
<mml:mrow>
<mml:mi mathvariant="normal">N</mml:mi>
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</inline-formula> ions up to 500 km.</p>
<fig id="F3" position="float">
<label>FIGURE 3</label>
<caption>
<p>First direct mass spectrometric measurements showing the altitude profile of positive ions of molecular (black line) and atomic nitrogen (orange line) in the atmosphere. Figure digitized and adapted from <xref ref-type="bibr" rid="B35">Istomin (1961)</xref>.</p>
</caption>
<graphic xlink:href="fspas-10-1224659-g003.tif"/>
</fig>
<p>These measurements indicated that at lower altitudes, below 150 km, the abundance of N<sup>&#x2b;</sup> is somewhat small, with N<sup>&#x2b;</sup> densities being less than 10<sup>2</sup> cm<sup>&#x2212;3</sup>; however, as the altitude increases, the N<sup>&#x2b;</sup> density increases rapidly by 2&#x2013;3 orders of magnitude. While the abundances of <inline-formula id="inf8">
<mml:math id="m8">
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</inline-formula> ions are a small fraction compared with those of the N<sup>&#x2b;</sup> component of the ionosphere, <inline-formula id="inf9">
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</mml:msubsup>
</mml:math>
</inline-formula> plays a crucial role in the overall ionization balance of the ionosphere (<xref ref-type="bibr" rid="B35">Istomin, 1961</xref>). This is because O<sup>&#x2b;</sup> is primarily produced from atomic oxygen, while N<sup>&#x2b;</sup> is formed via <inline-formula id="inf10">
<mml:math id="m10">
<mml:msubsup>
<mml:mrow>
<mml:mi mathvariant="normal">N</mml:mi>
</mml:mrow>
<mml:mrow>
<mml:mn>2</mml:mn>
</mml:mrow>
<mml:mrow>
<mml:mo>&#x2b;</mml:mo>
</mml:mrow>
</mml:msubsup>
</mml:math>
</inline-formula> dissociation, based on the different chemical binding energies of O<sub>2</sub> and N<sub>2</sub>.</p>
<p>The first U.S.-led detailed experimental study of atmospheric composition was based on data from the R.F. ion spectrometer onboard Polar Orbiting Geophysical Observatory (OGO 2), designed to measure thermal ions in the mass range of 1&#x2013;45 amu. <xref ref-type="fig" rid="F4">Figure 4</xref> shows the concentrations of H<sup>&#x2b;</sup>, He<sup>&#x2b;</sup>, N<sup>&#x2b;</sup>, and O<sup>&#x2b;</sup> ions as a function of dipole latitude and altitude (<xref ref-type="bibr" rid="B57">Taylor et al., 1968</xref>), as measured by OGO 2 on 15 October 1965 (quiet time, Dst &#x2208; [0, 2] nT) at dawn (panel a) and dusk (panel b). These measurements show that heavy ions dominate the atmospheric composition in the high latitude regions, while lighter ions prevail in the equatorial region. Furthermore, ion concentrations exhibit these high latitude variabilities both at dawn and at dusk local times. However, these observations not only showed evidence of latitudinal variation in the exospheric ion composition but also that N<sup>&#x2b;</sup> ions become significantly important at high latitudes, in the polar and auroral regions, where they can exceed the He<sup>&#x2b;</sup> abundances, and sometimes even the H<sup>&#x2b;</sup> (<xref ref-type="bibr" rid="B6">Brinton et al., 1968</xref>) density. Panel c) shows the N<sup>&#x2b;</sup> to O<sup>&#x2b;</sup> ratio, also as a function of dipole latitude and altitude. During the dusk pass, spacecraft measurements indicate that the <italic>N</italic>
<sup>&#x2b;</sup>/<italic>O</italic>
<sup>&#x2b;</sup> is significantly higher than during the dawn pass, showing over one order of magnitude difference between the two data sets. This is mainly due to the different sampling altitudes between dusk (&#x223c;1,300&#x2013;2,000 km) vs. dawn (&#x223c;400&#x2013;900 km). Furthermore, during the dusk pass (at a sampling altitude between &#x223c;1,300&#x2013;1,700 km), above 60&#xb0; latitude in the northern hemisphere, the <italic>N</italic>
<sup>&#x2b;</sup>/<italic>O</italic>
<sup>&#x2b;</sup> &#x2208; [0.2, 0.6], while measurements taken during the dusk pass (at a sampling altitude between &#x223c;600&#x2013;800 km) yield a <italic>N</italic>
<sup>&#x2b;</sup>/<italic>O</italic>
<sup>&#x2b;</sup> around 0.1.</p>
<fig id="F4" position="float">
<label>FIGURE 4</label>
<caption>
<p>Global distribution of ion composition observed by OGO 2 between 0111 (dawn - panel a) and 0256 UT (dusk -panel b) on 15 October 1965, showing the concentrations of H<sup>&#x2b;</sup> (light green), He<sup>&#x2b;</sup> (dark green), N<sup>&#x2b;</sup>(orange) and O<sup>&#x2b;</sup> (blue) ions as a function of dipole latitude and altitude. Panel <bold>(C)</bold> shows the <italic>N</italic>
<sup>&#x2b;</sup>/<italic>O</italic>
<sup>&#x2b;</sup>, based on measurements shown in <bold>(A)</bold> and <bold>(B)</bold>. Figure digitized and adapted from <xref ref-type="bibr" rid="B57">Taylor et al. (1968)</xref>.</p>
</caption>
<graphic xlink:href="fspas-10-1224659-g004.tif"/>
</fig>
<p>These measurements were also confirmed by the mass spectrometer data from the Explorer 31 (DME-A) satellite, which showed that N<sup>&#x2b;</sup> is a significant ionospheric constituent, often exceeding He<sup>&#x2b;</sup> in concentration (<xref ref-type="bibr" rid="B25">Hoffman, 1967</xref>). <xref ref-type="fig" rid="F5">Figure 5</xref> shows the ion concentration profiles during 15 August 1966 (quiet time), as measured by Explorer 31. N<sup>&#x2b;</sup> density was reported to vary between 5% and 30% of that of O<sup>&#x2b;</sup>, while H<sup>&#x2b;</sup> abundances were reported to be only 5% of the O<sup>&#x2b;</sup> concentration at these altitudes. These observational data sets suggest that, even during solar minimum conditions and geomagnetically quiet times, N<sup>&#x2b;</sup> ions are the second most abundant ion species found in the Earth&#x2019;s ionosphere (<xref ref-type="bibr" rid="B28">Hoffman, 1970</xref>), findings aligned and confirmed by earlier measurements (<xref ref-type="bibr" rid="B35">Istomin, 1961</xref>; <xref ref-type="bibr" rid="B29">Holmes et al., 1965</xref>).</p>
<fig id="F5" position="float">
<label>FIGURE 5</label>
<caption>
<p>Explorer 31 measurements of ion concentration vs. altitude and latitude: H<sup>&#x2b;</sup> (light green), N<sup>&#x2b;</sup>(orange), and O<sup>&#x2b;</sup> (blue). Figure digitized and adapted from <xref ref-type="bibr" rid="B28">Hoffman (1970)</xref>.</p>
</caption>
<graphic xlink:href="fspas-10-1224659-g005.tif"/>
</fig>
<p>Similarly, Explorer 32 (Atmosphere Explorer-B or AE-B), launched on 25 May 1966, was designed to measure temperatures, composition, densities, and pressures in the topside ionosphere. The spacecraft carried a Bennett RF ion spectrometer, which measured the abundances of thermal positive ions of 1&#x2013;4 and 12&#x2013;19 amu. Based on measurements collected during the 10-month-long lifespan of the spacecraft, a global study of the diurnal variation of the atmosphere revealed substantial altitude variations of ion composition between 58&#xb0; and 71&#xb0; geomagnetic latitude. In addition, measurements at altitudes between 500 and 1,500 km and during geomagnetically active times reported that the abundances of O<sup>&#x2b;</sup> and N<sup>&#x2b;</sup> ions were a factor of &#x223c;2.5 higher than during geomagnetically quiet times (<xref ref-type="bibr" rid="B5">Brinton et al., 1971</xref>).</p>
<p>The second satellite launched under the NASA International Satellite for Ionospheric Studies (ISIS) program, ISIS-2, was deployed on 1 April 1971, into an 88.1&#xb0; prograde orbit with apogee and perigee of 1,440 and 1,360 km, respectively. ISIS-2 carried out an Ion Mass Spectrometer (IMS) experiment designed to measure the composition and distribution of positive ions in the terrestrial ionosphere in the mass range of 1&#x2013;64 amu (<xref ref-type="bibr" rid="B28">Hoffman, 1970</xref>). The first measurements from the IMS instrument (<xref ref-type="bibr" rid="B26">Hoffman et al., 1974</xref>) showed significant variations in ion composition, particularly in the night-side equatorial region and in the daytime poleward of the plasmapause region. It was recorded that during daytime (summer conditions), above 20&#xb0; latitude, the O<sup>&#x2b;</sup> ion is the dominant species, and its abundance remains constant to the pole. The density of N<sup>&#x2b;</sup> ions consistently varies together with the density of O<sup>&#x2b;</sup> at roughly one order of magnitude lower concentration, except at mid to low latitudes, where the ratio of O<sup>&#x2b;</sup>/N<sup>&#x2b;</sup> is &#x223c;20. It is noted that the same ratio approaches &#x223c;3 on each side of the equatorial maximum abundance of O<sup>&#x2b;</sup> on the night-side. These features seem typical during undisturbed conditions (<xref ref-type="bibr" rid="B26">Hoffman et al., 1974</xref>) and in line with previous measurements.</p>
<p>During geomagnetically active times, the picture changes significantly. <xref ref-type="fig" rid="F6">Figure 6</xref> shows the ionic concentrations based on IMS observations during the double-dip geomagnetic storm of 4 August 1972, which recorded a minimum Dst of &#x2212;125 nT and a Kp &#x3d; 9. Measurements during the times when the Kp index reached the maximum value show that the N<sup>&#x2b;</sup> ion becomes the dominant outflowing species at 1,400 km, from 55&#xb0; latitude towards the pole (<xref ref-type="bibr" rid="B26">Hoffman et al., 1974</xref>). In addition, large concentrations (<inline-formula id="inf11">
<mml:math id="m11">
<mml:mo>&#x223c;</mml:mo>
<mml:mn>1</mml:mn>
<mml:msup>
<mml:mrow>
<mml:mn>0</mml:mn>
</mml:mrow>
<mml:mrow>
<mml:mn>3</mml:mn>
</mml:mrow>
</mml:msup>
</mml:math>
</inline-formula> cm<sup>&#x2212;3</sup>) of molecular ion species, such as <inline-formula id="inf12">
<mml:math id="m12">
<mml:msubsup>
<mml:mrow>
<mml:mi mathvariant="normal">N</mml:mi>
</mml:mrow>
<mml:mrow>
<mml:mn>2</mml:mn>
</mml:mrow>
<mml:mrow>
<mml:mo>&#x2b;</mml:mo>
</mml:mrow>
</mml:msubsup>
</mml:math>
</inline-formula>, NO<sup>&#x2b;</sup>, and <inline-formula id="inf13">
<mml:math id="m13">
<mml:msubsup>
<mml:mrow>
<mml:mi mathvariant="normal">O</mml:mi>
</mml:mrow>
<mml:mrow>
<mml:mn>2</mml:mn>
</mml:mrow>
<mml:mrow>
<mml:mo>&#x2b;</mml:mo>
</mml:mrow>
</mml:msubsup>
</mml:math>
</inline-formula>, are also observed at these times. During a similar event, measurements reported significant enhancements of N<sub>2</sub> at high altitudes, which could potentially provide the source of N<sup>&#x2b;</sup> and <inline-formula id="inf14">
<mml:math id="m14">
<mml:msubsup>
<mml:mrow>
<mml:mi mathvariant="normal">N</mml:mi>
</mml:mrow>
<mml:mrow>
<mml:mn>2</mml:mn>
</mml:mrow>
<mml:mrow>
<mml:mo>&#x2b;</mml:mo>
</mml:mrow>
</mml:msubsup>
</mml:math>
</inline-formula>, and therefore leading to the enhancement in their concentrations. The increase in the densities of molecular ion species during geomagnetically active times suggests that additional electrodynamic processes are required to explain the energization of these heavy ions, which under quiet conditions might go undetected (<xref ref-type="bibr" rid="B63">Wilson and Craven, 1998</xref>).</p>
<fig id="F6" position="float">
<label>FIGURE 6</label>
<caption>
<p>ISIS 2 measurements of ion composition during August 1972 storm showing increased N<sup>&#x2b;</sup> (orange), O<sup>&#x2b;</sup> (blue) and molecular ions species abundances at 1,400 km. Figure digitized and adapted from <xref ref-type="bibr" rid="B26">Hoffman et al. (1974)</xref>.</p>
</caption>
<graphic xlink:href="fspas-10-1224659-g006.tif"/>
</fig>
<p>Furthermore, the Akebono spacecraft (launched on 22 February 1989) carried the Suprathermal Ion Mass Spectrometer (SMS) (<xref ref-type="bibr" rid="B61">Whalen et al., 1990</xref>), which sampled the two-dimensional thermal (0&#x2013;25.5 eV) and suprathermal (55 eV/q-4.1 keV/q) ion energy distributions in the satellite spin plane. SMS measurements (<xref ref-type="bibr" rid="B61">Whalen et al., 1990</xref>) also confirmed the presence of N<sup>&#x2b;</sup> above the ionosphere. Spin averaged data taken on 7 November 1989, when the satellite was at 5,000 km in the southern hemisphere auroral zone near local noon, revealed the existence of a peak near <italic>m</italic>/<italic>q</italic> &#x3d; 16 with a noticeable shoulder on the lower mass side. Inspection of the high-resolution data indicated that in fact both N<sup>&#x2b;</sup> and O<sup>&#x2b;</sup> ions were present at this time and with a O<sup>&#x2b;</sup>/N<sup>&#x2b;</sup> density ratio of <inline-formula id="inf15">
<mml:math id="m15">
<mml:mo>&#x223c;</mml:mo>
<mml:mn>2</mml:mn>
</mml:math>
</inline-formula>.</p>
<p>Furthermore, cold atomic N<sup>&#x2b;</sup>, and molecular <inline-formula id="inf16">
<mml:math id="m16">
<mml:msubsup>
<mml:mrow>
<mml:mi mathvariant="normal">N</mml:mi>
</mml:mrow>
<mml:mrow>
<mml:mn>2</mml:mn>
</mml:mrow>
<mml:mrow>
<mml:mo>&#x2b;</mml:mo>
</mml:mrow>
</mml:msubsup>
</mml:math>
</inline-formula> and NO<sup>&#x2b;</sup> species have been measured by the CASSIOPE Enhanced Polar Outflow Probe (e-POP) mission data (<xref ref-type="bibr" rid="B68">Yau et al., 2009</xref>), and these observations suggest that N<sup>&#x2b;</sup> can contribute up to 10%&#x2013;50% to the plasma density at all times, independent of geomagnetic activity (<xref ref-type="bibr" rid="B65">Yau et al., 2019</xref>).</p>
</sec>
<sec id="s4">
<title>4 Observations of nitrogen ions in the magnetosphere</title>
<p>The ionosphere and the solar wind constitute the mass and energy source for the terrestrial magnetosphere. At the same time, the ionosphere is the primary supply of cold plasma to the plasmasphere and also a critical source for the plasmasheet population (e.g., <xref ref-type="bibr" rid="B55">Shelley et al., 1972</xref>; <xref ref-type="bibr" rid="B13">Cladis, 1988</xref>; <xref ref-type="bibr" rid="B30">Horwitz et al., 1990</xref>; <xref ref-type="bibr" rid="B54">Seki et al., 2015</xref>; <xref ref-type="bibr" rid="B36">Kistler et al., 2016</xref>; <xref ref-type="bibr" rid="B60">Welling and Liemohn, 2016</xref>), and a sufficient reservoir for the magnetosphere under any geomagnetic condition (<xref ref-type="bibr" rid="B9">Chappell et al., 1987</xref>). The first discovery of nitrogen ions (both N<sup>&#x2b;</sup> and N<sup>&#x2b;&#x2b;</sup>) in the magnetosphere was made by the Dynamic Explorer 1 (DE-1) (<xref ref-type="bibr" rid="B8">Chappell et al., 1982</xref>) mission, which carried the first mass spectrometer that could resolve masses near O<sup>&#x2b;</sup> peak in the mass spectrum, with a projected mass resolution <italic>&#x3b4;m</italic>/<italic>m</italic> &#x3d; 3%. The Retarding Ion Mass Spectrometer (RIMS) Experiment onboard the DE-1 satellite measured ions with a mass between 1 and 32 amu and energies ranging from 0 to 50 eV. During the moderate geomagnetic storm of 30 December 1981 (when the Kp index reached a maximum of 6), the RIMS instrument recorded the presence of N<sup>&#x2b;</sup> and N<sup>&#x2b;&#x2b;</sup> in the 04 to 16 MLT sector in the magnetosphere. <xref ref-type="fig" rid="F7">Figure 7</xref>, adapted and digitized from (<xref ref-type="bibr" rid="B8">Chappell et al., 1982</xref>), shows the mass spectra measured in the high mass channel for two time periods: when the spacecraft was in the plasmasphere (solid line for measurements taken at 10:06 UT) and in the polar cap (dashed line at 07:37 UT). It is noted that the N<sup>&#x2b;</sup> and O<sup>&#x2b;</sup> peaks are clearly resolved in both cases, while no He<sup>&#x2b;</sup> counts are being recorded during both these times. Measurements from 30 December 1981, show cold (<inline-formula id="inf17">
<mml:math id="m17">
<mml:mo>&#x3c;</mml:mo>
<mml:mn>30</mml:mn>
</mml:math>
</inline-formula> eV) N<sup>&#x2b;</sup> ions outflowing from the polar ionosphere up to 3 <italic>R</italic>
<sub>
<italic>E</italic>
</sub> altitude in the polar cap (<xref ref-type="bibr" rid="B8">Chappell et al., 1982</xref>), with density profiles similar to the ones of O<sup>&#x2b;</sup>. The recorded fluxes of N<sup>&#x2b;</sup> are 5%&#x2013;10% of those of O<sup>&#x2b;</sup>, also in agreement with previous measurements and supporting evidence that N<sup>&#x2b;</sup> is a constant companion of O<sup>&#x2b;</sup> (<xref ref-type="bibr" rid="B16">Craven et al., 1995</xref>).</p>
<fig id="F7" position="float">
<label>FIGURE 7</label>
<caption>
<p>DE-RIMS measurements showing counts per accumulation <italic>versus</italic> mass. Figure adapted and digitized from <xref ref-type="bibr" rid="B8">Chappell et al. (1982)</xref>.</p>
</caption>
<graphic xlink:href="fspas-10-1224659-g007.tif"/>
</fig>
<p>In addition, the largest enhancements on the N<sup>&#x2b;</sup> fluxes are seen at the outer edge of the plasmasphere, suggesting the possibility of an existing N<sup>&#x2b;</sup> torus, analogous to the previously reported O<sup>&#x2b;</sup> torus features (<xref ref-type="bibr" rid="B8">Chappell et al., 1982</xref>). Furthermore, based on spacecraft position, peak flux, and flow velocity, it was inferred that these outflowing N<sup>&#x2b;</sup> ions could be interpreted as 0.3 eV field aligned N<sup>&#x2b;</sup> ion beams with a density of 0.8 cm<sup>&#x2212;3</sup>, and they present similar characteristics as the low energy O<sup>&#x2b;</sup>. A possible explanation of these observed enhancements of N<sup>&#x2b;</sup> fluxes at the outer edge of the plasmasphere is provided by the fact that the N<sup>&#x2b;</sup> undergoes more efficient charge-exchange reactions than O<sup>&#x2b;</sup> does and has a shorter average lifetime in the inner magnetosphere primarily due to the difference in charge exchange cross sections between the two species and the ambient neutral hydrogen. These differences imply that O<sup>&#x2b;</sup> ions are more likely to be transported inwards, towards lower L-shells, before they charge exchange with the ambient neutral H population, while energetic N<sup>&#x2b;</sup> ions have a shorter lifetime in the inner magnetosphere as they lost via charge exchange reaction significantly faster. This prohibits their transport deeper into the inner magnetosphere, and therefore they tend to populate the outer edge of the plasmasphere (<xref ref-type="bibr" rid="B39">Liu et al., 2022</xref>).</p>
<p>As <xref ref-type="fig" rid="F7">Figure 7</xref> shows, during this time, the highest fluxes of N<sup>&#x2b;</sup> are seen in the plasmasphere region as high as 3 R<sub>
<italic>E</italic>
</sub> and the count rate ratio N<sup>&#x2b;</sup>/O<sup>&#x2b;</sup> is about 0.1. These observations of magnetospheric N<sup>&#x2b;</sup> are aligned with the measurements reported in the low altitude ionosphere (<xref ref-type="bibr" rid="B5">Brinton et al., 1971</xref>; <xref ref-type="bibr" rid="B26">Hoffman et al., 1974</xref>). The low energy N<sup>&#x2b;</sup> were reported to exhibit seemingly similar characteristics with the low energy O<sup>&#x2b;</sup> and numerical modeling results suggest that, for low energy ions (<inline-formula id="inf18">
<mml:math id="m18">
<mml:mo>&#x3c;</mml:mo>
</mml:math>
</inline-formula>50 eV), the ratio of N<sup>&#x2b;</sup>/O<sup>&#x2b;</sup> varies between 0.1 and 0.5 for L &#x3d; 2, and from 0.25 to 1.0 for L &#x3d; 4 at the equator at noon local time, findings in agreement with measurements from RIMS instrument on board Dynamic Explorer 1 spacecraft (<xref ref-type="bibr" rid="B15">Craven et al., 1993</xref>).</p>
<p>Energetic nitrogen ions of above 10 keV have also been detected at higher altitudes in the magnetosphere by the Active Magnetospheric Particle Tracer Explorers (AMPTE) charge-energy-mass (CHEM) instrument (<xref ref-type="bibr" rid="B23">Hamilton et al., 1988</xref>). <xref ref-type="fig" rid="F8">Figure 8</xref> shows the measurements for the energy density at low and high L shells during the first great magnetic storm of 9 February 1986 (with a recorded Dst minimum of &#x2212;312 nT), after the launch of AMPTE spacecraft. The top panel shows the hourly Dst index throughout the storm, while the following two panels show measurements of the energy density for ring current species, at L &#x3d; 3&#x2013;5 and L &#x3d; 5&#x2013;7, respectively. While at all L-shells, the bulk of energy density is mostly carried by the H<sup>&#x2b;</sup> population, the N<sup>&#x2b;</sup> energy density closely follows the trend seen for O<sup>&#x2b;</sup>. In addition, all ring current species show an increase in density during the storm period, but the relative increase of O<sup>&#x2b;</sup> and N<sup>&#x2b;</sup> ions is much larger at all distances. At lower L shells, during storm maximum, oxygen ions seem to be the dominant species, with nitrogen ions following closely, while at higher L shells, most of the energy density is carried by the H<sup>&#x2b;</sup> population.</p>
<fig id="F8" position="float">
<label>FIGURE 8</label>
<caption>
<p>Top panel shows the hourly Dst index through the storm, together with the inverted energy density. The periods during the eight orbits when the spacecraft was inside L &#x3d; 7 are shown using horizontal lines. Middle and bottom panels show the energy density as a function of time for H<sup>&#x2b;</sup> (light green), He<sup>&#x2b;</sup> (dark green), N<sup>&#x2b;</sup> (orange) and O<sup>&#x2b;</sup> (blue) for L &#x3d; 3&#x2013;5, and L &#x3d; 5&#x2013;7 respectively. Figure digitized and adapted from <xref ref-type="bibr" rid="B23">Hamilton et al. (1988)</xref>.</p>
</caption>
<graphic xlink:href="fspas-10-1224659-g008.tif"/>
</fig>
<p>
<xref ref-type="fig" rid="F9">Figure 9</xref> shows the energy spectra for H<sup>&#x2b;</sup> (light green), He<sup>&#x2b;</sup> (dark green), N<sup>&#x2b;</sup> (orange) and O<sup>&#x2b;</sup> (blue) ions, adapted from (<xref ref-type="bibr" rid="B23">Hamilton et al., 1988</xref>). These measurements also show that the fluxes of high energy ring current N<sup>&#x2b;</sup> are comparable with those of O<sup>&#x2b;</sup> during active times and tend to be at least one order of magnitude higher than those of He<sup>&#x2b;</sup> ions. Furthermore, Magnetospheric Multiscale (MMS) observations showed that the high energy population (<inline-formula id="inf19">
<mml:math id="m19">
<mml:mo>&#x3e;</mml:mo>
</mml:math>
</inline-formula>150 keV) of the middle magnetosphere (beyond 7R<sub>
<italic>E</italic>
</sub>) is dominated by heavy ions species, which exist at higher intensities than protons at energies 175 keV, contradicting prior assumptions that protons are the dominant species in this region (<xref ref-type="bibr" rid="B14">Cohen et al., 2017</xref>). However, the charge states of these heavy ions hint at a solar wind origin rather than at an ionospheric source.</p>
<fig id="F9" position="float">
<label>FIGURE 9</label>
<caption>
<p>Energy spectra (left) and energy density (right) of ring current ions species, H<sup>&#x2b;</sup> (light green), He<sup>&#x2b;</sup> (dark green), N<sup>&#x2b;</sup> (orange) and O<sup>&#x2b;</sup> (blue), during 9 February 1986, geomagnetic storm. Figure digitized and adapted from <xref ref-type="bibr" rid="B23">Hamilton et al. (1988)</xref>.</p>
</caption>
<graphic xlink:href="fspas-10-1224659-g009.tif"/>
</fig>
<p>While solar activity controls the ionic composition of the upper atmosphere (<xref ref-type="bibr" rid="B70">Young et al., 1982</xref>; <xref ref-type="bibr" rid="B42">Moore et al., 1999</xref>; <xref ref-type="bibr" rid="B17">Cully et al., 2003</xref>; <xref ref-type="bibr" rid="B48">Peterson et al., 2006</xref>; <xref ref-type="bibr" rid="B4">Brambles et al., 2013</xref>; <xref ref-type="bibr" rid="B10">Chappell, 2015</xref>), the mass density in the magnetosphere, and hence the abundances of heavy ions of ionospheric origin in the near-Earth plasma are increasing with geomagnetic activity (<xref ref-type="bibr" rid="B18">Daglis, 1997</xref>; <xref ref-type="bibr" rid="B44">Nos&#xe9; et al., 2003</xref>). This suggests that throughout the main phase of a magnetic storm, not only O<sup>&#x2b;</sup>, but also N<sup>&#x2b;</sup> ions have the potential to become the dominant ring current ions (<xref ref-type="bibr" rid="B23">Hamilton et al., 1988</xref>; <xref ref-type="bibr" rid="B31">Ilie et al., 2021</xref>) in terms of energy density.</p>
<p>The Suprathermal Ion Composition Spectrometer (STICS) of the Geotail/EPIC (Energetic Particles and Ion Composition) instrument (<xref ref-type="bibr" rid="B62">Williams et al., 1994</xref>) had the capability to measure the mass and mass per charge of energetic ions within the energy range of 9.4&#x2013;210 keV/e. Therefore, Geotail observations also show that both O<sup>&#x2b;</sup> and N<sup>&#x2b;</sup> are major constituents of the dayside (11&#x2013;16 MLT) outer ring current, especially during increased geomagnetic activity (<xref ref-type="bibr" rid="B12">Christon et al., 2002</xref>). Furthermore, the density of N<sup>&#x2b;</sup> ions is trailing after hydrogen and oxygen ions, even during moderate geomagnetic storms. <xref ref-type="fig" rid="F10">Figure 10</xref>, adapted from (<xref ref-type="bibr" rid="B12">Christon et al., 2002</xref>), shows the solar cycle variations of F10.7, Dst, and Kp indices, together with the N<sup>&#x2b;</sup>/O<sup>&#x2b;</sup> ratio, from 1990 to 2002. Tracking the N<sup>&#x2b;</sup>/O<sup>&#x2b;</sup> ratio together with the F10.7 index, a proxy for solar radiation and hence solar activity, reveals an inverse relationship between the N<sup>&#x2b;</sup>/O<sup>&#x2b;</sup> ratio and solar cycle. It can be seen that this ratio ranges between 0.36 and 0.42 during low solar activity and decreases to 0.21&#x2013;0.27 during times of increased solar activity. Therefore, one can note a drop by a factor of <inline-formula id="inf20">
<mml:math id="m20">
<mml:mo>&#x223c;</mml:mo>
<mml:mn>2</mml:mn>
</mml:math>
</inline-formula> in the N<sup>&#x2b;</sup>/O<sup>&#x2b;</sup> as the solar cycle transitions from solar minimum to solar maximum. Similar findings are reported based on CRRES/MICS measurements, showing that the N<sup>&#x2b;</sup>/O<sup>&#x2b;</sup> ratio in the ring current (2.5<inline-formula id="inf21">
<mml:math id="m21">
<mml:mo>&#x3c;</mml:mo>
</mml:math>
</inline-formula>L<inline-formula id="inf22">
<mml:math id="m22">
<mml:mo>&#x3c;</mml:mo>
</mml:math>
</inline-formula>6.5) region, even during geomagnetically quiet times during solar maximum is about &#x223c;0.31 (<xref ref-type="bibr" rid="B40">Liu et al., 2005</xref>).</p>
<fig id="F10" position="float">
<label>FIGURE 10</label>
<caption>
<p>Solar cycle variations, average Dst and average Kp (top panel), and outer ring current N<sup>&#x2b;</sup>/O<sup>&#x2b;</sup> ratio together with F10.7 (bottom panel), for intervals when Geotail was in the afternoon local sector, from 1990 to 2002. Figure digitized and adapted from <xref ref-type="bibr" rid="B12">Christon et al. (2002)</xref>.</p>
</caption>
<graphic xlink:href="fspas-10-1224659-g010.tif"/>
</fig>
<p>
<xref ref-type="fig" rid="F11">Figure 11</xref>, adapted from (<xref ref-type="bibr" rid="B12">Christon et al., 2002</xref>), shows histograms of nitrogen and oxygen ion pulse-height analyzed events for different solar and geomagnetic conditions. These measurements, based on 12 years of Geotail data, reveal large variations in the ratio of N<sup>&#x2b;</sup>/O<sup>&#x2b;</sup> in the dayside outer ring current, ranging from 0.14 during active times at solar maximum to larger than unity during quiet times at solar minimum. This ratio is also affected by geomagnetic activity, but to a lesser extent, and it is likely due to the fact that solar activity is the dominant factor in this analysis, as it is responsible for altering the ionospheric source population and means of acceleration for heavy ion outflow. Nevertheless, even during modest geomagnetic storms, N<sup>&#x2b;</sup> is generally the third most abundant magnetospheric ion in the 22.7&#x2013;210 keV/q range, after H<sup>&#x2b;</sup> and O<sup>&#x2b;</sup> in the dayside outer ring current.</p>
<fig id="F11" position="float">
<label>FIGURE 11</label>
<caption>
<p>Histograms of N<sup>&#x2b;</sup> and O<sup>&#x2b;</sup> pulseheight analyzed events in the 10&#x2013;20 M/q (mass-per-charge) range for varying solar and geomagnetic conditions <bold>(A)</bold> solar minimum - quiet time, <bold>(B)</bold> solar minimum - storm time, <bold>(C)</bold> solar maximum - storm time, <bold>(D)</bold> solar maximum - quiet time. Figure adapted from <xref ref-type="bibr" rid="B12">Christon et al. (2002)</xref>.</p>
</caption>
<graphic xlink:href="fspas-10-1224659-g011.tif"/>
</fig>
<p>These findings complement measurements based on instrumentation onboard the WIND spacecraft (<xref ref-type="bibr" rid="B41">Mall et al., 2002</xref>), which showed that the abundance of nitrogen ions in the magnetosphere displays both a solar cycle and a day-night variation. The N<sup>&#x2b;</sup> density has been reported to vary by as much as a factor of 2 with solar activity (<xref ref-type="bibr" rid="B12">Christon et al., 2002</xref>). Furthermore, the ratio of N<sup>&#x2b;</sup>/O<sup>&#x2b;</sup> displays a solar cycle relationship with a higher value (0.45) at solar minimum conditions than at solar maximum when it reaches only 0.2 (<xref ref-type="bibr" rid="B41">Mall et al., 2002</xref>). <xref ref-type="fig" rid="F12">Figure 12</xref>, adapted from (<xref ref-type="bibr" rid="B41">Mall et al., 2002</xref>), shows the variation of N<sup>&#x2b;</sup>/O<sup>&#x2b;</sup> ratio with solar activity in the outer ring current region at 9&#x2013;15 R<sub>
<italic>E</italic>
</sub>. The factor of two variations has been linked to the altitude and latitude variations in ionospheric N<sup>&#x2b;</sup>/O<sup>&#x2b;</sup> ratio since at times of enhanced ionospheric outflow, the ratio of magnetospheric N<sup>&#x2b;</sup>/O<sup>&#x2b;</sup> approaches the ratio of N<sup>&#x2b;</sup>/O<sup>&#x2b;</sup> at the topside ionosphere (<xref ref-type="bibr" rid="B12">Christon et al., 2002</xref>). In addition, Geotail data shows that oxygen and nitrogen ions are detected together in the outer ring current region nearly continuously, findings that are consistent with previous measurements coming from AMPTE/CCE data (<xref ref-type="bibr" rid="B22">Gloeckler and Hamilton, 1987</xref>) and a more recent study by <xref ref-type="bibr" rid="B11">Christon et al. (2020)</xref>.</p>
<fig id="F12" position="float">
<label>FIGURE 12</label>
<caption>
<p>The ratio of N<sup>&#x2b;</sup>/O<sup>&#x2b;</sup> (energy/charge interval of 10&#x2013;210 keV/e) and normalized F10.7 cm flux as a function of time as inferred from the WIND/STICS data. Figure digitized and adapted from <xref ref-type="bibr" rid="B41">Mall et al. (2002)</xref>.</p>
</caption>
<graphic xlink:href="fspas-10-1224659-g012.tif"/>
</fig>
<p>More recently, the first observation of the N<sup>&#x2b;</sup> band of electromagnetic ion cyclotron (EMIC) (<xref ref-type="bibr" rid="B3">Bashir and Ilie, 2021</xref>) waves has been reported by Van Allen probe wave observation during the recovery phase of a geomagnetic storm. The existence of the N<sup>&#x2b;</sup> band indirectly suggests the presence of N<sup>&#x2b;</sup> ions in the inner magnetosphere, as reported by the past observations (<xref ref-type="bibr" rid="B8">Chappell et al., 1982</xref>; <xref ref-type="bibr" rid="B23">Hamilton et al., 1988</xref>) and also theoretically inferred N<sup>&#x2b;</sup> composition using the indirect method for EMIC waves (<xref ref-type="bibr" rid="B2">Bashir and Ilie, 2018</xref>).</p>
</sec>
<sec sec-type="discussion" id="s5">
<title>5 Discussion</title>
<p>These observations reopen the question of ionic composition in the ionosphere-magnetosphere system and the need for caution when interpreting O<sup>&#x2b;</sup> measurements. Understanding plasma composition requires ultimately including a variety of ions that are currently known, although less reported, to be present in the low-altitude ionosphere. <xref ref-type="table" rid="T1">Table 1</xref> summarizes the N<sup>&#x2b;</sup> measuring space missions and relevant details regarding orbits and onboard instrumentation. This review is intended to motivate and guide the development of instrumentation and possibly space missions, capable of measuring abundances and tracking the transport of both O<sup>&#x2b;</sup> and N<sup>&#x2b;</sup> ions, which are not quantified, nor understood, at this time (<xref ref-type="bibr" rid="B32">Ilie and Liemohn, 2016</xref>). Knowledge of the different behavior and paths of energization for O<sup>&#x2b;</sup> and N<sup>&#x2b;</sup> will provide the context for the interpretation and analysis of data from many currently operating ionospheric and magnetospheric missions.</p>
<table-wrap id="T1" position="float">
<label>TABLE 1</label>
<caption>
<p>List of N<sup>&#x2b;</sup> measuring space missions, including launch dates, orbital details, relevant instrumentation, and reported O<sup>&#x2b;</sup>/N<sup>&#x2b;</sup> ratio.</p>
</caption>
<table>
<thead valign="top">
<tr>
<th rowspan="2" align="left">Mission</th>
<th rowspan="2" align="center">Lifetime</th>
<th colspan="4" align="center">Orbit</th>
<th rowspan="2" align="center">Energy range &#x26; measurement type</th>
<th rowspan="2" align="center">O<sup>&#x2b;</sup>/N<sup>&#x2b;</sup>
</th>
<th rowspan="2" align="center">References</th>
</tr>
<tr>
<th align="left">Perigee</th>
<th align="left">Apogee</th>
<th align="center">Inclination</th>
<th align="center">Period</th>
</tr>
</thead>
<tbody valign="top">
<tr>
<td align="left">Sputnik 3</td>
<td align="center">Launch Date: 15 May1958 Decay Date: 6 April 1960</td>
<td align="center">217 km</td>
<td align="center">1864 km</td>
<td align="center">65.18&#xb0;</td>
<td align="center">105.9 min</td>
<td align="center">Bennett type radio-frequency quadrupole mass spectrometer</td>
<td align="center">N/A</td>
<td align="center">
<xref ref-type="bibr" rid="B35">Istomin (1961)</xref>
</td>
</tr>
<tr>
<td align="left">Explorer 31</td>
<td align="center">Launch Date: 29 Nov 1965 Decay Date: 21 Feb 1967</td>
<td align="center">505 km</td>
<td align="center">2,978 km</td>
<td align="center">79.8&#xb0;</td>
<td align="center">121.4 min</td>
<td align="center">Magnetic Ion-Mass Spectrometer</td>
<td align="center">3&#x2013;20</td>
<td align="center">
<xref ref-type="bibr" rid="B25">Hoffman (1967)</xref>
</td>
</tr>
<tr>
<td align="left">Explorer 32</td>
<td align="center">Launch Date: 25 May 1966 Decay Date: 22 February 1985</td>
<td align="center">276 km</td>
<td align="center">2,725 km</td>
<td align="center">64.67&#xb0;</td>
<td align="center">116 min</td>
<td align="center">Bennett RF ion spectrometer</td>
<td align="center">2.5&#x2013;20</td>
<td align="center">
<xref ref-type="bibr" rid="B5">Brinton et al. (1971)</xref>
</td>
</tr>
<tr>
<td align="left">OGO 2</td>
<td align="center">Launch Date: 14 Oct 1965 Decay Date: 17 Sep 1981</td>
<td align="center">414 km</td>
<td align="center">1,510 km</td>
<td align="center">87.4&#xb0;</td>
<td align="center">104 min</td>
<td align="center">Bennett RF ion spectrometer</td>
<td align="center">5&#x2013;100</td>
<td align="center">
<xref ref-type="bibr" rid="B57">Taylor et al. (1968)</xref>
</td>
</tr>
<tr>
<td align="left">OGO 6</td>
<td align="center">Launch Date: 5 Jun 1969 Decay Date: 12 Oct 1979</td>
<td align="center">413 km</td>
<td align="center">1,077 km</td>
<td align="center">82&#xb0;</td>
<td align="center">99.7 min</td>
<td align="center">Bennett Ion-Mass spectrometer or Magnetic Ion-Mass spectrometer</td>
<td align="center">10&#x2013;100</td>
<td align="center">
<xref ref-type="bibr" rid="B58">Taylor Jr. (1971)</xref>; <xref ref-type="bibr" rid="B15">Craven et al. (1993)</xref>; <xref ref-type="bibr" rid="B24">Hoegy et al. (1991)</xref>
</td>
</tr>
<tr>
<td align="left">ISIS 2</td>
<td align="center">Launch Date: 1 Apr 1971 Decay Date: 1 Oct 1979</td>
<td align="center">1,360 km</td>
<td align="center">1,440 km</td>
<td align="center">88.1&#xb0;</td>
<td align="center">113.6 min</td>
<td align="center">Ion Mass Spectrometer</td>
<td align="center">3&#x2013;20</td>
<td align="center">
<xref ref-type="bibr" rid="B26">Hoffman et al. (1974)</xref>
</td>
</tr>
<tr>
<td align="left">AE-C</td>
<td align="center">Launch Date: 16 Dec 1973 Decay Date: 12 Dec 1978</td>
<td align="center">149 km</td>
<td align="center">4,294 km</td>
<td align="center">68.1&#xb0;</td>
<td align="center">132.3 min</td>
<td align="center">Bennett Ion-Mass spectrometer or Magnetic Ion-Mass spectrometer</td>
<td align="center">3&#x2013;20</td>
<td align="center">
<xref ref-type="bibr" rid="B26">Hoffman et al. (1974)</xref>; <xref ref-type="bibr" rid="B7">Brinton et al. (1973)</xref>; <xref ref-type="bibr" rid="B27">Hoffman et al. (1973)</xref>; <xref ref-type="bibr" rid="B15">Craven et al. (1993)</xref>; <xref ref-type="bibr" rid="B24">Hoegy et al. (1991)</xref>
</td>
</tr>
<tr>
<td align="left">DE -1</td>
<td align="center">Launch Date: 3 Aug 1981 Decay Date: 28 Feb 1991</td>
<td align="center">488 km</td>
<td align="center">23,289 km</td>
<td align="center">89.9&#xb0;</td>
<td align="center">409 min</td>
<td align="center">Retarding Ion Mass Spectrometer (RIMS) 0&#x2013;45 eV</td>
<td align="center">10&#x2013;20</td>
<td align="center">
<xref ref-type="bibr" rid="B8">Chappell et al. (1982)</xref>
</td>
</tr>
<tr>
<td align="left">AMPTE</td>
<td align="center">Launch Date: 17 Aug 1984 Decay Date: July 1989</td>
<td align="center">1,084 km</td>
<td align="center">56,062 km</td>
<td align="center">4.8&#xb0;</td>
<td align="center">960 min</td>
<td align="center">Charge-Energy-Mass Spectrometer(CHEM) 1&#x2013;300 keV/e</td>
<td align="center">2&#x2013;10</td>
<td align="center">
<xref ref-type="bibr" rid="B23">Hamilton et al. (1988)</xref>
</td>
</tr>
<tr>
<td align="left">Akebono</td>
<td align="center">Launch Date: 21 Feb 1989 Decay Date: 23 Apr 2015</td>
<td align="center">275 km</td>
<td align="center">10,500 km</td>
<td align="center">75&#xb0;</td>
<td align="center">211 min</td>
<td align="center">Suprathermal Ion Mass Spectrometer (SMS) 0&#x2013;25.5 eV; 55 eV/q&#x2013;4.1 keV/q</td>
<td align="center">2&#x2013;10</td>
<td align="center">
<xref ref-type="bibr" rid="B61">Whalen et al. (1990)</xref>
</td>
</tr>
<tr>
<td align="left">Geotail</td>
<td align="center">Launch Date: 24 July 1992</td>
<td align="center">51,328 km</td>
<td align="center">190,664 km</td>
<td align="center">10.51&#xb0;</td>
<td align="center">7,539.86 min</td>
<td align="center">Suprathermal Ion Composition Spectrometer (STICS) 9.4&#x2013;210 keV/e</td>
<td align="center">2.5&#x2013;5</td>
<td align="center">
<xref ref-type="bibr" rid="B62">Williams et al. (1994)</xref>; <xref ref-type="bibr" rid="B12">Christon et al. (2002)</xref>
</td>
</tr>
<tr>
<td align="left">WIND</td>
<td align="center">Launch date: 1 November 1994</td>
<td align="center">31,890 km</td>
<td align="center">1,690,170 km</td>
<td align="center">19.6&#xb0;</td>
<td align="center">111,600 min</td>
<td align="center">STICS (SupraThermal Ion Composition Spectrometer): 8&#x2013;226 KeV/e</td>
<td align="center">1.6&#x2013;5</td>
<td align="center">
<xref ref-type="bibr" rid="B41">Mall et al. (2002)</xref>
</td>
</tr>
<tr>
<td align="left">e-POP</td>
<td align="center">Launch Date: September 29, 2013</td>
<td align="center">325 km</td>
<td align="center">1,500 km</td>
<td align="center">81&#xb0;</td>
<td align="center">103 min</td>
<td align="center">Imaging and Rapid-Scanning Ion Mass Spectrometer (IRM); measures the composition and 3-dimensional velocity distributions of low-energy (1&#x2013;90 eV/e) ions in the mass-per-charge (M/q) range of 1&#x2013;40 AMU/e</td>
<td align="center">N/A</td>
<td align="center">
<xref ref-type="bibr" rid="B69">Yau et al. (2006)</xref>; <xref ref-type="bibr" rid="B67">Yau and Howarth (2016)</xref>
</td>
</tr>
</tbody>
</table>
</table-wrap>
</sec>
</body>
<back>
<sec id="s6">
<title>Author contributions</title>
<p>All authors listed have made a substantial, direct, and intellectual contribution to the work and approved it for publication.</p>
</sec>
<sec id="s7">
<title>Funding</title>
<p>Work at the University of Illinois at Urbana-Champaign was performed with financial support from AFOSR YIP award no. AF FA 9550-18-1-0195, the NASA grant 80NSSC20K1231, and the NSF ICER Award No.1664078. MB acknowledges support from the NASA grants 80NSSC20K1270, and 80NSSC23K0403. M-YL would like to thank the financial support from NASA FINESST Fellowship 80NSSC21K1425.</p>
</sec>
<sec sec-type="COI-statement" id="s8">
<title>Conflict of interest</title>
<p>The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.</p>
</sec>
<sec sec-type="disclaimer" id="s9">
<title>Publisher&#x2019;s note</title>
<p>All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors and the reviewers. Any product that may be evaluated in this article, or claim that may be made by its manufacturer, is not guaranteed or endorsed by the publisher.</p>
</sec>
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