ChemicalâMineralogical Systems That Are Able To Generate Nitrogen

Article Cite This: ACS Earth Space Chem. XXXX, XXX, XXX−XXX

Chemical−Mineralogical Systems That Are Able To Generate Nitrogen Compounds on Earth and Even Mars Vasile Gutsanu* Moldova State University, 60 Mateevich Street, MD 2009 Chisinau, Moldova ABSTRACT: The formation of nitrogen compounds by chemical fixing of atmospheric nitrogen in ambient conditions in only one technological step is of particular interest for the chemical industry and science. The effect is achieved by air bubbling through the reactor containing a cross-linked ionic polymer with strongly basic functional groups and sulfate solution of a trivalent metal. The lower the temperature of the reactor, the higher the yield production of nitrogen compounds. In the polymer phase, jarositetype compound formation occurs that participates in the redox processes, followed by the partial destruction and synthesis of nitrogen compounds. The results from this work demonstrate that, under certain conditions, systems containing a strongly basic cross-linked polymer and solution of three valence metal sulfates (Fe3+, Ga3+, and others) are able to generate nitrogen-containing compounds, using atmospheric nitrogen. The spontaneous and uncontrolled processes of nitrogen compound generation could occur in nature, which would explain the stability of some minerals on Earth and even Mars. KEYWORDS: nitrogen fixation, strongly basic polymer, jarosite-type compounds, metal cation sorption, iron, gallium, indium

1. INTRODUCTION It is well-known that some bacteria are able to fixate atmospheric nitrogen in soft conditions. It is also known that some metal compounds of iron can coordinate molecular nitrogen but cannot turn into compounds.1−3 In industry, fixation of nitrogen from atmospheric air to obtain nitrite or nitrate compounds is a complicated process, which occurs in many steps and in rigid conditions. It seems incredible, but atmospheric nitrogen can be chemically converted into nitrate under ambient conditions and in a single technological stage. This is possible as a result of complex redox reactions involving ionic cross-linked polymers, containing strongly basic groups, during synthesis in their phase of jarosite-type compounds. When contacted with sulfate solutions of some trivalent metals, in the phase of polymers containing strong basic groups of type −N(CH3)3Cl, unusual processes take place. These types of polymers do not contain negatively charged or electron donor atoms in their matrix. Therefore, theoretically, they are not able to interact with inorganic cations from solution and adsorb them. However, in our previous study,4−9 it was shown that, in certain conditions, these polymers may interact with cations in M2 (SO4 ) 3 solutions, where M is Fe3+, Al3+, Cr3+, Ga3+, or In3+. From MCl3 or M(NO3)3 solutions, the sorption of cations does not take place. Using Mössbauer spectroscopy, we found that, in the polymer phase, the retention of these cations from solutions takes place through the formation of ultrafine particles of jarosite-type compounds: R4N[Fe3(OH)6(SO4)2] and H3O[Fe3(OH)6(SO4)2], where R4N+ are functional groups of the polymer.6−9 It is known that, in nature, jarosite (Na,K)© XXXX American Chemical Society

[Fe3(OH)6(SO4)2] and its isostructural analogue, alunite (Na,K)[Al3(OH)6(SO4)2], exist. However, in laboratory conditions, many jarosite-type compounds were obtained and investigated, including Cr3+, V3, and others.10−15 The jarositetype compounds are formed as pseudo-layers of 3 and/or 6 octahedral cycles.16 The OH groups are located in the equatorial plane, forming a bridge between metal ions, and SO42− groups are located in the axial position, with each of them coordinating three metal ions of three octahedra. Between the jarosite polymer layers, mobile R4N+, H3O+, or other cations retained by Coulomb electrostatic interactions are located. The R4N + and H3O+ ions from jarosite-type compounds can be exchanged by different cations and SO42− with different anions or molecules capable of forming coordination bonds with central metal ions.17 Upon heating in water (T ≥ 80 °C) synthetic Na[Fe3(OH)6(SO4)2] is converted to α-FeOOH.18 However, in the case of jarosite-type compounds in the polymer phase upon boiling in water, relatively massive and magnetically ordered β-FeOOH particles are formed. A portion of β-FeOOH particles remains in the highly dispersed superparamagnetic state distributed in the narrow pores of the polymer.6,9 The jarosite-type compounds in the polymer phase are non-crystalline, and the state of metal in the compounds depends upon many factors.9 With investigation of the formation of Fe−jarosite in the polymer Received: Revised: Accepted: Published: A

January 14, 2018 February 13, 2018 February 15, 2018 February 15, 2018 DOI: 10.1021/acsearthspacechem.8b00006 ACS Earth Space Chem. XXXX, XXX, XXX−XXX

Article

ACS Earth and Space Chemistry

Figure 1. Scheme of the installation used for investigation of the nitrite/nitrate formation: (1) air pump, (2) separating funnel, (3) reactor I, (4) recipient, and (5) reactor II.

phase, we have noticed that a part of the Fe3+ cations is reduced to Fe2+. Later, we found that, upon reducing the metal cations in the polymer phase, concomitant formation of nitrogen compounds takes place. The purpose of this paper was to investigate the factors that influence the formation of nitrogen compounds in systems containing strongly basic polymer and iron(III) or gallium(III) sulfate solution. The fundamental issue was the identification of the source of nitrogen compound formation. As known, thermodynamics do not allow for the chemical interaction of atmospheric nitrogen with oxygen (and not only) under normal conditions. It is also important to know if the processes of formation and destruction of jarosite with the formation of nitrogen compounds can occur in nature and not only in the laboratory.

the polymer sample (mg/mL), respectively, V is the solution volume in contact with the polymer sample (mL), and m is the mass of the polymer sample in contact with the solution (g). 2.4. Method of Statistical Mathematics. To evaluate the influence of different factors [concentration of Fe2(SO4)3 or Ga2(SO4)3, Na2SO4, KCl, temperature, pH of solution, rate of air bubbling through the solution, and polymer with solution contact duration] on metal-containing cation sorption and NO2− and NO3− ion generation, the response surface methodology (Box and Wilson method) was used.22 The experiments were carried out according to the matrix of fractional factorial experiment plan type FFE 27−4. The Student criterion of the coefficient of significance in the regression equations (bsig) was calculated at a level of significance of 5% and number degree of freedom f = 7. 2.5. Mö ssbauer Spectroscopy. The 57Fe Mössbauer spectrum was recorded at 300 K on a conventional spectrometer in the constant-acceleration mode (MS4, Edina, MN, U.S.A.). The 57Co in a Cr matrix was used as the γ-ray source. Isomer shifts (δ, mm/s) are given relative to sodium nitroprusside. The spectrum was fitted using the Mössbauer spectral analysis software WMOSS4, version F. The error limit for each experimental point in the spectrum is ±0.02 mm/s.

2. EXPERIMENTAL SECTION 2.1. Experiment Procedures. The used AV-17(Cl) is a commercial polymer, containing −N(CH3)3Cl groups. The geltype polymer has a polystyrene−divinylbenzene matrix and a full anion exchange capacity of 3.5−4.2 mequiv/g.19 Air-dried samples (0.2 g) of the polymer were contacted with solution (100 mL) of Fe2(SO4)3, Ga2(SO4)3, or In2(SO4)3. The pH 1.7−2.0 of the solution−polymer systems was maintained constant using either H2SO4 or KOH solutions. The solution− polymer sample system temperature was maintained constant, with an error of ±1 °C. The kinetic curves of metal, containing cation sorption from 0.01 M Ga2(SO4)3 or 0.01 M In2(SO4)3 solutions, were obtained over the temperature range of 17−60 °C. The histograms of Ga(III)-containing cation sorption as a function of the polymer granule sizes were obtained at 60 °C. For investigation, the following polymer granule fractions 0.1− 0.25, 0.25−0.50, and 0.5−1.2 mm in diameter have been used. 2.2. Chemical Analysis. The content of metallic cations in the polymer phase was determined photocolorimetrically20 after desorption upon contact for 2 h of metal-containing polymer samples (0.2 g) with 3.0 M H2SO4 solution (5 mL) at 60 °C. Nitrite ions were determined photocolorimetrically using the Griess reagent.21 Nitrate ions were determined by the potentiometric method with an ion-selective electrode. 2.3. Calculation of Sorption. Calculation of cation sorption was made using the following equation (eq 1): S=

Co − Ce m

3. RESULTS AND DISCUSSION In the study of the Fe−jarosite formation in the polymer phase, the infrared (IR) spectrum revealed a new intensive spectral line at 1283 cm−1. According to ref 23, this absorption band belongs to the NO3− ions. The NO3− ions could not be in the polymer phase as a result of anion exchange, if to assume that the used salt was contaminated with NO3−, because the solution concentration of Fe2(SO4)3, which was contacted with the polymer, was relatively high (4−8 g/L). It should be noted that the appearance of an absorption band at 1283 cm −1 in the Fourier transform infrared (FTIR) spectrum of the polymer containing such compounds is extremely rarely observed because the SO42− concentration in the system is incomparably high compared to the NO3− concentration. One of the first works is pointed to the formation of nitrogen compounds in the system containing strongly basic cross-linked ionic polymer and Fe2(SO4)3.24 The investigation of nitrite/nitrate formation by the system, containing strongly basic cross-linked polymer AV-17(Cl) and Fe2(SO4)3 solution with pH 1.7−2.0, has been performed using installation given in Figure 1. The polymer AV-17(Cl) and solution of Fe2(SO4)3 were inserted into reactor II. In reactor I, NaHCO3 was introduced to obtain CO2, KMnO4 was

(1)

where S is the sorption value (mg/g), Co and Ce are the metal cation concentrations in solution before and after contact with B

DOI: 10.1021/acsearthspacechem.8b00006 ACS Earth Space Chem. XXXX, XXX, XXX−XXX

Article

ACS Earth and Space Chemistry Table 1. Results Obtained during the Passage of Different Gases through the System experimental number

gas bubbled through the system

pHo

pHe

m(NO3−) (mg/g)

m(NO2− + NO3−) (mg/g)

m(Fe2+) (mg/g)

m(Fe3+) (mg/g)

1 2 3 4

O2 CO2 O2 + CO2 air

10 10 10 10

10 8.2 8.0 8.1

0 0 0 1.75

0 0 0 180

3.20 0.76 2.36 0.68

7.57 3.92 4.06 3.66

gases were bubbled for 8 h at 0 °C. Oxygen was obtained according to reaction 3

introduced to obtain O2, or Mn(OH)2 was introduced to absorb air oxygen. The separating funnel contained HCl acid solution to obtain CO2 upon interaction with NaHCO3. The system was bubbled air at a rate of 1 or 2 L/min. The recipient (4 in Figure 1) contains alkalized distilled water with pH 10. The system is air-bubbled for 7 h. After that, the contents of Fe3+ and Fe2+ in the polymer phase and contents of nitrate and nitrite ions in the recipient have been determined. To evaluate the influence of different factors [X1, Fe2(SO4)3 (2−3 g/L); X4, Na2SO4 (0.01−0.02 mequiv/L); X2, temperature (40−50 °C); X3, pH (1.7−1.9); X5, speed of air bubbling through the solution (0−1 L/min); X6, polymer mass, (0.2−0.4 g); and X7, polymer with solution contact duration (5−7 h)] on the Fe3+ and Fe2+ ion contents in the polymer phase and on the NO2− and NO3− ion contents in the recipient, the method of statistical mathematics was used. Parameter variation levels are indicated in parentheses. The regression equation (eq 2), where Y is the content of NO3− relative to 1 g of polymer (mg of NO3−/g), is as follows:

2KMnO4 = K 2MnO4 + MnO2 + O2

and CO2 were obtained from pure marble upon interaction with pure HCl according to reaction 4. CaCO3 + 2HCl = CaCl 2 + H 2O + CO2

bsig = 0.18

(4)

The experiment was performed in such a way that nitrogen (air) does not appear in the system. For comparison, an experiment was additionally carried out in the presence of air. The results are shown in Table 1. The data from Table 1 (where pHo and pHe are the pH of the water in the container at the beginning and end of the experiment, respectively) clearly show that nitrogen-containing compounds are formed involving atmospheric nitrogen. The Fe2+ and Fe3+ content data in the polymer phase suggest that CO2 influences the redox processes that take place in the system. No doubt that, in the system containing polymer and iron(III) sulfate, complex redox processes occur. In addition, this is confirmed by the formation of Fe2+ ions in the system.8 The Fe2+ ions are not able to form jarosite-type compounds; therefore, in the result of the redox processes in the polymer phase, decomposition of iron(III) compounds takes place. Therefore, a part of Fe2+ ions pass from the polymer in the liquid phase. Experimental data confirm this. After interruption of the process of formation of the jarositetype compounds by separating the polymer from solution for 10 h after 2.5 h and placing it again in solution, the content of Fe3+ in the polymer phase has decreased.8 Because in the solution of Fe2(SO4)3, which has been in contact with the polymer, no NO3− ions were found, we consider that in the system, nitrogen oxides NOx were initially formed, which were then converted into nitric acid. When the experiment was repeated after the iron was removed from the polymer used to obtain the nitrogen compounds in the previous experiment, almost the same amount of NO3− ions was obtained. This means that functional groups (R4N+) of the polymer do not directly participate in the redox processes. Therefore, we believe that, in the formation process of nitrogen compounds in the system, nitrogen participated from the air. Thus, the system containing strongly basic polymer and iron(III) sulfate solution is able to fix atmospheric nitrogen in soft conditions, resulting in obtaining nitric acid in one technological step. In industry, as already mentioned, the fixation of atmospheric nitrogen with the formation of ammonia, followed by nitric acid, occurs in several technological stages and at high temperature and pressure. Jarosite-type compounds in the polymer phase interact with oxygen and nitrogen from air, forming nitrogen compounds. As a result of these redox processes occurring in the system, partial destruction of jarosite takes place. The investigation demonstrated9 that the functional groups of the polymer −N(CH3)+ are part of the composition of jarosite-type compounds. However, the mobility of these groups is limited by the

Y = 1.66 + 0.023X1 − 0.46X 2 + 0.22X3 − 0.042X4 + 0.22X5 − 0.62X6 − 0.42X 7 ,

(3)

(2)

It was found that, after the experiment is completed, the nitrite content in the recipient is very small but that of the nitrate ions is quite large. The increase of the Fe2(SO4)3 concentration and solution pH positively influences the content of NO3− in the recipient and Fe3+ in the polymer phase. The more iron content in the polymer phase, the greater the amount of nitrate ions in the recipient. The rate of air bubbling through the solution of Fe2(SO4)3 leads on an increase of NO3− ion content in the recipient. With the temperature decrease of the system from 40 to 0 °C, containing 0.25 g of AV-17(Cl) and 100 mL of solution with a concentration of 2.5 g of Fe2(SO4)3/L and pH 2.0 at a rate of air bubbling through the system of 2 L/min, after 7 h, the content of NO3− ions in the recipient increased from 2.21 to 3.93 mg/g. As known, the solubility of the air in water increases with the temperature decreasing. Undoubtedly, some components of air are involved in the formation of nitrogen compounds, but it is unclear which of them (O2, N2, or CO2) contribute to nitrogen compound formation. To check whether oxygen participates in the formation of nitrogen compounds, we have performed experiments in the absence of oxygen but in the presence of nitrogen and carbon dioxide. In the same conditions, air was passed through the suspension of Mn(OH)2 and then through the system containing polymer and Fe2(SO4)3 solution. In this case, the content of NO3− in water was much less. This means that oxygen from air is involved in the process of nitrogen compound formation. To demonstrate that atmospheric nitrogen is directly involved in the formation of nitrogen compounds in the system, we have carried out additional experiments. Through the system containing 0.2 g of AV-17 polymer (from another factory) and 100 mL of solution containing 8 g/L Fe2(SO4)3, different C


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ACS Earth and Space Chemistry flexibility of the polymer chains. Therefore, both octahedra and octahedral cycles of the jarosite-type compounds in the pores of different dimensions of the polymer are distorted. Probably in the polymer phase, N2, O2, and CO2 interact in some cavities of cycles of jarosite. The packaging of structural units in natural or synthetic jarosite is compact. Thus, the stability and reactivity of jarosites in the polymer phase are different in natural or synthetic jarosites. However, does the mineralogical science say anything about the interaction of the natural jarosite with the components of air? Where do such processes take place in the presence of jarosite in nature? We think that in nature such processes occur. Although it is difficult to detect the formation of nitrogen compounds; in contrast, the partial destruction of jarosite with the formation of iron hydroxide (III) (as a result of the Fe2+ formation, followed by air oxidation) is observed. According to ref 25, jarosite in nature is always accompanied by Fe(OH)3, although we believe that it would rather be one of the modifications of FeOOH. Using Mössbauer spectroscopy, we have investigated the freshly prepared sample and after 9 months of storage in air of the polymer AV-17(Cl) in the phase of which was synthesized R4 N[Fe3 (OH) 6(SO 4) 2]. The Mössbauer spectra were obtained at room temperature. The Mössbauer spectrum of the freshly prepared sample represents a single doublet with the following parameters: isomeric shift δ = 0.384 mm/s, and quadrupole splitting ΔEQ = 1.142 mm/s. The Mössbauer spectrum of the sample that was stored in air up to 9 months consists of two doublets, which means that, in the polymer phase, the Fe3+ ions are in two different states. According to ref 26, a doublet (2 in Figure 2) with ΔEQ = 0.682

the same way. Therefore, it has been shown that jarosite in the polymer phase, kept in air, is also partially destroyed similar natural jarosite. However, natural jarosite and jarosite in the polymer phase are not destroyed completely upon interaction with components of air. This is clearly seen in the following research. The Ga2(SO4)3 and In2(SO4)3 solutions interact with ionic cross-linked polymers containing strongly basic groups. However, R4N[Ga3(OH)6(SO4)2] and R4N[In3(OH)6(SO4)2] compounds in the polymer phase are more unstable than R4N[Fe3(OH)6(SO4)2] and especially R4N[Cr3(OH)6(SO4)2]. As seen in Figures 3 and 4, sorption over time of Ga(III)- or In(III)-containing cations on anion exchanger AV-17(Cl) from

Figure 3. Kinetic curves of the Ga(III)-containing cation sorption on AV-17(Cl) polymer, in the conditions of (1) pH 2.0 and 17 °C, (2) pH 1.8 and 60 °C, (3) pH 2.0 and 60 °C, and (4) pH 2.0 and 60 °C with interrupting (phase separation for 4 h and then mixing them) the sorption process.

Figure 4. Kinetic curves of the In(III)-containing cation sorption on the AV-17 polymer at (1) 22 °C, (2) 54 °C, and (3) 60 °C.

Figure 2. Mössbauer spectrum of the polymer sample, containing jarosite, which was kept in the air up to 9 months: (1) Fe−jarosite and (2) FeOOH.

0.01 M Ga2(SO4)3 or In2(SO4)3 solutions goes through the maximum. This fact shows that, in time, a part of jarosite from the polymer phase is destroyed. The fact that the sorption of metal cations increases with the temperature demonstrates that processes in the system are chemical and not physical. The interactions of jarosite-type compounds with air components take place on the surface of the polymer granules. The histogram (Figure 5) clearly demonstrates that the retention of Ga3+ cations increases with increasing the specific surface of the polymer. As expected, the increase of the Ga2(SO4)3 and Na2SO4 concentrations, temperature, and solution pH results in increasing the Ga(III)-containing cation sorption. The existence of Cl− ions (KCl) in solution and air bubbling through the system negatively influences the metal cation sorption. The influence of Cl− ions is explained by the fact that they substitute SO42− ions in the polymer phase.

mm/s and δ = 0.520 mm/s belongs to Fe(OH)3 and the other with ΔEQ = 1.205 mm/s and δ = 0.492 mm/s (1 in Figure 2) belongs to the compound R4N[Fe3(OH)6(SO4)2].7,9 We consider that the internal doublet of the spectrum rather belongs to one of a modification of FeOOH in a superparamagnetic state. Considering that the initial polymer was in the form of Cl−, we can say that we have the β-FeOOH modification. According to refs 27−29, the formation of β-FeOOH occurs in the presence of Cl− or F− ions, although there are papers that indicated that β-FeOOH can be formed and in their absence. Suzdalev30 demonstrated that the spontaneous formation and transformation of α-, and γ-Fe2O3 from one modification to another depends upon the size of the particles. It is not excluded that α-, β-, δ-, and γ-FeOOH formation takes place in D


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Figure 6. Kinetic curves of (1) Ga(III)-containing and (2) In(III)containing cation sorption on the AV-17 polymer at 60 °C.

Figure 5. Histograms of Ga(III)-containing cation sorption depending upon polymer granule diameter: (1) 0.11−0.25, (2) 0.25−0.50, and (3) 0.50−1.2 mm, after (a) 14 h, (b) 18 h, and (c) 24 h of polymer contacting with Ga2(SO4)3 solution at 60 °C.

The main effect of the jarosite-type compounds in the polymer phase is their interaction with the air components in nitrogen fixation, resulting in the formation of nitrates under very soft conditions of pressure and temperature. The mechanism of the redox processes in the polymer−M2(SO4)3 solution system is very complicated and will remain for future investigations. At this stage, it can be assumed that atmospheric nitrogen and oxygen, getting in the cavity of distorted octahedral cycles of the jarosite compounds, lead to the formation of NOx. On the other hand, the investigation of different factors that influence the formation and destruction of jarosite compounds may be useful to understand some processes occurring in mineralogy. Furthermore, these investigations could have an impact on understanding some processes that occurred on some planets. It is known that using Mössbauer spectroscopy, in 2004, jarosite was discovered on Mars by Opportunity, one of the Mars exploration rovers of National Aeronautics and Space Administration (NASA). For scientists, it was an argument that, on Mars, water once existed.31,32 The Mössbauer spectra of rocks on Mars show that jarosite is accompanied by other iron compounds, including iron(II) and magnetic ordered phases (goethite and hematite).31,33 It is known that jarosite-type compounds are formed in an acid medium, but goethite and hematite are formed in a basic medium. It is also known34 that goethite at temperatures of 292 °C and higher turns into hematite. Therefore, we believe that the formation of goethite and hematite on the surface of Mars can be as a result of jarosite decomposition. There are many publications about possible destruction processes of jarosite on Mars.33,35 Could these processes, described in this paper about the destruction of jarosite and the

However, it is known that compounds of the jarosite type are not formed in the absence of SO42− ions. According to the regression equation, which expresses the degree of influence of various factors on the formation of nitrate ions, the factors that positively influence Ga3+ ion sorption negatively influence the formation of nitrate ions. Coefficients of the regression equation allowed us to perform the experiment (Table 2) to optimize the formation of nitrate ions in the recipient. In this experiment, X1 is the concentration of Ga2(SO4)3 (g/L), X2 is the temperature (°C), X3 is the pH of the solution, X4 is the concentration of Na2SO4 (mol/L), and X6 is the duration of contact of the polymer with the solution (h). The air bubble rate through the system was constant and equal to 1 L/min. The data from Table 2 show that the nitrogen compounds are produced in a larger amount than in the solution of Fe2(SO4). In the system containing polymer AV-17(Cl) and Ga2(SO4)3 solution, in the recipient (4 in Figure 1), 15.35 mg of NO3−/g was found. The Cl− ions in the solution contribute to the formation of nitrogen compounds and the destruction of metal compounds in the polymer phase. Over time, the processes of formation and destruction of Ga−jarosite and In−jarosite in the polymer phase occur cyclically (Figure 6). From Figures 3−6, it is clear that the compounds of Ga(III) and In(III) in the polymer phase do not break down completely. This can be explained by the fact that not all of the octahedral cycles of jarosite in the polymer phase participate in redox processes that lead to their destruction.

Table 2. Optimizing the Formation Process of NO3− Ions in Water by the System Containing AV-17(Cl) and a Solution of Ga2(SO4)3 X1

X2

X3

X4

X6

X7

step and number of experiment

−0.0002

−5

+0.1

−0.015

+0.003

+1

1 2 3 4 5 6 7 8 9 10 11

0.0123 0.0121 0.0119 0.0117 0.0115 0.0113 0.0111 0.0109 0.0105 0.0103 0.0101

45 40 35 30 25 20 20 0 0 0 0

1.9 2.0 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1

0.010 0.005 0 0 0 0 0 0 0 0 0

0.018 0.021 0.024 0.027 0.030 0.033 0.036 0.039 0.042 0.045 0.048

6 7 8 9 10 11 12 12 12 12 12

E

Y (mg of NO3−/g)

4.96 7.78 15.53 15.53 4.96


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(8) Gutsanu, V.; Schitco, C.; Drutsa, R. Unforeseen Factors Influencing Fe(III)-Containing Cations Sorption on Strongly Basic Anion Exchangers. J. Appl. Polym. Sci. 2008, 109, 2643−2647. (9) Gutsanu, V.; Schitco, C.; Lisa, G.; Turta, C. Ultra Dispersed Particles of Fe(III) Compounds in the Strongly Basic Crosslinked Ionic Polymer-Precursors for New Sorbents and Catalysts. Mater. Chem. Phys. 2011, 130, 853−861. (10) Dutrizac, J. E.; Kaiman, S. Synthesis and Properties of JarositeType Compounds. Can. Mineral. 1976, 14, 151−158. (11) Dutrizac, J. E.; Chen, T. E. Factors Affecting the Precipitation of Chromium(III) in Jarosite-Type Compounds. Metall. Mater. Trans. B 2005, 36, 33−42. (12) Dutrizac, J. E.; Chen, T. E. The Behavior of Scandium, Yttrium and Uranium during Jarosite Precipitation. Hydrometallurgy 2009, 98, 128−135. (13) Dutrizac, J. E.; Chen, T. E. Synthesis and Properties of V3+ Analogues of Jarosite-Group Minerals. Can. Mineral. 2003, 41 (2), 479−488. (14) Morimoto, T.; Nishiyama, M.; Maegawa, S.; Oka, Y. Magnetization of New Kagomé Lattice Antiferromagnets: Cr-Jarosites, ACr3(OH)6(SO4)2 [A = Na, K, Rb, NH4]. J. Phys. Soc. Jpn. 2003, 72, 2085−2090. (15) Papoutsakis, D.; Grohol, D.; Nocera, D. G. Magnetic Properties of a Homologous Series of Vanadium Jjarosite Compounds. J. Am. Chem. Soc. 2002, 124, 2647−2656. (16) Archipenco, D. K.; Devyatkina, E. T.; Palichik, N. A. Cristallochemical Partucularities of Synthetic Jarosites; Nauka: Novosibirsk, Russia, 1987 (in Russian). (17) Gutsanu, V. Ionic-Molecular Constructions in the Polymer PhaseA New Way To Obtain Different Materials with Selective Properties. IJIRSET 2015, 4, 8989−9001. (18) Matashige, O.; Ohzabu, U. A Study of the Precipitates Formed by Hydrolysis of Fe(III) Nitrate Solution Conaining Na+ and SO42−. J. Inorg. Nucl. Chem. 1981, 43, 1948−1949. (19) Lurie, A. A. Sorbents and Chromatographic Carriers; Nauka: Moscow, Russia, 1972. (20) Marchenko, Z. Photometrical Determination of Elements; Mir: Moscow, Russia, 1972. (21) Roman, L.; Sandulescu, R. Analytical Chemistry. Qualitative Chemical Analyses; Didactica si Pedagogica R.A.: Bucharest, Romania, 1999 (in Romanian). (22) Bondar, A. Mathematical Modeling in Chemical Technology; Visha Shkola, Kiev, Ukraine, 1973 (in Russian). (23) Nakamoto, K. Infrared and Raman Spectra of Inorganic and Coordination Compounds; Mir: Moscow, Russia, 1991. (24) Gutsanu, V. Unforeseeable Processes in the Systems Containing Strongly Basic Crosslinked Ionic Polymer and Fe2(SO4)3. Adv. Chem. Sci. 2013, 2, 96−99. (25) Betehtin, A. G. Mineralogy Course; Book House “University”: Moscow, Russia, 2010. (26) Goldanskii, V. I. Chemical Applications of Mössbauer Spectroscopy; Mir: Moscow, Russia, 1970. (27) Ohyabu, M.; Ujihara, Y. Study of the Chemical States of Chlorine and Fluorine in Akaganétte. J. Inorg. Nucl. Chem. 1981, 43, 3125−3129. (28) Šarić, A.; Musić, S.; Nomura, K.; Popović, S. Microstructural Properties of Fe-Oxide Powders Obtained by Precipitation from FeCl3 Solutions. Mater. Sci. Eng., B 1998, 56, 43−52. (29) Musić, S.; Krehula, S.; Popović, S.; Skoko, Ž . Some Factors Influencing Forced Hydrolysis of FeCl3 Solutions. Mater. Lett. 2003, 57, 1096−1102. (30) Suzdalev, I. P. Gamma Resonance Spectroscopy of Proteins and Model Compounds; Mir: Moscow, Russia, 1991. (31) Elwood Madden, M. E.; Bodnar, R. J.; Rimstidt, J. D. Jarosites as an Indicator of Water-Limited Chemical Weathering on Mars. Nature 2004, 431, 821−823. (32) Rull, F.; Fleischer, I.; Maretinez-Frias, J.; San, A.; Upadhyay, C.; Klingelhofer, G. Raman and Mössbauer Spectroscopic Characterization of Sulfate Minerals from the Mars Analogue Sites at Rio Tinto

formation of nitrogen compounds, have occurred on Mars? As known, the Martian atmosphere contains small amounts of nitrogen compounds (N2O and NH3),36,37 and we assume that such a process would have taken place on Mars. Finally, it is to be said that processes of jarosite-type compounds and nitrogen compound formation take place not only using polymer AV-17(Cl). Experiments have shown that they take place in the systems containing such strongly basic polymers as Purolite A-400, Dowx 1X8, Varion AD, and Ionenausta Uscher (III) as well.

4. CONCLUSION The investigated nitrogen fixation processes are carried out in a system containing cross-linked ionic polymer and sulfate solution of trivalent metal (Fe3+, Ga3+, In3+, and others). In this system, the formation and partial destruction of jarositetype compounds takes place in the polymer phase, which results in the formation of nitrogen compounds (NO2− and NO3−). The nitrogen fixation takes place in very soft (0 °C and 1 atm) conditions in one technological step. We anticipate our paper to be a starting point for obtaining more interesting results in chemistry (in catalysis and technology), mineralogy, geochemistry, and maybe even cosmochemistry.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Vasile Gutsanu: 0000-0002-0159-415X Notes

The author declares no competing financial interest.

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ACKNOWLEDGMENTS The author thanks Ala Shishianu for providing language help and A. Paholnitsky for participation in the performance of some experiments.

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REFERENCES

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