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Review

Nitrous Oxide from Abiotic Processes of Hydroxylamine and Nitrite in Estuarine and Coastal Ecosystems: A Review

1
Key Laboratory for Humid Subtropical Eco-Geographical Processes of the Ministry of Education, Fujian Normal University, Fuzhou 350007, China
2
Fujian Provincial Key Laboratory for Plant Eco-Physiology, Fujian Normal University, Fuzhou 350007, China
3
Fujian Provincial Key Laboratory of Coastal Basin Environment, Fujian Polytechnic Normal University, Fuzhou 350300, China
*
Author to whom correspondence should be addressed.
J. Mar. Sci. Eng. 2022, 10(5), 623; https://doi.org/10.3390/jmse10050623
Submission received: 27 March 2022 / Revised: 27 April 2022 / Accepted: 29 April 2022 / Published: 2 May 2022
(This article belongs to the Special Issue Advances in Marine Nitrogen Cycle)

Abstract

:
Abiotic processes of nitrogen (N) are suggested to contribute to nitrous oxide (N2O) production; however, the important role of these processes in N2O emissions is invariably ignored. This review synthesized the main abiotic processes of hydroxylamine and nitrite and associated biogeochemical controls in estuarine and coastal ecosystems. Abiotic processes of hydroxylamine and nitrite are availably detected in estuarine and coastal environments. The abiotic processes of hydroxylamine contribute more to N2O production than the abiotic processes of nitrite in estuarine and coastal environments, suggesting that hydroxylamine plays an important role in N2O production. The isotopic fractionation effects of N can occur during the abiotic processes of hydroxylamine and nitrite and are enriched with the increasing rates of N reactions. In addition, abiotic processes of hydroxylamine and nitrite are highly dependent on pH, oxygen, Fe2+, Fe3+, and Mn4+ and are also triggered by the increasing substrate contents. These results suggest that abiotic processes of hydroxylamine and nitrite have been greatly concerned for the estuarine and coastal environments, whereas the dynamics of these processes are still sparse for projecting N fates and dynamics in response to environmental factors changes. This review highlights the importance of abiotic processes of N and associated environmental implications and presents the future trend of N cycling in estuarine and coastal environments.

1. Introduction

Over the past five decades, human activities have doubled the nitrogen (N) loads in the Earth system [1]. The extensive N loads not only deteriorate the water quality but also trigger the N2O emissions [2,3,4,5]. It was reported that the atmosphere N2O concentration has increased from 270 ppb to 325 ppb since the industrial revolution [6,7]. In addition, the N pollution and sources show diversification characteristics under climate changes and human activities [8,9,10], which altered N cycling and made the pathways of N2O production more complicated [3,11,12]. Recently, more and more studies have been concerned about the abiotic processes of N, contributing to the improvement of the N cycling mechanism, and promoting the understanding of the importance of abiotic pathways of N conversion in N2O production [13]. Therefore, more studies are required on the abiotic processes of N cycling and their contributions to N2O production.
Hydroxylamine and nitrite are the important intermediate products in nitrification. Although hydroxylamine and nitrite are short-term and not favorably accumulated in environments, they can contribute to N2O production through biotic and abiotic processes [13,14]. The abiotic processes of hydroxylamine and nitrite were deleted, playing parts in N2O production. The abiotic process of hydroxylamine (NH2OH) coupled with iron/ manganese oxides are below [15,16]:
4Fe3+ + 2NH2OH → 4Fe2+ + N2O + H2O + 4H+
2Mn4+ + 2NH2OH → 2Mn2+ + N2O + H2O + 4H+
Abiotic processes of nitrite (NO2) is generally coupled with Fe2+ and Mn2+ to generate N2O (Picardal, 2012) [17]:
4Fe2+ + 2NO2 + 5H2O → 2Fe3+ + N2O + 6H+
2Mn2+ + 2NO2 + 6H+ → 2Mn4+ + N2O + 3H2O
Because these substrates are enriched in aquatic environments, their abiotic processes are favorable to occur in such environments and contribute to parts of N2O production. There are many studies on N2O production from the abiotic processes of hydroxylamine in the context of paddy soils, cropland, and forests [13,18,19]. More importantly, Otte et al. [20] also reported that the chemdenitrification (nitrite-induced) contributed 15–25% of N2O production in coastal sediments, suggesting that the abiotic process is an important contributor to N2O emissions. These results, therefore, indicate abiotic processes of N should be received attention in the estuarine and coastal environments.
Understanding the mechanisms of N2O production is critical for projecting N2O emissions and environmental effects in estuarine and coastal ecosystems. Therefore, N2O production processes in estuarine and coastal environments attracted considerable attention and achieved great progress. By progressing through the abiotic processes of N cycling, this study reviews potential abiotic reactions of hydroxylamine and nitrite in the estuarine and coastal environments. Although numerous studies on abiotic processes of N were found in laboratory and natural environments over four decades, the data for hydroxylamine and nitrite are sparse for estuarine and coastal environments. This manuscript reveals previous abiotic studies in the context of abiotic processes of hydroxylamine and nitrite in the estuarine and coastal environments. The main objectives of this review were: (1) N2O production from abiotic processes of hydroxylamine and nitrite; (2) isotopic effects of N2O production from abiotic processes of hydroxylamine and nitrite; (3) key factors of N2O production from abiotic processes of hydroxylamine and nitrite. This review attempted to provide deeper insights into the potential or simultaneous abiotic reactions of N and into interpreting the relative contributions of abiotic processes in studies of total N2O production.

2. N2O Production from Abiotic Processes of Hydroxylamine and Nitrite

Estuarine and coastal environments are the important ecosystems on the Earth, playing a critical role in global biogeochemical cycling. Most studies reported that estuarine and coastal environments are important sources of N2O emissions [3,21,22,23]. N2O is the intermediate and by-product of the N transformation, and exploring the pathways of N2O production is increasingly concerned. Traditionally, nitrification and denitrification are the main process of N2O production) [3,24,25]; however, the coupled nitrification–denitrification and nitrifier denitrification can also generate N2O (Figure 1) [26]. It was reported that nitrification and nitrifier denitrification contributed to 44.3–47.7% and 26.7–53.9% of the Yellow River Estuary [27]. In addition, nitrification and nitrifier denitrification are responsible for 4.52–12.6% and 13.9–21.6%, where denitrification is the dominant process accounting for 69.8–80.1% of N2O emissions [28]. These results suggest that these processes that contribute to the N2O emissions differed across the estuarine and coastal environments. The sources of N are more complicated under the high human activities, likely affecting N transformation and N2O pathways [9,29,30]. In addition, dry–wet cycling can alter the N2O pathways most due to the periodic waterlogging and air exposure, which can trigger the abiotic processes of N2O production.
Recently, abiotic processes of N2O production were evidenced by the improvement of methods and technology [3,19,31,32,33]. It was reported that the chemical processes of hydroxylamine and nitrite can be coupled with iron/manganese oxides and humus [13] and are the main abiotic pathways of N2O production [13,32,34,35]. The first report showed that MnO2 can oxide hydroxylamine to produce N2O in forest soil, and N2O emissions increased with the increasing MnO2 contents, indicating the abiotic process of hydroxylamine coupled with the MnO2 is the important pathway of N2O production [18]. Sun et al. [27] found that abiotic processes contributed 93.4–1194% of N2O emissions. However, this study could not distinguish the specific process for N2O production. Wankel et al. [36] reported that chemodenitrification could be responsible for parts of N2O emissions from the coastal sediments, but the contribution has not been quantified. Subsequently, 15–25% of N2O emissions were generated from nitrite coupled with Fe2+ oxidation (chemodenitrification) in the coastal sediments [20]. Other studies emphasized that hydroxylamine oxidation could be the main process of N2O production because metal oxides can cause oxide hydroxylamine to generate much N2O [37]. Therefore, these results suggest that abiotic processes of hydroxylamine and nitrite are the important pathways of N2O formation; however, there are limited studies regarding their relative contribution to N2O emissions in estuarine and coastal environments.

3. Isotopic Fractionation Effects of N2O Production from Abiotic Processes of Hydroxylamine and Nitrite

Isotopic values of N and O are the very available method for distinguishing N2O production pathways [31]. Many studies used the isotopic method to discriminate the N2O sources and have achieved greatly [13,38]. The site preference of 15N-N2O generated from microbially mediated nitrification and denitrification is in a range of 33–37‰ and −10–0‰, respectively [39], which are not overlapped. Gao et al. [28] reported that the SP-N2O was 4.09–13.69‰, which did not overlap with nitrification and denitrification, indicating that the N2O derived from a mixture of nitrification and denitrification. It was reported that the SP-N2O ranged from 2 to 21‰ in the coastal sediments, which overlapped with chemodenitrification (SP, 2–25‰) [32,35]. Another study also reported that the SP-N2O of chemodenitrification was −4‰, which was comparable with the value of bacterial denitrification [40]. Therefore, it is difficult to discriminate the biotic and abiotic processes of N2O sources based on only SP. Recently, the SP-N2O from the abiotic processes of hydroxylamine and nitrite was studied, further understanding the mechanisms of N2O production from abiotic processes. Heil et al [31] also reported that the SP-N2O from abiotic processes of NH2OH coupled with NO2, Fe3+, Fe2+ and Cu2+ are very stable, with a value of 34–35‰ that did not change with the changes in conditions (Figure 2).
The NO2 reduction coupled with Fe2+ oxidation can generate the SP of 10–22‰, indicating that NO2 abiotic processes can cause large isotopic effects [32]. In addition, Buchwald et al. [35] also found a similar result that chemodenitrification produces the N2O of SP > 10‰, and high concentrations of Fe2+ could stimulate chemodenitrification, leading to the increase in SP to 26‰. However, the SP-N2O produced from the coupled NO2 and organics abiotic processes showed a large difference (Δ20‰) and changed with time changes [41]. Therefore, the isotopic effects of N and O are highly dependent on N2O production pathways. The relationship of δ15N-N2O with NO2 and NH2OH could be consistent across different environments, which likely correlated with the low N2O rates [31]. It was reported that the isotopic value of δ15N-N2O decreased from −5‰ to −8‰, while the value was −1.93‰ for δ15N-NH2OH, suggesting that δ15N-N2O from NH2OH oxidation was depleted [31]. Buchwald et al [35] used the dual isotopes of N and O to study the abiotic processes of the coupled Fe2+ and NO2, indicating that the δ15N and δ18O were −19.8–−3.0‰ and +29.3–+46.4‰, respectively, and they showed a good correlation. The isotopic values of N and O during the chemodenitrfication (NO2) are altered, of which ε15N and ε18O were 6–45‰ and 6–33‰, respectively, indicating that N and O depletion effects occurred [35]. However, Grabb et al. [19] found that NO2 reduction was driven by Fe2+ to generate N2O, leading to ε15N of 2–11‰ and ε18O of 4–10‰, which can decrease with the increasing chemodenitrification rates. The microbially mediated NO2 reduction to N2O can cause the N isotope enrichment, and Δδ15N is 1–9‰ [36], which differed from the abiotic processes of NO2 and Fe2+ (Δδ15N, 16–38‰) [19,32,35], suggesting that the fractionation effects of 15N differed greatly between biotic and abiotic processes. Currently, although the SP is increasingly used to discriminate the N2O pathways, there is limited study on the SP-N2O from abiotic processes of hydroxylamine and nitrite coupled with iron/manganese. The characteristics of N and O isotope fractionation of N2O produced by abiotic processes hydroxylamine and nitrite coupled with iron/manganese in estuarine wetlands remain unclear, which limits the understanding of the mechanisms of N2O production.

4. Key Factors of N2O Production from Abiotic Processes of Hydroxylamine and Nitrite

The N2O production is not only affected by N transformations but also influenced by substrates and environmental factors; therefore, there are many studies on the influencing factors of N2O production. It was reported that human activities that drive the N loads increases could shift from a net sink to net sources of N2O, of which C:N:P could be the main factor that drives the N2O emissions [3]. The nitrification can switch to nitrifiers denitrification under the low oxygen and organic carbon conditions, leading to N2O production through denitrification [42]. Cavazos et al. [37] found that the abiotic process of hydroxylamine is the main process of N2O production, mostly due to the fact that metal oxides can stimulate nitrification to produce much hydroxylamine, indicating that metal oxides contents can affect the abiotic processes of N2O production. Most studies reported that mineral classification and surface-bound Fe2+ could catalyze the NO2 reduction; thus, iron mineral classification can affect the extensity of chemodenitrification and isotopic fractionation effects [17,19,32,35]. In addition, the different forms of iron have different processes of N2O, of which Fe2+ oxidation coupled with NO2 and NO3 to produce N2O, Fe(III) can oxide NH2OHto produce N2O [13]. Because of large N2O production by chemodenitrification (NO2), chemodenitrification (NO2) can produce more N2O under the riched-NO2 environments [41]. Therefore, the nitrification could accumulate NO2, NO2 level is an important factor for the N2O production.
Abiotic processes of hydroxylamine and nitrite are dependent on pH because pH can affect their fate and reaction activity [43,44]. The pH > 7 conditions are favorable for NO2 fate and can easily react with Fe2+ [35]. Under alkaline conditions, hydroxylamine can generate N2O through abiotic processes [45]. The high nitrification can be favorable for the hydroxylamine availability responsible for the large N2O production [13]. Therefore, estuarine wetlands are favorable for the accumulations of hydroxylamine and nitrite, leading to more N2O production. A recent study indicated that the abiotic process of NH2OH can generate more N2O than NO2; this is due to the fact that low organic carbon and high Mn4+ are more favorable for the NH2OH oxidation to N2O [45]. The hypoxia condition can stimulate the NO2 reduction and generate more N2O. However, hypoxia condition can decrease NH2OH for the N2O production, indicating oxygen level is also an important factor in modifying NH2OH and NO2 [45,46]. However, NO2 can react with phenolic compounds and humus to produce N2O [47], and NO2 is also coupled with Cu2+ and Mn2+ to produce minor N2O [13]. Although Otte et al. [20] reported that coastal sediment chemodenitrification (NO2) contributed 15–25% of N2O, influencing factors have not been revealed. In addition, the crucial variables affecting the abiotic processes of hydroxylamine and nitrite in estuarine and coastal environments remain unclear, which could limit the modifying mechanisms.

5. Study Limitation and Future Outlook

Abiotic processes of hydroxylamine and nitrite are the important N cycling in estuarine and coastal environments. However, abiotic processes of hydroxylamine and nitrite can generate N2O, an important greenhouse gas leading to global warming. The relative contributions of the abiotic processes of hydroxylamine and nitrite to N2O emissions remain unclear, mostly due to the limited studies for estuarine and coastal environments. In addition, some studies only report that abiotic processes may generate N2O, but the associated influencing factors were well investigated in the estuarine and coastal environments. Some study contents are required in the future. The contributions of hydroxylamine and nitrite through abiotic processes to N2O production are quantized to highlight the importance of abiotic processes in N biogeochemical cycling. The isotope fractionation effects of N and O from hydroxylamine and nitrite to N2O can elucidate the mechanisms of N2O production by the abiotic processes. In addition, the variations in N2O production through the abiotic processes of hydroxylamine and nitrite should be illustrated to project the N2O emissions from estuarine and coastal environments better. Last but not least, the physical dynamics of hydroxylamine and nitrite should be paid more attention to because the estuarine and coastal environments are typical ecosystems of tidal hydrodynamics that can greatly affect the N transformations.

6. Conclusions

This study concluded that there are limited studies on abiotic processes of hydroxylamine and nitrite in estuarine and coastal environments due to the difficult achievements. In addition, the contribution of hydroxylamine and nitrite abiotic processes to N2O production remains unclear, which may limit the understanding of the importance of abiotic processes of N transformation in N2O production. In addition, the dynamics of isotope fractionation of N and O by the N2O production from abiotic processes of hydroxylamine and nitrite are critical for understanding the mechanisms of N2O production; unfortunately, associated contents were not conducted in the estuarine and coastal environments. The hydroxylamine could contribute more N2O production than the nitrite by abiotic processes. However, this should be verified in the estuarine and coastal environments. Therefore, abiotic processes of N transformations play an important role in N cycling, and more studies are required in the future.

Author Contributions

Conceptualization, C.X., X.L. and W.L.; methodology, X.L.; formal analysis, C.X. and X.L.; writing—original draft preparation, C.X., M.Q., W.L. and X.L.; writing—review and editing, C.X., M.Q., W.L. and X.L.; funding acquisition, C.X. and X.L. All authors have read and agreed to the published version of the manuscript.

Funding

This research was supported by the National Science Foundation of China (Grants 42071130, 41601008), the General Program of Natural Science Foundation of Fujian Province of China (Grants 2020J01184, 2018J01737), the project of Fujian Forestry Bureau (2021FKJ29), and Open Foundation of Fujian Provincial Key Laboratory of Coastal Basin Environment (S1-KF2004).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. Main processes of N2O production in aquatic environments.
Figure 1. Main processes of N2O production in aquatic environments.
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Figure 2. Isotopic fractionation of N and O during the N2O production from abiotic processes of NH2OH and NO2.
Figure 2. Isotopic fractionation of N and O during the N2O production from abiotic processes of NH2OH and NO2.
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Xu, C.; Qi, M.; Lin, W.; Li, X. Nitrous Oxide from Abiotic Processes of Hydroxylamine and Nitrite in Estuarine and Coastal Ecosystems: A Review. J. Mar. Sci. Eng. 2022, 10, 623. https://doi.org/10.3390/jmse10050623

AMA Style

Xu C, Qi M, Lin W, Li X. Nitrous Oxide from Abiotic Processes of Hydroxylamine and Nitrite in Estuarine and Coastal Ecosystems: A Review. Journal of Marine Science and Engineering. 2022; 10(5):623. https://doi.org/10.3390/jmse10050623

Chicago/Turabian Style

Xu, Chaobin, Mengting Qi, Weisheng Lin, and Xiaofei Li. 2022. "Nitrous Oxide from Abiotic Processes of Hydroxylamine and Nitrite in Estuarine and Coastal Ecosystems: A Review" Journal of Marine Science and Engineering 10, no. 5: 623. https://doi.org/10.3390/jmse10050623

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