Abiotic hydroxylamine nitrification involving manganese- and iron-bearing minerals

Rue, Kristie; Rusevova, Klara; Biles, Caleb L.; Huling, Scott G.

doi:10.1016/j.scitotenv.2018.06.397

Cited by 15 publications

(5 citation statements)

References 25 publications

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“…Our previous research has shown that NH 2 OH reacts rapidly in seawater with MnO 2 , with near-complete conversion to the potent greenhouse gas nitrous oxide (Cavazos et al 2018). We hypothesize that the high flux of nitrous oxide emissions from coastal waters, including the Louisiana Shelf (Walker et al 2010;Kim 2018), may be at least partially due to coupled biotic-abiotic reactions between Mn(III/IV)O x particles and reactive intermediates in nitrogen cycle, such as hydroxylamine similar to reactions in soils (Rue et al 2018). This hypothesis awaits further testing.…”

Section: Discussionmentioning

confidence: 91%

Simul‐staining manganese oxides and microbial cells

Cavazos

Glass

2020

Limnology & Ocean Methods

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Manganese oxide minerals (Mn(III/IV)Ox) are ubiquitous in natural environments and interactions between Mn(III/IV)Ox and microbes play important roles in biogeochemical cycles. Current techniques for determining the spatial distribution of microbes with Mn(III/IV)Ox include electron microscopy and synchrotron radiation analyses. However, these techniques may not be readily available in most laboratories or may be cost prohibitive. Here we present a rapid, cost‐effective “simul‐staining” method for imaging particulate Mn(III/IV)Ox and cells on the same filter using epifluorescence microscopy with differential interference contrast (DIC) capability as a prescreening tool before higher resolution and/or more time‐intensive analyses. This method uses leucoberbelin blue (LBB) dye, which turns blue when oxidized by particulate Mn(III/IV)Ox on filters, and the fluorescent nucleic acid stain, SYBR Green, which fluoresces when bound to nucleic acids. First, the DIC configuration is used to locate blue “haloes” of oxidized LBB around Mn(III/IV)Ox particles. Second, a filter set that excites dyes with blue light and emits green fluorescence is used to image SYBR Green bound to nucleic acids in cells. Third, ImageJ is used for image analysis to associate Mn(III/IV)Ox particles and microbes. We demonstrate that this simul‐staining is suitable for laboratory cultures of manganese‐oxidizing bacteria as well as environmental samples from a marine oxycline.

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Section: Discussionmentioning

confidence: 91%

Simul‐staining manganese oxides and microbial cells

Cavazos

Glass

2020

Limnology & Ocean Methods

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“…10,11 N 2 O can be produced from NH 2 OH by bacteria 12 and archaea, 10 and it can also be produced abiotically from interactions among these reactive intermediates and metals such as ferrous iron and manganese. 13,14 During denitrification, nitrate (NO 3 − ) is reduced step-wise to nitrogen gas (N 2 ), with nitrite (NO 2 − ), nitric oxide (NO), and nitrous oxide (N 2 O) as intermediate products. 15 Since each step of this modular process can be performed by different microorganisms, the balance between NO reduction and N 2 O reduction can result in either net production or consumption of N 2 O. Abiotic or "hybrid" (the abiotic conversion of microbially produced hydroxylamine) production of N 2 O via hydroxylamine oxidation has also been reported.…”

Section: Introductionmentioning

confidence: 99%

“…Multiple microbially mediated processes, including nitrification and denitrification, can produce N 2 O . During nitrification, ammonium (NH 4 + ) is oxidized to nitrite (NO 2 – ) and then nitrate (NO 3 – ), with reactive compounds including hydroxylamine (NH 2 OH) and nitric oxide (NO) as intermediate products. , N 2 O can be produced from NH 2 OH by bacteria and archaea, and it can also be produced abiotically from interactions among these reactive intermediates and metals such as ferrous iron and manganese. , During denitrification, nitrate (NO 3 – ) is reduced step-wise to nitrogen gas (N 2 ), with nitrite (NO 2 – ), nitric oxide (NO), and nitrous oxide (N 2 O) as intermediate products . Since each step of this modular process can be performed by different microorganisms, the balance between NO reduction and N 2 O reduction can result in either net production or consumption of N 2 O. Abiotic or “hybrid” (the abiotic conversion of microbially produced hydroxylamine) production of N 2 O via hydroxylamine oxidation has also been reported. , Understanding how different N 2 O cycling processes and the associated microbial community respond to fertilization holds the key to predicting and managing N 2 O emissions from salt marsh ecosystems.…”

Section: Introductionmentioning

confidence: 99%

Long-Term Fertilization Alters Nitrous Oxide Cycling Dynamics in Salt Marsh Sediments

Peng

Angell

et al. 2021

Environ. Sci. Technol.

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Salt marsh sediments are known hotspots for nitrogen cycling, including the production and consumption of nitrous oxide (N2O), a potent greenhouse gas and ozone-depleting agent. Coastal eutrophication, particularly elevated nitrogen loading from the application of fertilizers, is accelerating nitrogen cycling processes in salt marsh sediments. Here, we examine the impact of long-term fertilization on nitrogen cycling processes with a focus on N2O dynamics in a New England salt marsh. By combining 15N-tracer experiments with numerical modeling, we found that both nitrification and denitrification contribute to net N2O production in fertilized sediments. Long-term fertilization increased the relative importance of nitrification to N2O production, likely a result of increased oxygen penetration from nutrient-induced increases in marsh elevation. Substrate utilization rates of key nitrogen cycling processes revealed links between functions and the corresponding microbial communities. Higher specific substrate utilization rates leading to N2O production from nitrification in fertilized sediments indicate a shift in the community composition of ammonia oxidizers, whereas the lack of change in specific substrate utilization of N2O production from denitrification under long-term fertilization suggests resilience of the denitrifying communities. Both are consistent with previous studies on the functional gene community composition in these experimental plots.

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“…performed laboratory experiments that showed rapid production of N2O from reaction of the phyllomanganate birnessite and NH2OH under environmental conditions. Similarly, Rue et al (2018) reacted NH2OH with pyrolusite and poorly crystalline MnO2(s) and found 82-86% transformed to N2O. Taken together, these studies suggest oxidized mineral forms of Mn also play an important role in transforming NH2OH to N2O.…”

Section: Potential Environmental Relevancementioning

confidence: 77%

“…In recent years, increasing evidence has emerged implicating abiotic processes in N2O production Zhu-Barker et al 2015). Manganese (Mn) in the form of Mn(III,IV) (oxy)(hydr)oxides (hereinafter Mn oxides) has also been linked to production of N2O both in laboratory experiments (Toyoda et al 2005;) and in soils (Bremner et al 1980;Duan et al 2020;Heil et al 2015a;Liu et al 2017b;Liu et al 2019;Rue et al 2018). While many of these studies assume Mn is in the form of either soluble Mn(II) or solid Mn oxides, in recent years soluble Mn(III) has been shown to be stabilized by ligands and may in fact represent the dominant Mn species in some environments Oldham et al 2015).…”

Section: Introductionmentioning

confidence: 99%

Coupled cycling of metals with nitrogen and carbon in marine sediments

Karolewski

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Cross element processes are complex and often understudied components within biogeochemical cycles. In this thesis, I use stable isotopes of carbon, nitrogen, and oxygen as the primary tools to interrogates these complex reactions. First, I report abiotic oxidation of nitrite to nitrate by manganese(III)-pyrophosphate. This reaction can occur even in the absence of oxygen, unlike biological nitrite oxidation. Reaction rates were measured at a range of environmentally relevant pH values (5-8) with the reaction proceeding more quickly at lower pH. Reaction order was second order with respect to manganese(III) and first order with respect to nitrous acid. No reversibility of reaction was observed upon addition of isotopically distinct nitrate. An inverse kinetic isotope effect of +19.9 ± 0.7‰ was calculated, which was comparable in magnitude and direction to that of biological nitrite oxidation. In natural waters, such as estuaries, this reaction could potentially play an important role in the nitrogen cycle. Next, I report an abiotic reaction between hydroxylamine and manganese(III)-pyrophosphate which forms nitrous oxide, nitrite, and likely dinitrogen gas. In artificial seawater (pH = 8), this reaction proceeds rapidly, with the ratio of products highly dependent on the reactant ratio. Nitrous oxide site preference (SP) of +35.5 ± 0.6‰ was observed, consistent with the isotopic signatures of several marine nitrifying organisms. This suggests that “leakage” of intermediate hydroxylamine from nitrifier cells could potentially react with manganese(III) in a mixed biotic-abiotic process without previously being noticed. Finally, I performed experiments using carbon-13 labelling to measure rates of anaerobic oxidation of methane (AOM) in cold seep sediments collected at Cascadia Margin. Four forms of oxidized manganese and four forms of oxidized iron were added to treatments in order to evaluate how these altered rates of AOM. In contrast to previous work, addition of metals did not overall increase rates of AOM above those of an unamended control and some treatments in fact reduced it. However, energy yields from microbes using metal as an electron acceptor are higher per mole of methane reduced than that of using sulfate so even with these lower rates, energy yields would have exceeded those of controls. Additionally, doubling times for the archaea performing AOM are long enough that the microbial community may not have been able to adapt on the timescale of the experiment. Overall, the results of this thesis illuminate the need for further study of abiotic and coupled cycling reactions when considering biogeochemical cycles.

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Abiotic hydroxylamine nitrification involving manganese- and iron-bearing minerals

Cited by 15 publications

References 25 publications

Simul‐staining manganese oxides and microbial cells

Simul‐staining manganese oxides and microbial cells

Long-Term Fertilization Alters Nitrous Oxide Cycling Dynamics in Salt Marsh Sediments

Coupled cycling of metals with nitrogen and carbon in marine sediments

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