Nitrate/nitrite-dependent
anaerobic methane oxidation (n-DAMO)
is critical for mitigating methane emission and returning reactive
nitrogen to the atmosphere. The genomes of n-DAMO archaea show that
they have the potential to couple anaerobic oxidation of methane to
dissimilatory nitrate reduction to ammonium (DNRA). However, physiological
details of DNRA for n-DAMO archaea were not reported yet. This work
demonstrated n-DAMO archaea coupling the anaerobic oxidation of methane
to DNRA, which fueled Anammox in a methane-fed membrane biofilm reactor
with nitrate as only electron acceptor. Microelectrode analysis revealed
that ammonium accumulated where nitrite built up in the biofilm. Ammonium
production and significant upregulation of gene expression for DNRA
were detected in suspended n-DAMO culture with nitrite exposure, indicating
that nitrite triggered DNRA by n-DAMO archaea. 15N-labeling
batch experiments revealed that n-DAMO archaea produced ammonium from
nitrate rather than from external nitrite. Localized gradients of
nitrite produced by n-DAMO archaea in biofilms induced ammonium production
via the DNRA process, which promoted nitrite consumption by Anammox
bacteria and in turn helped n-DAMO archaea resist stress from nitrite.
As biofilms predominate in various ecosystems, anaerobic oxidation
of methane coupled with DNRA could be an important link between the
global carbon and nitrogen cycles that should be investigated in future
research.
A series of new lanthanoid thioarsenates [Ln(teta)(μ-η(1):η(2):η(1)-As(III)S3)]n {Ln = Ce (Ia), Pr (Ib), Nd (Ic), and Sm (Id); teta = triethylenetetramine} and [Ln(teta)(en)(μ-η(1):η(1):η(1)-As(V)S4)]n {Ln = La (IIa), Ce (IIb), Pr (IIc), and Nd (IId); en = ethylenediamine} were prepared by the solvothermal reaction of K3AsO3, S, LnCl3 and organic amines and structurally characterized. Compounds Ia–d crystallise in the orthorhombic space group Aba2 and display 1-D neutral chains [Ln(teta)(μ-η(1):η(2):η(1)-As(III)S3)]n, which represent the first examples of 1-D organic hybrid lanthanoid sulfides built up from trigonal-pyramidal [As(III)S3](3-) acting as tetradentate bridging ligands to interlink [Ln(teta)](3+) ions, while compounds IIa–d crystallise in the orthorhombic space group P2(1)2(1)2(1) and consist of other 1-D neutral chains [Ln(teta)(en)(μ-η(1):η(1):η(1)-As(V)S4)]n, which are built up from the linkages of the tetrahedral [As(V)S4](3-) ion and the [Ln(teta)(en)](3+) ion. To learn more about the influence of lanthanide contraction on the formation of lanthanoid thioarsenates, three organic hybrid lanthanoid thioarsenates [Ln(teta)(en)As(V)S4] [Ln = Dy (IIIa), Ho (IIIb), and Tm (IIIc)] with the neutral molecular structure type in the monoclinic centrosymmetric space group P2(1)/c are also presented. Their optical and magnetic properties have been investigated, and density functional theory calculations of Ia and IIa have also been performed.
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