Copper availability governs nitrous oxide accumulation in wetland soils and stream sediments

Denitrification is microbially-mediated through enzymes containing metal cofactors. Laboratory studies of pure cultures have highlighted that the availability of Cu, required for the multicopper enzyme nitrous oxide reductase, can limit N2O reduction. However, in natural aquatic systems, such as wetlands and hyporheic zones in stream beds, the role of Cu in controlling denitrification remains incompletely understood. In this study, we collected soils and sediments from three natural environments -- riparian wetlands, marsh wetlands, and a stream -- to investigate their nitrogen species transformation activity at background Cu levels and different supplemented Cu loadings. All of the systems displayed low solid-phase associated Cu (40 - 280 nmol g-1), which made them appropriate sites for evaluating the effect of limited Cu availability on denitrification. In laboratory incubation experiments, high concentrations of N2O accumulated in all microcosms lacking Cu amendment except for one stream sediment sample. With Cu added to provide dissolved concentrations at trace levels (10-300 nM), reduction of N2O to N2 in the wetland soils and stream sediments was enhanced. A kinetic model could account for the trends in nitrogen species by combining the reactions for microbial reduction of NO3- to NO2-/N2O/N2 and abiotic reduction of NO2- to N2. The model revealed that the rate of N2O to N2 conversion increased significantly in the presence of Cu. For riparian wetland soils and stream sediments, the kinetic model also suggested that overall denitrification is driven by abiotic reduction of NO2- in the presence of inorganic electron donors. This study demonstrated that natural aquatic systems containing Cu at concentrations less than or equal to crustal abundances may display incomplete reduction of N2O to N2 that would cause N2O accumulation and release to the atmosphere.

Abiotic Reduction of Mercury(II) in the Presence of Sulfidic Mineral Suspensions

Monomethylmercury (CH3Hg) is a neurotoxic pollutant that biomagnifies in aquatic food webs. In sediments, the production of CH3Hg depends on the bacterial activity of mercury (Hg) methylating bacteria and the amount of bioavailable inorganic divalent mercury (HgII). Biotic and abiotic reduction of HgII to elemental mercury (Hg0) may limit the pool of HgII available for methylation in sediments, and thus the amount of CH3Hg produced. Knowledge about the transformation of HgII is therefore primordial to the understanding of the production of toxic and bioaccumulative CH3Hg. Here, we examined the reduction of HgII by sulfidic minerals (FeS(s) and CdS(s)) in the presence of dissolved iron and dissolved organic matter (DOM) using low, environmentally relevant concentrations of Hg and ratio of HgII:FeS(s). Our results show that the reduction of HgII by Mackinawite (FeS(s)) was lower (<15% of the HgII was reduced after 24 h) than when HgII was reacted with DOM or dissolved iron. We did not observe any formation of Hg0 when HgII was reacted with CdS(s) (experiments done under both acidic and basic conditions for up to four days). While reactions in solution were favorable under the experimental conditions, Hg was rapidly removed from solution by co-precipitation. Thermodynamic calculations suggest that in the presence of FeS(s), reduction of the precipitated HgII is surface catalyzed and likely involves S−II as the electron donor. The lack of reaction with CdS may be due to its stronger M-S bond relative to FeS, and the lower concentrations of sulfide in solution. We conclude that the reaction of Hg with FeS(s) proceeds via a different mechanism from that of Hg with DOM or dissolved iron, and that it is not a major environmental pathway for the formation of Hg0 in anoxic environments.

Abiotic reduction of nitrite by Fe(II): A comparison of rates and N2O production

Abiotic reduction of nitrite (NO2-) by Fe(II) species (i.e., chemodenitrification) has been demonstrated in a variety of natural environments and laboratory studies, and is a potentially significant source of atmospheric...

Abiotic Transient Nitrite Occurrences from Nitrate Reduction through Goethite-Mediated Fe(III)/Fe(II) Cycle with Labile Organic Materials and Ammonia

The abiotic reduction of NO3− to NO2−—coupled with the oxidation of labile organic materials such as citric acid, syringic acid and natural organic matter (NOM) and NH4+ through the goethite-mediated Fe(III)/Fe(II) cycle under anaerobic condition—was investigated at pH values of 4 and 7. The concentrations of the produced Fe2+ and NO2− were monitored. At a pH of 4, concentrations of Fe2+ increased, except for citric acid; no NO2− was detected. The reason why it was not detected is unclear. A possible reaction was the adsorption of NO2− onto goethite at pH < point of zero charge (pzc) of goethite (6.42) due to electrical attractive force. The maximum production of NO2− at a pH of 7 was in the order of citric acid >> syringic acid > NOM. However, Fe2+ was not detected at this pH even though Fe2+ should be required for NO2− production. To better understand of these phenomena, the adsorptive removal of Fe2+ and NO2− onto goethite was experimentally investigated. More than 90% of the produced Fe2+ and NO2− could be removed rapidly by adsorption onto the surface of goethite at pH 7 and 4, respectively. In addition, the reaction of Fe2+ with NO3− appeared to determine the overall reaction rate of the Fe(III)/Fe(II) cycle because of its relatively slow reaction rate. Using these results, we conclude that NO2− can be produced from NO3− reduction through Fe(III)/Fe(II) cycle with labile organic materials and ammonium at a pH of 7; especially, Fe(III)/Fe(II) cycle with citric acid results the maximum NO2− production higher than 600 μM for a long time (over 200 h) and then disappeared. But, the reasons for its disappearance were not addressed in this study.