Manganese (Mn) oxide solids widely exist in nature, serving as both electron donors and acceptors for a variety of redox reactions. Previous studies have highlighted the adsorption of dissolved organic matter (DOM) on Mn oxides, as well as the reduction of Mn oxides by DOM. Here, we show the underappreciated roles of photolytic reactions of DOM in Mn2+(aq) oxidation and its consequential formation of Mn oxide solids. During the photolysis of DOM, reactive intermediates including excited triplet state DOM (3DOM*), hydroxyl radical (•OH), superoxide radical (O2•−), hydrogen peroxide (H2O2), and singlet oxygen (1O2) can be generated. Among them, we found that O2•− was responsible for Mn oxidation. In addition, in the presence of bromide ions (Br−), the photolytic reactions between DOM and Br− formed reactive bromide radicals and facilitated the oxidation of Mn2+(aq) to Mn oxide solids. Moreover, the composition of DOM affected its oxidative capability. When DOM contained more aromatic functional groups, we observed more oxidation of Mn2+ to Mn oxides. These new findings advance our knowledge of natural Mn2+ oxidation and Mn(III/IV) oxide formation, as well as the hitherto overlooked oxidative role of DOM in the oxidation of metal ions in surface water under sunlight illumination.
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Manganese Cycling in the Oceans
Manganese (Mn) is an essential element for life. Although its concentration is at (sub)nanomolar levels throughout the ocean, it affects the oxygen concentration of the ocean because it is central to the photosynthetic formation of dioxygen, O2, in photosystem center II. Mn inputs into the ocean are from atmospheric transport of particles and their dissolution to form dissolved Mn, and from the flux of dissolved Mn from rivers, sediments and hydrothermal vents. The main removal mechanism is transport of particulate Mn from dust and organic matter to the sediments. The environmental chemistry of manganese centers on its +2, +3 and +4 oxidation states. Most recent data show that Mn(II) is dissolved, that Mn(IV) is particulate MnO2, and that Mn(III) can be particulate or dissolved when bound to organic complexes [denoted as Mn(III)-L]. Mn(II) is oxidized primarily by microbial processes whereas MnO2 is reduced by abiotic and biotic processes. Photochemical processing aids redox cycling in surface waters. In suboxic zones, which are defined as areas with dissolved O2 concentrations below 3 M, both oxidation and reduction processes can occur but usually at different depths. In suboxic zones, dissolved Mn is also released from organic matter during its decomposition and from MnO2 reduction.
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- Award ID(s):
- 1807158
- NSF-PAR ID:
- 10179969
- Date Published:
- Journal Name:
- Encyclopedia of Water: Science, Technology, and Society
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract We present full water depth sections of size‐fractionated (1–51 μm; >51 μm) concentrations of suspended particulate matter and major particle phase composition (particulate organic matter [POM], including its carbon isotopic composition [POC‐δ13C] and C:N ratio, calcium carbonate [CaCO3], opal, lithogenic particles, and iron and manganese [oxyhydr]oxides) from the U.S. GEOTRACES Arctic Cruise (GN01) in the western Arctic in 2015. Whereas biogenic particles (POM and opal) dominate the upper 1,000 m, lithogenic particles are the most abundant particle type at depth. Minor phases such as manganese (Mn) oxides are higher in GN01 than in any other U.S. GEOTRACES cruises so far. Extremely depleted POC‐δ13C, as low as ~ −32‰, is ubiquitous at the surface of the western Arctic Ocean as a result of different growth rates of phytoplankton. Moderate penetration of depleted POC‐δ13C to depth indicates active sinking of large particles in the central basin. Lateral transport from the Chukchi shelf is also of significance in the western Arctic, as is evident from increases in biogenic silica to POC ratios and Mn oxide concentrations in the halocline, as well as lithogenic element contents in the deep waters. Our study supports previous suggestions of the near absence of CaCO3in the Arctic Basin. This study presents the first data set of concentration and composition of suspended particles in the western Arctic Ocean and sheds new light on the vertical and lateral processes that govern particle distribution in this enclosed ocean basin.
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Dissolved natural organic matter (DOM) is a complex matrix of organic matter that is ubiquitous in natural aquatic environments. So far, substantial research has been conducted on the DOM adsorption on Mn oxides as well as the reduction processes of Mn oxides by DOM. However, little is known about the oxidative roles of DOM in oxidizing Mn2+(aq) to Mn(III/IV) oxide solids. Sunlight-driven processes can initiate the degradation of DOM accompanied by the formation of photochemically produced reactive intermediates, including excited triplet state DOM (3DOM*), hydroxyl radical (•OH), superoxide radical (O2•−), hydrogen peroxide (H2O2), and singlet oxygen (1O2). Further, in the presence of halide ions, reactive halogen species can be generated by reactions between 3DOM* and halide ions, and by reactions between •OH and halide ions. In this study, we found that the solution pH controlled the oxidation of Mn2+(aq) to Mn oxide solids during photolysis of DOM. Among the reactive oxygen species, Mn2+(aq) was found to be oxidized to Mn oxide solids mainly by O2•−. The DOM with different quantities of aromatic functional groups affected its oxidative capability. With the addition of bromide ions (Br−), Mn2+(aq) oxidation was promoted further by formation Br radicals, which can also oxidize Mn2+(aq) to Mn oxide solids. These findings can help us better understand the oxidative role of DOM in the formation of Mn oxide solids in organic-rich surface water. In addition, this study assists in comprehending the impacts of the photolytic reactions between DOM and halide ions and their resulting reactive oxygen and halogen species on the oxidation and reduction processes of other transition metal oxides in the environment.more » « less
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Abstract The Southern Ocean plays a critical role in regulating global uptake of atmospheric CO2. Trace elements like iron (Fe), cobalt (Co), and manganese (Mn) have been shown to modulate this primary productivity. Despite limited data, the vertical profiles for Mn, Fe, and Co in the Ross Sea show no evidence of scavenging, as typically observed in oceanic sites. This was previously attributed to low‐particle abundance and/or by mixing rates exceeding scavenging rates. Scavenging of some trace metals such as cobalt (Co) is thought to be largely governed by Mn (oxyhydr)oxides, assumed to be the main component of particulate Mn (pMn). However, our data show that pMn has an average oxidation state below 3 and with nondetectable Mn oxides. In addition, soluble Co profiles show no evidence of scavenging and Co uptake measurements show little Co uptake in the euphotic zone and low/no scavenging at depth. Instead, high concentrations of dissolved Mn (dMn, up to 90 nM), which is primarily complexed as Mn(III)‐L (up to 100%), are observed. Average dMn concentrations (10 ± 14 nM) are highest in bottom and surface waters. Manganese sources may include sediments and sea‐ice melt, as elevated dMn was measured in sea ice (12 nM) compared to its surrounding waters (3 nM), and sea ice dMn was 97% Mn(III)‐L. We contend that the lack of Co scavenging in the Ross Sea is due to a unique Mn redox cycle that favors the stabilization of Mn(III)‐complexes at the expense of Mn oxide particle formation.
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In the marine sediment record, concentrations and isotope ratios of chromium (Cr) can be used to reconstruct ocean biogeochemical conditions. These reconstructions rely on a detailed understanding of the chemical pathways that Cr undergoes as it is transferred from the water column to the sediment record. We examined Cr concentrations in marine pore fluids and sediments from six continental margin sites, which can be grouped into two basic environments: (1) sites where sediments are oxygenated and rich in solid phase Mn (herein termed oxic), and (2) sites where sediments are organic C (Corg)-rich and oxygen is depleted (anoxic). We found Cr concentrations to be lower (maximum of 12 nM in pore fluids and 124 ppm sediment solid phase) at oxic sites compared with anoxic sites (maximum of 77 nM and 184 ppm). Our findings confirm previously published interpretations of dissolved Cr in pore fluids (Brumsack and Gieskes, 1983; Shaw et al., 1990). In oxic surface sediments, particulate Cr(III) can be oxidised by Mn oxides, which leads to elevated concentrations of dissolved Cr co-occurring at the same depth as elevated Mn concentrations in the sediment. Under these oxidising conditions, down-core sediments contain relatively low solid-phase Cr concentrations. In oxic sediments, Cr speciation reveals that most of the pore fluid Cr is in the Cr(VI) state. At the site where Mn oxide-rich sediments rest below an oxic water column, oxidative loss of Cr from the sediment to the bottom water leads to the lowest estimated Cr burial efficiency of the sites examined here. Under anoxic Corg-rich conditions, both pore fluids and sediment solid phases contain high Cr concentrations, with 40–80% of dissolved pore fluid Cr present as Cr(III). This enrichment of Cr appears to be tightly linked to the presence of high total organic carbon (TOC) content and scavenging of Cr by (organic) particles in the water column. Combined, these data highlight the strong dependence of Cr on both sedimentary redox conditions as well as biological productivity. Based on the data from modern continental margin sediments, we propose that Cr concentrations and isotope compositions of the authigenic sediment fraction may record a combination of redox conditions and biological productivity in the water column. If confirmed by Cr isotope analyses, these findings will add support for the notion that Cr may serve as a proxy for ocean biological and chemical sedimentological conditions. Thus, careful assessment of the impact of organic matter on Cr is required for reconstructions of redox conditions with sedimentary records.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Conference Paper:
- https://doi.org/10.1002/9781119300762.wsts0065
