Trace amounts of manganese is essential to human health. Now, a team of scientists from the University of Delaware, Scripps Institution of Oceanography, the University of Hawaii, and Oregon Health and Science University has found that a dissolved form of manganese, Mn(III), is important in waterways such as the Black Sea and Chesapeake Bay. It can keep toxic hydrogen sulfide (sulphide) zones in check.1
The research is based on research conducted in 2003 that explored the chemistry of the Black Sea. Nearly 90% of the mile-deep system is a no-oxygen "dead zone," containing large amounts of naturally produced hydrogen sulfide (sulphide), which is lethal to most marine life. Only specialized microbes can survive in this underwater region.
Above this "dead zone" in the Black Sea lies another aquatic layer, the "suboxic zone,". This has both minimal amounts of oxygen and minimal amounts of hydrogen sulfide. This layer may be up to 40 metres (130 feet) deep in the Black Sea, but only 4 metres (13 feet) deep in the Chesapeake Bay.
The research team found that a chemical form of dissolved manganese, Mn(III), can maintain the existence of the suboxic zone by reacting as a reductant with oxygen and as an oxidant with hydrogen sulfide, preventing deadly hydrogen sulfide from reaching the surface layer of water, which is where most fish, algae and microscopic plants live. The scientists used an electrochemical analyzer to locate and map the chemistry of the suboxic zone in real time under changing salinity, temperature and depth.
The finding is surprising, George Luther (Delaware) said, because dissolved manganese as Mn(III) was assumed not to form in the environment and thus was largely ignored by scientists. The research team conclude that "Manganese in natural oxygen-poor waters can persist in a +3 oxidation state, a state previously seen only in the lab, necessitating a major revision of the current understanding of manganese aqueous geochemistry".
"Now we've learned that this form of dissolved manganese [Mn(III)] can constitute almost all the dissolved manganese in suboxic water columns and can react with hydrogen sulfide and other compounds that only solid manganese(IV) phases were thought to be doing," Luther noted. "It is also more reactive than the solid phases."
"Our research shows that the impact of dissolved manganese(III) is significant in any aquatic environment, including lakes, plus sediments on the seafloor and soils on land," Luther said. "And for the public who live near the water, dissolved manganese(III) actually helps prevent naturally occurring hydrogen sulfide from getting to the surface, so it prevents both fish kills and the foul odours from this compound's telltale 'rotten egg' smell."
Abstract: soluble manganese(III) [Mn(III)] has been thought to disproportionate to soluble Mn(II) and particulate MnIVO2 in natural waters, although it persists as complexes in laboratory solutions. We report that, in the Black Sea, soluble Mn(III) concentrations were as high as 5 micromolar and constituted up to 100% of the total dissolved Mn pool. Depth profiles indicated that soluble Mn(III) was produced at the top of the suboxic zone by Mn(II) oxidation and at the bottom of the suboxic zone by MnIVO2 reduction, then stabilized in each case by unknown natural ligands. We also found micromolar concentrations of dissolved Mn(III) in the Chesapeake Bay. Dissolved Mn(III) can maintain the existence of suboxic zones because it can act as either an electron acceptor or donor. Our data indicate that Mn(III) should be ubiquitous at all water column and sediment oxic/anoxic interfaces in the environment.Soluble Mn (III) in suboxic zones, , science, Jan, (2006)