Rapid, concurrent formation of organic sulfur and iron sulfides during
experimental sulfurization of sinking marine particles
Abstract
Organic matter (OM) sulfurization can enhance the preservation and
sequestration of carbon in anoxic sediments, and it has been observed in
sinking marine particles from marine O2-deficient zones. The magnitude
of this effect on carbon burial remains unclear, however, because the
transformations that occur when sinking particles encounter sulfidic
conditions remain undescribed. Here, we briefly expose sinking marine
particles from the eastern tropical North Pacific O2-deficient zone to
environmentally relevant sulfidic conditions (20C, 0.5 mM
[poly]sulfide, two days) and then characterize the resulting
solid-phase organic and inorganic products in detail. During these
experiments, the abundance of organic sulfur in both hydrolyzable and
hydrolysis-resistant solids roughly triples, indicating extensive OM
sulfurization. Lipids also sulfurize on this timescale, albeit less
extensively. In all three pools, OM sulfurization produces organic
monosulfides, thiols, and disulfides. Hydrolyzable sulfurization
products appear within ≤ 200-m regions of relatively homogenous
composition that are suggestive of sulfurized extracellular polymeric
substances (EPS). Concurrently, reactions with particulate iron
oxyhydroxides generate low and fairly uniform concentrations of iron
sulfide (FeS) within these same EPS-like materials. Iron oxyhydroxides
were not fully consumed during the experiment, which demonstrates that
organic materials can be competitive with reactive iron for sulfide.
These experiments support the hypothesis that sinking, OM- and EPS-rich
particles in a sulfidic water mass can sulfurize within days,
potentially contributing to enhanced sedimentary carbon sequestration.
Additionally, sulfur-isotope and chemical records of organic S and iron
sulfides in sediments have the potential to incorporate signals from
water column processes.