Michael R. Shields

Positive priming of terrestrially derived dissolved organic matter in a freshwater microcosm system

The role of priming processes in the remineralization of terrestrially derived dissolved organic carbon (TDOC) in aquatic systems has been overlooked. We provide evidence for TDOC priming using a lab-based microcosm experiment in which TDOC was primed by the addition of 13C-labeled algal dissolved organic carbon (ADOC) or a 13C-labeled disaccharide (trehalose). The rate of TDOC remineralization to carbon dioxide (CO2) occurred 4.1 ± 0.9 and 1.5 ± 0.3 times more rapidly with the addition of trehalose and ADOC, respectively, relative to experiments with TDOC as the sole carbon source over the course of a 301 h incubation period. Results from these controlled experiments provide fundamental evidence for the occurrence of priming of TDOC by ADOC and a simple disaccharide. We suggest that priming effects on TDOC should be considered in carbon budgets for large-river deltas, estuaries, lakes, hydroelectric reservoirs, and continental shelves.

Deepwater Horizon oil in Gulf of Mexico waters after 2 years: transformation into the dissolved organic matter pool.

Recent work has shown the presence of anomalous dissolved organic matter (DOM), with high optical yields, in deep waters 15 months after the Deepwater Horizon (DWH) oil spill in the Gulf of Mexico (GOM). Here, we continue to use the fluorescence excitation-emission matrix (EEM) technique coupled with parallel factor analysis (PARAFAC) modeling, measurements of bulk organic carbon, dissolved inorganic carbon (DIC), oil indices, and other optical properties to examine the chemical evolution and transformation of oil components derived from the DWH in the water column of the GOM. Seawater samples were collected from the GOM during July 2012, 2 years after the oil spill. This study shows that, while dissolved organic carbon (DOC) values have decreased since just after the DWH spill, they remain higher at some stations than typical deep-water values for the GOM. Moreover, we continue to observe fluorescent DOM components in deep waters, similar to those of degraded oil observed in lab and field experiments, which suggest that oil-related fluorescence signatures, as part of the DOM pool, have persisted for 2 years in the deep waters. This supports the notion that some oil-derived chromophoric dissolved organic matter (CDOM) components could still be identified in deep waters after 2 years of degradation, which is further supported by the lower DIC and partial pressure of carbon dioxide (pCO2) associated with greater amounts of these oil-derived components in deep waters, assuming microbial activity on DOM in the current water masses is only the controlling factor of DIC and pCO2 concentrations.

Enhanced terrestrial carbon preservation promoted by reactive iron in deltaic sediments

We examined the role of reactive iron (FeR) in preserving organic carbon (OC) across a subaerial chronosequence of the Wax Lake Delta, a prograding delta within the Mississippi River Delta complex. We found that ~15.0% of the OC was bound to FeR, and the dominant binding mechanisms varied from adsorption in the youngest subaerial region to coprecipitation at the older, vegetated sites. The δC of the iron-associated OC was more negative than the total OC (mean= 2.6‰), indicating greater preference for terrestrial material and/or compounds with more negative δC values. However, only the adsorbed OC displayed preferential binding of lignin phenols. We estimate that ~8% of the OC initially deposited in deltaic systems is bound to FeR (equivalent to 6 × 10 12 gC yr ), and this percentage increases postdepositionally, as coprecipitation of FeR and OC allows for an even greater amount of OC to be bound to FeR.

Dissolved Organic Matter Composition Drives the Marine Production of Brominated Very Short-Lived Substances

Brominated very short-lived substances (BrVSLS), such as bromoform, are important trace gases for stratospheric ozone chemistry. These naturally derived trace gases are formed via bromoperoxidase-mediated halogenation of dissolved organic matter (DOM) in seawater. Information on DOM type in relation to the observed BrVSLS concentrations in seawater, however, is scarce. We examined the sensitivity of BrVSLS production in relation to the presence of specific DOM moieties. A total of 28 model DOM compounds in artificial seawater were treated with vanadium bromoperoxidase (V-BrPO). Our results show a clear dependence of BrVSLS production on DOM type. In general, molecules that comprise a large fraction of the bulk DOM pool did not noticeably affect BrVSLS production. Only specific cell metabolites and humic acid appeared to significantly enhance BrVSLS production. Amino acids and lignin phenols suppressed enzyme-mediated BrVSLS production and may instead have formed halogenated nonvolatile molecules. Dibromomethane production was not observed in any experiments, suggesting it is not produced by the same pathway as the other BrVSLS. Our results suggest that regional differences in DOM composition may explain the observed BrVSLS concentration variability in the global ocean. Ultimately, BrVSLS production and concentrations are likely affected by DOM composition, reactivity, and cycling in the ocean.

Paleoreconstruction of organic carbon inputs to an oxbow lake in the Mississippi River watershed : effects of dam construction and land use change on regional inputs

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