The Interplay of Phototrophic and Heterotrophic Microbes Under Oil Exposure: A Microcosm Study.

Microbial interactions influence nearly one-half of the global biogeochemical flux of major elements of the marine ecosystem. Despite their ecological importance, microbial interactions remain poorly understood and even less is known regarding the effects of anthropogenic perturbations on these microbial interactions. The Deepwater Horizon oil spill exposed the Gulf of Mexico to ∼4.

Molecular Interaction of Aqueous Iodine Species with Humic Acid Studied by I and C K-Edge X-ray Absorption Spectroscopy.

Iodine-129 is one of three key risk drivers at several US Department of Energy waste management sites. Natural organic matter (NOM) is thought to play important roles in the immobilization of aqueous iodide (I) and iodate (IO) in the environment, but molecular interactions between NOM and iodine species are poorly understood. In this work, we investigated iodine and carbon speciation in three humic acid (HA)-I systems using I K-edge XANES and EXAFS and C K-edge XANES spectroscopy: (1) I in the presence of laccase (an oxidase enzyme) and a mediator, 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) in a pH 4 buffer, (2) I in the presence of lactoperoxidase (LPO) and HO in a pH 7 buffer, and (3) IO in a pH 3 groundwater.

The interplay of extracellular polymeric substances and oil/Corexit to affect the petroleum incorporation into sinking marine oil snow in four mesocosms.

Large amounts of oil containing mucous-like marine snow formed in surface waters adjacent to the Deepwater Horizon spill that was implicated in oil delivery to the seafloor. However, whether chemical dispersants that were used increased or decreased the oil incorporation and sedimentation efficiency, and how exopolymeric substances (EPS) are involved in this process remains unresolved. To investigate the microbial responses to oil and dispersants in different oceanic settings, indicated by EPS production, petro- and non-petro carbon sedimentation, four mesocosm (M) experiments were conducted: 1) nearshore seawater with a natural microbial consortia (M2); 2) offshore seawater with f/20 nutrients (M3); 3) coastal seawater with f/20 nutrients (M4); 4) nearshore seawater with a natural microbial consortia for a longer duration (M5).

Role of Polysaccharides in Diatom and its Associated Bacteria in Hydrocarbon Presence.

Diatoms secrete a significant amount of polysaccharides, which can serve as a critical organic carbon source for bacteria. The 2010 Deepwater Horizon oil spill exposed the Gulf of Mexico to substantial amounts of oil that also impacted the phytoplankton community. Increased production of exopolymeric substances was observed after this oil spill.

Nagasaki sediments reveal that long-term fate of plutonium is controlled by select organic matter moieties.

Forecasting the long-term fate of plutonium (Pu) is becoming increasingly important as more worldwide military and nuclear-power waste is being generated. Nagasaki sediments containing bomb-derived Pu that was deposited in 1945 provided a unique opportunity to explore the long-term geochemical behavior of Pu. Through a combination of selective extractions and molecular characterization via electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS), we determined that 55 ± 3% of the bomb-derived Pu was preferentially associated with more persistent organic matter compounds in Nagasaki sediments, particularly those natural organic matter (NOM) stabilized by Fe oxides (NOM).

Iodine speciation in a silver-amended cementitious system.

Silver-impregnated zeolite (AgIZ) has been used for removing radioiodine from contaminated groundwater and nuclear waste streams and the worldwide inventory of such secondary waste is rapidly increasing. The objective of this study was to 1) quantify the effectiveness of two grout waste forms for disposing of the used AgIZ, and 2) determine the I speciation leached from AgIZ encapsulated in grout. A 60-day kinetics batch experiment demonstrated that AgIZ encapsulated in slag-free grout was extremely effective at immobilizing I and Ag, a potential non-radioactive carcinogen.

Rapid Degradation of Oil in Mesocosm Simulations of Marine Oil Snow Events.

Following the Deepwater Horizon oil spill in the Gulf of Mexico, natural marine snow interacted with oil and dispersants forming marine oil snow (MOS) that sank from the water column to sediments. Mesocosm simulations demonstrate that Macondo surrogate oil incorporates into MOS and can be isolated, extracted, and analyzed via Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). Up to 47% of the FTICR-MS signal from MOS extracts can be attributed to formulas also found in Macondo surrogate oil demonstrating extensive oil incorporation.

Extracellular polymeric substances (EPS) producing and oil degrading bacteria isolated from the northern Gulf of Mexico.

Sinking marine oil snow was found to be a major mechanism in the transport of spilled oil from the surface to the deep sea following the Deepwater Horizon (DwH) oil spill. Marine snow formation is primarily facilitated by extracellular polymeric substances (EPS), which are mainly composed of proteins and carbohydrates secreted by microorganisms. While numerous bacteria have been identified to degrade oil, there is a paucity of knowledge on bacteria that produce EPS in response to oil and Corexit exposure in the northern Gulf of Mexico (nGoM).

Sunlight induced aggregation of dissolved organic matter: Role of proteins in linking organic carbon and nitrogen cycling in seawater.

Organic matter export from the euphotic zone is a key component of oceanic carbon (C) and nitrogen (N) cycles. Although interactions between these two cycles are important, studies on geochemical processes to directly connect them are limited. Here we show that sunlight can induce chemical aggregation of dissolved organic matter (DOM) into high N containing photo-aggregates.

Diagnostic tool to ascertain marine phytoplankton exposure to chemically enhanced water accommodated fraction of oil using Fourier Transform Infrared spectroscopy.

Phytoplankton alter their macromolecule composition in response to changing environmental conditions. Often these changes are consistent and can be used as indicators to predict their exposure to a given condition. FTIR-spectroscopy is a powerful tool that provides rapid snapshot of microbial samples.

Extracellular Enzyme Activity Profile in a Chemically Enhanced Water Accommodated Fraction of Surrogate Oil: Toward Understanding Microbial Activities After the Deepwater Horizon Oil Spill.

Extracellular enzymes and extracellular polymeric substances (EPS) play a key role in overall microbial activity, growth and survival in the ocean. EPS, being amphiphilic in nature, can act as biological surfactant in an oil spill situation. Extracellular enzymes help microbes to digest and utilize fractions of organic matter, including EPS, which can stimulate growth and enhance microbial activity.

Sediment accumulation and mixing in the Penobscot River and estuary, Maine.

Mercury (Hg) was discharged in the late 1960s into the Penobscot River by the Holtra-Chem chlor-alkali production facility, which was in operation from 1967 to 2000. To assess the transport and distribution of total Hg, and recovery of the river and estuary system from Hg pollution, physical and radiochemical data were assembled from sediment cores collected from 58 of 72 coring stations sampled in 2009. These stations were located throughout the lower Penobscot River, and included four principal study regions, the Penobscot River (PBR), Mendall Marsh (MM), the Orland River (OR), and the Penobscot estuary (ES).

Radionuclide uptake by colloidal and particulate humic acids obtained from 14 soils collected worldwide.

Uptake of six particle-reactive and/or redox-sensitive radionuclides (Pb, Th, Be, Fe, Np and Pa) by 14 humic acids (HAs) was investigated in artificial groundwater under mildly acidic conditions (pH~5.5). In HA-groundwater slurry, Pb, Be, Fe and Pa bound strongly to particulate HA (>0.

Mercury inputs and redistribution in the Penobscot River and estuary, Maine.

We examined total mercury (Hg) distributions in sediments from the Penobscot River and estuary, Maine, a site of extensive Hg releases from HoltraChem (1967-2000). Our objectives were to quantify: (1) bottom sediment Hg inventories (upper ~1m; 50-100 y); (2) sediment accumulation rates; and (3) contemporary Hg fluxes to bottom sediments; by sampling the Penobscot River (PBR), Mendall Marsh (MM), the Orland River (OR) and the Penobscot estuary (ES). Hg was rapidly distributed here, and the cumulative total (9.

Microbial Transformation of Iodine: From Radioisotopes to Iodine Deficiency.

Iodine is a biophilic element that is important for human health, both as an essential component of several thyroid hormones and, on the other hand, as a potential carcinogen in the form of radioiodine generated by anthropogenic nuclear activity. Iodine exists in multiple oxidation states (-1, 0, +1, +3, +5, and +7), primarily as molecular iodine (I), iodide (I), iodate [Formula: see text] , or organic iodine (org-I). The mobility of iodine in the environment is dependent on its speciation and a series of redox, complexation, sorption, precipitation, and microbial reactions.

Plutonium Partitioning Behavior to Humic Acids from Widely Varying Soils Is Related to Carboxyl-Containing Organic Compounds.

In order to examine the influence of the HA molecular composition on the partitioning of Pu, ten different kinds of humic acids (HAs) of contrasting chemical composition, collected and extracted from different soil types around the world were equilibrated with groundwater at low Pu concentrations (10 M). Under mildly acidic conditions (pH ∼ 5.5), 29 ± 24% of the HAs were released as colloidal organic matter (>3 kDa to <0.

Light-induced aggregation of microbial exopolymeric substances.

Sunlight can inhibit or disrupt the aggregation process of marine colloids via cleavage of high molecular weight compounds into smaller, less stable fragments. In contrast, some biomolecules, such as proteins excreted from bacteria can form aggregates via cross-linking due to photo-oxidation. To examine whether light-induced aggregation can occur in the marine environment, we conducted irradiation experiments on a well-characterized protein-containing exopolymeric substance (EPS) from the marine bacterium Sagitulla stellata.

Estimates of recovery of the Penobscot River and estuarine system from mercury contamination in the 1960's.

Mercury (Hg) was discharged in the late 1960s into the Penobscot River by a chlor-alkali production facility, HoltraChem. Using total Hg concentration profiles from 56 stations (58 sediment cores) in the Penobscot River (PBR), Mendall Marsh (MM), Orland River (OR) and Penobscot Estuary (ES), and sediment accumulation rates derived using detailed profiles of total Hg concentrations and radionuclide activities (Cs, Pu, Pb), recovery from system-wide Hg pollution was assessed. Total Hg concentration profiles showed sharp maxima at depths attributed in time to a 1967 release date, and were divided into two sections: the first 21years (1967-1988; rapid recovery), and the recent 21years (1988-2009; slower recovery).

Recent advances in the detection of specific natural organic compounds as carriers for radionuclides in soil and water environments, with examples of radioiodine and plutonium.

Among the key environmental factors influencing the fate and transport of radionuclides in the environment is natural organic matter (NOM). While this has been known for decades, there still remains great uncertainty in predicting NOM-radionuclide interactions because of lack of understanding of radionuclide interactions with the specific organic moieties within NOM. Furthermore, radionuclide-NOM studies conducted using modelled organic compounds or elevated radionuclide concentrations provide compromised information related to true environmental conditions.

Role of natural organic matter on iodine and (239)(,240)Pu distribution and mobility in environmental samples from the northwestern Fukushima Prefecture, Japan.

In order to assess how environmental factors are affecting the distribution and migration of radioiodine and plutonium that were emitted from the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident, we quantified iodine and (239,240)Pu concentration changes in soil samples with different land uses (urban, paddy, deciduous forest and coniferous forest), as well as iodine speciation in surface water and rainwater. Sampling locations were 53-63 km northwest of the FDNPP within a 75-km radius, in close proximity of each other. A ranking of the land uses by their surface soil (<4 cm) stable (127)I concentrations was coniferous forest > deciduous forest > urban > paddy, and (239,240)Pu concentrations ranked as deciduous forest > coniferous forest > paddy ≥ urban.

Evidence for Hydroxamate Siderophores and Other N-Containing Organic Compounds Controlling (239,240)Pu Immobilization and Remobilization in a Wetland Sediment.

Pu concentrations in wetland surface sediments collected downstream of a former nuclear processing facility in F-Area of the Savannah River Site (SRS), USA, were ∼2.5 times greater than those measured in the associated upland aquifer sediments; similarly, the Pu concentration solid/water ratios were orders of magnitude greater in the wetland than in the low-organic matter content aquifer soils. Sediment Pu concentrations were correlated to total organic carbon and total nitrogen contents and even more strongly to hydroxamate siderophore (HS) concentrations.

Radioiodine sorption/desorption and speciation transformation by subsurface sediments from the Hanford Site.

During the last few decades, considerable research efforts have been extended to identify more effective remediation treatment technologies to lower the (129)I concentrations to below federal drinking water standards at the Hanford Site (Richland, USA). Few studies have taken iodate into consideration, though recently iodate, instead of iodide, was identified as the major species in the groundwater of 200-West Area within the Hanford Site. The objective of this study was thus to quantify and understand aqueous radioiodine species transformations and uptake by three sediments collected from the semi-arid, carbonate-rich environment of the Hanford subsurface.

Radioiodine Biogeochemistry and Prevalence in Groundwater.

I is commonly either the top or among the top risk drivers, along with Tc, at radiological waste disposal sites and contaminated groundwater sites where nuclear material fabrication or reprocessing has occurred. The risk stems largely from I having a high toxicity, a high bioaccumulation factor (90% of all the body's iodine concentrates in the thyroid), a high inventory at source terms (due to its high fission yield), an extremely long half-life (16M years), and rapid mobility in the subsurface environment. Another important reason that I is a key risk driver is that there is uncertainty regarding its biogeochemical fate and transport in the environment.