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Previous work has suggested that apparent old 14C ages for oceanic DOC are the result of mixing of different organic carbon fractions. This report provides direct evidence for a contemporary 14C age of a high-molecular-weight (HMW) fraction of colloidal organic carbon (≥10 kD). Colloidal organic matter, COM10 (from 10 kDaltons (kD) to 0.2 μm), isolated from the upper water column of the Gulf of Mexico and the Middle Atlantic Bight (MAB) region, generally has a contemporary age (i.e., younger than a few decades), while COM1 (from 1 kD to 0.2 μm), is apparently old: 380-4500 y bP. Thus, BMW COM10 (3-5% of DOC) from the upper water column is derived from living particulate organic matter (POM) and cycles rapidly, while a significant fraction of low-molecular-weight (≤1 kD) DOM is likely more refractory, and cycles on much longer time scales. The presence of pigment biomarker compounds in COM1 from the upper water column points to selected phytoplankton species as one of the sources of COM. Terrestrial carbon as another source of COM is suggested from the inverse correlation between Δ14C and δ13C values, as well as the increasing δ13C values with increasing salinity. 234Th-derived turnover times of COM10 and COM1 from both the Gulf of Mexico and MAB are consistently short, 1-20 and 3-30 days, respectively. These short residence times support the hypothesis that 14C ages of colloidal fractions of DOC are the result of COM fractions being a mixture of several endmembers with fast and slow turnover rates. © 1995.

Tims Branch riparian wetland located in South Carolina, USA has immobilized 94 % of the U released >50 years ago from a nuclear fuel fabrication facility. Sediment organic matter (OM) has been shown to play an important role in immobilizing U. Yet, uranium-OM-mineral interactions at the molecular scale have never been investigated at ambient concentrations. The objectives of this study were to extract, purify, and concentrate U-bound sediment OM along the stream water pathway and perform molecular characterization using Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS). Out of 9614 identified formulas, 715 contained U. These U-containing formulas were enriched with Fe, N, and/or S compared to the total OM. Lignin-like and protein-like molecules accounted for 40 % and 19 % of the U-containing formulas, respectively. Phosphorus-containing formulas were found to exert an insignificant influence on complexing U. U-containing formulas in the 'mobile' (groundwater extractable) OM fraction had lower (reduced) nominal oxidation states of carbon (NOSC); and less aromatic moieties than OM recovered from the 'immobile' (sodium pyrophosphate extractable) OM fraction. U-containing formulas in the redox interfacial zones (stream banks) compared to those in nearby up-slope zones tended to have smaller molecular weights; lower NOSC; higher contents of COO and/or CONO functional groups; and higher abundance of Fe-containing formulas. Fe was present in 38 % of the U-containing formulas but only 20 % of the total OM formulas. It is postulated that Fe played an important role in stabilizing the structure of sedimentary OM, especially U-containing compounds. The identification for the first time of hundreds of Fe-U-OM formulas demonstrates the complexity of such system is much greater than commonly believed and numerically predicting U binding behavior in OM-rich systems may require greater use of statistical or artificial intelligence approaches rather than deterministic approaches limited to measuring metal complexation with well-defined individual analogue organic ligands., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Isotopic evidence of groundwater and stream water is frequently used to investigate water exchanges with groundwater. Monthly sampling of rain, stream water, and groundwater was conducted at Tims Branch watershed in South Carolina for the oxygen and hydrogen stable isotope ( δ 2 O) measurement, as well as pH and oxidation-reduction potential (ORP). Together with a mass balance perspective, it was determined that it takes a few weeks to one month for groundwater in the hyporheic zone to fully exchange with stream water. From hydrodynamic modelling, we show that substantial (up to 70 %) groundwater exchange occurs at gaining and losing sites. Groundwater exfiltration, i.e. inflow into stream water, contributes up to 4 % to stream water, with the remainder from upstream exfiltration. A 2-4 % per day renewal rate of adjacent groundwater would indirectly indicate a groundwater residence time in the order of half a month to a full month (assuming either a well-mixed case or large dispersion rate in pulse flow case), in agreement with a greatly reduced variability of δ 18 O) measurement, as well as pH and oxidation-reduction potential (ORP). Together with a mass balance perspective, it was determined that it takes a few weeks to one month for groundwater in the hyporheic zone to fully exchange with stream water. From hydrodynamic modelling, we show that substantial (up to 70 %) groundwater exchange occurs at gaining and losing sites. Groundwater exfiltration, i.e. inflow into stream water, contributes up to 4 % to stream water, with the remainder from upstream exfiltration. A 2-4 % per day renewal rate of adjacent groundwater would indirectly indicate a groundwater residence time in the order of half a month to a full month (assuming either a well-mixed case or large dispersion rate in pulse flow case), in agreement with a greatly reduced variability of δ 2 H and δ 18 O of groundwater compared to stream water and rain. This reduced variability of stable isotope signal from groundwater confirms our hypothesis that riparian groundwater mixing at Tims Branch is more of a mixed type rather than a pulse flow type. A monthly time scale is sufficient for groundwater to become anoxic at exit points into stream water resulting in the episodic production of natural organic matter- and iron-rich flocs upon oxidation.

Taiwan has pledged to achieve net-zero carbon emissions by 2050, but the current extent of carbon sinks in Taiwan remains unclear. Therefore, this study aims to first review the existing nature-based carbon sinks on land and in the oceans around Taiwan. Subsequently, we suggest potential strategies to reduce CO 2 emissions and propose carbon dioxide removal methods (CDRs). The natural carbon sinks by forests, sediments, and oceans in and around Taiwan are approximately 21.5, 42.1, and 96.8 Mt-CO 2 y -1 , respectively, which is significantly less than Taiwan's CO 2 emissions (280 Mt-CO 2 y -1 ). Taiwan must consider decarbonization strategies like using electric vehicles, renewable energy, and hydrogen energy by formulating enabling policies. Besides more precisely assessing both terrestrial and marine carbon sinks, Taiwan should develop novel CDRs such as bioenergy with carbon capture and storage, afforestation, reforestation, biochar, seaweed cultivation, and ocean alkalinity enhancement, to reach carbon neutrality by 2050., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The objective of this study was to determine if U sediment concentrations in a U-contaminated wetland located within the Savannah River Site, South Carolina, were greater in the rhizosphere than in the nonrhizosphere. U concentrations were as much as 1100% greater in the rhizosphere than in the nonrhizosphere fractions; however and importantly, not all paired samples followed this trend. Iron (but not C, N, or S) concentrations were significantly enriched in the rhizosphere. XAS analyses showed that in both sediment fractions, U existed as UO 2 2+ coordinated with iron(III)-oxides and organic matter. A key difference between the two sediment fractions was that a larger proportion of U was adsorbed to Fe(III)-oxides, not organic matter, in the rhizosphere, where significantly greater total Fe concentrations and greater proportions of ferrihydrite and goethite existed. Based on 16S rRNA analyses, most bacterial sequences in both paired samples were heterotrophs, and population differences were consistent with the generally more oxidizing conditions in the rhizosphere. Finally, U was very strongly bound to the whole (unfractionated) sediments, with an average desorption K d value (U sediment /U aqueous ) of 3972 ± 1370 (mg-U/kg)/(mg-U/L). Together, these results indicate that the rhizosphere can greatly enrich U especially in wetland areas, where roots promote the formation of reactive Fe(III)-oxides.

Grout materials are commonly used to immobilize low-level radioactive waste. Organic moieties can be unintentionally present in common ingredients used to make these grout waste forms, which may result in the formation of organo-radionuclide species. These species can positively or negatively affect the immobilization efficiency. However, the presence of organic carbon compounds is rarely considered in models or characterized chemically. Here, we quantify the organic pool of grout formulations with and without slag, as well as the individual dry ingredients used to make the grout samples (ordinary Portland cement (OPC), slag and fly ash), including total organic carbon (TOC) and black carbon, followed by aromaticity evaluation and molecular characterization via Electro Spray Ionization Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FTICRMS). All dry grout ingredients contained significant amounts of organic carbon, ranging from 550 mg/kg to 6250 mg/kg for the TOC pool, with an averaged abundance of 2933 ± 2537 mg/kg, of which 60 ± 29% was composed of black carbon. The significant abundance of a black carbon pool implies the presence of the aromatic-like compounds, which was further identified by both phosphate buffer-assisted aromaticity evaluation (e.g., >1000 mg-C/kg as aromatic-like carbon in the OPC) and dichloromethane (DCM) extraction with ESI-FTICRMS analysis. Besides aromatic-like compounds, other organic moieties were also detected in the OPC, such as carboxyl-containing aliphatic molecules. While the organic compound only consists of minor fractions of the grout materials investigated, our observations of the presence of various radionuclide-binding organic moieties suggests the potential formation of organo-radionuclides, such as radioiodine, which might be present at lower molar concentrations than TOC. Evaluating the role of organic carbon complexation in controlling the disposed radionuclides, especially for those radionuclides with strong association with organic carbon, has important implications for the long-term immobilization of radioactive waste in grout systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

129 I is a nuclear fission decay product of concern because of its long half-life (16 Ma) and propensity to bioaccumulate. Microorganisms impact iodine mobility in soil systems by promoting iodination (covalent binding) of soil organic matter through processes that are not fully understood. Here, we examined iodide uptake by soils collected at two depths (0-10 and 10-20 cm) from 5 deciduous and coniferous forests in Japan and the United States. Autoclaved soils, and soils amended with an enzyme inhibitor (sodium azide) or an antibacterial agent (bronopol), bound significantly less 125 I tracer (93%, 81%, 61% decrease, respectively) than the untreated control soils, confirming a microbial role in soil iodide uptake. Correlation analyses identified the strongest significant correlation between 125 I uptake and three explanatory variables, actinobacteria soil biomass ( p = 6.04E-04, 1.35E-02 for Kendall-Tau and regression analysis, respectively), soil nitrogen content ( p = 4.86E-04, 4.24E-03), and soil oxidase enzyme activity at pH 7.0 using the substrate L-DOPA ( p = 2.83E-03, 4.33E-04) and at pH 5.5 using the ABTS ( p = 5.09E-03, 3.14E-03). Together, the results suggest that extracellular oxidases, primarily of bacterial origin, are the primary catalyst for soil iodination in aerobic, surface soils of deciduous and coniferous forests, and that soil N content may be indicative of the availability of binding sites for reactive iodine species., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Grandbois, Santschi, Xu, Mitchell, Kaplan and Yeager.)

Rapid growth in the aquaculture industry and corresponding increases in nutrient and organic carbon levels in coastal regions can lead to eutrophication and increased greenhouse gas emissions. Macroalgae are the organisms primarily responsible for the capture of CO 2 and removal of nutrients from coastal waters. In the current study, we developed a novel wastewater treatment system in which the red macroalga, Sarcordia suae, is used to capture CO 2 under thermostatic conditions in subtropical regions. In 2020 (without temperature control), the carbon capture rate (CCR) of Sarcordia suae varied considerably with the season: winter/spring (2.1-3.9 g-C m -2 d -1 ) and summer (0.09 g-C m -2 d -1 ). In 2021, solar powered cooling reduced summer seawater temperatures from 31 to 33 °C to 23-25 °C with a corresponding increase in the mean CCR: winter/spring (2-7 g-C m -2 d -1 ) and summer (1.33 g-C m -2 d -1 ). The proposed aquaculture wastewater system proved highly efficient in removing nitrogen (20.7 mg-N g -1 DW d -1 , DW = dry weight) and phosphorus (4.4 mg-P g -1 DW d -1 ). Furthermore, the high density of Sarcodia (1.10 ± 0.03 g cm -3 ) would permit the harvesting and subsequent dumping of Sarcodia in deep off-shore waters. This study demonstrated a low-cost land-based seaweed cultivation system for capturing CO 2 and excess nutrients from aquaculture wastewater year-round under temperature controlled environments in subtropical regions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Recent studies evaluating multiple years of groundwater radioiodine ( 129 I) concentration in a riparian wetland located in South Carolina, USA identified strong seasonal concentration fluctuations, such that summer concentrations were much greater than winter concentrations. These fluctuations were observed only in the wetlands but not in the upland portion of the plume and only with 129 I, and not with other contaminants of anthropogenic origin: nitrate/nitrite, strontium-90, technecium-99, tritium, or uranium. This unexplained observation was hypothesized to be the result of strongly coupled processes involving hydrology, water temperature, microbiology, and chemistry. To test this hypothesis, an extensive historical groundwater database was evaluated, and additional measurements of total iodine and iodine speciation were made from recently collected samples. During the summer, the water table decreased by as much as 0.7 m, surface water temperature increased by as much as 15 °C, and total iodine concentrations were consistently greater (up to 680%) than the following winter months. Most of the additional iodine observed in the summer could be attributed to proportional gains in organo-iodine, and not iodide or iodate. Furthermore, 129 I concentrations were observed to be two-orders-of-magnitude greater at the bottom of the upland aquifer than at the top. A coupled hydrological and biogeochemical conceptual model is proposed to tie these observations together. First, as the surface water temperature increased during the summer, microbial activity was enhanced, which in turn stimulated the formation of mobile organo-I. Hydrological processes were also likely involved in the observed iodine seasonal changes: (1) as the water table decreased in summer, the remaining upland water entering the wetland was comprised of a greater proportion of water containing elevated iodine concentrations from the low depths, and (2) water flow paths in summer changed such that the wells intercepted more of the contaminant plume and less of the diluting rainwater (due to evapotranspiration) and streamwater (as the lower levels promote a predominantly recharging system). These results underscore the importance of coupled processes influencing contaminant concentrations, and the need to assess seasonal contaminant variations to optimize long-term monitoring programs of wetlands., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The complex biogeochemical behavior of iodine (I) isotopes and their interaction with natural organic matter (NOM) pose a challenge for transport models. Here, we present results from iodination experiments with humic acid (HA) and fulvic acid (FA) using 1 H- 13 C heteronuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR) spectroscopy. Even though not a quantitative approach, 1 H- 13 C HSQC NMR corroborated that iodination of NOM occurs primarily through aromatic electrophilic substitution of proton by I, and also revealed how iodination chemically alters HA and FA in a manner that potentially affects the mobility of iodinated NOM in the environment. Three types of iodination experiments were conducted with HA and FA: a) non-enzymatic iodination by IO 3 (pH 3) and I - (pH 4 and 7), b) addition of lactoperoxidase to promote I - (pH 4 and 7), b) addition of lactoperoxidase to promote I - -iodination in the presence of the co-substrate, H 2 (pH 7), and c) addition of laccase for facilitating I 2 (pH 7), and c) addition of laccase for facilitating I - , with or without a mediator (pH 4). When mediators or H 2 , with or without a mediator (pH 4). When mediators or H 2 O 2 were present, extracellular oxidases and peroxidases enhanced I - incorporation into NOM by between 54% and 3400%. Iodination of HA, which was less than that of FA, enhanced HA's stability (inferred from increases in aliphatic compounds, decreases in carbohydrate moieties, and thus increased molecular hydrophobicity) yet reduced HA's tendency to incorporate more iodine. As such, HA is expected to act more as a sink for iodine in the environment. In contrast, iodination of FA appeared to generate additional iodine binding sites, which resulted in greater iodine uptake capability and enhanced mobility (inferred from decreases in aliphatic compounds, increases in carbohydrates, and thus decreases in molecular hydrophobicity). These results indicate that certain NOM moieties may enhance while others may inhibit radioiodine mobility in the aqueous environment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Marine gels (nano-, micro-, macro-) and marine snow play important roles in regulating global and basin-scale ocean biogeochemical cycling. Exopolymeric substances (EPS) including transparent exopolymer particles (TEP) that form from nano-gel precursors are abundant materials in the ocean, accounting for an estimated 700 Gt of carbon in seawater. This supports local microbial communities that play a critical role in the cycling of carbon and other macro- and micro-elements in the ocean. Recent studies have furthered our understanding of the formation and properties of these materials, but the relationship between the microbial polymers released into the ocean and marine snow remains unclear. Recent studies suggest developing a (relatively) simple model that is tractable and related to the available data will enable us to step forward into new research by following marine snow formation under different conditions. In this review, we synthesize the chemical and physical processes. We emphasize where these connections may lead to a predictive, mechanistic understanding of the role of gels in marine snow formation and the biogeochemical functioning of the ocean.

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 ∼4.9 million barrels of crude oil over 87 days. We determined the effects of oil exposure on microbial interactions using short- and long-term microcosm experiments with and without Macondo surrogate oil. Microbial activity determined using radiotracers revealed that oil exposure negatively affected substrate uptake by prokaryotes within 8 h and by eukaryotes over 72 h. Eukaryotic uptake of heterotrophic exopolymeric substances (EPS) was more severely affected than prokaryotic uptake of phototrophic EPS. In addition, our long-term exposure study showed severe effects on photosynthetic activity. Lastly, changes in microbial relative abundances and fewer co-occurrences among microbial species were mostly driven by photosynthetic activity, treatment (control vs. oil), and prokaryotic heterotrophic metabolism. Overall, oil exposure affected microbial co-occurrence and/or interactions possibly by direct reduction in abundance of one of the interacting community members and/or indirect by reduction in metabolism (substrate uptake or photosynthesis) of interacting members., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Kamalanathan, Schwehr, Labonté, Taylor, Bergen, Patterson, Claflin, Santschi and Quigg.)

Microgels play critical roles in a variety of processes in the ocean, including element cycling, particle interactions, microbial ecology, food web dynamics, air-sea exchange, and pollutant distribution and transport. Exopolymeric substances (EPS) from various marine microbes are one of the major sources for marine microgels. Due to their amphiphilic nature, many types of pollutants, especially hydrophobic ones, have been found to preferentially associate with marine microgels. The interactions between pollutants and microgels can significantly impact the transport, sedimentation, distribution, and the ultimate fate of these pollutants in the ocean. This review on marine gels focuses on the discussion of the interactions between gel-forming EPS and pollutants, such as oil and other hydrophobic pollutants, nanoparticles, and metal ions.

Organic particle dynamics in the surface ocean plays a critical part in the marine carbon cycle. Aggregation of marine organic particles drives their downward transport to support various marine organisms on their transit to the sediments. Extracellular polymeric substances (EPS) from various microbes are a major contributor to the oceanic organic particle pool. The stickiness of EPS is expected to play a determining role in the aggregation process of particles; however, stickiness parameters are usually indirectly estimated through data fitting without direct assessment. Here a magnetic tweezer method was developed to quantitatively assess the stickiness of three model EPS produced by: Amphora sp., (diatom), Emiliania huxleyi (coccolithophore), and Sagittula stellata (bacteria), under different in vitro environmental conditions (salinity or EDTA complexed cations) and surface matrices (EPS-EPS and bare glass). Our results showed the stickiness of three microbial EPS decreasing for S. stellata > E. huxleyi > Amphora sp., in line with their decreasing protein-to-carbohydrate (P/C) ratios (related to their relative hydrophobicity). The data not only emphasize the importance of hydrophobicity on EPS stickiness, but also demonstrates that salinity and the nature of the substrate surface can influence the stickiness. Furthermore, we investigated stickiness between various types of EPS, and the observed selective stickiness of EPS between species may shed light on the interactions among heterogeneous marine microorganisms. Overall, this newly developed system provides a platform to assess the EPS stickiness to advance our understanding of the aggregation and sedimentation process of organic particles that are critical for the fate of organic carbon as well as for biofilm formation and microbial colonization of surfaces in the ocean., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The cycling and fate of polycyclic aromatic hydrocarbons (PAHs) is not well understood in estuarine systems. It is critical now more than ever given the increased ecosystem pressures on these critical coastal habitats. A budget of PAHs and cycling has been created for Galveston Bay (Texas) in the northwestern Gulf of Mexico, an estuary surrounded by 30-50% of the US capacity of oil refineries and chemical industry. We estimate that approximately 3 to 4 mt per year of pyrogenic PAHs are introduced to Galveston Bay via gaseous exchange from the atmosphere (ca. 2 mt/year) in addition to numerous spills of petrogenic PAHs from oil and gas operations (ca. 1.0 to 1.9 mt/year). PAHs are cycled through and stored in the biota, and ca. 20 to 30% of the total (0.8 to 1.5 mt per year) are estimated to be buried in the sediments. Oysters concentrate PAHs to levels above their surroundings (water and sediments) and contain substantially greater concentrations than other fish catch (shrimp, blue crabs and fin fish). Smaller organisms (infaunal invertebrates, phytoplankton and zooplankton) might also retain a significant fraction of the total, but direct evidence for this is lacking. The amount of PAHs delivered to humans in seafood, based on reported landings, is trivially small compared to the total inputs, sediment accumulation and other possible fates (metabolic remineralization, export in tides, etc.), which remain poorly known. The generally higher concentrations in biota from Galveston Bay compared to other coastal habitats can be attributed to both intermittent spills of gas and oil and the bay's close proximity to high production of pyrogenic PAHs within the urban industrial complex of the city of Houston as well as periodic flood events that transport PAHs from land surfaces to the Bay., Competing Interests: The authors have declared that no competing interests exist

The substantial increase in plastic pollution in marine ecosystems raises concerns about its adverse impacts on the microbial community. Microorganisms (bacteria, phytoplankton) are important producers of exopolymeric substances (EPS), which govern the processes of marine organic aggregate formation, microbial colonization, and pollutant mobility. Until now, the effects of nano- and micro-plastics on characteristics of EPS composition have received little attention. This study investigated EPS secretion by four phytoplankton species following exposure to various concentrations of polystyrene nano- and microplastics (55 nm nanoparticles; 1 and 6 μm microparticles). The 55 nm nanoparticles induced less growth/survival (determined on a DNA basis) and produced EPS with higher protein-to-carbohydrate (P/C) ratios than the exposure to microplastic particles. The amount of DNA from the four marine phytoplankton showed a higher negative linear correlation with increasing P/C ratios, especially in response to nanoplastic exposure. These results provide evidence that marine phytoplankton are quite sensitive to smaller-sized plastics and actively modify their EPS chemical composition to cope with the stress from pollution. Furthermore, the release of protein-rich EPS was found to facilitate aggregate formation and surface modification of plastic particles, thereby affecting their fate and colonization. Overall, this work offers new insights into the potential harm of different-sized plastic particles and a better understanding of the responding mechanism of marine phytoplankton for plastic pollution. The data also provide needed information about the fate of marine plastics and biogenic aggregation and scavenging processes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Hurricane Harvey was the wettest hurricane in US history bringing record rainfall and widespread flooding in Houston, TX. The resulting storm- and floodwaters largely emptied into the Galveston Bay. Surface water was collected from 10 stations during five cruises to investigate the concentrations and sources of 16 priority polycyclic aromatic hydrocarbons (PAHs), and relative abundances of PAH-degrading bacteria. Highest PAH levels (102-167 ng/L) were detected during the first sampling event, decreasing to 36-69 ng/L within a week. Four sites had elevated concentrations of carcinogenic benzo[a]pyrene that exceeded the Texas Standard for Surface Water threshold. The highest relative abundances of known PAH-degrading bacteria Burkholderiaceae, Comamonadaceae, and Sphingomonadales were detected during the first and second sampling events. PAH origins were about 60% pyrogenic, 2% petrogenic, and the remainder of mixed sources. This study improves our understanding on the fate, source, and distributions of PAHs in Galveston Bay after an extreme flooding event.

Diatoms play a key role in the marine carbon cycle with their high primary productivity and release of exudates such as extracellular polymeric substances (EPS) and transparent exopolymeric particles (TEP). These exudates contribute to aggregates (marine snow) that rapidly transport organic material to the seafloor, potentially capturing contaminants like petroleum components. Ocean acidification (OA) impacts marine organisms, especially those that utilize inorganic carbon for photosynthesis and EPS production. Here we investigated the response of the diatom Thalassiosira pseudonana grown to present day and future ocean conditions in the presence of a water accommodated fraction (WAF and OAWAF) of oil and a diluted chemically enhanced WAF (DCEWAF and OADCEWAF). T. pseudonana responded to WAF/DCEWAF but not OA and no multiplicative effect of the two factors (i.e., OA and oil/dispersant) was observed. T. pseudonana released more colloidal EPS (< 0.7 μm to > 3 kDa) in the presence of WAF/DCEWAF/OAWAF/OADCEWAF than in the corresponding Controls. Colloidal EPS and particulate EPS in the oil/dispersant treatments have higher protein-to-carbohydrate ratios than those in the control treatments, and thus are likely stickier and have a greater potential to form aggregates of marine oil snow. More TEP was produced in response to WAF than in Controls; OA did not influence its production. Polyaromatic hydrocarbon (PAH) concentrations and distributions were significantly impacted by the presence of dispersants but not OA. PAHs especially Phenanthrenes, Anthracenes, Chrysenes, Fluorenes, Fluoranthenes, Pyrenes, Dibenzothiophenes and 1-Methylphenanthrene show major variations in the aggregate and surrounding seawater fraction of oil and oil plus dispersant treatments. Studies like this add to the current knowledge of the combined effects of aggregation, marine snow formation, and the potential impacts of oil spills under ocean acidification scenarios., Competing Interests: The authors have declared that no competing interests exist.

Microbial heterotopic metabolism in the ocean is fueled by a supply of essential nutrients acquired via exoenzymes catalyzing depolymerization of high-molecular-weight compounds. Although the rates of activity for a variety of exoenzymes across various marine environments are well established, the factors regulating the production of these exoenzymes, and to some extent their correlation with microbial community composition, are less known. This study focuses on addressing these challenges using a mesocosm experiment that compared a natural seawater microbial community (control) and exposed (to oil) treatment. Exoenzyme activities for β-glucosidase, leucine aminopeptidase (LAP), and lipase were significantly correlated with dissolved nutrient concentrations. We measured correlations between carbon- and nitrogen-acquiring enzymes ( β -glucosidase/lipase versus LAP) and found that the correlation of carbon-acquiring enzymes varies with the chemical nature of the available primary carbon source. Notably, a strong correlation between particulate organic carbon and β -glucosidase activity demonstrates their polysaccharide depolymerization in providing the carbon for microbial growth. Last, we show that exoenzyme activity patterns are not necessarily correlated with prokaryotic community composition, suggesting a redundancy of exoenzyme functions among the marine microbial community and substrate availability. This study provides foundational work for linking exoenzyme function with dissolved organic substrate and downstream processes in marine systems. IMPORTANCE Microbes release exoenzymes into the environment to break down complex organic matter and nutrients into simpler forms that can be assimilated and utilized, thereby addressing their cellular carbon, nitrogen, and phosphorus requirements. Despite its importance, the factors associated with the synthesis of exoenzymes are not clearly defined, especially for the marine environment. Here, we found that exoenzymes associated with nitrogen and phosphorus acquisition were strongly correlated with inorganic nutrient levels, while those associated with carbon acquisition depended on the type of organic carbon available. We also show a linear relationship between carbon- and nitrogen-acquiring exoenzymes and a strong correlation between microbial biomass and exoenzymes, highlighting their significance to microbial productivity. Last, we show that changes in microbial community composition are not strongly associated with changes in exoenzyme activity profiles, a finding which reveals a redundancy of exoenzyme activity functions among microbial community. These findings advance our understanding of previously unknown factors associated with exoenzyme production in the marine environment., (Copyright © 2020 Kamalanathan et al.)

The pervasive presence of plastic waste in the aquatic environment is widely viewed as one of the most serious environmental challenges for current and future generations. Microplastics ultimately degrade into nano and smaller-sizes. In turn, their biological and ecological impacts become more complicated and ambiguous. Nano-plastic particles travel from freshwater systems to estuarine and oceanic regions, during which they can interact with dissolved organic matter (DOM) to form microgels. Microgel formation is ubiquitous in aquatic systems, serving as a shunt between DOM and particulate organic matter (POM), as well as playing key roles in particle aggregation/sedimentation and pollutant transport. Currently the influences and mechanisms of the aggregation behavior and environmental fate of nano-plastics in different aquatic environments is poorly understood. Here, we report that 25 nm polystyrene nano-particles in lake and river water can promote POM (microgel) formation and accelerate the DOM-POM transition. We also adjusted various salinities of water samples to simulate scenarios based on plastic transport in waters flowing from rivers to seas. The results indicate polystyrene nanoparticles can interact with organic matter to form large organic particles, which may undergo further settling in response to specific salinity levels. Polystyrene-induced microgel formation appears to involve the hydrophobic interactions between plastics and DOM. Our data provides much needed information for modeling and understanding the retention and sedimentation of nano-plastics. We show that nano-plastics alter the DOM-POM shunt to cause unanticipated perturbations in the functionality of aquatic ecosystems., (Copyright © 2019 Elsevier B.V. All rights reserved.)

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). Four treatments were conducted in M2, M3 and M4 whereas only three in M5: 1) a water accommodated fraction of oil (WAF), 2) a chemically-enhanced WAF prepared with Corexit (CEWAF, not in M5), 3) a 10-fold diluted CEWAF (DCEWAF); and 4) controls. Overall, oil and dispersants input, nutrient and microbial biomass addition enhanced EPS production. Dispersant addition tended to induce the production of EPS with higher protein/carbohydrate (P/C) ratios, irrespective of oceanic regions. EPS produced in M4 was generally more hydrophobic than that produced in M3. The P/C ratio of EPS in both the aggregate and the colloidal fraction was a key factor that regulated oil contribution to sinking aggregates, based on the close correlation with %petro-carbon in these fractions. In the short term (4-5 days), both the petro and non-petro carbon sedimentation efficiencies showed decreasing trends when oil/dispersants were present. In comparison, in the longer-term (16 days), petro-carbon sedimentation efficiency was less influenced by dispersants, possibly due to biological and physicochemical changes of the components of the oil-EPS-mineral phase system, which cooperatively controlled the sinking velocities of the aggregates., (Copyright © 2019 Elsevier B.V. All rights reserved.)

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 3 - 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 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 H 2 in a pH 7 buffer, and (3) IO 2 in a pH 3 groundwater. Both oxidase and peroxidase systems could oxidize I 3 - in a pH 3 groundwater. Both oxidase and peroxidase systems could oxidize I - to I 2 or hypoiodide (HOI) leading to organo-I formation. However, the laccase-ABTS mediator was the most effective and enhanced I - uptake by HA up to 13.5 mg/g, compared to 1.9 mg/g for the LPO-H 2 O 2 . IO 3 - was abiotically reduced to I 2 or HOI leading to an organo-I formation. Pathways for HA iodination include covalent modification of aromatic-type rings by I 2 / HOI or iodine incorporation into newly formed benzoquinone species arising from the oxidation of phenolic C species. This study improves our molecular-level understanding of NOM-iodine interactions and stresses the important role that mediators may play in the enzymatic reactions between iodine and NOM.

Silver (Ag)-based technologies are amongst the most common approaches to removing radioiodine from aqueous waste streams. As a result, a large worldwide inventory of radioactive AgI waste presently exits, which must be stabilized for final disposition. In this work, the efficacy of silver-impregnated granular activated carbon (Ag-GAC) to remove iodide (I - ), iodate (IO 3 - ) and organo-iodine (org-I) from cementitious leachate was examined. In addition, cementitious materials containing I - , IO 3 - , or org-I loaded Ag-GAC were characterized by iodine K-edge XANES and EXAFS to provide insight into iodine stability and speciation in these waste forms. The Ag-GAC was very effective at removing I - and org-I, but ineffective at removing IO 3 - from slag-free grout leachate under oxic conditions. I - or org-I removal was due to the formation of insoluble AgI (s) or Ag-org-I (s) on the Ag-GAC. When I - -loaded Ag-GAC material was cured with slag-free and slag grouts, I - was released from AgI (s) to form a hydrated I - species. Conversely, when org-I loaded Ag-GAC material was cured in the two grout formulations, no change was observed in the iodine speciation, indicating the org-I species remained bound to the Ag. Because little IO 3 - was bound to the Ag-GAC, it was not detectable in the grout. Thus, grout formulation and I speciation in the waste stream can significantly influence the effectiveness of the long-term disposal of radioiodine associated with Ag-GAC in grout waste forms., (Published by Elsevier Ltd.)

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 239,240 Pu was preferentially associated with more persistent organic matter compounds in Nagasaki sediments, particularly those natural organic matter (NOM) stabilized by Fe oxides (NOM Fe-oxide ). Other organic matter compounds served as a secondary sink of these bomb-derived 239,240 Pu (31 ± 2% on average), and <20% of the 239,240 Pu was immobilized by inorganic mineral particles. In a narrow, 239,240 Pu-enriched layer of only 9-cm depth (total core depth was 600 cm), N-containing carboxyl aliphatic and/or alicyclic molecules (CCAM) in NOM Fe-oxide and other NOM fractions immobilized the majority of 239,240 Pu. Among the cluster of N-containing CCAM moieties, hydroxamate siderophores, the strongest known Pu chelators in nature, were further detected in these "aged" Nagasaki bomb residue-containing sediments. While present long-term disposal and environmental remediation modeling assume that solubility limits and sorption to mineral surfaces control Pu subsurface mobility, our observations suggest that NOM, which is present in essentially all subsurface systems, undoubtedly plays an important role in sequestrering Pu. Ignoring the role of NOM in controlling Pu fate and transport is not justified in most environmental systems., (Copyright © 2019 Elsevier B.V. All rights reserved.)

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. However, AgIZ encapsulated in slag-containing grout, the most common type of grout used for low-level radioactive waste disposal, was entirely ineffective at immobilizing I. While the slag-free grout with AgIZ released only 3.3 μg/L I total into the contact solution, the slag-containing grout released 19,269 μg/L I total . Based on thermodynamic calculations, the strongly reducing conditions of the slag-containing system (Eh was -392 mV) promoted the reductive dissolution of the AgI, forming Ag 0 (aq) and releasing iodide (I - ) into the aqueous phase. The slag-free grout system was maintained under more oxidizing conditions (Eh was 439 mV) and a minimal amount of I was released from the grout. In both grout systems, the aqueous I, originally added to the AgZ as iodide, was composed primarily of iodide and org-I, and essentially no iodate was detected. More organo-I was detected in the slag-free than the slag-containing grout system because the high redox potential of the former system was more conducive to the formation of oxidized I species, such as I 2 , which may be intermediates in the covalent bonding of I with organic C in grout. Iodine K-edge XANES analysis indicated that I existed exclusively as silver iodide in both AgIZ-grout samples. Together, these results indicate that subsurface grout disposal of AgIZ waste should be done under oxidizing conditions and that radioiodide released from AgIZ can undergo speciation transformations that have important implications on subsequent mobility and estimated risk., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

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. Additionally, oxygenation patterns for MOS extracts provide evidence for degraded oil compounds. Formulas having similar double bond equivalents but higher oxygen content (MOS CHO: CHO 2-9 , DBE 2-16 , MOS CHON: CHO 0-7 N 1 , DBE 9-18; Macondo CHO: CHO 1-4 , DBE 2-15 , CHON: CHO 0-3 N 1 , DBE 9-21 ) were found in MOS extracts generating isoabundance distributions similar to those of environmentally aged oil. Such shifts in molecular composition are consistent with the transformation of high DBE oil components, unobservable by FTICR-MS until oxygenation in the mesocosms. Low light conditions and the rapid proliferation of hydrocarbon-degraders observed in parallel studies suggest biological activity as the primary cause of oil degradation. MOS may thus represent an important microenvironment for oil degradation especially during its long transit below the euphotic zone to sediments.

Spilled oil treated with Corexit dispersant can cause unintended impacts on marine environment systems including altering marine organic matter dynamics; however, impacts on microgels and marine oil snow (MOS) formation are still debated and remain to be fully understood. Extracellular polymeric substances (EPS) are a major source of marine organic carbon for MOS and microgel formation. EPS initial aggregation plays key roles in the oil degrading process and various biogeochemical reactions. Here we used four types of EPS with water accommodated fraction (WAF), chemically-enhanced WAF (CEWAF) and Corexit, to represent potential situations during oil spills and post-application of Corexit. We found that Corexit alone can inhibit EPS aggregation and disperse pre-existing microgels. CEWAF can enhance EPS aggregation with efficiency by up to 80%-100% and more aggregates accumulated within the air-water interface. Additionally, more hydrophobic EPS aggregates showed high resistance to Corexit dispersion while hydrophilic EPS were more sensitive. Effects of oil spills on marine gel particle formation are primarily determined by chemical characteristics (hydrophobicity and protein content) of the constituent EPS. This study offers unique insights for organic particle dynamics and identifies controlling factors for MOS or gel particles associated with oil spills and Corexit dispersant used., (Copyright © 2018 Elsevier B.V. All rights reserved.)

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. The size of microgels in natural coastal seawaters increased by18~25% compared to corresponding dark controls. Within a relatively short time (1 h), the C and N sequestered into the photo-aggregates accounted for 10% and 13% of the bulk particulate C and N, respectively. The N/C ratio of the photo-aggregates was two times higher after sunlight irradiation. Furthermore, we show that the aggregation process was dependent on reactive oxygen species (ROS). To accommodate for the different organic material in the marine environment, we monitored the particle size in various extracellular polymeric substances (EPS) and model biopolymers using flow cytometry, dynamic laser scattering, and scanning electron microscopy. We found that proteins play important roles in light-induced aggregation, which is in contrast to previous views that sunlight can break down DOM and interrupt aggregation. The photo-flocculation process involving organic N provides new insights into DOM assembly, bioavailability, and sedimentation, and thus potentially link the C and N cycles., (Copyright © 2018. Published by Elsevier B.V.)

During the 2010 Deepwater Horizon oil spill, the chemical dispersant Corexit was applied over vast areas of the Gulf of Mexico. Marine phytoplankton play a key role in aggregate formation through the production of extracellular polymeric materials (EPS), an important step in the biological carbon pump. This study examined the impacts of oil and dispersants on the composition and physiology of natural marine phytoplankton communities from the Gulf of Mexico during a 72-hour mesocosm experiment and consequences to carbon export. The communities were treated using the water accommodated fraction (WAF) of oil, which was produced by adding Macondo surrogate oil to natural seawater and mixed for 24 h in the dark. A chemically enhanced WAF (CEWAF) was made in a similar manner, but using a mixture of oil and the dispersant Corexit in a 20:1 ratio as well as a diluted CEWAF (DCEWAF). Phytoplankton communities exposed to WAF showed no significant changes in PSII quantum yield (F v /F m ) or electron transfer rates (ETR max ) compared to Control communities. In contrast, both F v /F m and ETR max declined rapidly in communities treated with either CEWAF or DCEWAF. Analysis of other photophysiological parameters showed that photosystem II (PSII) antenna size and PSII connectivity factor were not altered by exposure to DCEWAF, suggesting that processes downstream of PSII were affected. The eukaryote community composition in each experimental tank was characterized at the end of the 72 h exposure time using 18S rRNA sequencing. Diatoms dominated the communities in both the control and WAF treatments (52 and 56% relative abundance respectively), while in CEWAF and DCEWAF treatments were dominated by heterotrophic Euglenozoa (51 and 84% respectively). Diatoms made up the largest relative contribution to the autotrophic eukaryote community in all treatments. EPS concentration was four times higher in CEWAF tanks compared to other treatments. Changes in particle size distributions (a proxy for aggregates) over time indicated that a higher degree of particle aggregation occurred in both the CEWAF and DCEWAF treatments than the WAF or Controls. Our results demonstrate that chemically dispersed oil has more negative impacts on photophysiology, phytoplankton community structure and aggregation dynamics than oil alone, with potential implications for export processes that affect the distribution and turnover of carbon and oil in the water column., (Copyright © 2018 Elsevier B.V. All rights reserved.)

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). In this study, we isolated bacteria from surface water of the nGoM that grow on oil or Corexit dispersant. Among the 100 strains isolated, nine were identified to produce remarkable amounts of EPS. 16S rRNA gene analysis revealed that six isolates (strains C1, C5, W10, W11, W14, W20) belong to the genus Alteromonas; the others were related to Thalassospira (C8), Aestuariibacter (C12), and Escherichia (W13a). The isolates preferably degraded alkanes (17-77%), over polycyclic aromatic hydrocarbons (0.90-23%). The EPS production was determined in the presence of a water accommodated fraction (WAF) of oil, a chemical enhanced WAF (CEWAF), Corexit, and control. The highest production of visible aggregates was found in Corexit followed by CEWAF, WAF, and control; indicating that Corexit generally enhanced EPS production. The addition of WAF and Corexit did not affect the carbohydrate content, but significantly increased the protein content of the EPS. On the average, WAF and CEWAF treatments had nine to ten times more proteins, and Corexit had five times higher than the control. Our results reveal that Alteromonas and Thalassospira, among the commonly reported bacteria following the DwH spill, produce protein rich EPS that could have crucial roles in oil degradation and marine snow formation. This study highlights the link between EPS production and bacterial oil-degrading capacity that should not be overlooked during spilled oil clearance., Competing Interests: Antonietta Quigg and Wei-Chun Chin are Academic Editors of PLOS ONE. This does not alter our adherence to PLOS ONE policies on sharing data and materials.

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). To provide the geochronology required to evaluate sedimentary total Hg profiles, 58 of 72 sediment cores were dated using the atmospheric radionuclide tracers 137 Cs, 210 Pb, and 239,240 Pu. Sediment cores were assessed for depths of mixing, and for the determination of sediment accumulation rates using both geochemical (total Hg) and radiochemical data. At most stations, evidence for significant vertical mixing, derived from profiles of 7 Be (where possible) and porosity, was restricted to the upper ~1-3cm. Thus, historic profiles of both total Hg and radionuclides were only minimally distorted, allowing a reconstruction of their depositional history. The pulse input tracers 137 Cs and 239,240 Pu used to assess sediment accumulation rates agreed well, while the steady state tracer 210 Pb exhibited weaker agreement, likely due to irregular lateral sediment inputs., (Copyright © 2018. Published by Elsevier B.V.)

Sediments from a waste pit in Houston Ship Channel (HSC) were characterized using a number of molecular markers of natural organic matter fractions (e.g., pyrogenic carbon residues, PAHs, lignins), in addition to dioxins, in order to test the hypothesis that the dispersal and mobility of dioxins from the waste pit in the San Jacinto River is minimal. Station SG-6, sampled at the site of the submerged waste pit, had the highest dioxin/furan concentrations reported for the Houston Ship Channel/Galveston Bay (HSC/GB) system (10,000-46,000 pg/g), which translated into some of the highest reported World Health Organization Toxic Equivalents (TEQs: 2000-11,000 pg/g) in HSC sediments. Using a multi-tracer approach, this study confirmed our hypothesis that sludges from chlorinated pulps are a very likely source of dioxins/furans to this pit. However, this material also contained large quantities of additional hydrophobic organic contaminants (PAHs) and pyrogenic markers (soot-BC, levoglucosan), pointing to the co-occurrence of petroleum hydrocarbons and combustion byproducts. Comparison of dioxin/furan signatures in the waste pit with those from sediments of the HSC and a control site suggests that the remobilization of contaminated particles did not occur beyond the close vicinity of the pit itself. The dioxins/furans in sediments outside the waste pit within the HSC are rather from other diffuse inputs, entering the sedimentary environment through the air and water, and which are comprised of a mixture of industrial and municipal sources. Fingerprinting of waste pit dioxins indicates that their composition is typical of pulp and paper sources. Measured pore water concentrations were 1 order of magnitude lower than estimated values, calculated from a multiphase sorption model, indicating low mobility of dioxins within the waste pit. This is likely accomplished by co-occurring and strong sorbing pyrogenic and petrogenic residues in the waste pit, which tend to keep dioxins strongly sorbed to particles., (Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.)

During the 20th century the impacts of industrialization and urbanization in Galveston Bay resulted in significant shifts in trace metals (Hg, Pb, Ni, Zn) and vascular plant biomarkers (lignin phenols) recorded within the surface sediments and sediment cores profile. A total of 22 sediment cores were collected in Galveston Bay in order to reconstruct the historical input of Hg, Pb, Ni, Zn and terrestrial organic matter. Total Hg (T-Hg) concentration ranged between 6 and 162 ng g -1 in surface sediments, and showed decreasing concentrations southward from the Houston Ship Channel (HSC) toward the open estuary. Core profiles of T-Hg and trace metals (Ni, Zn) showed substantial inputs starting in 1905, with peak concentrations between 1960 and 1970's, and decreasing thereafter with exception to Pb, which peaked around 1930-1940s. Stable carbon isotopes and lignin phenols showed an increasing input of terrestrial organic matter driven by urban development within the watershed in the early 1940s. Both the enrichment factor and the geoaccumulation index (I geo ) for T-Hg as a measure of the effectiveness of environmental management practices showed substantial improvements since the 1970s. The natural recovery rate in Galveston Bay since the peak input of T-Hg was non-linear and displayed a slow recovery during the twenty-first century., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

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 (9.28 metric tons) associated with sediments system-wide was within the range released (6-12 metric tons). Evidence of sediment/Hg remobilization was observed in cores primarily from the PBR, and to a lesser extent the ES, whereas cores from MM, most of the OR, the ES, and half from the PBR exhibited sharp peaks in Hg concentrations at depth, followed by gradual decreases towards the surface. Based on background PBR sediment Hg concentrations (100ngg -1 ), "elevated" (300ngg -1 ), or "highly elevated" (600ngg -1 ) Hg concentrations in sediments, and resulting inventories, we assessed impact levels ("elevated"≥270, or "highly elevated"≥540mgm -2 ). 71% of PBR stations had "elevated", and 29% had "highly elevated" Hg inventories; 45% of MM stations had "elevated", and 27% had "highly elevated" inventories; 80% of OR stations had "elevated" inventories only; and 17% of ES stations had "elevated" inventories only. Most "highly elevated" stations were located within 8km of HoltraChem, in MM, in the PBR, and in the OR. Near-surface sediments in the OR, PBR and MM were all "highly elevated", while those in the ES were "elevated", on average. Mean Hg fluxes to bottom sediments were greatest in the OR (554), followed by the PBR (469), then MM (452), and finally the ES (204ngcm -2 y -1 )., (Copyright © 2017 Elsevier B.V. All rights reserved.)

During the Deepwater Horizon (DWH) oil spill, massive quantities of oil were deposited on the seafloor via a large-scale marine oil-snow sedimentation and flocculent accumulation (MOSSFA) event. The role of chemical dispersants (e.g., Corexit) applied during the DWH oil spill clean-up in helping or hindering the formation of this MOSSFA event are not well-understood. Here, we present the first experiment related to the DWH oil spill to specifically investigate the relationship between microbial community structure, oil and Corexit®, and marine oil-snow in coastal surface waters. We observed the formation of micron-scale aggregates of microbial cells around droplets of oil and dispersant and found that their rate of formation was directly related to the concentration of oil within the water column. These micro-aggregates are potentially important precursors to the formation of larger marine oil-snow particles. Therefore, our observation that Corexit® significantly enhanced their formation suggests dispersant application may play a role in the development of MOSSFA events. We also observed that microbial communities in marine surface waters respond to oil and oil plus Corexit® differently and much more rapidly than previously measured, with major shifts in community composition occurring within only a few hours of experiment initiation. In the oil-amended treatments without Corexit®, this manifested as an increase in community diversity due to the outgrowth of several putative aliphatic- and aromatic-hydrocarbon degrading genera, including phytoplankton-associated taxa. In contrast, microbial community diversity was reduced in mesocosms containing chemically dispersed oil. Importantly, different consortia of hydrocarbon degrading bacteria responded to oil and chemically dispersed oil, indicating that functional redundancy in the pre-spill community likely results in hydrocarbon consumption in both undispersed and dispersed oils, but by different bacterial taxa. Taken together, these data improve our understanding of how dispersants influence the degradation and transport of oil in marine surface waters following an oil spill and provide valuable insight into the early response of complex microbial communities to oil exposure.

Uptake of six particle-reactive and/or redox-sensitive radionuclides ( 210 Pb, 234 Th, 7 Be, 59 Fe, 237 Np and 233 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 (>0.45 µm), supporting their application as tracers of soil erosion. Th bound strongly to the colloidal HA (3 kDa-0.45 µm) and as such, would not be a good candidate as a tracer for monitoring soil erosion. HAs likely reduced the oxidized neptunyl form (Np(V)O 4 + ) to Np(IV) based on its enhanced particle-reactivity and Np uptake by particulate HAs, partially retarding the movement of anthropogenic 237 Np in field polluted environments. Particulate/colloidal carbonyl/O-aryl (likely through hydroquinone/quinone) functionalities in the HA correlated to Np and Pa uptake, but only particulate O-aryl functionalities was responsible for Fe uptake. The carboxylate- and carbonyl/O-aryl-containing organic functionalities in the HA correlated strongly with Th uptake. In contrast, no significant correlations between organic parameters and Pb or Be uptake implied their predominance of uniform surface adsorption onto particles. This study provides novel insight into the binding of six radionuclides with different organic functionalities of three size fractions, as well as its possible impact on their application in the soil-tracing research.

The Deepwater Horizon oil spill stimulated the release of marine snow made up of dead/living plankton/bacteria and their exopolymeric polysaccharide substances (EPS), termed marine oil snow (MOS), promoting rapid removal of oil from the water column into sediments near the well site. Mesocosm simulations showed that Macondo surrogate oil readily associates with the marine snow. Quantitative solid-state 13 C NMR readily distinguishes this oil from naturally formed marine snow and reveals that adding the dispersant Corexit enhances the amount of oil associated with the MOS, thus contributing to rapid removal from the water column. Solvent extraction of MOS removes the oil-derived compounds for analysis by one and two-dimensional GC/MS and evaluation of potential transformations they undergo when associated with the EPS. The results reveal that the oil associated with EPS is subjected to rapid transformation, in a matter of days, presumably by bacteria and fungi associated with EPS., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Engineered nanoparticles (ENPs), products from modern nanotechnologies, can potentially impact the marine environment to pose serious threats to marine ecosystems. However, the cellular responses of marine phytoplankton to ENPs are still not well established. Here, we investigate four different diatom species (Odontella mobiliensis, Skeletonema grethae, Phaeodactylum tricornutum, Thalassiosira pseudonana) and one green algae (Dunaliella tertiolecta) for their extracellular polymeric substances (EPS) release under model ENP treatments: 25 nm titanium dioxide (TiO 2 ), 10-20 nm silicon dioxide (SiO 2 ), and 15-30 nm cerium dioxide (CeO 2 ). We found SiO 2 ENPs can significantly stimulate EPS release from these algae (200-800%), while TiO 2 ENP exposure induced the lowest release. Furthermore, the increase of intracellular Ca 2+ concentration can be triggered by ENPs, suggesting that the EPS release process is mediated through Ca 2+ signal pathways. With better understanding of the cellular mechanism mediated ENP-induced EPS release, potential preventative and safety measures can be developed to mitigate negative impact on the marine ecosystem.

Polybrominated diphenyl ethers (PBDEs), a persistent organic pollutant are ubiquitous in aquatic ecosystems, which are causing serious environmental concerns. In this study, we chose BDE-47 as a representative PBDEs, to investigate its toxic effects on two microalgal species and the response of their antioxidant system. The results indicated Alexandrium minutum (a dinoflagellate) was more sensitive to BDE-47 than Dunaliella salina (a chlorophyte), as determined by growth rates, cellular structure and photosynthetic parameters. Cellular reactive oxygen species (ROS) levels were significantly elevated under the exposure of BDE-47 in both species, corresponding to an increase of superoxide dismutase (SOD), catalase (CAT) and glutathione reductase (GR) activities, while glutathione peroxidase (GPX) activities decreased in D. salina and increased in A. minutum. The different enzymes responses between the two species indicated different mechanisms in their antioxidant system, and we deduced that A. minutum might have a higher efficiency for scavenging H 2 O 2 than D. salina., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

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 -14 M). Under mildly acidic conditions (pH ∼ 5.5), 29 ± 24% of the HAs were released as colloidal organic matter (>3 kDa to <0.45 μm), yet this HA fraction accounted for a vast majority of the bound Pu, 76 ± 13% on average. In comparison, the particulate HA fraction bound only 8 ± 4% on average of the added Pu. The truly dissolved Pu fraction was typically <1%. Pu binding was strongly and positively correlated with the concentrations of organic nitrogen in both particulate (>0.45 μm) and colloidal phases in terms of activity percentage and partitioning coefficient values (logK d ). Based on molecular characterization of the HAs by solid state 13 C nuclear magnetic resonance (NMR) and elemental analysis, Pu binding was correlated to the concentration of carboxylate functionalities and nitrogen groups in the particulate and colloidal phases. The much greater tendency of Pu to bind to colloidal HAs than to particulate HA has implications on whether NOM acts as a Pu source or sink during natural or man-induced episodic flooding.

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 ( 137 Cs, 239,240 Pu, 210 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). The recent 21years of Hg input were used to estimate 'apparent' recovery rates, yielding exponentially decreasing total Hg concentrations. Apparent recovery half-times (T 1/2 =ln2/α) were calculated from an exponential fit of Hg(t)=Hg(t=21)∗exp(-α∗t)+Hg(∞) to total Hg concentration profiles over the past 21years (assuming Hg(∞) of 0, 100, or 400ngg -1 ). Mean T 1/2 values were, at PBR 31years (16 of 24 cores), at MM 22years (9 of 11 cores), at ES 20 to 120years (mean of 78years; 12 of 18 cores), and at OR 69years (3 of 5 cores). In 18 out of 57 cores, concentrations either increased towards the surface or remained the same, indicating slower or incomplete 'communication' with the larger system. The Penobscot River and Estuary system has recovered substantially since 1967, and top 1cm sediment Hg concentrations (Hg(0)) from areas in rapid communication with the larger system are converging to 600-700ngg -1 (1967 maxima of 70,000 + ngg -1 ). However, to recover from Hg(0) of 700ngg -1 to a Hg(∞) of <100ngg -1 would require 3 or more half-times., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Corexit, an EPA-approved chemical dispersant, was intensively used during the 2010 Deepwater Horizon Oil Spill in the Gulf of Mexico. Current studies surrounding Corexit have mainly focused on its toxicity and oil removal capacity. The potential impact of Corexit on the surface ocean carbon dynamics has remained largely unknown. The spontaneous assembly of DOM (dissolved organic matter) polymers into microgels (POM, particulate organic matter) was demonstrated previously that it can influence various critical processes, such as colloidal pump, microbial loops, and nutrition availability in the surface ocean. Here, we report that Corexit alone can significantly inhibit DOM microgel formation and reduce the stability of pre-existing microgels. However, Corexit and oil, Chemically Enhanced Water Accommodated Fraction (CEWAF), could effectively facilitate DOM microgel formation. The unanticipated disturbance of Corexit and oil spills on the critical DOM-POM continuum warrant particular caution and thus should be considered for future application of Corexit during oil spills., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

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. Our results show that after 1 h sunlight irradiation, the turbidity level of soluble EPS was 60% higher than in the dark control. Flow cytometry also confirmed that more particles of larger sized were formed by sunlight. In addition, we determined a higher mass of aggregates collected on filter in the irradiated samples. This suggests light can induce aggregation of this bacterial EPS. Reactive oxygen species hydroxyl radical and peroxide played critical roles in the photo-oxidation process, and salts assisted the aggregation process. The observation that Sagitulla stellata EPS with relatively high protein content promoted aggregation, was in contrast to the case where no significant differences were found in the aggregation of a non-protein containing phytoplankton EPS between the dark and light conditions. This, together with the evidence that protein-to-carbohydrate ratio of aggregates formed under light condition is significantly higher than that formed under dark condition suggest that proteins are likely the important component for aggregate formation. Light-induced aggregation provides new insights into polymer assembly, marine snow formation, and the fate/transport of organic carbon and nitrogen in the ocean., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Contaminated soil organic matter from the Rocky Flats Environmental Technology Site (RFETS) has been previously shown to accumulate plutonium (Pu) in a colloidal subfraction and is hypothesized to contain cutin-like chemical structures cross-linked with hydroxamate functionality. The present study further characterizes this high Pu affinity subfraction using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) and discovers additional substructural components. The Pu-enriched fraction was extracted and purified through a series of ultrafiltration and isoelectric focusing (IEF) electrophoresis steps. Predominantly low H/C and high double-bond equivalence (DBE) aromatic and condensed aromatic molecular formulas were detected, 66% of which are included in a COO Kendrick mass defect (KMD) homologous series. This suggests the existence of polycarboxylated aromatic and condensed aromatic formulas, with CHON-type COO KMD formulas relatively more abundant in the purified subfraction where Pu had been observed than in the crude soil fractions which had successively lower Pu concentrations. Nitrogen contents increased with the progression of purification (bulk soil → crude colloid → IEF colloid) and coincided with the trend of Pu concentration; thus, we propose that these nitrogen and carboxyl functionalities of aromatic compounds may also impart significant Pu chelation character to the colloid.

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. Thus, sensitive techniques are required not only for the detection of radionuclides, and their different species, at ambient and/or far-field concentrations, but also for potential trace organic compounds that are chemically binding these radionuclides. GC-MS and AMS techniques developed in our lab are reviewed here that aim to assess how two radionuclides, iodine and plutonium, form strong bonds with NOM by entirely different mechanisms; iodine tends to bind to aromatic functionalities, whereas plutonium binds to N-containing hydroxamate siderophores at ambient concentrations. While low-level measurements are a prerequisite for assessing iodine and plutonium migration at nuclear waste sites and as environmental tracers, it is necessary to determine their in-situ speciation, which ultimately controls their mobility and transport in natural environments. More importantly, advanced molecular-level instrumentation (e.g., nuclear magnetic resonance (NMR) and Fourier-transform ion cyclotron resonance coupled with electrospray ionization (ESI-FTICRMS) were applied to resolve either directly or indirectly the molecular environments in which the radionuclides are associated with the NOM., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

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 2 ), 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. Over the last 15years, there have been significant advances in iodine biogeochemistry, largely spurred by renewed interest in the fate of radioiodine in the environment. We review the biogeochemistry of iodine, with particular emphasis on the microbial processes responsible for volatilization, accumulation, oxidation, and reduction of iodine, as well as the exciting technological potential of these fascinating microorganisms and enzymes., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Sediments in the Houston Ship Channel and upper Galveston Bay, Texas, USA, are polluted with polychlorinated dibenzo-p-dioxins/furans (PCDD/F; ≤46,000 ng/kg dry weight (wt.)) with 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), the most toxic congener, contributing >50 % of the total toxic equivalents (TEQ) at most locations. We measured PCDD/F concentrations in sediments and evaluated the potential for enhanced in situ biodegradation by surveying for Dehalococcoides mccartyi, an obligate organohalide respiring bacterium. Dehalococcoides spp. (98 % similar to D. mccartyi) and 22 other members of the class Dehalococcoidia were predominant 16S ribosomal RNA (rRNA) phylotypes. Dehalococcoides spp. were also present in the active fraction of the bacterial community. Presence/absence PCR screening detected D. mccartyi in sediment cores and sediment grab samples having at least 1 ng/kg dry wt. TEQ at salinities ranging from 0.6 to 19.5 PSU, indicating that they are widespread in the estuarine environment. Organic carbon-only and organic carbon + sulfate-amended sediment microcosm experiments resulted in ∼60 % reduction of ambient 2,3,7,8-TCDD in just 24 months leading to reductions in total TEQs by 38.4 and 45.0 %, respectively, indicating that 2,3,7,8-TCDD degradation is occurring at appreciable rates.