Organic Coatings on Sedimentary Mineral Grains

A pore protection hypothesis will be tested, provide a mechanistic basis for the observed patterns of organic carbon. Relationships between organic matter and mineral surfaces will be developed by: (1) Assessing the extent of organic matter coverage on mineral grains. Is organic carbon localized in small areas or is it widely dispersed? Wide dispersal implies that major fraction must reside in small pores. This question will be tested by completing development of a promising new method based on the of gas adsorption onto mineral surfaces. Completion work will focus on the nature of naked mineral surfaces, identifying variations that derive from mineralogy, microtopography, and source area; (2) Determining if natural organic matter resides preferentially inside small mesopores, by careful examination of the effects of removal of organic coatings on the size distribution of pores. This test will also involve the reverse process of adding artificial organic coatings to uncoated mineral grains, providing insight into the localization and mechanism of organic matter sorption. (3) Testing if these small mesopores on mineral grains can indeed exclude hydrolytic enzymes, by performing a series of size- exclusion and adsorption experiments. These approaches will be carried out on a wide variety of sediments from around the world. In addition to testing the pore hypothesis, results from this project will have important implications for carbon cycling, mineral-water interactions, and pollutant cycling

Photodissolution of Sedimentary Organic Matter

The field of marine photochemistry has previously focused on dissolved organic matter and trace metals. However, recent studies have shown that sediment suspensions in the ocean are also affected by sunlight and have the potential to dissolve most of their particulate organic carbon to the dissolved organic phase. A researcher from the University of Maine will determine the importance of photodissolution in the coastal Louisiana area, where riverine particulates are quickly deposited in shallow waters. Optical properties of the particulates will be examined to assess the photon fluxes and to determine the quantum yields of this photodissolution reaction. To determine the importance of this reaction, modeling of the turbid nearshore regimes, field-tests of the optical results, and developments of the markers from previous photodissolutions will be carried out. In addition to the optical properties of the particulates, the fate of the photodissolved organic matter will be assessed, addressing both photo-oxidation and biological mineralization reactions. In terms of the broader impacts, this research will provide new insights into the impact of photodegradation of particulate organic matter on the cycling of nutrients in the deltaic region of the Mississippi River. Outreach efforts based on the research activities at the K-12 and community level will be carried out. One graduate student and one undergraduate student will be supported and trained as part of the study

Food Substrates and Digestive Capabilitites of Marine Deposit Feeders

Deposit feeders play several important roles in determining whether organic material is demineralized or buried. These animals function to make surfaces available for microbial growth and move particles both horizontally and vertically within the seabed at a pace that far exceeds sedimentation. The central problem in understanding deposit feeders is to identify the materials that they utilize and to determine the sources of those materials. The interdisciplinary approach of this project is to combine a chemical reactor theory of digestion with measurements of the processing of enzymatically available amino acids, focusing on rates of hydrolysis in, and absorption from, the gut. In vitro and in vivo fluorometric methods will be developed to assay enzyme activity in the guts of small deposit feeders; these methods that will be applicable to planktonic animals as well. Chemical analyses and deposit-feeder bioassays will be conducted to test whether methionine or other essential amino acids become more limiting in laboratory simulations of diagenesis. In a shallow subtidal site the hypothesis that the holothuroid Parastichopus californicus is limited to feeding during times of relatively high methionine concentration will be tested. At a 200-m site the hypothesis that the burrowing urchin Brisaster latifrons will show greater hydrolytic and absorptive capacity for amino acids after the spring bloom than during winter will be tested

Rate and Apparent Quantum Yield of Photodissolution

We quantified rates of photochemical dissolution (photodissolution) of organic carbon in coastal Louisiana suspended sediments, conducting experiments under well-defined conditions of irradiance and temperature. Optical properties of the suspended sediments were characterized and used in a radiative transfer model to compute irradiances within turbid suspensions. Photodissolution rate increased with temperature (T), with activation energy of 32 ± 7 kJ mol−1, which implicates indirect (non-photochemical) steps in the net reaction. In most samples, dissolved organic carbon (DOC) concentration increased approximately linearly with time over the first 4 h of irradiation under broadband simulated sunlight, after higher rates in the initial hour of irradiation. Four-hour rates ranged from 2.3 µmol DOC m−3 s−1 to 3.2 µmol DOC m−3 s−1, but showed no relation to sample origin within the study area, organic carbon or reducible iron content, or mass-specific absorption coefficient. First-hour rates were higher—from 3.5 µmol DOC m−3 s−1 to 7.8 µmol DOC m−3 s−1—and correlated well with sediment reducible iron (itself often associated with organic matter). The spectral apparent quantum yield (AQY) for photodissolution was computed by fitting DOC photoproduction rates under different spectral irradiance distributions to corresponding rates of light absorption by particles. The photodissolution AQY magnitude is similar to most published dissolved-phase AQY spectra for dissolved inorganic carbon photoproduction, which suggests that in turbid coastal waters where particles dominate light absorption, DOC photoproduction from particles exceeds photooxidation of DOC

Concentrations and sources of polycyclic aromatic hydrocarbons in surface coastal sediments of the northern Gulf of Mexico

Zucheng Wang is with the Department of Geography, Northeast Normal University, Changchun, China. -- Zucheng Wang and Zhanfei Liu are with the Marine Science Institute, The University of Texas at Austin, Port Aransas, TX, USA. -- Kehui Xu is with the Department of Oceanography and Coastal Sciences, Louisiana State University, Baton Rouge, LA, USA – and – the Coastal Studies Institute, Louisiana State University, Baton Rouge, LA, USA. -- Lawrence M Mayer is with the School of Marine Sciences, University of Maine, Walpole, ME, USA. -- Zulin Zhang is with The James Hutton Institute, Aberdeen, UK. -- Alexander S. Kolker is with Louisiana Universities Marine Consortium, Chauvin, LA, USA. -- Wei Wu is with the Department of Coastal Sciences, Gulf Coast Research Laboratory, The University of Southern Mississippi, Ocean Springs, MS, USA.Background: Coastal sediments in the northern Gulf of Mexico have a high potential of being contaminated by petroleum hydrocarbons, such as polycyclic aromatic hydrocarbons (PAHs), due to extensive petroleum exploration and transportation activities. In this study we evaluated the spatial distribution and contamination sources of PAHs, as well as the bioavailable fraction in the bulk PAH pool, in surface marsh and shelf sediments (top 5 cm) of the northern Gulf of Mexico. Results: PAH concentrations in this region ranged from 100 to 856 ng g−1, with the highest concentrations in Mississippi River mouth sediments followed by marsh sediments and then the lowest concentrations in shelf sediments. The PAH concentrations correlated positively with atomic C/N ratios of sedimentary organic matter (OM), suggesting that terrestrial OM preferentially sorbs PAHs relative to marine OM. PAHs with 2 rings were more abundant than those with 5–6 rings in continental shelf sediments, while the opposite was found in marsh sediments. This distribution pattern suggests different contamination sources between shelf and marsh sediments. Based on diagnostic ratios of PAH isomers and principal component analysis, shelf sediment PAHs were petrogenic and those from marsh sediments were pyrogenic. The proportions of bioavailable PAHs in total PAHs were low, ranging from 0.02% to 0.06%, with higher fractions found in marsh than shelf sediments. Conclusion: PAH distribution and composition differences between marsh and shelf sediments were influenced by grain size, contamination sources, and the types of organic matter associated with PAHs. Concentrations of PAHs in the study area were below effects low-range, suggesting a low risk to organisms and limited transfer of PAHs into food web. From the source analysis, PAHs in shelf sediments mainly originated from direct petroleum contamination, while those in marsh sediments were from combustion of fossil fuels.Marine [email protected]

Rate and apparent quantum yield of photodissolution of sedimentary organic matter

Author Posting. © Association for the Sciences of Limnology and Oceanography, 2012. This article is posted here by permission of Association for the Sciences of Limnology and Oceanography for personal use, not for redistribution. The definitive version was published in Limnology and Oceanography 57 (2012): 1743-1756, doi:10.4319/lo.2012.57.6.1743.We quantified rates of photochemical dissolution (photodissolution) of organic carbon in coastal Louisiana suspended sediments, conducting experiments under well-defined conditions of irradiance and temperature. Optical properties of the suspended sediments were characterized and used in a radiative transfer model to compute irradiances within turbid suspensions. Photodissolution rate increased with temperature (T), with activation energy of 32 ± 7 kJ mol−1, which implicates indirect (non-photochemical) steps in the net reaction. In most samples, dissolved organic carbon (DOC) concentration increased approximately linearly with time over the first 4 h of irradiation under broadband simulated sunlight, after higher rates in the initial hour of irradiation. Four-hour rates ranged from 2.3 µmol DOC m−3 s−1 to 3.2 µmol DOC m−3 s−1, but showed no relation to sample origin within the study area, organic carbon or reducible iron content, or mass-specific absorption coefficient. First-hour rates were higher—from 3.5 µmol DOC m−3 s−1 to 7.8 µmol DOC m−3 s−1—and correlated well with sediment reducible iron (itself often associated with organic matter). The spectral apparent quantum yield (AQY) for photodissolution was computed by fitting DOC photoproduction rates under different spectral irradiance distributions to corresponding rates of light absorption by particles. The photodissolution AQY magnitude is similar to most published dissolved-phase AQY spectra for dissolved inorganic carbon photoproduction, which suggests that in turbid coastal waters where particles dominate light absorption, DOC photoproduction from particles exceeds photooxidation of DOC.We would like to acknowledge funding support from the National Science Foundation Chemical Oceanography program (L.M. and M.L.E.), a National Aeronautics and Space Administration Earth Systems Science Graduate Fellowship (M.L.E.), and the Office of Naval Research Environmental Optics program (E.B.)

DIGESTIVE PROTEASES OF THE LUGWORM (ARENICOLA MARINA) INHIBITED BY CU FROM CONTAMINATED SEDIMENTS

Abstract-We examined potential toxic effects of copper released from contaminated sediments during deposit feeding of the lugworm, Arenicola marina. Titration of Cu solution into gut fluids can result in decreases in protease activity if sufficient Cu is added. The effects of Cu on gut proteases were confirmed by incubation of gut fluids with Cu-contaminated harbor sediments. Monitoring of Cu titration into gut fluids shows that enzyme inhibition and quenching of gut protein fluorescence occur only when sufficient Cu has been added to allow inorganic Cu species to become abundant. This threshold level probably represents the exhaustion of strong binding sites that act as protection against enzyme inhibition. Thus, sediments contaminated with Cu may have inhibitory effects on digestive processes in lugworms

Role of Iron and Organic Carbon in Mass-specific Light Absorption by Particulate Matter from Louisiana Coastal Waters

We investigated the influences of organic content and mineralogical composition on light absorption by mostly mineral suspended particles in aquatic and coastal marine systems. Mass-specific absorption spectra of suspended particles and surface sediments from coastal Louisiana and the lower Mississippi and Atchafalaya rivers were measured with a centered sample-mount integrating sphere and analyzed in conjunction with organic carbon (OC), hydrochloric acid– (HCl-) extractable iron, and dithionite-extractable iron contents. Compositions and absorption properties were comparable to published values for similar particles. Dithionite-extractable iron was strongly correlated with absorption at ultraviolet (UV) and blue wavelengths, while OC and HCl-extractable iron were weakly but positively correlated. Oxidative removal of OC from sediments caused small and variable changes in absorption, while dithionite extraction of iron oxides strongly reduced absorption. Shoulders in the absorption spectra corresponded to absorption bands of iron oxide minerals, and their intensities were well correlated to dithionite-extractable iron contents of the samples. These findings support a primary role for iron oxide and hydroxide minerals in the mass-specific absorption of mostly inorganic particles from the terrestrially influenced coast of Louisiana. Riverine particles had higher dithionite-extractable iron contents and iron oxide–specific absorption features than did marine particles, consistent with current knowledge regarding differential transport of particulate iron oxides and hydroxides through estuarine salinity gradients and reductive alteration of these oxide phases on the Louisiana shelf. The quantifiable dependence of UV absorption features on iron oxide content suggests that, under certain conditions, in situ hyperspectral absorption measurements could be designed to monitor water-column iron mineral transport and transformation