Reddy Christopher M.

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Reddy
First Name
Christopher M.
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0000-0002-7814-2071

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Now showing 1 - 20 of 53
  • Article
    Divergent forms of pyroplastic: lessons learned from the M/V X-Press Pearl ship fire
    (American Chemical Society, 2022-07-29) James, Bryan D. ; de Vos, Asha ; Aluwihare, Lihini I. ; Youngs, Sarah ; Ward, Collin P. ; Michel, Anna P. M. ; Hahn, Mark E. ; Reddy, Christopher M.
    In late May 2021, the M/V X-Press Pearl container ship caught fire while anchored 18 km off the coast of Colombo, Sri Lanka and spilled upward of 70 billion pieces of plastic or “nurdles” (∼1680 tons), littering the country’s coastline. Exposure to combustion, heat, chemicals, and petroleum products led to an apparent continuum of changes from no obvious effects to pieces consistent with previous reports of melted and burned plastic (pyroplastic) found on beaches. At the middle of this continuum, nurdles were discolored but appeared to retain their prefire morphology, resembling nurdles that had been weathered in the environment. We performed a detailed investigation of the physical and surface properties of discolored nurdles collected on a beach 5 days after the ship caught fire and within 24 h of their arrival onshore. The color was the most striking trait of the plastic: white for nurdles with minimal alteration from the accident, orange for nurdles containing antioxidant degradation products formed by exposure to heat, and gray for partially combusted nurdles. Our color analyses indicate that this fraction of the plastic released from the ship was not a continuum but instead diverged into distinct groups. Fire left the gray nurdles scorched, with entrained particles and pools of melted plastic, and covered in soot, representing partial pyroplastics, a new subtype of pyroplastic. Cross sections showed that the heat- and fire-induced changes were superficial, leaving the surfaces more hydrophilic but the interior relatively untouched. These results provide timely and actionable information to responders to reevaluate cleanup end points, monitor the recurrence of these spilled nurdles, gauge short- and long-term effects of the spilled nurdles to the local ecosystem, and manage the recovery of the spill. These findings underscore partially combusted plastic (pyroplastic) as a type of plastic pollution that has yet to be fully explored despite the frequency at which plastic is burned globally.
  • Article
    Rapid degradation of cellulose diacetate by marine microbes
    (American Chemical Society, 2021-12-08) Mazzotta, Michael G. ; Reddy, Christopher M. ; Ward, Collin P.
    The persistence of cellulose diacetate (CDA), a biobased plastic used in textiles and single-use consumer products, in the ocean is currently unknown. Here, we probe the disintegration and degradation of CDA-based materials (25 μm films, 510 μm foam, and 97 g/m2 fabric) by marine microbes in a continuous flow seawater mesocosm. Photographic evidence and mass loss measurements demonstrate that CDA-based materials disintegrate in months. Disintegration is marked by the increasing esterase and cellulase activity of the biofilm community, suggesting that marine microbes degrade CDA. The natural abundance stable (13C) and radiocarbon (14C) isotopic signature of carbon dioxide respired during short-term bottle incubations confirms the rapid degradation of both acetyl and cellulosic components of CDA by seawater microbial communities. These findings challenge the paradigm set by governmental agencies and advocacy groups that CDA-based materials persist in the ocean for decades, and represent a positive step toward identifying high-utility, biobased plastics with low environmental persistence.
  • Article
    Alkenones as a promising green alternative for waxes in cosmetics and personal care products
    (MDPI AG, 2018-06-05) McIntosh, Kyle ; Smith, Amber ; Young, Lisa K. ; Leitch, Michael A. ; Tiwari, Amit K. ; Reddy, Christopher M. ; O’Neil, Gregory W. ; Liberatore, Matthew W. ; Chandler, Mark ; Baki, Gabriella
    The move toward green, sustainable, natural products has been growing in the cosmetic and personal care industry. Ingredients derived from marine organisms and algae are present in many cosmetic products. In this study, a new green ingredient, a wax (i.e., long-chain alkenones) derived from Isochyrsis sp., was evaluated as an alternative for cosmetic waxes. First, the melting point was determined (71.1–77.4 °C), then the alkenones’ thickening capability in five emollients was evaluated and compared to microcrystalline wax and ozokerite. Alkenones were compatible with three emollients and thickened the emollients similarly to the other waxes. Then, lipsticks and lip balms were formulated with and without alkenones. All products remained stable at room temperature for 10 weeks. Lipstick formulated with alkenones was the most resistant to high temperature. Finally, alkenones were compared to three cosmetic thickening waxes in creams. Viscosity, rheology, and stability of the creams were evaluated. All creams had a gel-like behavior. Both viscosity and storage modulus increased in the same order: cream with alkenones < cetyl alcohol < stearic acid < glyceryl monostearate. Overall, alkenones’ performance was comparable to the other three waxes. Alkenones can thus offer a potential green choice as a new cosmetic structuring agent.
  • Article
    Floating oil-covered debris from Deepwater Horizon : identification and application
    (IOP Publishing, 2012-01-18) Carmichael, Catherine A. ; Arey, J. Samuel ; Graham, William M. ; Linn, Laura J. ; Lemkau, Karin L. ; Nelson, Robert K. ; Reddy, Christopher M.
    The discovery of oiled and non-oiled honeycomb material in the Gulf of Mexico surface waters and along coastal beaches shortly after the explosion of Deepwater Horizon sparked debate about its origin and the oil covering it. We show that the unknown pieces of oiled and non-oiled honeycomb material collected in the Gulf of Mexico were pieces of the riser pipe buoyancy module of Deepwater Horizon. Biomarker ratios confirmed that the oil had originated from the Macondo oil well and had undergone significant weathering. Using the National Oceanic and Atmospheric Administration's records of the oil spill trajectory at the sea surface, we show that the honeycomb material preceded the front edge of the uncertainty of the oil slick trajectory by several kilometers. We conclude that the observation of debris fields deriving from damaged marine materials may be incorporated into emergency response efforts and forecasting of coastal impacts during future offshore oil spills, and ground truthing predicative models.
  • Article
    Natural organobromine in marine sediments : new evidence of biogeochemical Br cycling
    (American Geophysical Union, 2010-11-24) Leri, Alessandra C. ; Hakala, J. Alexandra ; Marcus, Matthew A. ; Lanzirotti, Antonio ; Reddy, Christopher M. ; Myneni, Satish C. B.
    Organobromine (Brorg) compounds, commonly recognized as persistent, toxic anthropogenic pollutants, are also produced naturally in terrestrial and marine systems. Several enzymatic and abiotic bromination mechanisms have been identified, as well as an array of natural Brorg molecules associated with various marine organisms. The fate of the carbon-bromine functionality in the marine environment, however, remains largely unexplored. Oceanographic studies have noted an association between bromine (Br) and organic carbon (Corg) in marine sediments. Even so, there has been no direct chemical evidence that Br in the sediments exists in a stable form apart from inorganic bromide (Brinorg), which is widely presumed conservative in marine systems. To investigate the scope of natural Brorg production and its fate in the environment, we probed Br distribution and speciation in estuarine and marine sediments using in situ X-ray spectroscopy and spectromicroscopy. We show that Brorg is ubiquitous throughout diverse sedimentary environments, occurring in correlation with Corg and metals such as Fe, Ca, and Zn. Analysis of sinking particulate carbon from the seawater column links the Brorg observed in sediments to biologically produced Brorg compounds that persist through humification of natural organic matter (NOM). Br speciation varies with sediment depth, revealing biogeochemical cycling of Br between organic and inorganic forms as part of the burial and degradation of NOM. These findings illuminate the chemistry behind the association of Br with Corg in marine sediments and cast doubt on the paradigmatic classification of Br as a conservative element in seawater systems.
  • Article
    Plastic formulation is an emerging control of its photochemical fate in the ocean
    (American Chemical Society, 2021-09-08) Walsh, Anna N. ; Reddy, Christopher M. ; Niles, Sydney F. ; McKenna, Amy M. ; Hansel, Colleen M. ; Ward, Collin P.
    Sunlight exposure is a control of long-term plastic fate in the environment that converts plastic into oxygenated products spanning the polymer, dissolved, and gas phases. However, our understanding of how plastic formulation influences the amount and composition of these photoproducts remains incomplete. Here, we characterized the initial formulations and resulting dissolved photoproducts of four single-use consumer polyethylene (PE) bags from major retailers and one pure PE film. Consumer PE bags contained 15–36% inorganic additives, primarily calcium carbonate (13–34%) and titanium dioxide (TiO2; 1–2%). Sunlight exposure consistently increased production of dissolved organic carbon (DOC) relative to leaching in the dark (3- to 80-fold). All consumer PE bags produced more DOC during sunlight exposure than the pure PE (1.2- to 2.0-fold). The DOC leached after sunlight exposure increasingly reflected the 13C and 14C isotopic composition of the plastic. Ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry revealed that sunlight exposure substantially increased the number of DOC formulas detected (1.1- to 50-fold). TiO2-containing bags photochemically degraded into the most compositionally similar DOC, with 68–94% of photoproduced formulas in common with at least one other TiO2-containing bag. Conversely, only 28% of photoproduced formulas from the pure PE were detected in photoproduced DOC from the consumer PE. Overall, these findings suggest that plastic formulation, especially TiO2, plays a determining role in the amount and composition of DOC generated by sunlight. Consequently, studies on pure, unweathered polymers may not accurately represent the fates and impacts of the plastics entering the ocean.
  • Preprint
    Determination of HBCD, PBDEs and MeO-BDEs in California sea lions (Zalophus californianus) stranded between 1993 and 2003
    ( 2005) Stapleton, H. M. ; Dodder, N. G. ; Kucklick, J. R. ; Reddy, Christopher M. ; Schantz, M. M. ; Becker, P. R. ; Gulland, Frances M. ; Porter, B. J. ; Wise, S. A.
    Blubber samples from male California sea lions (Zalphophus californianus) stranded between 1993 and 2003 were analyzed for 27 polybrominated diphenyl ether (PBDE) congeners, three isomers of hexabromocyclododecane (HBCD) and 14 methoxylated polybrominated diphenyl ether (MeO-BDE) congeners. Total PBDEs ranged from 450 ng/g to 4740 ng/g wet mass and total HBCD ranged from <0.3 ng/g to 12 ng/g wet mass. The concentration of HBCD increased from 0.7 ng/g to12.0 ng/g wet mass in sea lion blubber between 1993 and 2003. However, no significant temporal trend was observed for any of the other brominated compounds over this ten year period. Only one of the 14 MeO-BDE congeners was detected in the blubber samples, 6-methoxy- 2,2’,4,4’-tetrabromodiphenyl ether (6-MeO-BDE 47), and concentrations ranged from <0.2 ng/g to 12 ng/g wet mass. A bromo-, chloro- heterocyclic compound, 1,1’-dimethyl-tetrabromo-dichloro-2,2’-bipyrrole (DBP-Br4Cl2), previously reported in marine species along the Pacific coast, was also identified in the sea lion blubber. DBP-Br4Cl2 ranged from 44 ng/g wet mass to 660 ng/g wet mass and was present at concentrations rivaling the dominant PBDE congener, BDE 47 (2,2’,4,4’-tetrabromodiphenyl ether). Concentrations of DBP-Br4Cl2 were positively correlated with 6-MeO-BDE 47 (r= 0.7; p<0.05). Both of these compounds have been identified in marine algae and sponges, and studies suggest they are both produced from natural sources. This study demonstrates that brominated compounds from both anthropogenic and biogenic sources can accumulate to similar levels in marine mammals. In addition, HBCD concentrations appear to be increasing in California sea lion populations, whereas PBDE concentrations, between 1993 and 2003, were highly variable.
  • Article
    Significance of perylene for source allocation of terrigenous organic matter in aquatic sediments.
    (American Chemical Society, 2019-06-19) Hanke, Ulrich ; Lima-Braun, Ana L. ; Eglinton, Timothy I. ; Donnelly, Jeffrey P. ; Galy, Valier ; Poussart, Pascale F. ; Hughen, Konrad A. ; McNichol, Ann P. ; Xu, Li ; Reddy, Christopher M.
    Perylene is a frequently abundant, and sometimes the only polycyclic aromatic hydrocarbon (PAH) in aquatic sediments, but its origin has been subject of a longstanding debate in geochemical research and pollutant forensics because its historical record differs markedly from typical anthropogenic PAHs. Here we investigate whether perylene serves as a source-specific molecular marker of fungal activity in forest soils. We use a well-characterized sedimentary record (1735 to 1999) from the anoxic-bottom waters of the Pettaquamscutt River basin, RI, USA to examine mass accumulation rates and isotope records of perylene, and compare them with total organic carbon and the anthropogenic PAH fluoranthene. We support our arguments with radiocarbon (14C) data of higher plant leaf-wax n-alkanoic acids. Isotope-mass balance calculations of perylene and n-alkanoic acids indicate that ~40 % of sedimentary organic matter is of terrestrial origin. Further, both terrestrial markers are pre-aged on millennial time-scales prior to burial in sediments and insensitive to elevated 14C concentrations following nuclear weapons testing in the mid-20th Century. Instead, changes coincide with enhanced erosional flux during urban sprawl. These findings suggest that perylene is definitely a product of soil derived fungi, and a powerful chemical tracer to study spatial and temporal connectivity between terrestrial and aquatic environments.
  • Preprint
    Identification of highly brominated analogues of Q1 in marine mammals
    ( 2005-10-30) Teuten, Emma L. ; Pedler, Byron E. ; Hangsterfer, Alexandra N. ; Reddy, Christopher M.
    Three novel halogenated organic compounds (HOCs) have been identified in the blubber of marine mammals from coastal New England with the molecular formulae C9H3N2Br6Cl, C9H3N2Br7, and C9H4N2Br5Cl. They were identified using high and low resolution electron ionization (EI) and electron capture negative ionization (ECNI) gas chromatography mass spectrometry (GCMS) and appear to be highly brominated analogues of Q1, a heptachlorinated HOC that has been suspected to be naturally-produced. These new compounds were found in Atlantic white sided dolphin (Lagenorhynchus acutus), bottlenose dolphin (Tursiops truncatus), common dolphin (Delphinus delphis), Risso’s dolphin (Grampus griseus), harbor porpoise (Phocoena phocoena), beluga whale (Delphinapterus leucas), fin whale (Balaenoptera physalus), grey seal (Halichoerus grypus), harp seal (Phoca groenlandica) and a potential food source (Loligo pealei) with concentrations as high as 2.7 μg/g (lipid weight). The regiospecificity of C9H3N2Br6Cl is suggestive of a biogenic origin. Debromination of C9H3N2Br6Cl may be significant in the formation of C9H4N2Br5Cl.
  • Article
    Evaluation of alkenones, a renewably sourced, plant-derived wax as a structuring agent for lipsticks
    (Wiley, 2019-12-27) Huynh, An ; Maktabi, Briana ; Reddy, Christopher M. ; O’Neil, Gregory W. ; Chandler, Mark ; Baki, Gabriella
    OBJECTIVE Waxes are used as structuring agents in lipsticks. There are a variety of waxes combined in a single lipstick to provide good stability, pleasant texture and good pay‐off. Due to a significant growth for natural, green and sustainable products, there is a constant search for alternatives to animal‐derived and petroleum‐derived ingredients. In this study, a green, non‐animalderived wax, namely long‐chain ketones (referred to as alkenones), sourced from marine microalgae was formulated into lipsticks and evaluated as a structuring agent. METHODS Alkenones were used as a substitute for microcrystalline wax, ozokerite and candelilla wax, typical structuring agents. In total, 384 lipsticks were formulated: L1 (control, no alkenones), L2 (alkenones as a substitute for ozokerite), L3 (alkenones as a substitute for microcrystalline wax) and L4 (alkenones as a substitute for candelilla wax). Products were tested for hardness (bending force), stiffness, firmness (needle penetration), pay‐off (using a texture analyser and a consumer panel), friction, melting point and stability for 12 weeks at 25 and 45°C. RESULTS Alkenones influenced each characteristic evaluated. In general, lipsticks with alkenones (L2‐L4) became softer and easier to bend compared to the control (L1). In terms of firmness, lipsticks were similar to the control, except for L4, which was significantly (P < 0.05) firmer. The effect on pay‐off was not consistent. L2 and L3 had higher pay‐off to skin and fabric than L1. In addition, L4 had the lowest amount transferred, but it still had the highest colour intensity on skin. Alkenones influenced friction (glide) positively; the average friction decreased for L2‐L4. The lowest friction (i.e. best glide) was shown in L4. Melting point of the lipsticks was lower when alkenones were present. Overall, L4, containing 7% of 4 alkenones in combination with microcrystalline wax, ozokerite and carnauba wax, was found to have the most desirable attributes, including ease of bending, high level of firmness, low pay‐off in terms of amount, high colour intensity on skin and low friction (i.e. better glide). Consumers preferred L4 the most overall. CONCLUSION Results of this study indicate that alkenones offer a sustainable, non‐animal and non‐petroleum‐derived choice as a structuring agent for lipsticks.
  • Preprint
    Combining biomarker and bulk compositional gradient analysis to assess reservoir connectivity
    ( 2010-04-10) Pomerantz, Andrew E. ; Ventura, Gregory T. ; McKenna, Amy M. ; Canas, Jesus A. ; Auman, John ; Koerner, Kyle ; Curry, David ; Nelson, Robert K. ; Reddy, Christopher M. ; Rodgers, Ryan P. ; Marshall, Alan G. ; Peters, Kenneth E. ; Mullins, Oliver C.
    Hydraulic connectivity of petroleum reservoirs represents one of the biggest uncertainties for both oil production and petroleum system studies. Here, a geochemical analysis involving bulk and detailed measures of crude oil composition is shown to constrain connectivity more tightly than is possible with conventional methods. Three crude oils collected from different depths in a single well exhibit large gradients in viscosity, density, and asphaltene content. Crude oil samples are collected with a wireline sampling tool providing samples from well‐defined locations and relatively free of contamination by drilling fluids; the known provenance of these samples minimizes uncertainties in the subsequent analysis. The detailed chemical composition of almost the entire crude oil is determined by use of comprehensive two‐dimensional gas chromatography (GC×GC) to interrogate the nonpolar fraction and negative ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT‐ICR MS) to interrogate the polar fraction. The simultaneous presence of 25‐ norhopanes and mildly altered normal and isoprenoid alkanes is detected, suggesting that the reservoir has experienced multiple charges and contains a mixture of oils biodegraded to different extents. The gradient in asphaltene concentration is explained by an equilibrium model considering only gravitational segregation of asphaltene nanoaggregates; this grading can be responsible for the observed variation in viscosity. Combining these analyses yields a consistent picture of a connected reservoir in which the observed viscosity variation originates from gravitational segregation of asphaltene nanoaggregates in a crude oil with high asphaltene concentration resulting from multiple charges, including one charge that suffered severe biodegradation. Observation of these gradients having appropriate magnitudes suggests good reservoir connectivity with greater confidence than is possible with traditional techniques alone.
  • Article
    Weathering of oil spilled in the marine environment
    (The Oceanography Society, 2016-09) Tarr, Matthew ; Zito, Phoebe ; Overton, Edward B. ; Olson, Gregory M. ; Adhikari, Puspa L. ; Reddy, Christopher M.
    Crude oil is a complex mixture of many thousands of mostly hydrocarbon and nitrogen-, sulfur-, and oxygen-containing compounds with molecular weights ranging from below 70 Da to well over 2,000 Da. When this complex mixture enters the environment from spills, ruptures, blowouts, or seeps, it undergoes a continuous series of compositional changes that result from a process known as weathering. Spills of petroleum involving human activity generally result in more rapid input of crude oil or refined products (diesel, gasoline, heavy fuel oil, and diluted bitumens) to the marine system than do natural processes and urban runoffs. The primary physicochemical processes involved in weathering include evaporation, dissolution, emulsification, dispersion, sedimentation/flocculation, microbial degradation, and photooxidation.
  • Article
    Radiocarbon dating of alkenones from marine sediments : I. Isolation protocol
    (Dept. of Geosciences, University of Arizona, 2005) Ohkouchi, Naohiko ; Xu, Li ; Reddy, Christopher M. ; Montlucon, Daniel B. ; Eglinton, Timothy I.
    The chemical and isotopic compositions of long-chain (C36–C39) unsaturated ketones (alkenones), a unique class of algal lipids, encode surface ocean properties useful for paleoceanographic reconstruction. Recently, we have sought to extend the utility of alkenones as oceanic tracers through measurement of their radiocarbon contents. Here, we describe a method for isolation of alkenones from sediments as a compound class based on a sequence of wet chemical techniques. The steps involved, which include silica gel column chromatography, urea adduction, and silver nitrate-silica gel column chromatography, exploit various structural attributes of the alkenones. Amounts of purified alkenones estimated by GC/FID measurements were highly correlated with CO2 yields after sample combustion, indicating purities of greater than 90% for samples containing ≥100 μg C. The degree of alkenone unsaturation ( ) also varied minimally through the procedure. We also describe a high-performance liquid chromatography (HPLC) method to isolate individual alkenones for molecular-level structural and isotopic determination.
  • Preprint
    Decolorization improves the fuel properties of algal biodiesel from Isochrysis sp.
    ( 2016-03) O’Neil, Gregory W. ; Knothe, Gerhard ; Williams, John R. ; Burlow, Noah P. ; Reddy, Christopher M.
    Results from the comprehensive fuel testing according to American Society for Testing and Materials International (ASTM) standards of an alkenone-free and decolorized biodiesel produced from the industrially grown marine microalgae Isochrysis sp. are presented. Fatty acid methyl ester (FAME) profiles of the non-decolorized and subsequently decolorized biodiesel fuels were nearly identical, yet the fuel properties were remarkably different. Significant positive impacts on the cetane number, kinematic viscosity, and lubricity were observed, indicating a potential deleterious effect of pigments like chlorophylls and pheophytins on these fuel properties. The decolorization process using montmorillonite K10 gave on average 90% mass recovery, and allowed for an otherwise unobtainable cloud point determination. Oxidative stability of the decolorized Isochrysis biodiesel remained well below the minimum prescribed in biodiesel standards due to elevated content of highly polyunsaturated fatty acids, however other values were in the range of those prescribed in the ASTM standards. Overall, decolorization improved the fuel properties of biodiesel from Isochrysis and may provide a path toward improved biodiesel fuels from other algal species.
  • Article
    MV Wakashio grounding incident in Mauritius 2020: the world’s first major spillage of very low sulfur fuel oil
    (Elsevier, 2021-09-03) Scarlett, Alan G. ; Nelson, Robert K. ; Gagnon, Marthe Monique ; Holman, Alex I. ; Reddy, Christopher M. ; Sutton, Paul A. ; Grice, Kliti
    Very Low Sulfur Fuel Oils (VSLFO, <0.5% S) are a new class of marine fuel oils, introduced to meet recent International Maritime Organization regulations. The MV Wakashio was reported to have released 1000 t of VLSFO when it grounded on a reef in Mauritius on 25th July 2020. A field sample of oily residue contaminating the Mauritian coast was collected on 16th August 2020 and compared with the Wakashio fuel oil. Both oils were analyzed for organic and elemental content, and stable isotope ratios δ13C and δ2H measured. Comprehensive two-dimensional gas chromatography with high-resolution mass spectrometry was used to identify and compare biomarkers resistant to weathering. The aromatic content in the VLSFO was relatively low suggesting that the potential for ecosystem harm arising from exposure to toxic components may be less than with traditional fuel oil spills. The Wakashio oil spill is, to our knowledge, the first documented spill involving VLSFO.
  • Article
    Modeling comprehensive chemical composition of weathered oil following a marine spill to predict ozone and potential secondary aerosol formation and constrain transport pathways
    (John Wiley & Sons, 2015-11-09) Drozd, Greg T. ; Worton, David R. ; Aeppli, Christoph ; Reddy, Christopher M. ; Zhang, Haofei ; Variano, Evan ; Goldstein, Allen H.
    Releases of hydrocarbons from oil spills have large environmental impacts in both the ocean and atmosphere. Oil evaporation is not simply a mechanism of mass loss from the ocean, as it also causes production of atmospheric pollutants. Monitoring atmospheric emissions from oil spills must include a broad range of volatile organic compounds (VOC), including intermediate-volatile and semivolatile compounds (IVOC, SVOC), which cause secondary organic aerosol (SOA) and ozone production. The Deepwater Horizon (DWH) disaster in the northern Gulf of Mexico during Spring/Summer of 2010 presented a unique opportunity to observe SOA production due to an oil spill. To better understand these observations, we conducted measurements and modeled oil evaporation utilizing unprecedented comprehensive composition measurements, achieved by gas chromatography with vacuum ultraviolet time of flight mass spectrometry (GC-VUV-HR-ToFMS). All hydrocarbons with 10–30 carbons were classified by degree of branching, number of cyclic rings, aromaticity, and molecular weight; these hydrocarbons comprise ∼70% of total oil mass. Such detailed and comprehensive characterization of DWH oil allowed bottom-up estimates of oil evaporation kinetics. We developed an evaporative model, using solely our composition measurements and thermodynamic data, that is in excellent agreement with published mass evaporation rates and our wind-tunnel measurements. Using this model, we determine surface slick samples are composed of oil with a distribution of evaporative ages and identify and characterize probable subsurface transport of oil.
  • Article
    Oral and dermal toxicity of alkenones extracted from Isochrysis species
    (Bioscience Research Institute, 2020-01-01) McIntosh, Kyle ; Sarver, Jeffrey ; Mell, Kristopher ; Terrero, David J. ; Ashby, Charles R., Jr. ; Reddy, Christopher M. ; O’ Neil, Gregory ; Ramapuram, Jayachandra Babu ; Tiwari, Amit K.
    Isochrysis is commercially available marine algae used for animal feed, human nutrient supplements, and biodiesel. The Isochrysis species is one of five genera of haptophytes that produces unique, long-chain lipids known as alkenones that are promising new ingredients for green cosmetics, personal care products and pharmaceutical delivery. However, there is a lack of toxicity data for alkenones in animals, thus limiting their use in humans. In this study, we performed acute oral, acute dermal, and repeated 28-day dermal toxicity studies, using female SAS Sprague Dawley Rats. Our behavioral studies indicated that the specific alkenones had no overt behavioural effects at oral doses up to 4000 mg/kg. In the acute and chronic dermal toxicity studies, the alkenones produced less irritation and did not significantly damage the skin based on the Draize skin reaction scale and trans-epidermal water loss readings compared to the positive control, 1% sodium lauryl sulfate. Overall, our results indicated that alkenones are safe in Sprague Dawley rats, suggesting that they could be used for both oral and dermal formulations, although additional studies will be required.
  • Preprint
    Molecular evidence of Late Archean archaea and the presence of a subsurface hydrothermal biosphere
    ( 2006-12-13) Ventura, Gregory T. ; Kenig, Fabien ; Reddy, Christopher M. ; Schieber, Juergen ; Frysinger, Glenn S. ; Nelson, Robert K. ; Dinel, Etienne ; Gaines, Richard B. ; Schaeffer, Philippe
    Highly cracked and isomerized archaeal lipids and bacterial lipids, structurally changed by thermal stress, are present in solvent extracts of 2,707-2,685 million year old (Ma) metasedimentary rocks from Timmins, Ontario, Canada. These lipids appear in conventional gas chromatograms as unresolved complex mixtures (UCMs) and include cyclic and acyclic biphytanes, C36-C39 derivatives of the biphytanes, and C31-C35 extended hopanes. Biphytane and extended hopanes are also found in high pressure catalytic hydrogenation (HPCH) products released from solvent-extracted sediments,indicating that archaea and bacteria were present in Late Archean sedimentary environments. Post-depositional, hydrothermal gold mineralization and graphite precipitation occurred prior to metamorphism (~2,665 Ma). Late Archean metamorphism significantly reduced the kerogen’s adsorptive capacity and severely restricted sediment porosity, limiting the potential for post-Archean additions of organic matter to the samples. Argillites exposed to hydrothermal gold mineralization have disproportionately high concentrations of extractable archaeal and bacterial lipids relative to what is releasable from their respective HPCH product and what is observed for argillites deposited away from these hydrothermal settings. The addition of these lipids to the sediments likely results from a Late Archean subsurface hydrothermal biosphere of archaea and bacteria.
  • Article
    Synergy between sunlight, titanium dioxide, and microbes enhances cellulose diacetate degradation in the ocean
    (American Chemical Society, 2022-09-16) Walsh, Anna N. ; Mazzotta, Michael G. ; Nelson, Taylor F. ; Reddy, Christopher M. ; Ward, Collin P.
    Sunlight chemically transforms marine plastics into a suite of products, with formulationthe specific mixture of polymers and additivesdriving rates and products. However, the effect of light-driven transformations on subsequent microbial lability is poorly understood. Here, we examined the interplay between photochemical and biological degradation of fabrics made from cellulose diacetate (CDA), a biobased polymer used commonly in consumer products. We also examined the influence of ∼1% titanium dioxide (TiO2), a common pigment and photocatalyst. We sequentially exposed CDA to simulated sunlight and native marine microbes to understand how photodegradation influences metabolic rates and pathways. Nuclear magnetic resonance spectroscopy revealed that sunlight initiated chain scission reactions, reducing CDA’s average molecular weight. Natural abundance carbon isotope measurements demonstrated that chain scission ultimately yields CO2, a newly identified abiotic loss term of CDA in the environment. Measurements of fabric mass loss and enzymatic activities in seawater implied that photodegradation enhanced biodegradation by performing steps typically facilitated by cellulase. TiO2 accelerated CDA photodegradation, expediting biodegradation. Collectively, these findings (i) underline the importance of formulation in plastic’s environmental fate and (ii) suggest that overlooking synergy between photochemical and biological degradation may lead to overestimates of marine plastic persistence.
  • Article
    Production of two highly abundant 2-methyl-branched fatty acids by blooms of the globally significant marine cyanobacteria Trichodesmium erythraeum
    (American Chemical Society, 2021-08-26) Gosselin, Kelsey M. ; Nelson, Robert K. ; Spivak, Amanda C. ; Sylva, Sean P. ; Van Mooy, Benjamin A. S. ; Aeppli, Christoph ; Sharpless, Charles M. ; O’Neil, Gregory W. ; Arrington, Eleanor C. ; Reddy, Christopher M. ; Valentine, David L.
    The bloom-forming cyanobacteria Trichodesmium contribute up to 30% to the total fixed nitrogen in the global oceans and thereby drive substantial productivity. On an expedition in the Gulf of Mexico, we observed and sampled surface slicks, some of which included dense blooms of Trichodesmium erythraeum. These bloom samples contained abundant and atypical free fatty acids, identified here as 2-methyldecanoic acid and 2-methyldodecanoic acid. The high abundance and unusual branching pattern of these compounds suggest that they may play a specific role in this globally important organism.