ALBERT

Description: Coastal erosion and flooding transform terrestrial landscapes into marine environments. In the Arctic, these processes inundate terrestrial permafrost with seawater and create submarine permafrost. Permafrost begins to warm under marine conditions, which can destabilize the sea floor and may release greenhouse gases. We report on the transition of terrestrial to submarine permafrost at a site where the timing of inundation can be inferred from the rate of coastline retreat. On Muostakh Island in the central Laptev Sea, East Siberia, changes in annual coastline position have been measured for decades and vary highly spatially. We hypothesize that these rates are inversely related to the inclination of the upper surface of submarine ice-bonded permafrost (IBP) based on the consequent duration of inundation with increasing distance from the shoreline. We compared rapidly eroding and stable coastal sections of Muostakh Island and find permafrost-table inclinations, determined using direct current resistivity, of 1 and 5 %, respectively. Determinations of submarine IBP depth from a drilling transect in the early 1980s were compared to resistivity profiles from 2011. Based on borehole observations, the thickness of unfrozen sediment overlying the IBP increased from 0 to 14m below sea level with increasing distance from the shoreline. The geoelectrical profiles showed thickening of the unfrozen sediment overlying ice-bonded permafrost over the 28 years since drilling took place. We use geoelectrical estimates of IBP depth to estimate permafrost degradation rates since inundation. Degradation rates decreased from over 0.4ma-1 following inundation to around 0.1ma-1 at the latest after 60 to 110 years and remained constant at this level as the duration of inundation increased to 250 years. We suggest that long-term rates are lower than these values, as the depth to the IBP increases and thermal and porewater solute concentration gradients over depth decrease. For the study region, recent increases in coastal erosion rate and changes in benthic temperature and salinity regimes are expected to affect the depth to submarine permafrost, leading to coastal regions with shallower IBP.

Description: Holocene permafrost from ice wedge polygons in the vicinity of large seabird breeding colonies in the Thule District, NW Greenland, was drilled to explore the relation between permafrost aggradation and seabird presence. The latter is reliant on the presence of the North Water Polynya (NOW) in the northern Baffin Bay. The onset of peat accumulation associated with the arrival of little auks (Alle alle) in a breeding colony at Annikitisoq, north of Cape York, is radiocarbon-dated to 4400 cal BP. A thick-billed murre (Uria lomvia) colony on Appat (Saunders Island) in the mouth of the Wolstenholme Fjord started 5650 cal BP. Both species provide marine-derived nutrients (MDNs) that fertilize vegetation and promote peat growth. The geochemical signature of organic matter left by the birds is traceable in the frozen Holocene peat. The peat accumulation rates at both sites are highest after the onset, decrease over time, and were about 2-times faster at the little auk site than at the thick-billed murre site. High accumulation rates induce shorter periods of organic matter (OM) decomposition before it enters the perennially frozen state. This is seen in comparably high C=N ratios and less depleted 13C, pointing to a lower degree of OM decomposition at the little auk site, while the opposite pattern can be discerned at the thick-billed murre site. Peat accumulation rates correspond to 15N trends, where decreasing accumulation led to increasing depletion in 15N as seen in the little-auk-related data. In contrast, the more decomposed OM of the thick-billed murre site shows almost stable 15N. Late Holocene wedge ice fed by cold season precipitation was studied at the little auk site and provides the first stable-water isotopic record from Greenland with mean 18O of 8:00:8, mean D of 36:25:7, mean d excess of 7:70:7, and a 18O-D slope of 7.27, which is close to those of the modern Thule meteoric water line. The syngenetic ice wedge polygon development is mirrored in testacean records of the little auk site and delineates polygon low-center, dry-out, and polygon-high-center stages. The syngenetic permafrost formation directly depending on peat growth (controlled by bird activity) falls within the period of neoglacial cooling and the establishment of the NOW, thus indirectly following the Holocene climate trends.

Description: © The American Chemical Society, 2016. This is an open access article published under an ACS AuthorChoice License. The definitive version was published in Analytical Chemistry 88 (2016): 7154–7162, doi:10.1021/acs.analchem.6b01260.

Description: Discovery and identification of molecular biomarkers in large LC/MS data sets requires significant automation without loss of accuracy in the compound screening and annotation process. Here, we describe a lipidomics workflow and open-source software package for high-throughput annotation and putative identification of lipid, oxidized lipid, and oxylipin biomarkers in high-mass-accuracy HPLC-MS data. Lipid and oxylipin biomarker screening through adduct hierarchy sequences, or LOBSTAHS, uses orthogonal screening criteria based on adduct ion formation patterns and other properties to identify thousands of compounds while providing the user with a confidence score for each assignment. Assignments are made from one of two customizable databases; the default databases contain 14 068 unique entries. To demonstrate the software’s functionality, we screened more than 340 000 mass spectral features from an experiment in which hydrogen peroxide was used to induce oxidative stress in the marine diatom Phaeodactylum tricornutum. LOBSTAHS putatively identified 1969 unique parent compounds in 21 869 features that survived the multistage screening process. While P. tricornutum maintained more than 92% of its core lipidome under oxidative stress, patterns in biomarker distribution and abundance indicated remodeling was both subtle and pervasive. Treatment with 150 μM H2O2 promoted statistically significant carbon-chain elongation across lipid classes, with the strongest elongation accompanying oxidation in moieties of monogalactosyldiacylglycerol, a lipid typically localized to the chloroplast. Oxidative stress also induced a pronounced reallocation of lipidome peak area to triacylglycerols. LOBSTAHS can be used with environmental or experimental data from a variety of systems and is freely available at https://github.com/vanmooylipidomics/LOBSTAHS.

Description: This research was supported by the Gordon and Betty Moore Foundation through Grant GBMF3301 to B.A.S.V.M. This research was also funded in part by a grant to B.A.S.V.M. from the Simons Foundation and is a contribution of the Simons Collaboration on Ocean Processes and Ecology (SCOPE). J.R.C. acknowledges support from a U.S. Environmental Protection Agency (EPA) STAR Graduate Fellowship (Fellowship Assistance Agreement No. FP-91744301-0).

Description: Author Posting. © American Chemical Society, 2019. This article is posted here by permission of American Chemical Society for personal use, not for redistribution. The definitive version was published in Kivenson, V., Lemkau, K. L., Pizarro, O., Yoerger, D. R., Kaiser, C., Nelson, R. K., Carmichael, C., Paul, B. G., Reddy, C. M., & Valentine, D. L. (2019). Ocean Dumping of Containerized DDT Waste Was a Sloppy Process. Environmental Science and Technology (2019), doi:10.1021/acs.est.8b05859.

Description: Industrial-scale dumping of organic waste to the deep ocean was once common practice, leaving a legacy of chemical pollution for which a paucity of information exists. Using a nested approach with autonomous and remotely operated underwater vehicles, a dumpsite offshore California was surveyed and sampled. Discarded waste containers littered the site and structured the suboxic benthic environment. Dichlorodiphenyltrichloroethane (DDT) was reportedly dumped in the area, and sediment analysis revealed substantial variability in concentrations of p,p-DDT and its analogs, with a peak concentration of 257 μg g–1, ∼40 times greater than the highest level of surface sediment contamination at the nearby DDT Superfund site. The occurrence of a conspicuous hydrocarbon mixture suggests that multiple petroleum distillates, potentially used in DDT manufacture, contributed to the waste stream. Application of a two end-member mixing model with DDTs and polychlorinated biphenyls enabled source differentiation between shelf discharge versus containerized waste. Ocean dumping was found to be the major source of DDT to more than 3000 km2 of the region’s deep seafloor. These results reveal that ocean dumping of containerized DDT waste was inherently sloppy, with the contents readily breaching containment and leading to regional scale contamination of the deep benthos.

Description: This material is based upon work supported by the National Science Foundation Graduate Research Fellowship for V.K. under Grant No. 1650114. Expeditions AT-18-11 and AT-26-06 were funded by the NSF (OCE-0961725 and OCE-1046144). Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. We thank the captain and crew of the RV Atlantis, the pilots and crew of the ROV Jason, the crew of the AUV Sentry, the scientific party of the AT-18-11 and AT-26-06 expeditions, Justin Tran for assistance with the preparation of multibeam data, M. Indira Venkatesan for a helpful discussion of the NOAA datasets, and Nathan Dodder for advice on the procedure for compound identification.

Description: Author Posting. © American Chemical Society, 2019. This is an open access article published under an ACS AuthorChoice License. The definitive version was published in Environmental Science and Technology 53(16), (2019): 9398-9406, doi:10.1021/acs.est.9b02395.

Description: Geochemical data from 40 water wells were used to examine the occurrence and sources of radium (Ra) in groundwater associated with three oil fields in California (Fruitvale, Lost Hills, South Belridge). 226Ra+228Ra activities (range = 0.010–0.51 Bq/L) exceeded the 0.185 Bq/L drinking-water standard in 18% of the wells (not drinking-water wells). Radium activities were correlated with TDS concentrations (p 〈 0.001, ρ = 0.90, range = 145–15,900 mg/L), Mn + Fe concentrations (p 〈 0.001, ρ = 0.82, range = 〈0.005–18.5 mg/L), and pH (p 〈 0.001, ρ = −0.67, range = 6.2–9.2), indicating Ra in groundwater was influenced by salinity, redox, and pH. Ra-rich groundwater was mixed with up to 45% oil-field water at some locations, primarily infiltrating through unlined disposal ponds, based on Cl, Li, noble-gas, and other data. Yet 228Ra/226Ra ratios in pond-impacted groundwater (median = 3.1) differed from those in oil-field water (median = 0.51). PHREEQC mixing calculations and spatial geochemical variations suggest that the Ra in the oil-field water was removed by coprecipitation with secondary barite and adsorption on Mn–Fe precipitates in the near-pond environment. The saline, organic-rich oil-field water subsequently mobilized Ra from downgradient aquifer sediments via Ra-desorption and Mn/Fe-reduction processes. This study demonstrates that infiltration of oil-field water may leach Ra into groundwater by changing salinity and redox conditions in the subsurface rather than by mixing with a high-Ra source.

Description: This article was improved by the reviews of John Izbicki and anonymous reviewers for the journal. This work was funded by the California State Water Resources Control Board’s Regional Groundwater Monitoring in Areas of Oil and Gas Production Program and the USGS Cooperative Water Program. A.V., A.J.K., and Z.W were supported by USDA-NIFA grant (#2017-68007-26308). Any use of trade, firm, or product names is for description purposes only and does not imply endorsement by the U.S. Government.

Description: Author Posting. © American Chemical Society, 2019. This is an open access article published under an ACS AuthorChoice License. The definitive version was published in Environmental Science and Technology 53(14), (2019):8244-8251, doi:10.1021/acs.est.9b02344.

Description: 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.

Description: We thank John King, Sean Sylva, Brad Hubeny, Peter Sauer, and Jim Broda for their help in sampling; Carl Johnson and Daniel Montluçon for their incessant help with analyses; as well as Mark Yunker for critical discussion on the perils of perylene. Professor Phil Meyers and two anonymous reviewers provided comments that improved the quality of the manuscript. U.M.H. acknowledges the Swiss National Science Foundation for his postdoctoral fellowship and T.I.E. and K.A.H. acknowledges the NSF for research grants CHE-0089172 and OCE-9708478.

Description: 2020-06-19

Description: © American Chemical Society, 2016. This article is distributed under the terms of the AuthorsChoice License. The definitive version was published in Environmental Science & Technology 50 (2016): 7397–7408, doi:10.1021/acs.est.5b04617.

Description: With the expansion of offshore petroleum extraction, validated models are needed to simulate the behaviors of petroleum compounds released in deep (〉100 m) waters. We present a thermodynamic model of the densities, viscosities, and gas–liquid−water partitioning of petroleum mixtures with varying pressure, temperature, and composition based on the Peng–Robinson equation-of-state and the modified Henry’s law (Krychevsky−Kasarnovsky equation). The model is applied to Macondo reservoir fluid released during the Deepwater Horizon disaster, represented with 279–280 pseudocomponents, including 131–132 individual compounds. We define 〉n-C8 pseudocomponents based on comprehensive two-dimensional gas chromatography (GC × GC) measurements, which enable the modeling of aqueous partitioning for n-C8 to n-C26 fractions not quantified individually. Thermodynamic model predictions are tested against available laboratory data on petroleum liquid densities, gas/liquid volume fractions, and liquid viscosities. We find that the emitted petroleum mixture was ∼29–44% gas and ∼56–71% liquid, after cooling to local conditions near the broken Macondo riser stub (∼153 atm and 4.3 °C). High pressure conditions dramatically favor the aqueous dissolution of C1−C4 hydrocarbons and also influence the buoyancies of bubbles and droplets. Additionally, the simulated densities of emitted petroleum fluids affect previous estimates of the volumetric flow rate of dead oil from the emission source.

Description: This research was made possible by grants from the NSF (OCE- 0960841, OCE-1043976, and EAR-0950600) and the Gulf of Mexico Research Initiative (GoMRI) to the C-IMAGE and DEEP-C consortia.

Description: © American Chemical Society, 2015. This article is posted here by permission of American Chemical Society; copying and redistribution for non-commercial research and education purposes only. The definitive version was published in ACS Nano 10 (2016): 6-37, doi:10.1021/acsnano.5b07826.

Description: The microbiome presents great opportunities for understanding and improving the world around us and elucidating the interactions that compose it. The microbiome also poses tremendous challenges for mapping and manipulating the entangled networks of interactions among myriad diverse organisms. Here, we describe the opportunities, technical needs, and potential approaches to address these challenges, based on recent and upcoming advances in measurement and control at the nanoscale and beyond. These technical needs will provide the basis for advancing the largely descriptive studies of the microbiome to the theoretical and mechanistic understandings that will underpin the discipline of microbiome engineering. We anticipate that the new tools and methods developed will also be more broadly useful in environmental monitoring, medicine, forensics, and other areas.

Description: This research was supported by the Office of Naval Research Grant #N000141410051 (P.S.W., G.C.L.W., and T.Y.), the Genomic Science Program of the U.S. DOE-OBER,

Description: Author Posting. © American Chemical Society, 2018. This is an open access article published under an ACS AuthorChoice License. The definitive version was published in Environmental Science and Technology Letters 5 (2018): 226–231, doi:10.1021/acs.estlett.8b00084.

Description: Chemical dispersants are one of many tools used to mitigate the overall environmental impact of oil spills. In principle, dispersants break up floating oil into small droplets that disperse into the water column where they are subject to multiple fate and transport processes. The effectiveness of dispersants typically decreases as oil weathers in the environment. This decrease in effectiveness is often attributed to evaporation and emulsification, with the contribution of photochemical weathering assumed to be negligible. Here, we aim to test this assumption using Macondo well oil released during the Deepwater Horizon spill as a case study. Our results indicate that the effects of photochemical weathering on Deepwater Horizon oil properties and dispersant effectiveness can greatly outweigh the effects of evaporative weathering. The decrease in dispersant effectiveness after light exposure was principally driven by the decreased solubility of photo-oxidized crude oil residues in the solvent system that comprises COREXIT EC9500A. Kinetic modeling combined with geospatial analysis demonstrated that a considerable fraction of aerial applications targeting Deepwater Horizon surface oil had low dispersant effectiveness. Collectively, the results of this study challenge the paradigm that photochemical weathering has a negligible impact on the effectiveness of oil spill response and provide critical insights into the “window of opportunity” to apply chemical dispersants in response to oil spills in sunlit waters.

Description: This work was supported, in part, by National Science Foundation Grant OCE-1333148, Gulf of Mexico Research Initiative Grants 015, SA 16-30, the DEEP-C consortium, and the Clark Family Foundation, Inc. EPA funding was provided to R.N.C. from the Oil Spill Liability Trust Fund.

Description: Warming of the Arctic led to an increase in permafrost temperatures by about 0.3 �C during the last decade. Permafrost warming is associated with increasing sediment water content, permeability, and diffusivity and could in the long term alter microbial community composition and abundance even before permafrost thaws. We studied the long-term effect (up to 2500 years) of submarine permafrost warming on microbial communities along an onshore–offshore transect on the Siberian Arctic Shelf displaying a natural temperature gradient of more than 10 �C. We analysed the in situ development of bacterial abundance and community composition through total cell counts (TCCs), quantitative PCR of bacterial gene abundance, and amplicon sequencing and correlated the microbial community data with temperature, pore water chemistry, and sediment physicochemical parameters. On timescales of centuries, permafrost warming coincided with an overall decreasing microbial abundance, whereas millennia after warming microbial abundance was similar to cold onshore permafrost. In addition, the dissolved organic carbon content of all cores was lowest in submarine permafrost after millennial-scale warming. Based on correlation analysis, TCC, unlike bacterial gene abundance, showed a significant rank-based negative correlation with increasing temperature, while bacterial gene copy numbers showed a strong negative correlation with salinity. Bacterial community composition correlated only weakly with temperature but strongly with the pore water stable isotopes �18O and �D, as well as with depth. The bacterial community showed substantial spatial variation and an overall dominance of Actinobacteria, Chloroflexi, Firmicutes, Gemmatimonadetes, and Proteobacteria, which are amongst the microbial taxa that were also found to be active in other frozen permafrost environments. We suggest that, millennia after permafrost warming by over 10 �C, microbial community composition and abundance show some indications for proliferation but mainly reflect the sedimentation history and paleoenvironment and not a direct effect through warming.