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Stukel, MR, Kelly TB, Aluwihare LI, Barbeau KA, Goericke R, Krause JW, Landry MR, Ohman MD.  2019.  The Carbon:(234)Thorium ratios of sinking particles in the California current ecosystem 1: relationships with plankton ecosystem dynamics. Marine Chemistry. 212:1-15.   10.1016/j.marchem.2019.01.003   AbstractWebsite

We investigated variability in the C:Th-234 ratio of sinking particles and its relationship to changing water column characteristics and plankton ecological dynamics during 29 Lagrangian experiments conducted on six cruises of the California Current Ecosystem Long-Term Ecological Research (CCE-LTER) Program. C:Th-234 ratios of sinking particles collected by a surface-tethered sediment trap ((CThST)-Th-:234) varied from 2.3 to 20.5 mu mol C dpm(-1) over a depth range of 47-150 m. C:Th-234(ST) was significantly greater (by a factor of 1.8) than C:Th-234 ratios of suspended > 51-mu m particles collected in the same water parcels with in situ pumps. C:Th-234 ratios of large (> 200-mu m) sinking particles also exceeded those of smaller sinking particles. C:Th-234(ST) decreased with depth from the base of the euphotic zone through the upper twilight zone. C:Th-234(ST) was positively correlated with several indices of ecosystem productivity including particulate organic carbon (POC) and chlorophyll (Chl) concentrations, mesozooplankton biomass, and the fraction of Chl > 20-mu m. Principal component analysis and multiple linear regression suggested that decaying phytoplankton blooms exhibited higher C:Th-234(ST) than actively growing blooms at similar biomass levels. C:Th-234(ST) was positively correlated with indices of the fractional contribution of fecal pellets in sediment traps when the proportion of fecal pellets was low in the traps, likely because of a correlation between mesozooplankton biomass and other indices of ecosystem productivity. However, when fecal pellets were a more important component of sinking material, C:Th-234(ST) decreased with increasing fecal pellet content. C:Th-234(ST) was also positively correlated with the Si:C ratio of sinking particles. Across the dataset (and across depths) a strong correlation was found between C:Th-234(ST) and the ratio of vertically-integrated POC to vertically-integrated total water column Th-234 (C-v:Th-234(tot)). A mechanistic one-layer, two-box model of thorium sorption and desorption was invoked to explain this correlation. Two empirical models (one using C-v:Th-234(tot); one using depth and vertically-integrated Chl) were developed to predict C:Th-234 ratios in this coastal upwelling biome. The former regression (log(10)(C:Th-234(ST)) = 0.43 x log(10)(C-v:Th-234(tot)) + 0.53) was found to also be a reasonable predictor for C:Th-234(ST) from diverse regions including the Southern Ocean, Sargasso Sea, Subarctic North Pacific, and Eastern Tropical North Pacific.

Stukel, MR, Aluwihare LI, Barbeau KA, Chekalyuk AM, Goericke R, Miller AJ, Ohman MD, Ruacho A, Song H, Stephens BM, Landry MR.  2017.  Mesoscale ocean fronts enhance carbon export due to gravitational sinking and subduction. Proceedings of the National Academy of Sciences of the United States of America. 114:1252-1257.   10.1073/pnas.1609435114   AbstractWebsite

Enhanced vertical carbon transport (gravitational sinking and subduction) at mesoscale ocean fronts may explain the demonstrated imbalance of new production and sinking particle export in coastal upwelling ecosystems. Based on flux assessments from U-238:Th-234 disequilibrium and sediment traps, we found 2 to 3 times higher rates of gravitational particle export near a deep-water front (305 mg C.m(-2).d(-1)) compared with adjacent water or to mean (nonfrontal) regional conditions. Elevated particle flux at the front wasmechanistically linked to Fe-stressed diatoms and high-mesozooplankton fecal pellet production. Using a data assimilative regional ocean model fit to measured conditions, we estimate that an additional similar to 225 mg C.m(-2).d(-1) was exported as subduction of particle-rich water at the front, highlighting a transport mechanism that is not captured by sediment traps and is poorly quantified by most models and in situ measurements. Mesoscale fronts may be responsible for over a quarter of total organic carbon sequestration in the California Current and other coastal upwelling ecosystems.

Kumar, A, Borgen M, Aluwihare LI, Fenical W.  2017.  Ozone-activated halogenation of mono- and dimethylbipyrrole in seawater. Environmental Science & Technology. 51:589-595.   10.1021/acs.est.6b03601   AbstractWebsite

Polyhalogenated N-methylbipyrroles of two different structure classes have been detected worldwide in over 100 environmental samples including seawater, bird eggs, fish, dolphin blubber, and in the breast milk of humans that consume seafood. These molecules are concentrated in the fatty tissues in comparable abundance to some of the most important anthropogenic contaminants, such as the halogenated flame-retardants and pesticides. Although the origin of these compounds is still unknown, we present evidence that the production of these materials can involve the direct ozone activated seawater halogenation of N-methylbipyrrole precursors. This observation shows that environmental polyhalogenated bipyrroles can be produced via an abiotic process, and implies that the ozone activated halogenation of a variety of natural and anthropogenic seawater organics may be a significant process occurring in surface ocean waters.

Haskell, WZ, Prokopenko MG, Hammond DE, Stanley RHR, Berelson WM, Baronas JJ, Fleming JC, Aluwihare L.  2016.  An organic carbon budget for coastal Southern California determined by estimates of vertical nutrient flux, net community production and export. Deep-Sea Research Part I-Oceanographic Research Papers. 116:49-76.   10.1016/j.dsr.2016.07.003   AbstractWebsite

Organic carbon export and burial in coastal upwelling regions is an important mechanism for oceanic uptake of atmospheric CO2. In order to understand how these complex systems will respond to future climate forcing, further studies of nutrient input, biological production and export are needed. Using a Be-7-based approach, we produced an 18-month record of upwelling velocity estimates at the San Pedro Ocean Time-series (SPOT), Southern California Bight. These upwelling rates and vertical nutrient distributions have been combined to make estimates of potential new production (PNP), which are compared to estimates of net community oxygen production (NOP) made using a one-dimensional, two-box non-steady state model of euphotic zone biological oxygen supersaturation. NOP agrees within uncertainty with PNP, suggesting that upwelling is the dominant mechanism for supplying the ecosystem with new nutrients in the spring season, but negligible in the fall and winter. Combining this data set with estimates of sinking particulate organic carbon (POC) flux from water column Th-234:U-238 disequilibrium and sediment trap deployments, and an estimate of the ratio of dissolved organic carbon (DOC):POC consumption rates, we construct a simple box model of organic carbon in the upper 200 m of our study site. This box model (with uncertainties of +/- 50%) suggests that in spring, 28% of net production leaves the euphotic zone as DOC, of this, similar to 12% as horizontal export and 16% via downward mixing. The remaining similar to 72% of net organic carbon export exits as sinking POC, with only 10% of euphotic zone export reaching 200 m. We find the metabolic requirement for the local heterotrophic community below the euphotic zone, but above 200 m, is similar to 105 +/- 50 mmol C m(-2) d(-1), or similar to 80% of net euphotic zone production in spring. (C) 2016 Elsevier Ltd. All rights reserved.

Moran, MA, Kujawinski EB, Stubbins A, Fatland R, Aluwihare LI, Buchan A, Crump BC, Dorrestein PC, Dyhrman ST, Hess NJ, Howe B, Longnecker K, Medeiros PM, Niggemann J, Obernosterer I, Repeta DJ, Waldbauer JR.  2016.  Deciphering ocean carbon in a changing world. Proceedings of the National Academy of Sciences of the United States of America. 113:3143-3151.   10.1073/pnas.1514645113   AbstractWebsite

Dissolved organic matter (DOM) in the oceans is one of the largest pools of reduced carbon on Earth, comparable in size to the atmospheric CO2 reservoir. A vast number of compounds are present in DOM, and they play important roles in all major element cycles, contribute to the storage of atmospheric CO2 in the ocean, support marine ecosystems, and facilitate interactions between organisms. At the heart of the DOM cycle lie molecular-level relationships between the individual compounds in DOM and the members of the ocean microbiome that produce and consume them. In the past, these connections have eluded clear definition because of the sheer numerical complexity of both DOM molecules and microorganisms. Emerging tools in analytical chemistry, microbiology, and informatics are breaking down the barriers to a fuller appreciation of these connections. Here we highlight questions being addressed using recent methodological and technological developments in those fields and consider how these advances are transforming our understanding of some of the most important reactions of the marine carbon cycle.

Agarwal, V, Li J, Rahman I, Borgen M, Aluwihare LI, Biggs JS, Paul VJ, Moore BS.  2015.  Complexity of naturally produced polybrominated diphenyl ethers revealed via mass spectrometry. Environmental Science & Technology. 49:1339-1346.   10.1021/es505440j   AbstractWebsite

Polybrominated diphenyl ethers (PBDEs) are persistent and bioaccumulative anthropogenic and natural chemicals that are broadly distributed in the marine environment. PBDEs are potentially toxic due to inhibition of various mammalian signaling pathways and enzymatic reactions. PBDE isoforms vary in toxicity in accordance with structural differences, primarily in the number and pattern of hydroxyl moieties afforded upon a conserved core structure. Over four decades of isolation and discovery-based efforts have established an impressive repertoire of natural PBDEs. Based on our recent reports describing the bacterial biosyntheses of PBDEs, we predicted the presence of additional classes of PBDEs to those previously identified from marine sources. Using mass spectrometry and NMR spectroscopy, we now establish the existence of new structural classes of PBDEs in marine sponges. Our findings expand the chemical space explored by naturally produced PBDEs, which may inform future environmental toxicology studies. Furthermore, we provide evidence for iodinated PBDEs and direct attention toward the contribution of promiscuous halogenating enzymes in further expanding the diversity of these polyhalogenated marine natural products.

Goldberg, SJ, Ball GI, Allen BC, Schladow SG, Simpson AJ, Masoom H, Soong R, Graven HD, Aluwihare LI.  2015.  Refractory dissolved organic nitrogen accumulation in high-elevation lakes. Nature Communications. 6   10.1038/ncomms7347   AbstractWebsite

The role of dissolved organic matter (DOM) as either a sink for inorganic nutrients or an additional nutrient source is an often-neglected component of nutrient budgets in aquatic environments. Here, we examined the role of DOM in reactive nitrogen (N) storage in Sierra Nevada (California, USA) lakes where atmospheric deposition of N has shifted the lakes toward seasonal phosphorus (P)-limitation. Nuclear magnetic resonance (NMR) spectroscopy and isotope analyses performed on DOM isolated from Lake Tahoe reveal the accumulation of refractory proteinaceous material with a 100-200-year residence time. In contrast, smaller lakes in the same watershed contain DOM with typical terrestrial characteristics, indicating that proteins in Lake Tahoe are autochthonously produced. These data support the role of DOM as a possible sink for reactive N in these lake ecosystems and identify a potential role for DOM in affecting the inorganic nutrient stoichiometry of these environments.

Collins, DB, Ault AP, Moffet RC, Ruppel MJ, Cuadra-Rodriguez LA, Guasco TL, Corrigan CE, Pedler BE, Azam F, Aluwihare LI, Bertram TH, Roberts GC, Grassian VH, Prather KA.  2013.  Impact of marine biogeochemistry on the chemical mixing state and cloud forming ability of nascent sea spray aerosol. Journal of Geophysical Research-Atmospheres. 118:8553-8565.   10.1002/jgrd.50598   AbstractWebsite

The composition and properties of sea spray aerosol, a major component of the atmosphere, are often controlled by marine biological activity; however, the scope of impacts that ocean chemistry has on the ability for sea spray aerosol to act as cloud condensation nuclei (CCN) is not well understood. In this study, we utilize a mesocosm experiment to investigate the impact of marine biogeochemical processes on the composition and mixing state of sea spray aerosol particles with diameters<0.2 mu m produced by controlled breaking waves in a unique ocean-atmosphere facility. An increase in relative abundance of a distinct, insoluble organic particle type was observed after concentrations of heterotrophic bacteria increased in the seawater, leading to an 86 +/- 5% reduction in the hygroscopicity parameter () at 0.2% supersaturation. Aerosol size distributions showed very little change and the submicron organic mass fraction increased by less than 15% throughout the experiment; as such, neither of these typical metrics can explain the observed reduction in hygroscopicity. Predictions of the hygroscopicity parameter that make the common assumption that all particles have the same bulk organic volume fractions lead to overpredictions of CCN concentrations by 25% in these experiments. Importantly, key changes in sea spray aerosol mixing state that ultimately influenced CCN activity were driven by bacteria-mediated alterations to the organic composition of seawater.

Close, HG, Shah SR, Ingalls AE, Diefendorf AF, Brodie EL, Hansman RL, Freeman KH, Aluwihare LI, Pearson A.  2013.  Export of submicron particulate organic matter to mesopelagic depth in an oligotrophic gyre. Proceedings of the National Academy of Sciences of the United States of America. 110:12565-12570.   10.1073/pnas.1217514110   AbstractWebsite

Sixty percent of the world ocean by area is contained in oligotrophic gyres [Longhurst A (1995) Prog Oceanog 36:77-16], the biomass of which is dominated by picophytoplankton, including cyanobacteria and picoeukaryotic algae, as well as picoheterotrophs. Despite their recognized importance in carbon cycling in the surface ocean, the role of small cells and their detrital remains in the transfer of particulate organic matter (POM) to the deep ocean remains disputed. Because oligotrophic marine conditions are projected to expand under current climate trends, a better understanding of the role of small particles in the global carbon cycle is a timely goal. Here we use the lipid profiles, radiocarbon, and stable carbon isotopic signatures of lipids from the North Pacific Subtropical Gyre to show that in the surface ocean, lipids from submicron POM (here called extra-small POM) are distinct from larger classes of suspended POM. Remarkably, this distinct extra-small POM signature dominates the total lipids collected at mesopelagic depth, suggesting that the lipid component of mesopelagic POM primarily contains the exported remains of small particles. Transfer of submicron material to mesopelagic depths in this location is consistent with model results that claim the biological origin of exported carbon should be proportional to the distribution of cell types in the surface community, irrespective of cell size [Richardson TL, Jackson GA (2007) Science 315:838-840]. Our data suggest that the submicron component of exported POM is an important contributor to the global biological pump, especially in oligotrophic waters.

Prather, KA, Bertram TH, Grassian VH, Deane GB, Stokes MD, DeMott PJ, Aluwihare LI, Palenik BP, Azam F, Seinfeld JH, Moffet RC, Molina MJ, Cappa CD, Geiger FM, Roberts GC, Russell LM, Ault AP, Baltrusaitis J, Collins DB, Corrigan CE, Cuadra-Rodriguez LA, Ebben CJ, Forestieri SD, Guasco TL, Hersey SP, Kim MJ, Lambert WF, Modini RL, Mui W, Pedler BE, Ruppel MJ, Ryder OS, Schoepp NG, Sullivan RC, Zhao DF.  2013.  Bringing the ocean into the laboratory to probe the chemical complexity of sea spray aerosol. Proceedings of the National Academy of Sciences of the United States of America. 110:7550-7555.   10.1073/pnas.1300262110   AbstractWebsite

The production, size, and chemical composition of sea spray aerosol (SSA) particles strongly depend on seawater chemistry, which is controlled by physical, chemical, and biological processes. Despite decades of studies in marine environments, a direct relationship has yet to be established between ocean biology and the physicochemical properties of SSA. The ability to establish such relationships is hindered by the fact that SSA measurements are typically dominated by overwhelming background aerosol concentrations even in remote marine environments. Herein, we describe a newly developed approach for reproducing the chemical complexity of SSA in a laboratory setting, comprising a unique ocean-atmosphere facility equipped with actual breaking waves. A mesocosm experiment was performed in natural seawater, using controlled phytoplankton and heterotrophic bacteria concentrations, which showed SSA size and chemical mixing state are acutely sensitive to the aerosol production mechanism, as well as to the type of biological species present. The largest reduction in the hygroscopicity of SSA occurred as heterotrophic bacteria concentrations increased, whereas phytoplankton and chlorophyll-a concentrations decreased, directly corresponding to a change in mixing state in the smallest (60-180 nm) size range. Using this newly developed approach to generate realistic SSA, systematic studies can now be performed to advance our fundamental understanding of the impact of ocean biology on SSA chemical mixing state, heterogeneous reactivity, and the resulting climate-relevant properties.

Samo, TJ, Pedler BE, Ball GI, Pasulka AL, Taylor AG, Aluwihare LI, Azam F, Goericke R, Landry MR.  2012.  Microbial distribution and activity across a water mass frontal zone in the California Current Ecosystem. Journal of Plankton Research. 34:802-814.   10.1093/plankt/fbs048   AbstractWebsite

Ocean fronts with accumulated biomass and organic matter may be significant sites of enhanced microbial activity. We sampled a frontal region (the A-Front) separating oligotrophic and mesotrophic water masses within the California Current Ecosystem (CCE) to assess the influence of frontal hydrography on several microbial parameters. Samples for heterotrophic bacterial, viral and flagellate abundance, dissolved and particulate carbon and nitrogen, transparent particles and bacterial carbon production were collected at 6 depths from the surface to 100 m with 59 conductivity/temperature/depth casts along a 26-km northerly transect across the front. Relative to adjacent oligotrophic and mesotrophic waters, the frontal transition displayed peaks in the mean estimates of cell-specific bacterial carbon and bulk bacterial production, particulate organic carbon and particulate organic nitrogen concentrations, and the abundance and size of transparent particles. Bacterial carbon production increased approximate to 5-fold northward from oligotrophic waters to the frontal zone, in agreement with an increase in the frequency of dividing cells, but bacterial abundance was lower than at adjacent stations. This may be partially explained by high chlorophyll, elevated virus:bacteria ratios and low nanoflagellate grazer abundance at the front. Our data suggest that CCE fronts can facilitate intense biological transformation and physical transport of organic matter, in sharp contrast to adjacent low productivity waters, and harbor dynamic microbial populations that influence nutrient cycling.

Ball, GI, Xu L, McNichol AP, Aluwihare LI.  2012.  A two-dimensional, heart-cutting preparative gas chromatograph facilitates highly resolved single-compound isolations with utility towards compound-specific natural abundance radiocarbon (C-14) analyses. Journal of Chromatography A. 1220:122-131.   10.1016/j.chroma.2011.11.021   AbstractWebsite

Motivated by the need to develop clean, high purity preparative enrichments of individual compounds for micro-scale compound-specific natural abundance isotope and radiocarbon (C-14) analyses, we describe a new, two-dimensional, heart-cutting, low-bleed, three-oven, single GC preparative system, demonstrate its resolving capabilities as applied to a typically complex environmental sample matrix, and investigate the robustness with which it preserves the authigenic C-13/C-12 and C-14/C-12 ratios of individual compounds it targets for preparative enrichment. The system is comprised of a programmable temperature vaporizing (PTV) inlet, a single GC oven, two modular, door-mounted, resistively heated low thermal mass (LTM) columns, a preparative fraction collector (PFC), and a Deans pneumatic switching device which facilitates heart-cutting between the system's 1 degrees and 2 degrees chromatographic dimensions. Further, the system's inlet and trapping parameters are optimized for the efficient preparative enrichment of the methyl ether and ester derivatives of the lignin phenol compound class. The lignin phenols include such compounds as the vanillyl and syringyl aldehydes, ethanones, and acids and are unrivaled biomarkers of terrestrial organic matter, some of which are also important components of fragrances and flavors. Using this suite of compounds, the suitability of this augmented preparative capillary GC (PCGC) system was investigated for micro-scale compound-specific (CS) stable isotope and natural abundance radiocarbon analyses (RA). Analysis of a >300 injection enrichment scheme reveals the instrument to fractionate C-13 in predictable ways and to preserve the authigenic Delta C-14 of compounds it targets for preparative enrichment to within 6.7 +/- 5.0 parts per thousand, demonstrating the promising new utility of such systems towards micro-scale CSRA investigations for which clean and high resolution separation techniques are prerequisite. (C) 2011 Elsevier B.V. All rights reserved.

Gaston, CJ, Furutani H, Guazzotti SA, Coffee KR, Bates TS, Quinn PK, Aluwihare LI, Mitchell BG, Prather KA.  2011.  Unique ocean-derived particles serve as a proxy for changes in ocean chemistry. Journal of Geophysical Research-Atmospheres. 116   10.1029/2010jd015289   AbstractWebsite

Oceans represent a significant natural source of gases and particles to the atmosphere. Relative to gas phase compounds, less is known regarding the influence of changes in biological activity in the ocean on the chemistry of sea spray aerosols produced in marine environments. To gain insight into the influence of ocean biology and chemistry on atmospheric aerosol chemistry, simultaneous real-time measurements were made of atmospheric aerosol size and chemical mixing-state, gas phase dimethyl sulfide (DMS), as well as seawater DMS and chlorophyll a. In three different marine environments with elevated chlorophyll a and DMS, unique Mg particles were detected containing Mg(2+), Ca(2+), K(+), and organic carbon. These particles were segregated from sea salt particles highlighting that two subpopulations within the sea spray were being ejected from the ocean. Strong temporal correlations were observed between these unique ocean-derived particles and freshly emitted sea salt particles (R(2) = 0.86), particularly as wind speed increased to at least 10 m/s, and atmospheric DMS (R(2) = 0.76). Time series correlations between ocean measurements and atmospheric aerosol chemistry suggest that chlorophyll a and DMS serve as indicators of changes in the chemistry of the ocean, most likely an increase in organic material, which is directly reflected in the single particle mixing-state. This is the first time such real-time correlations are shown between ocean chemistry and atmospheric aerosol mixing-state. The reasons behind these observed changes in aerosol chemistry are critical for understanding the heterogeneous reactivity, water uptake, and cloud forming potential of sea spray aerosols.

Beaupre, SR, Aluwihare L.  2010.  Constraining the 2-component model of marine dissolved organic radiocarbon. Deep-Sea Research Part Ii-Topical Studies in Oceanography. 57:1494-1503.   10.1016/j.dsr2.2010.02.017   AbstractWebsite

Keeling plots of dissolved organic carbon (DOC) concentration and Δ14C depth profiles imply rapid, diapycnal transport of DOC to the meso- and bathypelagic zones, but do not constrain the mechanism of redistribution. We review the 2-component Keeling plot model, and present an alternative formulation explicitly based on homogenization of water parcels. Applying this new model to DOC and dissolved inorganic carbon (DIC) depth profiles suggests that the dominant controls on DOC redistribution differ throughout the water column. DOC concentration and Δ14C gradients were consistent with biogeochemical processing in the epipelagic and advection in the mesopelagic. Vertical gradients in DOC concentration and Δ14C were insufficient for further interpretation in the bathypelagic. Ultimately, additional concurrent measurements of DOC and DIC concentrations and Δ14C values throughout the water column at more locations are needed to constrain the applicability of two-component mixing models to marine DOC.

Eglinton, TI, Aluwihare LI, Bauer JE, Druffel ERM, McNichol AP.  1996.  Gas chromatographic isolation of individual compounds from complex matrices for radiocarbon dating. Analytical Chemistry. 68:904-912.   10.1021/ac9508513   AbstractWebsite

This paper describes the application of a novel, practical approach for isolation of individual compounds from complex organic matrices for natural abundance radiocarbon measurement. This is achieved through the use of automated preparative capillary gas chromatography (PCGC) to separate and recover sufficient quantities of individual target compounds for C-14 analysis by accelerator mass spectrometry (AMS). We developed and tested this approach using a suite of samples (plant lipids, petroleums) whose ages spanned the C-14 time scale and which contained a variety of compound types (fatty acids, sterols, hydrocarbons), Comparison of individual compound and bulk radiocarbon signatures for the isotopically homogeneous samples studied revealed that Delta(14)C values generally agreed well (+/- 10%). Background contamination was assessed at each stage of the isolation procedure, and incomplete solvent removal prior to combustion was the only significant source of additional carbon, Isotope fractionation was addressed through compound-specific stable carbon isotopic analyses, Fractionation of isotopes during isolation of individual compounds was minimal (< 5 parts per thousand for delta(13)C), provided the entire peak was collected during PCGC, Trapping of partially coeluting peaks did cause errors, and these results highlight the importance of conducting stable carbon isotopic measurements of each trapped compound in concert with AMS for reliable radiocarbon measurements, The addition of carbon accompanying derivatization of functionalized compounds (e.g., fatty acids and sterols) prior to chromatographic separation represents a further source of potential error, This contribution can be removed using a simple isotopic mass balance approach, Based on these preliminary results, the PCGC-based approach holds promise for accurately determining C-14 ages on compounds specific to a given source within complex, heterogeneous samples.