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1.
Proc Natl Acad Sci U S A ; 119(41): e2209152119, 2022 10 11.
Artículo en Inglés | MEDLINE | ID: mdl-36201540

RESUMEN

Marine dissolved organic matter (DOM) is a major reservoir that links global carbon, nitrogen, and phosphorus. DOM is also important for marine sulfur biogeochemistry as the largest water column reservoir of organic sulfur. Dissolved organic sulfur (DOS) can originate from phytoplankton-derived biomolecules in the surface ocean or from abiotically "sulfurized" organic matter diffusing from sulfidic sediments. These sources differ in 34S/32S isotope ratios (δ34S values), with phytoplankton-produced DOS tracking marine sulfate (21‰) and sulfurized DOS mirroring sedimentary porewater sulfide (∼0 to -10‰). We measured the δ34S values of solid-phase extracted (SPE) DOM from marine water columns and porewater from sulfidic sediments. Marine DOMSPE δ34S values ranged from 14.9‰ to 19.9‰ and C:S ratios from 153 to 303, with lower δ34S values corresponding to higher C:S ratios. Marine DOMSPE samples showed consistent trends with depth: δ34S values decreased, C:S ratios increased, and δ13C values were constant. Porewater DOMSPE was 34S-depleted (∼-0.6‰) and sulfur-rich (C:S ∼37) compared with water column samples. We interpret these trends as reflecting at most 20% (and on average ∼8%) contribution of abiotic sulfurized sources to marine DOSSPE and conclude that sulfurized porewater is not a main component of oceanic DOS and DOM. We hypothesize that heterogeneity in δ34S values and C:S ratios reflects the combination of sulfurized porewater inputs and preferential microbial scavenging of sulfur relative to carbon without isotope fractionation. Our findings strengthen links between oceanic sulfur and carbon cycling, supporting a realization that organic sulfur, not just sulfate, is important to marine biogeochemistry.


Asunto(s)
Materia Orgánica Disuelta , Azufre , Carbono , Nitrógeno/análisis , Fósforo , Fitoplancton , Sulfatos/análisis , Sulfuros , Isótopos de Azufre , Agua
2.
Proc Natl Acad Sci U S A ; 119(5)2022 02 01.
Artículo en Inglés | MEDLINE | ID: mdl-35101918

RESUMEN

Metabolites exuded by primary producers comprise a significant fraction of marine dissolved organic matter, a poorly characterized, heterogenous mixture that dictates microbial metabolism and biogeochemical cycling. We present a foundational untargeted molecular analysis of exudates released by coral reef primary producers using liquid chromatography-tandem mass spectrometry to examine compounds produced by two coral species and three types of algae (macroalgae, turfing microalgae, and crustose coralline algae [CCA]) from Mo'orea, French Polynesia. Of 10,568 distinct ion features recovered from reef and mesocosm waters, 1,667 were exuded by producers; the majority (86%) were organism specific, reflecting a clear divide between coral and algal exometabolomes. These data allowed us to examine two tenets of coral reef ecology at the molecular level. First, stoichiometric analyses show a significantly reduced nominal carbon oxidation state of algal exometabolites than coral exometabolites, illustrating one ecological mechanism by which algal phase shifts engender fundamental changes in the biogeochemistry of reef biomes. Second, coral and algal exometabolomes were differentially enriched in organic macronutrients, revealing a mechanism for reef nutrient-recycling. Coral exometabolomes were enriched in diverse sources of nitrogen and phosphorus, including tyrosine derivatives, oleoyl-taurines, and acyl carnitines. Exometabolites of CCA and turf algae were significantly enriched in nitrogen with distinct signals from polyketide macrolactams and alkaloids, respectively. Macroalgal exometabolomes were dominated by nonnitrogenous compounds, including diverse prenol lipids and steroids. This study provides molecular-level insights into biogeochemical cycling on coral reefs and illustrates how changing benthic cover on reefs influences reef water chemistry with implications for microbial metabolism.


Asunto(s)
Antozoos/metabolismo , Materia Orgánica Disuelta/análisis , Algas Marinas/metabolismo , Animales , Antozoos/genética , Antozoos/crecimiento & desarrollo , Carbono/metabolismo , Arrecifes de Coral , Ecosistema , Biología Marina/métodos , Metabolómica/métodos , Nitrógeno/metabolismo , Nutrientes , Fósforo/metabolismo , Polinesia , Agua de Mar/química , Algas Marinas/genética , Algas Marinas/crecimiento & desarrollo
3.
Glob Chang Biol ; 30(7): e17394, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38988095

RESUMEN

Water-logged peatlands store tremendous amounts of soil carbon (C) globally, accumulating C over millennia. As peatlands become disturbed by human activity, these long-term C stores are getting destabilized and ultimately released as greenhouse gases that may exacerbate climate change. Oxidation of the dissolved organic carbon (DOC) mobilized from disturbed soils to streams and canals may be one avenue for the transfer of previously stored, millennia-aged C to the atmosphere. However, it remains unknown whether aged peat-derived DOC undergoes oxidation to carbon dioxide (CO2) following disturbance. Here, we use a new approach to measure the radiocarbon content of CO2 produced from the oxidation of DOC in canals overlying peatland soils that have undergone widespread disturbance in Indonesia. This work shows for the first time that aged DOC mobilized from drained and burned peatland soils is susceptible to oxidation by both microbial respiration and photomineralization over aquatic travel times for DOC. The bulk radiocarbon age of CO2 produced during canal oxidation ranged from modern to ~1300 years before present. These ages for CO2 were most strongly influenced by canal water depth, which was proportional to the water table level where DOC is mobilized from disturbed soils to canals. Canal microbes preferentially respired older or younger organic C pools to CO2, and this may have been facilitated by the use of a small particulate organic C pool over the dissolved pool. Given that high densities of canals are generally associated with lower water tables and higher fire risk, our findings suggest that peatland areas with high canal density may be a hotspot for the loss of aged C on the landscape. Taken together, the results of this study show how and why aquatic processing of organic C on the landscape can enhance the transfer of long-term peat C stores to the atmosphere following disturbance.


Asunto(s)
Dióxido de Carbono , Carbono , Suelo , Suelo/química , Dióxido de Carbono/análisis , Carbono/análisis , Indonesia , Oxidación-Reducción
4.
Philos Trans A Math Phys Eng Sci ; 381(2261): 20230081, 2023 Nov 27.
Artículo en Inglés | MEDLINE | ID: mdl-37807687

RESUMEN

Radiocarbon (14C) is a critical tool for understanding the global carbon cycle. During the Anthropocene, two new processes influenced 14C in atmospheric, land and ocean carbon reservoirs. First, 14C-free carbon derived from fossil fuel burning has diluted 14C, at rates that have accelerated with time. Second, 'bomb' 14C produced by atmospheric nuclear weapon tests in the mid-twentieth century provided a global isotope tracer that is used to constrain rates of air-sea gas exchange, carbon turnover, large-scale atmospheric and ocean transport, and other key C cycle processes. As we write, the 14C/12C ratio of atmospheric CO2 is dropping below pre-industrial levels, and the rate of decline in the future will depend on global fossil fuel use and net exchange of bomb 14C between the atmosphere, ocean and land. This milestone coincides with a rapid increase in 14C measurement capacity worldwide. Leveraging future 14C measurements to understand processes and test models requires coordinated international effort-a 'decade of radiocarbon' with multiple goals: (i) filling observational gaps using archives, (ii) building and sustaining observation networks to increase measurement density across carbon reservoirs, (iii) developing databases, synthesis and modelling tools and (iv) establishing metrics for identifying and verifying changes in carbon sources and sinks. This article is part of the Theo Murphy meeting issue 'Radiocarbon in the Anthropocene'.

5.
Environ Microbiol ; 24(11): 5408-5424, 2022 11.
Artículo en Inglés | MEDLINE | ID: mdl-36222155

RESUMEN

The exchange of metabolites mediates algal and bacterial interactions that maintain ecosystem function. Yet, while thousands of metabolites are produced, only a few molecules have been identified in these associations. Using the ubiquitous microalgae Pseudo-nitzschia sp., as a model, we employed an untargeted metabolomics strategy to assign structural characteristics to the metabolites that distinguished specific diatom-microbiome associations. We cultured five species of Pseudo-nitzschia, including two species that produced the toxin domoic acid, and examined their microbiomes and metabolomes. A total of 4826 molecular features were detected by tandem mass spectrometry. Only 229 of these could be annotated using available mass spectral libraries, but by applying new in silico annotation tools, characterization was expanded to 2710 features. The metabolomes of the Pseudo-nitzschia-microbiome associations were distinct and distinguished by structurally diverse nitrogen compounds, ranging from simple amines and amides to cyclic compounds such as imidazoles, pyrrolidines and lactams. By illuminating the dark metabolomes, this study expands our capacity to discover new chemical targets that facilitate microbial partnerships and uncovers the chemical diversity that underpins algae-bacteria interactions.


Asunto(s)
Diatomeas , Microbiota , Diatomeas/metabolismo , Espectrometría de Masas en Tándem , Metaboloma
6.
Proc Natl Acad Sci U S A ; 114(6): 1252-1257, 2017 02 07.
Artículo en Inglés | MEDLINE | ID: mdl-28115723

RESUMEN

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 238U:234Th 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 was mechanistically 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 ∼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.

7.
Proc Natl Acad Sci U S A ; 113(12): 3143-51, 2016 Mar 22.
Artículo en Inglés | MEDLINE | ID: mdl-26951682

RESUMEN

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.


Asunto(s)
Ciclo del Carbono , Carbono/química , Geología/métodos , Biología Marina/métodos , Agua de Mar/análisis , Carbono/metabolismo , Ecosistema , Ciencia de la Información , Microbiota , Océanos y Mares , Compuestos Orgánicos/análisis , Fitoplancton/metabolismo , Solubilidad , Movimientos del Agua
8.
Environ Sci Technol ; 51(1): 589-595, 2017 01 03.
Artículo en Inglés | MEDLINE | ID: mdl-27983826

RESUMEN

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.


Asunto(s)
Halogenación , Ozono , Monitoreo del Ambiente , Retardadores de Llama , Agua de Mar/química , Contaminantes Químicos del Agua
9.
Proc Natl Acad Sci U S A ; 111(20): 7202-7, 2014 May 20.
Artículo en Inglés | MEDLINE | ID: mdl-24733921

RESUMEN

Marine dissolved organic carbon (DOC) encompasses one of the largest reservoirs of carbon on Earth. Heterotrophic bacteria are the primary biotic force regulating the fate of this material, yet the capacity of individual strains to significantly contribute to carbon cycling is unknown. Here we quantified the ability of a single Alteromonas strain [Alteromonas sp. strain Scripps Institution of Oceanography (AltSIO)] to drawdown ambient DOC in a coastal ecosystem. In three experiments, AltSIO alone consumed the entire pool of labile DOC, defined here as the quantity consumed by the submicron size fraction of ambient microbial assemblages within 5 d. These findings demonstrate that complete removal of the labile DOC pool in coastal surface seawater can be achieved by a single taxon. During long-term incubations (>1 y) testing semilabile DOC consumption, AltSIO entered dormancy but remained viable, while the diverse assemblages continued to consume carbon. Given that AltSIO is a large bacterium and thus subject to increased grazing pressure, we sought to determine the ecological relevance of this phenotype. Growth dynamics in natural seawater revealed that AltSIO rapidly outgrew the native bacteria, and despite intense grazing pressure, was never eliminated from the population. A survey in the California Current Ecosystem revealed that large bacteria (≥40 fg C⋅cell(-1)) were persistent, accounting for up to 12% of total bacterial abundance and 24% of total bacterial biomass. We conclude that large, rapidly growing bacteria have the potential to disproportionately alter the fate of carbon in the mesotrophic ocean and play an important role in ecosystem function.


Asunto(s)
Alteromonas/fisiología , Agua de Mar/microbiología , Alteromonas/genética , Biomasa , California , Carbono/química , Ciclo del Carbono , Dióxido de Carbono/química , Ecosistema , Cadena Alimentaria , Hibridación Fluorescente in Situ , Datos de Secuencia Molecular , Nitrógeno/química , Océanos y Mares , Temperatura , Factores de Tiempo
10.
Microb Ecol ; 71(2): 401-8, 2016 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-26377203

RESUMEN

Hopanoids are bacterial membrane lipid biomarker molecules that feature prominently in the molecular fossil record. In the modern marine water column, recent reports implicate bacteria inhabiting low-oxygen environments as important sources of hopanoids to marine sediments. However, the preliminary biogeography reported by recent studies and the environmental conditions governing such distributions can only be confirmed when the numerical abundance of these organisms is known with more certainty. In this study, we employ two different approaches to examine the quantitative significance of phylogenetically distinct hopanoid producers in low-oxygen environments. First, we develop a novel quantitative PCR (qPCR) assay for the squalene hopene cyclase (sqhC) gene, targeting a subset of hopanoid producers previously identified to be important in the eastern North Pacific Ocean. The results represent the first quantitative gene abundance data of any kind for hopanoid producers in the marine water column and show that these putative alphaproteobacterial hopanoid producers are rare, comprising at most 0.2 % of the total bacterial community in our samples. Second, a complementary analysis of existing low-oxygen metagenomic datasets further examined the generality of the qPCR observation. We find that the dominant sqhC sequences in these metagenomic datasets are associated with phyla such as Nitrospinae rather than Proteobacteria, consistent with the qPCR finding that alphaproteobacterial hopanoid producers are not very abundant in low-oxygen environments. In fact, positive correlations between sqhC gene abundance and environmental parameters in these samples identify nitrite availability as a potentially important factor in the ecology of hopanoid producers that dominate low-oxygen environments.


Asunto(s)
Bacterias/aislamiento & purificación , Bacterias/metabolismo , Oxígeno/análisis , Agua de Mar/microbiología , Triterpenos/metabolismo , Bacterias/clasificación , Bacterias/genética , Proteínas Bacterianas/genética , Proteínas Bacterianas/metabolismo , Oxígeno/metabolismo , Océano Pacífico , Filogenia , Agua de Mar/análisis
11.
Environ Sci Technol ; 50(22): 12129-12137, 2016 Nov 15.
Artículo en Inglés | MEDLINE | ID: mdl-27737539

RESUMEN

Nontargeted GC×GC-TOF/MS analysis of blubber from 8 common bottlenose dolphins (Tursiops truncatus) inhabiting the Southern California Bight was performed to identify novel, bioaccumulative DDT-related compounds and to determine their abundance relative to the commonly studied DDT-related compounds. We identified 45 bioaccumulative DDT-related compounds of which the majority (80%) is not typically monitored in environmental media. Identified compounds include transformation products, technical mixture impurities such as tris(chlorophenyl)methane (TCPM), the presumed TCPM metabolite tris(chlorophenyl)methanol (TCPMOH), and structurally related compounds with unknown sources, such as hexa- to octachlorinated diphenylethene. To investigate impurities in pesticide mixtures as possible sources of these compounds, we analyzed technical DDT, the primary source of historical contamination in the region, and technical Dicofol, a current use pesticide that contains DDT-related compounds. The technical mixtures contained only 33% of the compounds identified in the blubber, suggesting that transformation products contribute to the majority of the load of DDT-related contaminants in these sentinels of ocean health. Quantitative analysis revealed that TCPM was the second most abundant compound class detected in the blubber, following DDE, and TCPMOH loads were greater than DDT. QSPR estimates verified 4,4',4″-TCPM and 4,4'4,″-TCPMOH are persistent and bioaccumulative.


Asunto(s)
Delfín Mular/metabolismo , DDT/metabolismo , Tejido Adiposo/química , Animales , California , Delfines , Monitoreo del Ambiente , Cromatografía de Gases y Espectrometría de Masas , Contaminantes Químicos del Agua
12.
Proc Natl Acad Sci U S A ; 110(31): 12565-70, 2013 Jul 30.
Artículo en Inglés | MEDLINE | ID: mdl-23858459

RESUMEN

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.


Asunto(s)
Organismos Acuáticos/fisiología , Cianobacterias/fisiología , Sedimentos Geológicos , Biología Marina/métodos , Océano Pacífico
13.
Proc Natl Acad Sci U S A ; 110(19): 7550-5, 2013 May 07.
Artículo en Inglés | MEDLINE | ID: mdl-23620519

RESUMEN

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.


Asunto(s)
Aerosoles/química , Atmósfera/química , Bacterias/metabolismo , Fitoplancton/metabolismo , Agua de Mar/química , Clorofila/química , Clorofila A , Ecología , Oceanografía , Océanos y Mares
14.
Environ Sci Technol ; 49(7): 4097-105, 2015 Apr 07.
Artículo en Inglés | MEDLINE | ID: mdl-25769031

RESUMEN

The chemical complexity of dissolved organic matter (DOM) obstructs our ability to definitively recover source compounds from within DOM, an objective which has the capacity to alter our understanding of carbon sequestration on a global scale. To advance compositional studies of DOM we have applied a previously published reduction method to an environmental standard, Suwannee River Fulvic Acid (SRFA). The reduction products, comprising 12% of the prereduced carbon, were then separated by comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOF-MS). Results indicate that the majority of observed reduced compounds corresponded to alicyclic hydrocarbons in the size range C10 to C17. Cyclic terpenoids are the only biomolecule class with contiguous, alicyclic carbon backbones of this size. These terpenoid reduction products contain series offset by CH2 and exhibit great isomeric diversity, features previously inferred from ultrahigh resolution mass spectrometry and NMR studies of unreduced SRFA. Reduction of Taxodium leaf litter as a source material to SRFA confirmed the prevalence of terpenoids in SRFA and provided insight into the parent compounds that must be diagenetically modified on relatively short time scales. These data corroborate several recent studies that suggest alicyclic hydrocarbons to be important components of longer-lived DOM.


Asunto(s)
Benzopiranos/química , Ríos/química , Terpenos/análisis , Cromatografía de Gases y Espectrometría de Masas , Espectroscopía de Resonancia Magnética , Hojas de la Planta/química , Taxodium/química
15.
Environ Sci Technol ; 49(3): 1328-38, 2015 Feb 03.
Artículo en Inglés | MEDLINE | ID: mdl-25526519

RESUMEN

Targeted environmental monitoring reveals contamination by known chemicals, but may exclude potentially pervasive but unknown compounds. Marine mammals are sentinels of persistent and bioaccumulative contaminants due to their longevity and high trophic position. Using nontargeted analysis, we constructed a mass spectral library of 327 persistent and bioaccumulative compounds identified in blubber from two ecotypes of common bottlenose dolphins (Tursiops truncatus) sampled in the Southern California Bight. This library of halogenated organic compounds (HOCs) consisted of 180 anthropogenic contaminants, 41 natural products, 4 with mixed sources, 8 with unknown sources, and 94 with partial structural characterization and unknown sources. The abundance of compounds whose structures could not be fully elucidated highlights the prevalence of undiscovered HOCs accumulating in marine food webs. Eighty-six percent of the identified compounds are not currently monitored, including 133 known anthropogenic chemicals. Compounds related to dichlorodiphenyltrichloroethane (DDT) were the most abundant. Natural products were, in some cases, detected at abundances similar to anthropogenic compounds. The profile of naturally occurring HOCs differed between ecotypes, suggesting more abundant offshore sources of these compounds. This nontargeted analytical framework provided a comprehensive list of HOCs that may be characteristic of the region, and its application within monitoring surveys may suggest new chemicals for evaluation.


Asunto(s)
Delfín Mular , Hidrocarburos Clorados/análisis , Contaminantes Químicos del Agua/análisis , Animales , California , Ecotipo , Monitoreo del Ambiente , Masculino
16.
Environ Sci Technol ; 49(3): 1339-46, 2015 Feb 03.
Artículo en Inglés | MEDLINE | ID: mdl-25559102

RESUMEN

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.


Asunto(s)
Éteres Difenilos Halogenados/análisis , Poríferos , Animales , Espectroscopía de Resonancia Magnética , Espectrometría de Masas
17.
ISME J ; 18(1)2024 Jan 08.
Artículo en Inglés | MEDLINE | ID: mdl-38624181

RESUMEN

Iron is an essential nutrient for all microorganisms of the marine environment. Iron limitation of primary production has been well documented across a significant portion of the global surface ocean, but much less is known regarding the potential for iron limitation of the marine heterotrophic microbial community. In this work, we characterize the transcriptomic response of the heterotrophic bacterial community to iron additions in the California Current System, an eastern boundary upwelling system, to detect in situ iron stress of heterotrophic bacteria. Changes in gene expression in response to iron availability by heterotrophic bacteria were detected under conditions of high productivity when carbon limitation was relieved but when iron availability remained low. The ratio of particulate organic carbon to dissolved iron emerged as a biogeochemical proxy for iron limitation of heterotrophic bacteria in this system. Iron stress was characterized by high expression levels of iron transport pathways and decreased expression of iron-containing enzymes involved in carbon metabolism, where a majority of the heterotrophic bacterial iron requirement resides. Expression of iron stress biomarkers, as identified in the iron-addition experiments, was also detected insitu. These results suggest iron availability will impact the processing of organic matter by heterotrophic bacteria with potential consequences for the marine biological carbon pump.


Asunto(s)
Bacterias , Carbono , Procesos Heterotróficos , Hierro , Agua de Mar , Hierro/metabolismo , Carbono/metabolismo , Bacterias/metabolismo , Bacterias/genética , Bacterias/clasificación , Bacterias/aislamiento & purificación , Agua de Mar/microbiología , California , Microbiota
18.
Commun Biol ; 7(1): 160, 2024 Feb 13.
Artículo en Inglés | MEDLINE | ID: mdl-38351328

RESUMEN

Coral bleaching is a well-documented and increasingly widespread phenomenon in reefs across the globe, yet there has been relatively little research on the implications for reef water column microbiology and biogeochemistry. A mesocosm heating experiment and bottle incubation compared how unbleached and bleached corals alter dissolved organic matter (DOM) exudation in response to thermal stress and subsequent effects on microbial growth and community structure in the water column. Thermal stress of healthy corals tripled DOM flux relative to ambient corals. DOM exudates from stressed corals (heated and/or previously bleached) were compositionally distinct from healthy corals and significantly increased growth of bacterioplankton, enriching copiotrophs and putative pathogens. Together these results demonstrate how the impacts of both short-term thermal stress and long-term bleaching may extend into the water column, with altered coral DOM exudation driving microbial feedbacks that influence how coral reefs respond to and recover from mass bleaching events.


Asunto(s)
Antozoos , Animales , Antozoos/fisiología , Arrecifes de Coral , Calor , Agua
19.
Appl Environ Microbiol ; 79(23): 7491-501, 2013 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-24077702

RESUMEN

Hopanoids are pentacyclic triterpenoid lipids produced by many prokaryotes as cell membrane components. The structural variations of composite hopanoids, or bacteriohopanepolyols (BHPs), produced by various bacterial genera make them potentially useful molecular biomarkers of bacterial communities and metabolic processes in both modern and ancient environments. Building on previous work suggesting that organisms in low-oxygen environments are important contributors to BHP production in the marine water column and that there may be physiological roles for BHPs specific to these environments, this study investigated the relationship between trends in BHP structural diversity and abundance and the genetic diversity of BHP producers for the first time in a low-oxygen environment of the Eastern Tropical North Pacific. Amplification of the hopanoid biosynthesis gene for squalene hopene cyclase (sqhC) indicated far greater genetic diversity than would be predicted by examining BHP structural diversity alone and that greater sqhC genetic diversity exists in the marine environment than is represented by cultured representatives and most marine metagenomes. In addition, the genetic relationships in this data set suggest microaerophilic environments as potential "hot spots" of BHP production. Finally, structural analysis of BHPs showed that an isomer of the commonly observed BHP bacteriohopanetetrol may be linked to a producer that is more abundant in low-oxygen environments. Results of this study increase the known diversity of BHP producers and provide a detailed phylogeny with implications for the role of hopanoids in modern bacteria, as well as the evolutionary history of hopanoid biosynthesis, both of which are important considerations for future interpretations of the marine sedimentary record.


Asunto(s)
Bacterias/clasificación , Bacterias/genética , Biodiversidad , Metagenoma , Agua de Mar/microbiología , Triterpenos/metabolismo , California , Análisis por Conglomerados , ADN Bacteriano/química , ADN Bacteriano/genética , Liasas/genética , Datos de Secuencia Molecular , Oxígeno/análisis , Filogenia , Agua de Mar/química , Análisis de Secuencia de ADN
20.
Nat Commun ; 14(1): 7412, 2023 Dec 05.
Artículo en Inglés | MEDLINE | ID: mdl-38052790

RESUMEN

Although massive biomass fluctuations of coastal-pelagic fishes are an iconic example of the impacts of climate variability on marine ecosystems, the mechanisms governing these dynamics are often elusive. We construct a 45-year record of nitrogen stable isotopes measured in larvae of Northern Anchovy (Engraulis mordax) in the California Current Ecosystem to assess patterns in food chain length. Larval trophic efficiency associated with a shortened food chain increased larval survival and produced boom periods of high adult biomass. In contrast, when larval food chain length increased, and energy transfer efficiency decreased, the population crashed. We propose the Trophic Efficiency in Early Life (TEEL) hypothesis, which states that larval fishes must consume prey that confer sufficient energy for survival, to help explain natural boom-bust dynamics of coastal pelagic fishes. Our findings illustrate a potential for trophic indicators to generally inform larval survival and adult population dynamics of coastal-pelagic fishes.


Asunto(s)
Ecosistema , Peces , Animales , Larva , Cadena Alimentaria , Dieta , Isótopos de Nitrógeno/análisis
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